U.S. patent application number 10/390692 was filed with the patent office on 2004-02-05 for sulfonamide derivatives.
Invention is credited to Nakayama, Masaharu, Tabuchi, Takanori, Yamamoto, Tetsuhiro.
Application Number | 20040023938 10/390692 |
Document ID | / |
Family ID | 14853728 |
Filed Date | 2004-02-05 |
United States Patent
Application |
20040023938 |
Kind Code |
A1 |
Tabuchi, Takanori ; et
al. |
February 5, 2004 |
Sulfonamide derivatives
Abstract
The present invention relates to microbicides for agricultural
or horticultural use containing sulfonamide derivative of, for
example, a formula (I): 1 or a salt thereof, [wherein A.sup.1 is
(1) an aryl group which may be substituted or (2) a heterocyclic
group which may be substituted, X.sup.1 is (1) a chemical bond, (2)
a methylene group which may be substituted, or (3) a vinylene group
which may be substituted, B.sup.1 is a five-membered heterocyclic
group comprising nitrogen or sulfur atoms as the ring-constructing
atoms except for carbon atoms and may be substituted or a condensed
heterocyclic group which may be substituted, Z.sup.1 is (1) a
hydrocarbon group which may be substituted, (2) an acyl group which
may be substituted, (3) formyl group, (4) an amino group which may
be substituted, (5) a group represented by --N.dbd.CR.sup.1R.sup.2
(wherein each of R.sup.1 and R.sup.2 is a hydrogen atom or a
hydrocarbon group which may be substituted), (6) a cyclic amino
group, (7) a group represented by --OR.sup.3 (wherein R.sup.3 is a
hydrogen atom, a hydrocarbon group which may be substituted, an
acyl group which may be substituted, formyl group or an
alkylsulfonyl group which may be substituted) or (8)
--S(O).sub.nR.sup.4 (wherein n stands for an integer from 0 to 2,
R.sup.4 stands for a hydrogen atom or a hydrocarbon group which may
be substituted). The said compounds or the salts thereof are
sulfonamide derivatives with microbicidal action, are useful as
excellent microbicides for agricultural or horticultural use,
because they are safe, and they have little influence on human
beings, farm animals, natural enemies, or the environment, and
exert excellent control effects even on resistant microbes.
Inventors: |
Tabuchi, Takanori;
(Tsukuba-shi, JP) ; Yamamoto, Tetsuhiro;
(Toride-shi, JP) ; Nakayama, Masaharu;
(Tsukuba-shi, JP) |
Correspondence
Address: |
WENDEROTH, LIND & PONACK, L.L.P.
2033 K STREET N. W.
SUITE 800
WASHINGTON
DC
20006-1021
US
|
Family ID: |
14853728 |
Appl. No.: |
10/390692 |
Filed: |
March 19, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10390692 |
Mar 19, 2003 |
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09958953 |
Dec 18, 2001 |
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6586617 |
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09958953 |
Dec 18, 2001 |
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PCT/JP00/02764 |
Apr 17, 2000 |
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Current U.S.
Class: |
514/183 ;
514/210.17; 514/217.12; 514/330; 514/423; 514/424; 514/601 |
Current CPC
Class: |
C07C 311/49 20130101;
C07C 323/63 20130101; C07C 2601/02 20170501; A01N 43/58 20130101;
A01N 43/82 20130101; C07C 327/48 20130101; C07C 311/51 20130101;
C07C 327/58 20130101; C07C 311/46 20130101; C07C 323/49 20130101;
C07C 317/48 20130101; C07C 317/36 20130101; A01N 43/50 20130101;
A01N 2300/00 20130101; C07C 311/21 20130101; A01N 43/60 20130101;
A01N 43/40 20130101; A01N 41/06 20130101; A01N 43/56 20130101; A01N
43/90 20130101; A01N 43/42 20130101; C07C 311/44 20130101; C07C
311/13 20130101; A01N 41/06 20130101; C07C 311/48 20130101; C07C
311/29 20130101; A01N 43/10 20130101; A01N 43/80 20130101; A01N
43/653 20130101 |
Class at
Publication: |
514/183 ;
514/217.12; 514/330; 514/423; 514/424; 514/210.17; 514/601 |
International
Class: |
A01N 043/00; A01N
043/40; A01N 041/06; A01N 043/36 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 28, 1999 |
JP |
123162/1999 |
Claims
1. A microbicidal composition for agricultural or horticultural use
comprising a compound of Formula (I): 47or salt thereof [wherein
A.sup.1 is (1) an aryl group which may be substituted or (2) a
heterocyclic group which may be substituted, X.sup.1 is (1) a
chemical bond, (2) a methylene group which may be substituted, or
(3) a vinylene group which may be substituted, B.sup.1 is a
five-membered heterocyclic group (except for an isooxazolyl group)
or a condensed heterocyclic group which may be substituted, Z.sup.1
is (1) a hydrocarbon group which may be substituted, (2) an acyl
group which may be substituted, (3) formyl group, (4) an amino
group which may be substituted, (5) a group which is represented by
--N.dbd.CR.sup.1R.sup.2 (wherein each R.sup.1 and R.sup.2 is
repectively a hydrogen atom or a hydrocarobon group which may be
substituted), (6) a cyclic amino group, (7) a group which is
represented by --OR.sup.3 (wherein R.sup.3 is a hydrogen atom, a
hydrocarbon group which may be substituted, an acyl group which may
be substituted, formyl group or an alkylsulfonyl group which may be
substituted) or (8) a group represented by --S(O).sub.nR.sup.4
(wherein, n stands for an integer from 0 to 2, R.sup.4 stands for a
hydrogen atom or a hydrocarbon group which may be
substituted).]
2. A microbicidal composition for agricultural or horticultural use
as claimed in claim 1, wherein B.sup.1 is a five-membered
heterocyclic group which contains hetero-atoms selected from
nitrogen atoms and sulfur atoms as the ring-constructing hetero
atom in addition to the carbon atoms which may be substituted, or
B.sup.1 is a condensed heterocyclic group which may be
substituted.
3. A microbicidal composition as claimed in claim 1, wherein
A.sup.1 is (1) an aryl group which may be substituted with 1 to 5
substituents selected from a group of substituents (T) which
consists of (i) a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 substituents selected from halogens, hydroxyl, imino,
hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) a C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substitutents selected from halogen, cyano, and nitro,
(iv) a C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxyl group, (vii) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogen and C.sub.1-4 alkoxy group,
(viii) formyloxy group, (ix) a C.sub.1-4 alkyl-carbonyloxy group
which may be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) a sulfamoyl group, (xviii) a mono- or di-
C.sub.1-4 alkylsulfamoyl group, (xix) a group represented by
48(wherein, ring C is a 3- to 6-membered heterocyclic group
containing nitrogen), (xx) an amino group which may be substituted
with one or two substituents selected from a C.sub.1-4 alkyl,
C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4 alkoxy,
formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and C.sub.1-4
alkyl-carbonyl, (xxi) a 3- to 6-membered cyclic amino group, (xxii)
formyl group. (xxiii) a C.sub.1-4 alkyl-carbonyl group which may be
substituted with 1 to 5 halogens, (xxiv) a C.sub.1-4
alkoxy-carbonyl group which may be substituted with 1 to 5
halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group, (xxvi) a
C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxiv) a
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 49(wherein, ring C is a 3- to 6-membered
heterocyclic group containing nitrogen), (xxxi) thiocarbamoyl
group, (xxxii) a mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group,
(xxxiii) a group represented by 50(wherein, ring C is a 3- to
6-membered heterocyclic group containing nitrogen), (xxxiv) halogen
atom, (xxxv) carboxyl group, (xxxvi) thiocyanato group, (xxxvii)
isothiocyanato group, (xxxviii) cyano group, (xxxix) isocyano
group, (xl) azido group, (xli) nitoroso group, (xlii) nitro group,
(xliii) azocyano group, (xliv) azoxycyano group and (xlv) sulfo
group, or (2) a heterocyclic group which may be substituted with 1
to 5 substituents selected from the group of substituents (T)
mentioned above, X.sup.1 is (1) a chemical bond, (2) a methylene
group which may be substituted with one or two substituents
selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4
alkylthio, halogen atom and cyano or (3) a vinylene group which may
be substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, halogen atom, and
cyano, B.sup.1 is (1) a five-membered heterocyclic group which is
composed of the ring-constructing heteroatoms besides carbon atoms
selected from nitrogen and sulfur atoms, and which may be
substituted with 1 to 5 substituents selected from the group of
substituents (T) mentioned above, or (2) a condensed heterocyclic
group which is constructed either with a five- to six-membered
heterocyclic ring and benzene rings or with a five- to six-membered
heterocyclic ring and another (the same or different) five- to
six-membered heterocyclic rings and may be substituted with
substituents selected from the group of substituents (T) mentioned
above, Z.sup.1 is (1) a hydrocarbon group which is selected from
(i) a C.sub.1-6 alkyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (l)
carbamoyl and (m) a mono- or di-C.sub.1-4 alkyl-carbamoyl groups,
(ii) a C.sub.2-6 alkenyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl, and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iii) a
C.sub.2-6 alkynyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono-or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl, and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iv) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl, and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (v) a
C.sub.3-6 alkadienyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- and
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (l)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl or (vi)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (2) an
acyl group selected from (i) C.sub.1-4 alkyl-carbonyl, (ii)
C.sub.1-4 alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv)
C.sub.1-4 alkoxy-thiocarbonyl, (v) C.sub.1-4
alkylthio-thiocarbonyl, (vi) mono- or di-C.sub.1-4 alkyl-carbamoyl
and (vii) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, each of which
may be substituted with 1 to 5 halogens, (3) formyl group, (4) an
amino group which may be mono- or substituted with one or two
substituents selected from (a) C.sub.1-4 alkyl, (b) C.sub.1-4
alkyl-carbonyl which may be substituted with 1 to 5 halogens, (c)
C.sub.1-4 alkoxy-carbonyl, (d) mono- or di-C.sub.1-4
alkyl-carbamoyl and (e) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl,
(5) a group represented by --N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1
and R.sup.2 are the same or different, and are a hydrogen arom and
a C.sub.1-4 alkyl group), (6) a three- to six-membered cyclic amino
group, (7) a group represented by --OR.sup.3 (wherein R.sup.3 is a
hydrogen atom, a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 halogens, a C.sub.1-4 alkyl-carbonyl group which may be
substituted with 1 to 5 halogens, a C.sub.1-4 alkoxy-carbonyl group
which may be substituted with 1 to 5 halogens, formyl group or a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens), or (8) a group represented by --S(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, and R.sup.4 is (a) hydrogen
atom, (b) a C.sub.1-4 alkyl group which may be substituted with 1
to 5 halogens or (c) a C.sub.6-14 aryl group which may be
substituted with 1 to 5 C.sub.1-4 alkyl groups.
4. A microbicidal composition for agricultural or horticultural use
as claimed in claim 1, where A.sup.1 is a C.sub.6-14 aryl group
which may be substituted with 1 to 3 alkyl group, X.sup.1 is a
chemical bond, B.sup.1 is a thienyl group, a pyrazolyl group, an
isothiazolyl group, an imidazolyl group, a thiazolyl group, a
thiadiazolyl group, a dioxaindanyl group or a imidazopyridyl group,
each of which may be substituted with 1 to 5 substituents selected
from C.sub.1-4 alkyl which may be substituted with 1 to 5 halogens,
C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, cyano, halogens and nitro,
Z.sup.1 is a C.sub.1-6 alkyl group or a C.sub.1-4 alkoxy group.
5. A microbicidal composition for agricultural or horticultural use
comprising a compound of Formula (II): 51or salt thereof, [wherein,
A.sup.2 is (1) an aryl group which may be substituted with 1 to 5
substituents selected from a group of substitutents (T') which
consists of (i) a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 substituents selected from halogen, hydroxy, imino,
hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) a C.sub.2-4 alkenyl group which may be substituted
with substituents selected from halogens, cyano and nitro, (iv) a
C.sub.3-.sub.6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxy group, (vii) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substitutents selected from halogens and C.sub.1-4 alkoxy, (viii)
formyloxy group, (ix) a C.sub.1-4 alkyl-carbonyloxy group which may
be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens,(xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 52(wherein, ring
C is a three- to six-membered heterocyclic group containing
nitrogen), (xx) an amino group which may be mono- or disubstituted
with one or two substituents selected from C.sub.1-4 alkyl,
C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4 alkoxy,
formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and C.sub.1-4
alkyl-carbonyl, (xxi) a three- to six-membered cyclic amino group,
(xxii) formyl group, (xxiii) a C.sub.1-4 alkyl-carbonyl group which
may be substituted with 1 to 5 halogens, (xxiv) a C.sub.1-4
alkoxy-carbonyl group which may be substituted with 1 to 5
halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group, (xxvi) a
C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) a C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxix) a
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 53(wherein, ring C is a three- to six-membered
heterocyclic group containing nitrogen), (xxxi) thiocarbamoyl
group, (xxxii) a mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group,
(xxxiii) a group represented by 54(wherein, ring C is a three- to
six-membered heterocyclic group containing nitrogen), (xxxiv)
halogen atom, (xxxv) carboxyl group, (xxxvi) thiocyanato group,
(xxxvii) isothiocyanato group, (xxxviii) cyano group, (xxxix)
isocyano group, (xl) azido group, (xli) nitroso group, (xlii) nitro
group, (xliii) azocyano group and (xliv) sulfo group or (2) a
heterocyclic group, which may be substituted. X.sup.2 is (1) a
chemical bond, (2) a methylene group which may be substituted or
(3) a vinylene group which may be substituted, B.sup.2 is an aryl
group which may be substituted, Z.sup.2 is (1) an alkyl group which
may be substituted with substitutents selected from mono- or
di-C.sub.1-6 alkylamino, hydroxy, halogens, C-.sub.1-6 alkoxy,
C.sub.1-6 alkoxy-carbonyl, C.sub.1-6 alkylthio and cyano, (2) vinyl
group, (3) an allyl group, (4) a propadienyl group, (5) an alkynyl
group which may be substituted, (6) a cycloalkyl group which may be
substituted, (7) an aryl group which may be substituted, (8) an
acyl group which may be substituted, (9) formyl group, (10) an
amino group which may be substituted, (11) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the same
or different, and are a hydrogen atom and a hydrocarbon group which
may be substituted respectively), (12) a cyclic amino group, (13) a
group represented by --OR.sup.3 (wherein R.sup.3 is a hydrogen
atom, a hydrocarbon group which may be substituted, an acyl group
which may be substituted, formyl group, or an alkylsulfonyl group
which may be substituted), or (14) a group represented by
--S(O).sub.nR.sup.4 (wherein, n is an integer from 0 to 2, and
R.sup.4 is hydrogen atom or a hydrocarbon group which may be
substituted).
6. A microbicidal composition for agricultural or horticultural use
as claimed in claim 5, [wherein, A.sup.2 is (1) a C.sub.6-14 aryl
group which may be substituted with 1 to 5 substituents selected
from a group of substitutents (T') which consists of (i) a
C.sub.1-4 alkyl group which may be substituted with 1 to 5
substituents selected from halogen, hydroxy, imino, hydroxyimino,
C.sub.1-4 alkoxyimino, hydrazono, mono- or di-C.sub.1-4
alkylhydrazono and C.sub.1-4 alkylthio, (ii) a C.sub.3-6 cycloalkyl
group which may be substituted with 1 to 5 halogens, (iii)
C.sub.2-4 alkenyl group which may be substituted with 1 to 5
substituents selected from halogens, cyano and nitro, (iv) a
C.sub.3-6 cycloalkenyl group which may be substituted with 1 to 5
halogens, (v) a C.sub.2-4 alkynyl group which may be substituted
with 1 to 5 halogens, (vi) hydroxy group, (vii) a C.sub.1-4 alkoxy
group which may be substituted with 1 to 5 substitutents selected
from halogen and C.sub.1-4 alkoxy, (viii) formyloxy group, (ix) a
C.sub.1-4 alkyl-carbonyloxy group which may be substituted with 1
to 5 halogens, (x) a C.sub.1-4 alkoxy-carbonyloxy group which may
be substituted with 1 to 5 halogens, (xi) mercapto group, (xii) a
C.sub.1-4 alkylthio group which may be substituted with 1 to 5
halogens, (xiii) a C.sub.1-4 alkyl-carbonylthio group which may be
substituted with 1 to 5 halogens, (xiv) a C.sub.1-4
alkoxy-carbonylthio group which may be substituted with 1 to 5
halogens, (xv) a C.sub.1-4 alkylsulfinyl group which may be
substituted with 1 to 5 halogens, (xvi) a C.sub.1-4 alkylsulfonyl
group which may be substituted with 1 to 5 halogens, (xvii)
sulfamoyl group, (xviii) a mono- or di-C.sub.1-4 alkylsulfamoyl
group, (xix) a group represented by 55(wherein, ring C is a three-
to six-membered heterocyclic group containing nitrogen), (xx) an
amino group which may be substituted with one or two substituents
selected from C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4
alkynyl, hydroxy, C.sub.1-4 alkoxy, formyloxy, C.sub.1-4
alkyl-carbonyloxy, formyl and C.sub.1-4 alkyl-carbonyl, (xxi) a
three to six-membered cyclic amino group, (xxii) formyl group,
(xxiii) a C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 5 halogens, (xxiv) a C.sub.1-4 alkoxy-carbonyl group
which may be substituted with 1 to 5 halogens, (xxv) a C.sub.1-4
alkylthio-carbonyl group, (xxvi) a C.sub.1-4 alkoxy-thiocarbonyl
group, (xxvii) a C.sub.1-4 alkylthio-thiocarbonyl group, (xxviii)
carbamoyl group, (xxix) a mono- or di-C.sub.1-4 alkylcarbamoyl
group, (xxx) a group represented by 56(wherein, ring C is a three-
to six-membered heterocyclic group containing nitrogen), (xxxi)
thiocarbamoyl group (xxxii) a mono- or di-C.sub.1-4
alkyl-thiocarbamoyl group, (xxxiii) a group represented by
57(wherein, ring C is a three- to six-membered heterocyclic group
containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl group,
(xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii)
cyano group, (xxxix) isocyano group, (xl) azido group, (xli)
nitroso group, (xlii) nitro group, (xliii) azocyano group and
(xliv) sulfo group, or (2) heterocyclic group which may be
substituted with 1 to 5 substituents selected from a group of
substitutents (T) which consists of (i) C.sub.1-4 alkyl group which
may be substituted with 1 to 5 substituents selected from halogens,
hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono,
mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii)
a C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substituents selected from halogen, cyano and nitro,
(iv) C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxy group, (vii)
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substitutents selected from halogen and C.sub.1-4 alkoxy, (viii)
formyloxy group, (ix) C.sub.1-4 alkyl-carbonyloxy group which may
be substituted with 1 to 5 halogens, (x) C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 58(wherein, ring
C is a three- to six-membered heterocyclic group containing
nitrogen), (xx) an amino group which may be substituted with one or
two substituents selected from C.sub.1-4 alkyl, C.sub.2-4 alkenyl,
C.sub.2-4 alkynyl, hydroxy, C.sub.1-4 alkoxy, formyloxy, C.sub.1-4
alkyl-carbonyloxy, formyl and C.sub.1-4 alkyl-carbonyl, (xxi)
three- to six-membered cyclic amino group, (xxii) formyl group,
(xxiii) C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 5 halogens, (xxiv) C.sub.1-4 alkoxy-carbonyl group which
may be substituted with 1 to 5 halogens, (xxv) C.sub.1-4
alkylthio-carbonyl group, (xxvi) a C.sub.1-4 alkoxy-thiocarbonyl
group, (xxvii) C.sub.1-4 alkylthio-thiocarbonyl group, (xxviii) a
carbamoyl group, (xxix) mono- or di-C.sub.1-4 alkylcarbamoyl group,
(xxx) group represented by 59(wherein, ring C is a three- to
six-membered heterocyclic group containing nitrogen), (xxxi)
thiocarbamoyl group, (xxxii) mono- or di-C.sub.1-4
alkyl-thiocarbamoyl group, (xxxiii) group represented by
60(wherein, ring C is a three- to six-membered heterocyclic group
containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl group,
(xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii)
cyano group, (xxxix) isocyano group, (xl) azido group, (xli)
nitroso group, (xlii) nitro group, (xliii) azocyano group and
(xliv) azoxycyano group, and (xlv) sulfo group, X.sup.2 is (1) a
chemical bond, (2) a methylene group which may be substituted with
one or two substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 alkylthio, halogen atoms, and cyano, or (3)
vinylene group which may be substituted with one or two
substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 alkylthio, halogen atom and cyano, B.sup.2 is an aryl
group which may be substituted with 1 to 5 substituents selected
from the group of substituents (T) described above, Z.sup.2 is (1)
C.sub.1-6 alkyl group which may be substituted with 1 to 5
substitutents selected from mono- or di-C.sub.1-4 alkylamino,
hydroxy, halogen, C.sub.1-4 alkoxy, C.sub.1-4 alkoxy-carbonyl,
C.sub.1-4 alkylthio and cyano, (2) vinyl group, (3) allyl group,
(4) propadienyl group, (5) C.sub.2-6 alkynyl group which may be
substituted with 1 to 5 substituents selected from (a) halogen, (b)
amino, (c) mono- or di-C.sub.1-4 alkylamino, (d) hydroxy, (e) a
C.sub.1-4 alkoxy substituted with 1 to 5 halogens, (f) mercapto,
(g) C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (6)
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (7)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogens, (c) amino, (d)
mono- or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy
which may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (8) acyl
group which may be selected from (i) C.sub.1-4 alkyl-carbonyl, (ii)
C.sub.1-4 alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv)
C.sub.1-4 alkoxy-thiocarbonyl, (v) C.sub.1-4
alkylthio-thiocarbonyl, (vi) mono- or di-C.sub.1-4 alkyl-carbamoyl
and (vii) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, each of which
may be substituted with 1 to 5 halogens, (9) formyl group, (10)
amino group which may be substituted with one or two substituents
selected from (a) C.sub.1-4 alkyl, (b) C.sub.1-4 alkyl-carbonyl
which may be substituted with 1 to 5 halogens, (c) C.sub.1-4
alkoxy-carbonyl, (d) mono- or di-C.sub.1-4 alkyl-carbamoyl and (e)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, (11) a group represented
by --N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the
same or different, and are hydrogen atom and a C.sub.1-4 alkyl
group), (12) three- to six-membered cyclic amino group, (13) a
group represented by --OR.sup.3 (wherein R.sup.3 is hydrogen atom,
a C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, a C.sub.1-4 alkoxy-carbonyl group which may be
substituted with 1 to 5 halogens, formyl group, or C.sub.1-4
alkylsulfonyl group which may be substituted with 1 to 5 halogens),
or (14) a group represented by --S(O).sub.nR.sup.4 (wherein n is an
integer from 0 to 2, and R.sup.4 (a) hydrogen atom, (b) C.sub.1-4
alkyl group which may be substituted with 1 to 5 halogens or (c)
C.sub.6-14 aryl group which may be substituted with 1 to 5
C.sub.1-4 alkyl groups).
7. A microbicidal composition for agricultural or horticultural use
as claimed in claim 5, wherein A.sup.2 is (1) C.sub.6-14 aryl
group, which may be substituted with 1 to 5 substituents selected
from (i) C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, (ii) C.sub.1-4 alkoxy group which may be substituted with
1 to 5 halogens, (iii) amino group which may be substituted with
one or two C.sub.1-4 alkyl-carbonyl grouop, (iv) C.sub.1-4
alkoxy-carbonyl group, (v) halogen atom, (vi) cyano group and (vii)
nitro group, or (2) thienyl group, triazolyl group, imidazolyl
group, isooxazolyl group, pyrazolyl group, pyridyl group, quinolyl
group, a benzothiadiazolyl group, an imidazothiazolyl group or an
imidazopyridyl group, which may be substituted with 1 to 5
substituents selected from (i) C.sub.1-4 alkyl group, (ii)
C.sub.1-4 alkoxy-carbonyl group, (iii) carbamoyl group, (iv) mono-
or di-C.sub.1-4 alkylcarbamoyl group, (v) C.sub.1-4 alkylsulfonyl
group, (vi) halogen atom, (vii) carboxyl group and (viii) cyano
group, X.sup.2 is (1) a chemical bond, (2) a methylene group which
may substituted with one or two C.sub.1-4 alkyl group, or (3) a
vinylene group which may be substituted with one or two C.sub.1-4
alkyl, B.sup.2 is a C.sub.6-14 aryl group which may be substituted
with 1 to 5 Substituents selected from (1) a C.sub.1-4 alkyl group
which may be substituted with 1 to 5 substituents selected from
halogen, hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino,
hydrazono,mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4
alkylthio, (2) C.sub.2-4 alkynyl group, (3) hydroxy group, (4) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substitutents selected from halogens and C.sub.1-4 alkoxy, (5) a
C.sub.1-4 alkyl-carbonyloxy group, (6) a C.sub.1-4 alkylthio group,
(7) a C.sub.1-4 alkylsulfinyl group, (8) a C.sub.1-4 alkylsulfonyl
group, (9) mono- or di-C.sub.1-4 alkylsulfamoyl group, (10) amino
group, (11) formyl group, (12) C.sub.1-4 alkoxy-carbonyl group,
(13) carbamoyl group, (14) mono- or di-C.sub.1-4 alkylcarbamoyl
group, (15) thiocarbamoyl group, (16) halogen atom, (17) carboxyl
group, (18) thiocyanato group, (19) cyano group, (20) nitroso group
and (21) nitro group, Z.sup.2 is (1) a C.sub.1-6 alkyl group which
may be substituted with 1 to 5 substituents selected from mono- or
di-C.sub.1-4 alkylamino, hydroxy, halogen, C.sub.1-4 alkoxy,
C.sub.1-4 alkoxy-carbonyl, C.sub.1-4 alkylthio and cyano, (2) vinyl
group, (3) allyl group, (4) propadienyl group, (5) C.sub.2-6
alkynyl group which may be substituted with 1 to 5 halogens, (6)
C.sub.3-6 cycloalkyl group, (7) C.sub.6-14 aryl group, (8)
C.sub.1-4 alkyl-carbonyl which may be substituted with 1 to 5
halogens, (9) an amino group which may be substituted with one or
two substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkyl-carbonyl and C.sub.1-4 alkoxy-carbonyl, (10) a group
represented by --N.dbd.CR.sup.1R.sup.2 (wherein, both R.sup.1 and
R.sup.2 are the same or different C.sub.1-4 alkyl groups), (11) a
group represented by --OR.sup.3 (wherein R.sup.3 is a C.sub.1-4
alkyl group or a C.sub.1-4 alkyl-carbonyl group), or (12) a group
represented by --S(O).sub.nR.sup.4 (wherein n is an integer from 0
to 2, R.sup.4 is (a) a C.sub.1-4 alkyl group which may be
substituted with 1 to 5 halogens, or (b) a C.sub.6-14 aryl group
which may be substituted with 1 to 5 C.sub.1-4 alkyl groups).
8. A microbicidal composotion for agricultural or horticultural use
as claimed in claim 5, wherein 61or salt thereof, [wherein, A.sup.3
is (1) an aryl group which may be substituted or (2) a heterocyclic
group which may be substituted, X.sup.3 is (1) a chemical bond, (2)
a methylene group which may be substituted, or (3) a vinylene group
which may be substituted, B.sup.3 is a six-membered heterocyclic
group which is substituted with substituents selected from the
group of substituents (T), which consists of (i) a C.sub.1-4 alkyl
group which may be substituted with 1 to 5 substituents selected
from halogen, hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino,
hydrazono, mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4
alkylthio, (ii) C.sub.3-6 cycloalkyl group which may be substituted
with 1 to 5 halogen, (iii) a C.sub.2-4 alkenyl group which may be
substituted with 1 to 5 substituents selected from halogens, cyano
and nitro, (iv) a C.sub.3-6 cycloalkenyl group which may be
substituted with 1 to 5 halogens, (v) a C.sub.2-4 alkynyl group
which may be substituted with 1 to 5 halogens, (vi) hydroxy group,
(vii) a C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substitutents selected from halogen and C.sub.1-4 alkoxy group,
(viii) formyloxy group, (ix) C.sub.1-4 alkyl-carbonyloxy group
which may be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogen, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 62(wherein, ring
C is a three- to six-membered heterocyclic group containing
nitrogen), (xx) an amino group which may be substituted with one or
two substituents selected from C.sub.1-4 alkyl, C.sub.2-4 alkenyl,
C.sub.2-4 alkynyl, hydroxy, C.sub.1-4 alkoxy, formyloxy, C.sub.1-4
alkyl-carbonyloxy, formyl and C.sub.1-4 alkyl-carbonyl, (xxi) a
three- to six-membered cyclic amino group, (xxii) formyl group,
(xxiii) a C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 5 halogens, (xxiv) a C.sub.1-4 alkoxy-carbonyl group
which may be substituted with 1 to 5 halogens, (xxv) a C.sub.1-4
alkylthio-carbonyl group, (xxvi) a C.sub.1-4 alkoxy-thiocarbonyl
group, (xxvii) a C.sub.1-4 alkylthio-thiocarbonyl group, (xxviii)
carbamoyl group, (xxix) a mono- or di-C.sub.1-4 alkylcarbamoyl
group, (xxx) a group represented by 63(wherein, ring C is a three-
to six-membered heterocyclic group containing nitrogen), (xxxi)
thiocarbamoyl group, (xxxii) mono- or di-C.sub.1-4
alkyl-thiocarbamoyl group, (xxxiii) a group which is represented by
64(wherein, ring C is a three- to six-membered heterocyclic group
containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl group,
(xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii)
cyano group, (xxxix) isocyano group, (xl) azido group, (xli)
nitroso group, (xlii) nitro group, (xliii) azocyano group (xliv)
azoxycyano group, and (xlv) sulfo group, Z.sup.3 is (1) a
hydrocarbon group which may be substituted, (2) an acyl group which
may be substituted, (3) formyl group, (4) an amino group which may
be substituted, (5) a group represented by --N.dbd.CR.sup.1R.sup.2
(wherein, R.sup.1 and R.sup.2 are the same or different, and a
hydrogen atom or hydrocarbon group which may be substituted), (6)
cyclic amino group, (7) a group represented by --OR.sup.3 (wherein,
R.sup.3 stands for a hydrogen atom, a hydrocarbon group which may
be substituted, an acyl group which may be substituted, formyl
group or sulfonyl group which may be substituted), or (8) a group
represented by --S(O).sub.nR.sup.4 (wherein, n is an integer from 0
to 2, R.sup.4 is hydrogen atom or a hydrocarbon group which may be
substituted)].
11. A microbicidal composition for agricultural or horticultural
use as claimed in claim 10, wherein A.sup.3 is (1) C.sub.6-14 aryl
group which may be substituted with 1 to 5 substituents selected
from (i) C1-4 alkyl group which may be substituted with 1 to 5
substituents selected from halogens, hydroxy, imino, hydroxyimino,
C.sub.1-4 alkoxyimino, hydrazono, mono- or di-C.sub.1-4
alkylhydrazono and C.sub.1-4 alkylthio, (ii) C.sub.3-6 cycloalkyl
group which may be substituted with 1 to 5 halogens, (iii)
C.sub.2-4 alkenyl group which may be substituted with 1 to 5
substituents selected from halogen, cyano and nitro, (iv) C.sub.3-6
cycloalkenyl group which may be substituted with 1 to 5 halogens,
(v) C.sub.2-4 alkynyl group which may be substituted with 1 to 5
halogens, (vi) hydroxy group, (vii) C.sub.1-4 alkoxy group which
may be substituted with 1 to 5 substitutents selected from halogen
and C.sub.1-4 alkoxy, (viii) formyloxy group, (ix) C.sub.1-4
alkyl-carbonyloxy group which may be substituted with 1 to 5
halogens, (x) C.sub.1-4 alkoxy-carbonyloxy group which may be
substituted with 1 to 5 halogens, (xi) mercapto group, (xii)
C.sub.1-4 alkylthio group which may be substituted with 1 to 5
halogens, (xiii) C.sub.1-4 alkyl-carbonylthio group which may be
substituted with 1 to 5 halogens, (xiv) C.sub.1-4
alkoxy-carbonylthio group which may be substituted with 1 to 5
halogens, (xv) C.sub.1-4 alkylsulfinyl group which may be
substituted with 1 to 5 halogens, (xvi) C.sub.1-4 alkylsulfonyl
group which may be substituted with 1 to 5 halogens, (xvii)
sulfamoyl group, (xviii) mono- or di-C.sub.1-4 alkylsulfamoyl
group, (xix) group represented by 65(wherein, ring C is a three- to
six-membered heterocyclic group containing nitrogen), (xx) amino
group which may be substituted with one or two substituents
selected from C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4
alkynyl, hydroxy, C.sub.1-4 alkoxy, formyloxy, C.sub.1-4
alkyl-carbonyloxy, formyl and C.sub.1-4 alkyl-carbonyl, (xxi)
three- to six-membered cyclic amino group, (xxii) formyl group,
(xxiii) C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 5 halogens, (xxiv) C.sub.1-4 alkoxy-carbonyl group which
may be substituted with 1 to 5 halogens, (xxv) C.sub.1-4
alkylthio-carbonyl group, (xxvi) C.sub.1-4 alkoxy-thiocarbonyl
group, (xxvii) C.sub.1-4 alkylthio-thiocarbonyl group, (xxviii)
carbamoyl group, (xxix) mono- or di-C.sub.1-4 alkylcarbamoyl group,
(xxx) group represented by 66(wherein, ring C is a three- to
six-membered heterocyclic group containing nitrogen), (xxxi)
thiocarbamoyl group, (xxxii) mono- or di-C.sub.1-4
alkyl-thiocarbamoyl group, (xxxiii) a group represented by
67(wherein, ring C is a three- to six-membered heterocyclic group
containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl group,
(xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii)
cyano group, (xxxix) isocyano group, (xl) azido group, (xli)
nitroso group, (xlii) nitro group, (xliii) azocyano group (xliv)
azoxycyano group, and (xlv) sulfo group, or (2) a heterocyclic
group which may be substituted with 1 to 5 substituents selected
from a group of substituents (T) above, X.sup.3 is (1) chemical
bond, (2) methylene group which may be substituted with one or two
substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 alkylthio, halogen atoms and cyano, (3) a vinylene group
which may be substituted with one or two substituents selected from
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, halogen
atoms and cyano, B.sup.3 is a six-membered heterocyclic group which
is substituted with 1 to 5 substituents selected from the group of
substituents (T) mentioned above, Z.sup.3 is (1) a hydrocarbon
group which is selected from (i) a C.sub.1-6 alkyl group which may
be substituted with 1 to 5 substituents selected from (a) halogen,
(b) amino, (c) mono- or di-C.sub.1-4 alkylamino, (d) hydroxy, (e)
C.sub.1-4 alkoxy which may be substituted with 1 to 5 halogens, (f)
mercapto, (g) C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i)
C.sub.1-4 alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl,
(1) carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (ii)
C.sub.2-6 alkenyl which may be substituted with 1 to 5 substituents
selected from (a) halogens, (b) amino, (c) mono- or di-C.sub.1-4
alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which may be
substituted with 1 to 5 halogens, (f) mercapto, (g) C.sub.1-4
alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iii)
C.sub.2-6 alkynyl which may be substituted with 1 to 5 substituents
selected from (a) halogen, (b) amino, (c) mono- or di-C.sub.1-4
alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which may be
substituted with 1 to 5 halogens, (f) mercapto, (g) C.sub.1-4
alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iv)
C.sub.3-6 cycloalkyl groups which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (v)
C.sub.3-6 alkadienyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, and (vi)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from C.sub.1-4 alkyl which may be substituted
with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono- or
di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (2) an
acyl group selected from (i) C.sub.1-4 alkyl-carbonyl, (ii)
C.sub.1-4 alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv)
C.sub.1-4 alkoxy-thiocarbonyl, (v) C.sub.1-4
alkylthio-thiocarbonyl, (vi) mono- or di-C.sub.1-4 alkyl-carbamoyl
and (vii) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, each of these
groups may be substituted with 1 to 5 halogens, (3) formyl group,
(4) an amino group which may be substituted with one or two
substituents selected from (a) C.sub.1-4 alkyl, (b) C.sub.1-4
alkyl-carbonyl which may be substituted with 1 to 5 halogens, (c)
C.sub.1-4 alkoxy-carbonyl, (d) mono- or di-C.sub.1-4
alkyl-carbamoyl, (e) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, (5)
a group represented by --N.dbd.CR.sup.1R.sup.2 (wherein, R.sup.1
and R.sup.2 are the same or different, are hydrogen atom or
C.sub.1-4 alkyl group), (6) three- to six-membered cyclic amino
group, (7) a group represented by --OR.sup.3 (wherein, R.sup.3 is
hydrogen atom, a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 halogens, a C.sub.1-4 alkyl-carbonyl group which may be
substituted with 1 to 5 halogens, a C.sub.1-4 alkoxy-carbonyl group
which may be substituted with 1 to 5 halogens, formyl group or a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens), or (8) a group represented by --OS(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, R.sup.4 is (a) hydrogen atom,
(b) C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, or (c) C.sub.6-14 aryl group which may be substituted
with 1 to 5 C.sub.1-4 alkyl groups).
12. A microbicidal composition for agricultural or horticultural
use as claimed in claim 10, wherein A.sup.3 is phenyl group which
may be substituted with 1 to 5 C.sub.1-4 alkyl groups, or a
imidazolyl group which may be substituted with one or two C.sub.1-4
alkyl groups, X.sup.3 is a chemical bond, B.sup.3 is a pyridyl
group, a pyridazinyl group or a pyrimidinyl group which is
substituted with 1 to 5 substituents selected from C.sub.1-4 alkyl
which may be substituted with 1 to 5 halogens, C.sub.1-4 alkoxy,
halogen, nitro and cyano, Z.sup.3 is a C.sub.1-6 alkyl group, a
C.sub.3-6 cycloalkyl group or a C.sub.1-4 alkoxy group.
13. A microbicidal composition for agricultural or horticultural
use comprising a compound of Formula (IV) 68or salt thereof,
[wherein, A.sup.4 is (1) an aryl group which may be substituted, or
(2) a heterocyclic group which may be substituted, X.sup.4 is (1) a
chemical bond, (2) a methylene group which may be substituted, or
(3) a vinylene group which may be substituted, B.sup.4 is a
pyridazinyl group or a pyrazinyl group, Z.sup.4 is (1) a
hydrocarbon group which may be substituted, (2) an acyl group which
may be substituted, (3) formyl group, (4) an amino group which may
be substituted, (5) a group represented by --N.dbd.CR.sup.1R.sup.2
(wherein R.sup.1 and R.sup.2 are the same or different, and
hydrogen atom or hydrocarbon group which may be substituted), (6) a
cyclic amino group, (7) a group represented by --OR.sup.3 (wherein,
R.sup.3 is hydrogen atom, a hydrocarbon group which may be
substituted, an acyl group which may be substituted, formyl group
or a sulfonyl group which may be substituted), or (8) a group
represented by --S(O).sub.nR.sup.4 (wherein, n is an integer from 0
to 2, R.sup.4 is hydrogen atom or a hydrocarbon group which may be
substituted)].
14. A microbicide for agricultural or horticultural use comprising
a compound of Formula (V) 69or salt thereof, [wherein A.sup.5 is
the 4-methylphenyl group, X.sup.5 is a chemical bond, B.sup.5 is a
pyridyl or pyrimidinyl group, and Z.sup.5 is a C.sub.1-4 alkyl
group].
15. A compound of Formula (VI): 70or salt thereof, [wherein A.sup.6
is a phenyl group which may be substituted with a substituent or
substituents selected from C.sub.1-4 alkyl, halogens and cyano,
x.sup.6 is a chemical bond, B.sup.6 is a 2-nitrophenyl group or
2-cyanophenyl group which may be substituted with a substituent or
substituents selected from halogens, nitro and cyano, Z.sup.6 is
ethyl, isopropyl, cyclopropyl, methoxy, ethoxy or isopropoxy
group].
16. A compound or a salt thereof as claimed in claim 15, wherein
A.sup.6 is a phenyl group which may be substituted with a
substituent or substituents selected from C.sub.1-4 alkyl, halogens
and cyano, X.sup.6 is a chemical bond, B.sup.6 is a 2-nitrophenyl
group which is substituted with a substituent or substituents
selected from halogens, nitro and cyano, Z.sup.6 is ethyl,
isopropyl, or cyclopropyl group).
17. A compound or a salt thereof as claimed in claim 15, the
compound is 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide,
2',4'-dinitro-N-ethyl-p-toluenesulfonanilide,
2',4'-dicyano-N-ethyl-p-tol- uenesulfonanilide,
4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide,
2',4'-dinitro-N-isopropyl-p-toluenesulfonanilide,
4'-nitro-N-isopropyl-2'- -cyano-p-toluenesulfonanilide,
2'-cyano-N-methoxy-4'-nitro-p-toluenesulfon- anilide or
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt
thereof.
18. A method for manufacturing a compound represented by a Formula:
71or a salt thereof (wherein each symbol has the same meaning as
defined in claim 15 characterized by: (1) reacting a compound
represented by a Formula: 72or a salt thereof (wherein each symbol
has the same meaning as defined in claim 15 with an electrophile
represented by Formula Z.sup.6-L" (wherein L" is a leaving group,
and Z.sup.6 has the same meaning as defined in claim 15, (2)
reacting a compound represented by a Formula:
A.sup.6-X.sup.6--SO.sub.2-L or a salt thereof, (wherein L is a
leaving group, and each of other symbols has the same meanings as
those defined in claim 15, respectively) with an amine or a salt
thereof represented by Formula Z.sup.6HN--B.sup.6 (wherein each
symbol has the same meaning as defined in claim 15, or, by (3)
reacting a compound represented by a Formula:
A.sup.6-X.sup.6--SO.sub.2--NHZ.sup.6 or a salt thereof (wherein,
each symbol has the same meaning as described in claim 15 to react
with a compound or a salt thereof represented by Formula L'-B.sup.6
(wherein L' is a leaving group, and the other symbol has the same
meaning as defined in claim 15, respectively), or (4) nitrating a
compound represented by a Formula: 73or a salt thereof (wherein,
B.sup.7 is a phenyl group which is substituted with a substituent
or substituents selected from halogen, nitro and cyano, provided
that both 2- and 6-positions are not substituted at the same time).
Description
TECHNICAL FIELD
[0001] This invention relates to sulfonamide derivatives useful as
microbicides for agricultural or horticultural use.
BACKGROUND ART
[0002] A lot of microbicides have ever been synthesized and used as
microbicides for agriculture or horticulture. They have contributed
greatly to supply agricultural products constantly. However, it is
well-known that frequent use of restricted number of compounds has
led to outbreak of microbes which are resistant to those drugs. In
addition, recent rise in demand for the safety and environmental
influence of chemical substances has made it desirable to develop
safer microbicides for agricultural or horticultural use. This has
given an intention to the researches to explore and research novel
compounds with microbicidal activity. As for sulfonamide
derivatives, a lot of compounds have also been synthesized so far
from the interests in their biological or chemical characteristics.
A majority of them are, however, synthetic intermediates,
medicines, compounds prepared for the aim of elucidating chemical
reaction mechanism or reagents. As for sulfonamide derivatives
related to microbicides, there may be cited those described in
Japanese Patent Publication for Laid-Open 286366/1986, Japanese
Patent Publication for Laid-Open 239264/1988, Japanese Patent
Publication for Laid-Open 238006/1988, Japanese Patent Publication
for Laid-Open 307851/1988, Japanese Patent Publication for
Laid-Open 156952/1989, and in J. Med. Chem. 1983, 26, 1741, and in
DE19725447, and so on. Nevertheless, no sulfonamide derivative has
been developed yet, which is safe and has little influence on human
beings and firm animals, natural enemies, and the environment, and
exert excellent protective effects even on drug-resistant
microbes.
DISCLOSURE OF INVENTION
[0003] The present inventors have made intensive efforts for many
years in order to find out compounds which have excellent
microbicidal action and solve the problems mentioned above. As the
results, they have found that the compounds represented by the
formula I.sup.0 or salts thereof. 2
[0004] [wherein, A.sup.0 is (1) an aryl group which may be
substituted, or (2) a heterocyclic group which may be substituted,
X.sup.0 is (1) a chemical bond, (2) a methylene group which may be
substituted or (3) a vinylene group which may be substituted,
B.sup.0 is a heterocyclic group which may be substituted or an aryl
group which may be substituted, Z.sup.0 is (1) a hydrocarbon group
which may be substituted, (2) an acyl group which may be
substituted, (3) formyl group, (4) an amino group which maybe
substituted, (5) --N.dbd.CR.sup.1R.sup.2(wherein R.sup.1 and
R.sup.2is a hydrogen atom or a hydrocarbon group which may be
substituted), (6) a cyclic amino group, (7) --OR.sup.3(wherein
R.sup.3 is a hydrogen atom, a hydrocarbon group which may be
substituted, an acyl group which may be substituted, formyl group
or an alkylsulfonyl group which may be substituted), or (8) a
--S(O).sub.nR.sup.4(wherein n represents an integer from 0 to 2,
and R.sup.4 is a hydrogen atom or a hydrocarbon group which may be
substituted)], (hereafter, they may also be mentioned as compounds
(I.sup.0)), or more specifically compounds (I) to (V) (as will be
stated below) or salts thereof have unexpectedly a very strong
microbicidal activity, while, on the contrary, they revealed only a
low toxicity to human being and farm animals, fishes and natural
enemies. The present inventors carried out an intensive research
based on these findings and have completed the present
invention.
[0005] Thus, the present invention relates to:
[0006] [1] A microbicidal composition for agricultural or
horticultural use comprising a compound of Formula (I): 3
[0007] or a salt thereof
[0008] [wherein A.sup.1 is (1) an aryl group which may be
substituted or (2) a heterocyclic group which may be substituted,
X.sup.1 is (1) a chemical bond, (2) a methylene group which may be
substituted, or (3) a vinylene group which may be substituted,
B.sup.1 is a five-membered heterocyclic group (except for an
isoxazolyl group) or a condensed heterocyclic group which may be
substituted, Z.sup.1 is (1) a hydrocarbon group which may be
substituted, (2) an acyl group which may be substituted, (3) formyl
group, (4) an amino group which may be substituted, (5) a group
which is represented by --N.dbd.CR.sup.1R.sup.2(- wherein each
R.sup.1 and R.sup.2is respectively a hydrogen atom or a hydrocarbon
group which may be substituted), (6) a cyclic amino group, (7) a
group which is represented by --OR.sup.3 (wherein R.sup.3 is a
hydrogen atom, a hydrocarbon group which may be substituted, an
acyl group which may be substituted, formyl group or an
alkylsulfonyl group which may be substituted) or (8) a group
represented by --S(O).sub.nR.sup.4 (wherein, n stands for an
integer from 0 to 2, R.sup.4 stands for a hydrogen atom or a
hydrocarbon group which may be substituted).]
[0009] [2] A microbicidal composition for agricultural or
horticultural use described in [1] above, wherein B.sup.1 is a
five-membered heterocyclic group which contains hetero-atoms
selected from nitrogen atoms and sulfur atoms as the
ring-constructing hetero atom in addition to the carbon atoms which
may be substituted, or B.sup.1 is a condensed heterocyclic group
which may be substituted.
[0010] [3] A microbicidal composition described in [1] above,
wherein A.sup.1 is (1) an aryl group which may be substituted with
1 to 5 substituents selected from a group of substituents (T) which
consists of (i) a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 substituents selected from halogens, hydroxy, imino,
hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) a C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substituents selected from halogen, cyano, and nitro,
(iv) a C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxyl group, (vii) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogen and C.sub.1-4 alkoxy group,
(viii) formyloxy group, (ix) a C.sub.1-4 alkyl-carbonyloxy group
which may be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) a sulfamoyl group, (xviii) a mono- or di-
C.sub.1-4 alkylsulfamoyl group, (xix) a group represented by 4
[0011] (wherein, ring C is a 3- to 6-membered heterocyclic group
containing nitrogen), (xx) an amino group which may be substituted
with one or two substituents selected from a C.sub.1-4 alkyl,
C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4 alkoxy,
formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and C.sub.1-4
alkyl-carbonyl, (xxi) a 3- to 6-membered cyclic amino group, (xxii)
formyl group. (xxiii) a C.sub.1-4 alkyl-carbonyl group which may be
substituted with 1 to 5 halogens, (xxiv) a C.sub.1-4
alkoxy-carbonyl group which may be substituted with 1 to 5
halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group, (xxvi) a
C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxix) a
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 5
[0012] (wherein, ring C is a 3- to 6-membered heterocyclic group
containing nitrogen), (xxxi) thiocarbamoyl group, (xxxii) a mono-
or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
represented by 6
[0013] (wherein, ring C is a 3- to 6-membered heterocyclic group
containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl group,
(xxxvi) thiocyanato group, (xxxvii) isothiocyanato group, (xxxviii)
cyano group, (xxxix) isocyano group, (xl) azido group, (xli)
nitroso group, (xlii) nitro group, (xliii) azocyano group, (xliv)
azoxycyano group and (xlv) sulfo group, or (2) a heterocyclic group
which may be substituted with 1 to 5 substituents selected from the
group of substituents (T) mentioned above,
[0014] X.sup.1 is (1) a chemical bond, (2) a methylene group which
may be substituted with one or two substituents selected from
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, halogen
atom and cyano or (3) a vinylene group which may be substituted
with one or two substituents selected from C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, halogen atom, and cyano,
B.sup.1 is (1) a five-membered heterocyclic group which is composed
of the ring-constructing heteroatoms besides carbon atoms selected
from nitrogen and sulfur atoms, and which may be substituted with 1
to 5 substituents selected from the group of substituents (T)
mentioned above, or (2) a condensed heterocyclic group which is
constructed either with a five- to six-membered heterocyclic ring
and benzene rings or with a five- to six-membered heterocyclic ring
and another (the same or different) five- to six-membered
heterocyclic rings and may be substituted with substituents
selected from the group of substituents (T) mentioned above,
Z.sup.1 is (1) a hydrocarbon group which is selected from (i) a
C.sub.1-6 alkyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) a mono- or di-C.sub.1-4 alkyl-carbamoyl group,
(ii) a C.sub.2-6 alkenyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl, and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iii) a
C.sub.2-6 alkynyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i)C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl, and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iv) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl, and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (v) a
C.sub.3-6 alkadienyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- and
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h). C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (l)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl or (vi)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (2) an
acyl group selected from (i) C.sub.1-4 alkyl-carbonyl, (ii)
C.sub.1-4 alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv)
C.sub.1-4 alkoxy-thiocarbonyl, (v) C.sub.1-4
alkylthio-thiocarbonyl, (vi) mono- or di-C.sub.1-4 alkyl-carbamoyl
and (vii) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, each of which
may be substituted with 1 to 5 halogens, (3) formyl group, (4) an
amino group which may be substituted with one or two substituents
selected from (a) C.sub.1-4 alkyl, (b) C.sub.1-4 alkyl-carbonyl
which may be substituted with 1 to 5 halogens, (c) C.sub.1-4
alkoxy-carbonyl, (d) mono- or di-C.sub.1-4 alkyl-carbamoyl and (e)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, (5) a group represented
by --N.dbd.CR.sup.1R.sup.2(w- herein R.sup.1 and R.sup.2 are the
same or different, and are a hydrogen atom and a C.sub.1-4 alkyl
group), (6) a three- to six-membered cyclic amino group, (7) a
group represented by --OR.sup.3 (wherein R.sup.3 is a hydrogen
atom, a C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, a C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 5 halogens, a C.sub.1-4 alkoxy-carbonyl group which may
be substituted with 1 to 5 halogens, formyl group or a C.sub.1-4
alkylsulfonyl group which may be substituted with 1 to 5 halogens),
or (8) a group represented by --S(O).sub.nR.sup.4 (wherein n is an
integer from 0 to 2, and R.sup.4 is (a) a hydrogen atom, (b) a
C.sub.1-4 alkyl group which may be substituted with 1 to 5 halogens
or (c) a C.sub.6-14 aryl group which may be substituted with 1 to 5
C.sub.1-4 alkyl groups.
[0015] [4] A microbicidal composition for agricultural or
horticultural use described in [1] above, where A.sup.1 is a
C.sub.6-14 aryl group which may be substituted with 1 to 3 alkyl
group, X.sup.1 is a chemical bond, B.sup.1 is a thienyl group, a
pyrazolyl group, an isothiazolyl group, an imidazolyl group, a
thiazolyl group, a thiadiazolyl group, a dioxaindanyl group or an
imidazopyridyl group, each of which may be substituted with 1 to 5
substituents selected from C.sub.1-4 alkyl which may be substituted
with 1 to 5 halogens, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, cyano,
halogens and nitro, Z.sup.1 is a C.sub.1-6 alkyl group or a
C.sub.1-4 alkoxy group.
[0016] [5] A microbicidal composition for agricultural or
horticultural use comprising a compound of Formula (II): 7
[0017] or a salt thereof,
[0018] [wherein, A.sup.2 is (1)an aryl group which may be
substituted with 1 to 5 substituents selected from a group of
substituents (T') which consists of (i) a C.sub.1-4 alkyl group
which may be substituted with 1 to 5 substituents selected from
halogen, hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino,
hydrazono, mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4
alkylthio, (ii) a C.sub.3-6 cycloalkyl group which may be
substituted with 1 to 5 halogens, (iii) a C.sub.2-4 alkenyl group
which may be substituted with substituents selected from halogens,
cyano and nitro, (iv) a C.sub.3-6 cycloalkenyl group which may be
substituted with 1 to 5 halogens, (v) a C.sub.2-4 alkynyl group
which may be substituted with 1 to 5 halogens, (vi) hydroxy group,
(vii) a C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogens and C.sub.1-4 alkoxy, (viii)
formyloxy group, (ix) a C.sub.1-4 alkyl-carbonyloxy group which may
be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens,(xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 8
[0019] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xx) an amino group which may be mono-
or disubstituted with one or two substituents selected from
C.sub.1-4 alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy,
C.sub.1-4 alkoxy, formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl
and C.sub.1-4 alkyl-carbonyl, (xxi) a three- to six-membered cyclic
amino group, (xxii) formyl group, (xxiii) a C.sub.1-4
alkyl-carbonyl group which may be substituted with 1 to 5 halogens,
(xxiv) a C.sub.1-4 alkoxy-carbonyl group which may be substituted
with 1 to 5 halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group,
(xxvi) a C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) a C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxix) a
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 9
[0020] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxi) thiocarbamoyl group,(xxxii) a
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
represented by 10
[0021] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl
group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group,
(xxxviii) cyano group, (xxxix) isocyano group, (xl) azido group,
(xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and
(xliv) sulfo group or (2) a heterocyclic group, which may be
substituted.
[0022] X.sup.2 is (1) a chemical bond, (2) a methylene group which
may be substituted or (3) a vinylene group which may be
substituted, B.sup.2 is an aryl group which may be substituted,
Z.sup.2 is (1) an alkyl group which may be substituted with
substituents selected from mono- or di-C.sub.1-6 alkylamino,
hydroxy, halogens, C.sub.1-6 alkoxy, C.sub.1-6 alkoxy-carbonyl,
C.sub.1-6 alkylthio and cyano, (2) vinyl group, (3) an allyl group,
(4) a propadienyl group, (5) an alkynyl group which may be
substituted, (6) a cycloalkyl group which may be substituted, (7)
an aryl group which may be substituted, (8) an acyl group which may
be substituted, (9) formyl group, (10) an amino group which may be
substituted, (11) a group represented by --N.dbd.CR.sup.1R.sup.2
(wherein R.sup.1 and R.sup.2 are the same or different, and are a
hydrogen atom and a hydrocarbon group which may be substituted
respectively), (12) a cyclic amino group, (13) a group represented
by --OR.sup.3 (wherein R.sup.3 is a hydrogen atom, a hydrocarbon
group which may be substituted, an acyl group which may be
substituted, formyl group, or an alkylsulfonyl group which may be
substituted), or (14) a group represented by --S(O).sub.nR.sup.4
(wherein, n is an integer from 0 to 2, and R.sup.4 is a hydrogen
atom or a hydrocarbon group which may be substituted).
[0023] [6] A microbicidal composition for agricultural or
horticultural use described in [5] above, [wherein, A.sup.2 is (1)a
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from a group of substituents (T') which
consists of (i) a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 substituents selected from halogen, hydroxy, imino,
hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii) a
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substituents selected from halogens, cyano and nitro,
(iv) a C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxy group, (vii) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogens and C.sub.1-4 alkoxy, (viii)
formyloxy group, (ix) a C.sub.1-4 alkyl-carbonyloxy group which may
be substituted with 1 to 5 halogens, (x) a C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) a C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 11
[0024] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xx) an amino group which may be
substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4
alkoxy, formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and
C.sub.1-4 alkyl-carbonyl, (xxi) a three to six-membered cyclic
amino group, (xxii) formyl group, (xxiii) a C.sub.1-4
alkyl-carbonyl group which may be substituted with 1 to 5 halogens,
(xxiv) a C.sub.1-4 alkoxy-carbonyl group which may be substituted
with 1 to 5 halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group,
(xxvi) a C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) a C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxix) a
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 12
[0025] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxi) thiocarbamoyl group (xxxii) a
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
represented by 13
[0026] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl
group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group,
(xxxviii) cyano group, (xxxix) isocyano group, (xl) azido group,
(xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and
(xliv) sulfo group, or (2) heterocyclic group which may be
substituted with 1 to 5 substituents selected from a group of
substituents (T) which consists of (i) C.sub.1-4 alkyl group which
may be substituted with 1 to 5 substituents selected from halogens,
hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono,
mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii)
a C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substituents selected from halogens, cyano and nitro,
(iv) C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) a C.sub.2-4 alkynyl group which may be
substituted with 1 to 5 halogens, (vi) hydroxy group, (vii)
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogens and C.sub.1-4 alkoxy, (viii)
formyloxy group, (ix) C.sub.1-4 alkyl-carbonyloxy group which may
be substituted with 1 to 5 halogens, (x) C.sub.1-4
alkoxy-carbonyloxy group which may be substituted with 1 to 5
halogens, (xi) mercapto group, (xii) C.sub.1-4 alkylthio group
which may be substituted with 1 to 5 halogens, (xiii) a C.sub.1-4
alkyl-carbonylthio group which may be substituted with 1 to 5
halogens, (xiv) a C.sub.1-4 alkoxy-carbonylthio group which may be
substituted with 1 to 5 halogens, (xv) a C.sub.1-4 alkylsulfinyl
group which may be substituted with 1 to 5 halogens, (xvi) a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens, (xvii) sulfamoyl group, (xviii) a mono- or di-C.sub.1-4
alkylsulfamoyl group, (xix) a group represented by 14
[0027] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xx) an amino group which may be
substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4
alkoxy, formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and
C.sub.1-4 alkyl-carbonyl, (xxi) three- to six-membered cyclic amino
group, (xxii) formyl group, (xxiii) C.sub.1-4 alkyl-carbonyl group
which may be substituted with 1 to 5 halogens, (xxiv) C.sub.1-4
alkoxy-carbonyl group which may be substituted with 1 to 5
halogens, (xxv) C.sub.1-4 alkylthio-carbonyl group, (xxvi) a
C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) a carbamoyl group, (xxix)
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 15
[0028] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxi) thiocarbamoyl group, (xxxii)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
represented by 16
[0029] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl
group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group,
(xxxviii) cyano group, (xxxix) isocyano group, (xl) azido group,
(xli) nitroso group, (xlii) nitro group, (xliii) azocyano group and
(xliv) azoxycyano group, and (xlv) sulfo group, X.sup.2 is (1) a
chemical bond, (2) a methylene group which may be substituted with
one or two substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 alkylthio, halogen atoms, and cyano, or (3) a
vinylene group which may be substituted with one or two
substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 alkylthio, halogen atoms and cyano, B.sup.2 is an aryl
group which may be substituted with 1 to 5 substituents selected
from the group of substituents (T) described above, Z.sup.2 is (1)
C.sub.1-6 alkyl group which may be substituted with 1 to 5
substituents selected from mono- or di-C.sub.1-4 alkylamino,
hydroxy, halogen, C.sub.1-4 alkoxy, C.sub.1-4 alkoxy-carbonyl,
C.sub.1-4 alkylthio and cyano, (2) vinyl group, (3) allyl group,
(4) propadienyl group, (5) C.sub.2-6 alkynyl group which may be
substituted with 1 to 5 substituents selected from (a) halogen, (b)
amino, (c) mono- or di-C.sub.1-4 alkylamino, (d) hydroxy, (e) a
C.sub.1-4 alkoxy substituted with 1 to 5 halogens, (f) mercapto,
(g) C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (6)
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (7)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (8) acyl
group selected from (i) C.sub.1-4 alkyl-carbonyl, (ii) C.sub.1-4
alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv) C.sub.1-4
alkoxy-thiocarbonyl, (v) C.sub.1-4 alkylthio-thiocarbonyl, (vi)
mono- or di-C.sub.1-4 alkyl-carbamoyl and (vii) mono- or
di-C.sub.1-4 alkyl-thiocarbamoyl, each of which may be substituted
with 1 to 5 halogens, (9) formyl group, (10) amino group which may
be substituted with one or two substituents selected from (a)
C.sub.1-4 alkyl, (b) C.sub.1-4 alkyl-carbonyl which may be
substituted with 1 to 5 halogens, (C) C.sub.1-4 alkoxy-carbonyl,
(d) mono- or di-C.sub.1-4 alkyl-carbamoyl and (e) mono- or
di-C.sub.1-4 alkyl-thiocarbamoyl, (11) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the same
or different, and are a hydrogen atom and a C.sub.1-4 alkyl group),
(12) three- to six-membered cyclic amino group, (13) a group
represented by --OR.sup.3 (wherein R.sup.3 is a hydrogen atom, a
C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, a C.sub.1-4 alkoxy-carbonyl group which may be
substituted with 1 to 5 halogens, formyl group, or C.sub.1-4
alkylsulfonyl group which may be substituted with 1 to 5 halogens),
or (14) a group represented by --S(O).sub.nR.sup.4 (wherein n is an
integer from 0 to 2, and R.sup.4 is (a) hydrogen atom, (b)
C.sub.1-4 alkyl group which may be substituted with 1 to 5 halogens
or (c) C.sub.6-14 aryl group which may be substituted with 1 to 5
C.sub.1-4 alkyl groups).
[0030] [7] A microbicidal composition for agricultural or
horticultural use described in [5] above, wherein A.sup.2 is (1)
C.sub.6-14 aryl group, which may be substituted with 1 to 5
substituents selected from (i) C.sub.1-4 alkyl group which may be
substituted with 1 to 5 halogens, (ii) C.sub.1-4 alkoxy group which
may be substituted with 1 to 5 halogens, (iii) amino group which
may be substituted with one or two C.sub.1-4 alkyl-carbonyl group,
(iv) C.sub.1-4 alkoxy-carbonyl group, (v) halogen atom, (vi) cyano
group and (vii)-nitro group, or (2) thienyl group, triazolyl group,
imidazolyl group, isoxazolyl group, pyrazolyl group, pyridyl group,
quinolyl group, benzothiadiazolyl group, imidazothiazolyl group or
imidazopyridyl group, which may be substituted with 1 to 5
substituents selected from (i) C.sub.1-4 alkyl group, (ii)
C.sub.1-4 alkoxy-carbonyl group, (iii) carbamoyl group, (iv) mono-
or di-C.sub.1-4 alkylcarbamoyl group, (v) C.sub.1-4 alkylsulfonyl
group, (vi) halogen atom, (vii) carboxyl group and (viii) cyano
group, X.sup.2 is (1) a chemical bond, (2) a methylene group which
may be substituted with one or two C.sub.1-4 alkyl group, or (3) a
vinylene group which may be substituted with one or two C.sub.1-4
alkyl, B.sup.2 is a C.sub.6-14 aryl group which may be substituted
with 1 to 5 substituents selected from (1) a C.sub.1-4 alkyl group
which may be substituted with 1 to 5 substituents selected from
halogen, hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino,
hydrazono,mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4
alkylthio, (2) C.sub.2-4 alkynyl group, (3) hydroxy group, (4) a
C.sub.1-4 alkoxy group which may be substituted with 1 to 5
substituents selected from halogens and C.sub.1-4 alkoxy, (5) a
C.sub.1-4 alkyl-carbonyloxy group, (6) a C.sub.1-4 alkylthio group,
(7) a C.sub.1-4 alkylsulfinyl group, (8) a C.sub.1-4 alkylsulfonyl
group, (9) mono- or di-C.sub.1-4 alkylsulfamoyl group, (10) amino
group, (11) formyl group, (12) C.sub.1-4 alkoxy-carbonyl group,
(13) carbamoyl group, (14) mono- or di-C.sub.1-4 alkylcarbamoyl
group, (15) thiocarbamoyl group, (16) halogen atom, (17) carboxyl
group, (18) thiocyanato group, (19) cyano group, (20) nitroso group
and (21)nitro group, Z.sup.2 is (1) a C.sub.1-6 alkyl group which
may be substituted with 1 to 5 substituents selected from mono- or
di-C.sub.1-4 alkylamino, hydroxy, halogen, C.sub.1-4 alkoxy,
C.sub.1-4 alkoxy-carbonyl, C.sub.1-4 alkylthio and cyano, (2) vinyl
group, (3) allyl group, (4) propadienyl group, (5) C.sub.2-6
alkynyl group which may be substituted with 1 to 5 halogens, (6)
C.sub.3-6 cycloalkyl group, (7) C.sub.6-14 aryl group, (8)
C.sub.1-4 alkyl-carbonyl which may be substituted with 1 to 5
halogens, (9) an amino group which may be substituted with one or
two substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkyl-carbonyl and C.sub.1-4 alkoxy-carbonyl, (10) a group
represented by --N.dbd.CR.sup.1R.sup.2(wherein, both R.sup.1 and
R.sup.2 are the same or different C.sub.1-4 alkyl groups), (11) a
group represented by --OR.sup.3 (wherein R.sup.3 is a C.sub.1-4
alkyl group or a C.sub.1-4 alkyl-carbonyl group), or (12) a group
represented by --S(O).sub.nR.sup.4 (wherein n is an integer from 0
to 2, R.sup.4 is (a) a C.sub.1-4 alkyl group which may be
substituted with 1 to 5 halogens, or (b) a C.sub.6-14 aryl group
which may be substituted with 1 to 5 C.sub.1-4 alkyl groups).
[0031] [8] A microbicidal composition for agricultural or
horticultural use described in [5] above, wherein
[0032] A.sup.2is a phenyl group which may be substituted with 1 to
3 substituents selected from C.sub.1-4 alkyl groups, halogens and
cyano,
[0033] X.sup.2 is a chemical bond,
[0034] B.sup.2is a phenyl group which may be substituted with 1 to
5 substituents selected from (1) a C.sub.1-4 alkyl group which may
be substituted with 1 to 3 halogens, (2) C.sub.1-4 alkoxy group,
(3) C.sub.1-4 alkylthio group, (4) thiocarbamoyl group, (5) halogen
atom, (6) cyano group and (7) nitro group, Z.sup.2 is (1) a
C.sub.16 alkyl group which may be substituted with 1 to 3 C.sub.1-4
alkoxy groups, (2) C.sub.3-6 cycloalkyl group, (3) allyl group or
(4) C.sub.1-4 alkoxy group.
[0035] [9] A microbicidal composition for agricultural or
horticultural use described in [5] above, wherein the compound or
the salt thereof is
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide,
2',4'-dinitro-N-ethyl-p-toluenesulfonanilide,
2',4'-dicyano-N-ethyl-p-tol- uenesulfonanilide,
4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide,
2',4'-dinitro-N-isopropyl-p-toluenesulfonanilide,
2'-cyano-N-isopropyl-4'- -nitro-p-toluenesulfonanilide,
2'-cyano-N-methoxy-4'-nitro-p-toluenesulfon- anilide or
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt
thereof.
[0036] [10] A microbicidal composition for agricultural or
horticultural use comprising a compound of Formula (III): 17
[0037] or a salt thereof,
[0038] [wherein, A.sup.3 is (1) an aryl group which may be
substituted or (2) a heterocyclic group which may be substituted,
X.sup.3 is (1) a chemical bond, (2) a methylene group which may be
substituted, or (3) a vinylene group which may be substituted,
[0039] B.sup.3 is a six-membered heterocyclic group which is
substituted with substituents selected from the group of
substituents (T), which consists of (i) a C.sub.1-4 alkyl group
which may be substituted with 1 to 5 substituents selected from
halogen,hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino,
hydrazono, mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4
alkylthio, (ii) a C.sub.3-6 cycloalkyl group which may be
substituted with 1 to 5 halogen, (iii) a C.sub.2-4 alkenyl group
which may be substituted with 1 to 5 substituents selected from
halogens, cyano and nitro, (iv) a C.sub.3-6 cycloalkenyl group
which may be substituted with 1 to 5 halogens, (v) a C.sub.2-4
alkynyl group which may be substituted with 1 to 5 halogens, (vi)
hydroxy group, (vii) a C.sub.1-4 alkoxy group which may be
substituted with 1 to 5 substituents selected from halogen and
C.sub.1-4 alkoxy group, (viii) formyloxy group, (ix) C.sub.1-4
alkyl-carbonyloxy group which may be substituted with 1 to 5
halogens, (x) a C.sub.1-4 alkoxy-carbonyloxy group which may be
substituted with 1 to 5 halogens, (xi) mercapto group, (xii) a
C.sub.1-4 alkylthio group which may be substituted with 1 to 5
halogens, (xiii) a C.sub.1-4 alkyl-carbonylthio group which may be
substituted with 1 to 5 halogens,(xiv) a C.sub.1-4
alkoxy-carbonylthio group which may be substituted with 1 to 5
halogens, (xv) a C.sub.1-4 alkylsulfinyl group which may be
substituted with 1 to 5 halogens, (xvi) a C.sub.1-4 alkylsulfonyl
group which may be substituted with 1 to 5 halogens, (xvii)
sulfamoyl group, (xviii) a mono- or di-C.sub.1-4 alkylsulfamoyl
group, (xix) a group represented by 18
[0040] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xx) an amino group which may be
substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4
alkoxy, formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and
C.sub.1-4 alkyl-carbonyl, (xxi) a three- to six-membered cyclic
amino group, (xxii) formyl group, (xxiii) a C.sub.1-4
alkyl-carbonyl group which may be substituted with 1 to 5 halogens,
(xxiv) a C.sub.1-4 alkoxy-carbonyl group which may be substituted
with 1 to 5 halogens, (xxv) a C.sub.1-4 alkylthio-carbonyl group,
(xxvi) a C.sub.1-4 alkoxy-thiocarbonyl group,
[0041] (xxvii) a C.sub.1-4 alkylthio-thiocarbonyl group, (xxviii)
carbamoyl group, (xxix) a mono- or di-C.sub.1-4 alkylcarbamoyl
group, (xxx) a group represented by 19
[0042] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxi) thiocarbamoyl group, (xxxii)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
which is represented by 20
[0043] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl
group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group,
(xxxviii) cyano group, (xxxix) isocyano group, (xl) azido group,
(xli) nitroso group, (xlii) nitro group, (xliii) azocyano group
(xliv) azoxycyano group, and (xlv) sulfo group,
[0044] Z.sup.3 is (1) a hydrocarbon group which may be substituted,
(2) an acyl group which may be substituted, (3) formyl group, (4)
an amino group which may be substituted, (5) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein, R.sup.1 and R.sup.2 are the same
or different, and a hydrogen atom or a hydrocarbon group which may
be substituted), (6) cyclic amino group, (7) a group represented by
--OR.sup.3 (wherein, R.sup.3 stands for a hydrogen atom, a
hydrocarbon group which may be substituted, an acyl group which may
be substituted, formyl group or sulfonyl group which may be
substituted), or (8) a group represented by --S(O).sub.nR.sup.4
(wherein, n is an integer from 0 to 2, R.sup.4 is a hydrogen atom
or a hydrocarbon group which may be substituted)].
[0045] [11] A microbicidal composition for agricultural or
horticultural use described in [10] above, wherein A.sup.3 is (1)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from (i) C.sub.1-4 alkyl group which may be
substituted with 1 to 5 substituents selected from halogens,
hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono,
mono- or di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio, (ii)
C.sub.3-6 cycloalkyl group which may be substituted with 1 to 5
halogens, (iii) C.sub.2-4 alkenyl group which may be substituted
with 1 to 5 substituents selected from halogens, cyano and nitro,
(iv) C.sub.3-6 cycloalkenyl group which may be substituted with 1
to 5 halogens, (v) C.sub.2-4 alkynyl group which may be substituted
with 1 to 5 halogens, (vi) hydroxy group, (vii) C.sub.1-4 alkoxy
group which may be substituted with 1 to 5 substituents selected
from halogens and C.sub.1-4alkoxy, (viii) formyloxy group, (ix)
C.sub.1-4alkyl-carbonyloxy group which may be substituted with 1 to
5 halogens, (x) C.sub.1-4 alkoxy-carbonyloxy group which may be
substituted with 1 to 5 halogens, (xi) mercapto group, (xii)
C.sub.1-4 alkylthio group which may be substituted with 1 to 5
halogens, (xiii) C.sub.1-4 alkyl-carbonylthio group which may be
substituted with 1 to 5 halogens,(xiv) C.sub.1-4
alkoxy-carbonylthio group which may be substituted with 1 to 5
halogens, (xv) C.sub.1-4 alkylsulfinyl group which may be
substituted with 1 to 5 halogens, (xvi) C.sub.1-4 alkylsulfonyl
group which may be substituted with 1 to 5 halogens, (xvii)
sulfamoyl group, (xviii) mono- or di-C.sub.1-4 alkylsulfamoyl
group, (xix) a group represented by 21
[0046] (wherein,ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xx) amino group which may be
substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.2-4 alkenyl, C.sub.2-4 alkynyl, hydroxy, C.sub.1-4
alkoxy, formyloxy, C.sub.1-4 alkyl-carbonyloxy, formyl and
C.sub.1-4 alkyl-carbonyl, (xxi) three- to six-membered cyclic amino
group, (xxii) formyl group, (xxiii) C.sub.1-4 alkyl-carbonyl group
which may be substituted with 1 to 5 halogens,(xxiv) C.sub.1-4
alkoxy-carbonyl group which may be substituted with 1 to 5
halogens, (xxv) C.sub.1-4 alkylthio-carbonyl group, (xxvi)
C.sub.1-4 alkoxy-thiocarbonyl group, (xxvii) C.sub.1-4
alkylthio-thiocarbonyl group, (xxviii) carbamoyl group, (xxix)
mono- or di-C.sub.1-4 alkylcarbamoyl group, (xxx) a group
represented by 22
[0047] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxi) thiocarbamoyl group, (xxxii)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group, (xxxiii) a group
represented by 23
[0048] (wherein, ring C is a three- to six-membered heterocyclic
group containing nitrogen), (xxxiv) halogen atom, (xxxv) carboxyl
group, (xxxvi) thiocyanato group, (xxxvii) isothiocyanato group,
(xxxviii) cyano group, (xxxix) isocyano group, (xl) azido group,
(xli) nitroso group, (xlii) nitro group, (xliii) azocyano group
(xliv) azoxycyano group, and (xlv) sulfo group, or (2) a
heterocyclic group which may be substituted with 1 to 5
substituents selected from the group of substituents (T) above.
[0049] X.sup.3 is (1) chemical bond, (2) methylene group which may
be substituted with one or two substituents selected from C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, halogen atoms and
cyano, (3) a vinylene group which may be substituted with one or
two substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 alkylthio, halogen atoms and cyano,
[0050] B.sup.3 is a six-membered heterocyclic group which is
substituted with 1 to 5 substituents selected from the group of
substituents (T) mentioned above, Z.sup.3 is (1) a hydrocarbon
group which is selected from (i) a C.sub.1-6 alkyl group which may
be substituted with 1 to 5 substituents selected from (a) halogen,
(b) amino, (c) mono- or di-C.sub.1-4 alkylamino, (d) hydroxy, (e)
C.sub.1-4 alkoxy which may be substituted with 1 to 5 halogens, (f)
mercapto, (g) C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i)
C.sub.1-4 alkylsulfonyl,(j) cyano, (k) C.sub.1-4 alkoxy-carbonyl,
(1) carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (ii)
C.sub.2-6 alkenyl which may be substituted with 1 to 5 substituents
selected from (a) halogens, (b) amino, (c) mono- or di-C.sub.1-4
alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which may be
substituted with 1 to 5 halogens, (f) mercapto, (g) C.sub.1-4
alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iii)
C.sub.2-6 alkynyl which may be substituted with 1 to 5 substituents
selected from (a) halogen, (b) amino, (c) mono- or di-C.sub.1-4
alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which may be
substituted with 1 to 5 halogens, (f) mercapto, (g) C.sub.1-4
alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, (iv)
C.sub.3-6 cycloalkyl groups which may be substituted with 1 to 5
substituents selected from (a) C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono-
or di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (1) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (v)
C.sub.3-6 alkadienyl group which may be substituted with 1 to 5
substituents selected from (a) halogen, (b) amino, (c) mono- or
di-C.sub.1-4 alkylamino, (d) hydroxy, (e) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (f) mercapto, (g)
C.sub.1-4 alkylthio, (h) C.sub.1-4 alkylsulfinyl, (i) C.sub.1-4
alkylsulfonyl, (j) cyano, (k) C.sub.1-4 alkoxy-carbonyl, (1)
carbamoyl and (m) mono- or di-C.sub.1-4 alkyl-carbamoyl, and (vi)
C.sub.6-14 aryl group which may be substituted with 1 to 5
substituents selected from C.sub.1-4 alkyl which may be substituted
with 1 to 5 halogens, (b) halogen, (c) amino, (d) mono- or
di-C.sub.1-4 alkylamino, (e) hydroxy, (f) C.sub.1-4 alkoxy which
may be substituted with 1 to 5 halogens, (g) mercapto, (h)
C.sub.1-4 alkylthio, (i) C.sub.1-4 alkylsulfinyl, (j) C.sub.1-4
alkylsulfonyl, (k) cyano, (l) C.sub.1-4 alkoxy-carbonyl, (m)
carbamoyl and (n) mono- or di-C.sub.1-4 alkyl-carbamoyl, (2) an
acyl group selected from (i) C.sub.1-4 alkyl-carbonyl, (ii)
C.sub.1-4 alkoxy-carbonyl, (iii) C.sub.1-4 alkylthio-carbonyl, (iv)
C.sub.1-4 alkoxy-thiocarbonyl, (v) C.sub.1-4
alkylthio-thiocarbonyl, (vi) mono- or di-C.sub.1-4 alkyl-carbamoyl
and (vii) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, each of these
groups may be substituted with 1 to 5 halogens, (3) formyl group,
(4) an amino group which may be substituted with one or two
substituents selected from (a) C.sub.1-4 alkyl, (b) C.sub.1-4
alkyl-carbonyl which may be substituted with 1 to 5 halogens, (c)
C.sub.1-4 alkoxy-carbonyl, (d) mono- or di-C.sub.1-4
alkyl-carbamoyl, (e) mono- or di-C.sub.1-4 alkyl-thiocarbamoyl, (5)
a group represented by --N.dbd.CR.sup.1R.sup.2 (wherein, R.sup.1
and R.sup.2 are the same or different, are a hydrogen atom or a
C.sub.1-4 alkyl group), (6) three- to six-membered cyclic amino
group, (7) a group represented by --OR.sup.3 (wherein, R.sup.3 is a
hydrogen atom, a C.sub.1-4 alkyl group which may be substituted
with 1 to 5 halogens, a C.sub.1-4 alkyl-carbonyl group which may be
substituted with 1 to 5 halogens, a C.sub.1-4 alkoxy-carbonyl group
which may be substituted with 1 to 5 halogens, formyl group or a
C.sub.1-4 alkylsulfonyl group which may be substituted with 1 to 5
halogens), or (8) a group represented by --S(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, R.sup.4 is (a) hydrogen atom,
(b) C.sub.1-4 alkyl group which may be substituted with 1 to 5
halogens, or (c) C.sub.6-14 aryl group which may be substituted
with 1 to 5 C.sub.1-4 alkyl groups).
[0051] [12] A microbicidal composition for agricultural or
horticultural use described in [10] above, wherein A.sup.3 is
phenyl group which may be substituted with 1 to 5 C.sub.1-4 alkyl
groups, or an imidazolyl group which may be substituted with one or
two C.sub.1-4 alkyl groups, X.sup.3 is a chemical bond, B.sup.3 is
a pyridyl group, a pyridazinyl group or a pyrimidinyl group which
is substituted with 1 to 5 substituents selected from C.sub.1-4
alkyl which may be substituted with 1 to 5 halogens, C.sub.1-4
alkoxy, halogen, nitro and cyano, Z.sup.3 is a C.sub.1-6 alkyl
group, a C.sub.3-6 cycloalkyl group or a C.sub.1-4 alkoxy
group.
[0052] [13] A microbicidal composition for agricultural or
horticultural use comprising a compound of Formula (IV) 24
[0053] or a salt thereof, [wherein, A.sup.4 is (1) an aryl group
which may be substituted, or (2) a heterocyclic group which may be
substituted,
[0054] X.sup.4 is (1) a chemical bond, (2) a methylene group which
may be substituted, or (3) a vinylene group which may be
substituted,
[0055] B.sup.4 is a pyridazinyl group or a pyrazinyl group,
[0056] Z.sup.4 is (1) a hydrocarbon group which may be substituted,
(2) an acyl group which may be substituted, (3) formyl group, (4)
an amino group which may be substituted, (5) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the same
or different, and hydrogen atom or hydrocarbon group which may be
substituted), (6) a cyclic amino group, (7) a group represented by
--OR.sup.3 (wherein, R.sup.3 is a hydrogen atom, a hydrocarbon
group which may be substituted, an acyl group which may be
substituted, formyl group or a sulfonyl group which may be
substituted), or (8) a group represented by --S(O).sub.nR.sup.4
(wherein, n is an integer from 0 to 2, R.sup.4 is a hydrogen atom
or a hydrocarbon group which may be substituted)].
[0057] [14] A microbicidal composition for agricultural or
horticultural use comprising a compound of Formula (V) 25
[0058] or a salt thereof,
[0059] [wherein A.sup.5 is the 4-methylphenyl group, X.sup.5 is a
chemical bond, B.sup.5 is a pyridyl or pyrimidinyl group, and
Z.sup.5 is a C.sub.1-4 alkyl group].
[0060] [15] A compound of Formula (VI): 26
[0061] or a salt thereof,
[0062] [wherein A.sup.6 is a phenyl group which may be substituted
with a substituent or substituents selected from C.sub.1-4 alkyl,
halogens and cyano, X.sup.6 is a chemical bond, B.sup.6 is a
2-nitrophenyl group or a 2-cyanophenyl group which is substituted
with a substituent or substituents selected from halogens, nitro
and cyano, Z.sup.6 is ethyl, isopropyl, cyclopropyl, methoxy,
ethoxy or isopropoxy group].
[0063] [16] A compound or a salt thereof described in [15] above,
wherein A.sup.6 is a phenyl group which may be substituted with a
substituent or substituents selected from C.sub.1-4 alkyl, halogens
and cyano, X.sup.6 is a chemical bond, B.sup.6 is a 2-nitrophenyl
group which is substituted with a substituent or substituents
selected from halogens, nitro and cyano, Z.sup.6 is ethyl,
isopropyl, or cyclopropyl group].
[0064] [17] A compound or a salt thereof described in [15] above,
the compound is 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide,
2',4'-dinitro-N-ethyl-p-toluenesulfonanilide,
2',4'-dicyano-N-ethyl-p-tol- uenesulfonanilide,
4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide,
2',4'-dinitro-N-isopropyl-p-toluenesulfonanilide,
2'-cyano-N-isopropyl-4'- -nitro-p-toluenesulfonanilide,
2'-cyano-N-methoxy-4'-nitro-p-toluenesulfon- anilide or
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or a salt
thereof.
[0065] [18] A method for manufacturing a compound represented by a
Formula: 27
[0066] or a salt thereof (wherein each symbol has the same meaning
as defined in [15] above characterized by :
[0067] (1) reacting a compound represented by a Formula: 28
[0068] or a salt thereof
[0069] (wherein each symbol has the same meaning as defined in [15]
above with an electrophile represented by Formula Z.sup.6-L"
(wherein L" is a leaving group, and Z.sup.6 has the same meaning as
defined in [15] above,
[0070] (2) reacting a compound represented by a Formula:
A.sup.6-X.sup.6--SO.sub.2-L
[0071] or a salt thereof,
[0072] (wherein L is a leaving group, and each of other symbols has
the same meanings as those defined in [15] above, respectively)
with an amine or a salt thereof represented by Formula
Z.sup.6HN--B.sup.6 (wherein each symbol has the same meaning as
defined in [15] above, or, by
[0073] (3) reacting a compound represented by a Formula:
A.sup.6-X.sup.6--SO.sub.2--NHZ.sup.6
[0074] or a salt thereof
[0075] (wherein, each symbol has the same meaning as described in
[15] above to react with a compound or a salt thereof represented
by Formula L'-B.sup.6 (wherein L' is a leaving group, and the other
symbol has the same meaning as defined in [15] above,
respectively),or
[0076] (4) nitrating a compound represented by a Formula: 29
[0077] or a salt thereof
[0078] (wherein, B.sup.7 is a phenyl group which is substituted
with a substituent or substituents selected from halogen, nitro and
cyano, provided that both 2- and 6-positions are not substituted at
the same time).
[0079] Best Modes for Carrying Out the Invention
[0080] The compound (I.sup.0), belonging to sulfonamide
derivatives, may have optical isomers, diastereomers and/or any
geometrical isomers thereof, and the present invention contains all
the isomers and mixtures of them.
[0081] As the aryl group in the "aryl group which may be
substituted" regarding A.sup.0, there can be mentioned C.sub.6-14
aryl groups such as phenyl, naphthyl (for example, 1-naphthyl,
2-naphthyl) and so on.
[0082] As the substituents on the said aryl groups, there can be
mentioned (i) C.sub.1-4 alkyl groups (for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl)
optionally substituted with 1 to 5 substituents selected from
halogens, hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino (for
example, methoxyimino, ethoxyimino), hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono (for example, methylhydrazono,
ethylhydrazono, dimethylhydrazono) and C.sub.1-4 alkylthio (for
example, methylthio, ethylthio, n-propylthio, isopropylthio,
n-butylthio, sec-butylthio, isobutylthio, tert-butylthio), (ii)
C.sub.3-6 cycloalkyl groups (for example, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl) which may be substituted with 1 to 5
halogens,(iii) C.sub.2-4 alkenyl groups (for example, vinyl, allyl,
propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl,
3-butenyl) which may be substituted with 1 to 5 substituents
selected from halogens, cyano and nitro, (iv) C.sub.3-6
cycloalkenyl groups (for example, cyclopropenyl, cyclobutenyl,
cyclopentenyl, cyclohexenyl) which may be substituted with 1 to
5halogens, (v) C.sub.2-4 alkynyl groups (for example, ethynyl,
1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl) which may
be substituted with 1 to 5 halogens, (vi) a hydroxy group, (vii)
C.sub.1-4 alkoxy groups (for example, methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy) which may
be substituted with 1 to 5 substituents selected from halogens and
C.sub.1-4 alkoxy(for example,methoxy and ethoxy), (viii) formyloxy
group, (ix) C.sub.1-4 alkyl-carbonyloxy group (for example,
acetyloxy, propionyloxy, butyryloxy, isobutyryloxy) which may be
substituted with 1 to 5 halogens, (x) C.sub.1-4 alkoxy-carbonyloxy
group (for example, methoxycarbonyloxy, ethoxycarbonyloxy,
n-propoxycarbonyloxy,isopropoxycar- bonyloxy) which may be
substituted with 1 to 5 halogens, (xi) a mercapto group, (xii)
C.sub.1-4 alkylthio groups (for example methylthio, ethylthio,
n-propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio, tert-butylthio) which may be substituted with 1 to 5
halogens, (xiii) C.sub.1-4 alkyl-carbonylthio groups (for example,
acetylthio, propionylthio, butyrylthio, isobutyrylthio) which may
be substituted with 1 to 5 halogens, (xiv) C.sub.1-4
alkoxy-carbonylthio groups (for example, methoxycarbonylthio,
ethoxycarbonylthio, n-propoxycarbonylthio, isopropoxycarbonylthio)
which may be substituted with 1 to 5 halogens, (xv) C.sub.1-4
alkylsulfinyl groups (for example, methylsulfinyl, ethylsulfinyl,
n-propylsulfinyl, isopropylsulfinyl) which may be substituted with
1 to 5 halogens, (xvi) C.sub.1-4 alkylsulfonyl groups (for example,
methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl)
which may be substituted with 1 to 5 halogens, (xvii) a sulfamoyl
group, (xviii) mono- or di-C.sub.1 4 alkylsulfamoyl groups (for
example, methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl,
dimethylsulfamoyl, ethylmethylsulfamoyl, diethylsulfamoyl) , (xix)
groups represented by 30
[0083] [wherein ring C is a three- to six-membered heterocyclic
group containing nitrogen (for example, aziridino, azetidino,
pyrrolidino, piperidino, morpholino, thiomorpholino)], (xx) an
amino group which may be substituted with 1 or 2 substituents
selected from C.sub.1-4 alkyl(for example, methyl, ethyl,n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl), C.sub.2-4
alkenyl (for example, vinyl, allyl, propenyl, isopropenyl,
2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl), C.sub.2-4
alkynyl (for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,
2-butynyl, 3-butynyl), hydroxy, C.sub.1-4 alkoxy (for example,
methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,
sec-butoxy, tert-butoxy), formyloxy and C.sub.1-4 alkyl-carbonyloxy
(for example, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy),
formyl and C.sub.1-4 alkyl-carbonyl(for example, acetyl, propionyl,
butyryl, isobutyryl), (xxi) three- to six-membered cyclic amino
groups (for example, azilidino, azetidino, pyrrolidino, piperidino,
morpholino, thiomorpholino), (xxii) formyl group, (xxiii) C.sub.1-4
alkyl-carbonyl groups (for example, acetyl, propionyl, butyryl,
isobutyryl) which may be substituted with 1 to 5 halogens, (xxiv)
C.sub.1-4 alkoxy-carbonyl groups (for example, methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl) which may be
substituted with 1 to 5 halogens, (xxv) C.sub.1-4
alkylthio-carbonyl groups (for example, (methylthio)carbonyl,
(ethylthio)carbonyl,
(n-propylthio)carbonyl,(isopropylthio)carbonyl,
(n-butylthio)carbonyl, (isobutylthio)carbonyl,
(sec-butylthio)carbonyl, (tert-butylthio)carbonyl, (xxvi) C.sub.1-4
alkoxy-thiocarbonyl groups (for example, (methoxy)thiocarbonyl,
(ethoxy)thiocarbonyl, (n-propoxy)thiocarbonyl,
(isopropoxy)thiocarbonyl), (xxvii) C.sub.1-4 alkylthio-thiocarbonyl
groups (for example, (methylthio)thiocarbonyl,
(ethylthio)thiocarbonyl, (n-propylthio)thiocarbonyl,
(isopropylthio)thiocarbonyl, (n-butylthio)thiocarbonyl,
(isobutylthio)thiocarbonyl, (sec-butylthio)thiocarbonyl,
(tert-butylthio)thiocarbonyl), (xxviii) a carbamoyl group, (xxix)
mono- or di-C.sub.1-4 alkylcarbamoyl groups (for example,
methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl,
dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl), (xxx)
groups represented by 31
[0084] (wherein ring C is a three- to six-membered heterocyclic
group containing nitrogen (for example, aziridino, azetidino,
pyrrolidino, piperidino, morpholino, thiomorpholino)), (xxxi) a
thiocarbamoyl group, (xxxii) mono- or di-C.sub.1-4
alkyl-thiocarbamoyl groups (for example, (methyl) thiocarbamoyl,
(ethyl)thiocarbamoyl, (n-propyl)thiocarbamoyl,
(dimethyl)thiocarbamoyl, (ethylmethyl)thiocarbamoyl,
(diethyl)thiocarbamoyl), (xxxiii)groups represented by 32
[0085] (wherein ring C is a three- to six-membered heterocyclic
group containing nitrogen (for example, aziridino, azetidino,
pyrrolidino, piperidino, morpholino, thiomorpholino)), (xxxiv)
halogen atoms (for example, fluorine, chlorine, bromine, iodine),
(xxxv) carboxyl group, (xxxvi) thiocyanato group, (xxxvii)
isothiocyanato group, (xxxviii) cyano group, (xxxix) isocyano
group, (xl) azido group, (xli) nitroso group, (xlii) nitro group,
(xliii) azocyano group, (xliv) azoxycyano (--NO.dbd.N--CN)group,
and (xlv) sulfo group.
[0086] Hereinafter, the group of the above-mentioned substituents
from (i) to (xlv) may be in some cases described as the substituent
group (T), and the group of the above-mentioned substituents
consists of those from (i) to (xliii) and (xlv)may be in some cases
described as the substituent group (T'). (In the description of the
substituents above, "halogens" mean fluorine, chlorine, bromine,
and iodine.)
[0087] The number of substituents in the aryl group mentioned above
is from one to five (more preferably from one to three). As the
heterocyclic group of the "heterocyclic group which may be
substituted" regarding A.sup.0, there can be mentioned, for
example, a five- to six-membered heterocyclic group which contains
1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur
atoms, or a condensed heterocyclic group composed either of five-
to six-membered heterocyclic groups which contain 1 to 4 hetero
atoms selected from nitrogen, oxygen and sulfur atoms and benzene
rings, or of a five- to six-membered heterocyclic groups which
contain 1 to 4 heteroatoms selected from nitrogen, oxygen and
sulfur atoms and, the same or different, another five- to
six-membered heterocyclic groups which contain 1 to 4 heteroatoms
selected from nitrogen, oxygen and sulfur atoms.
[0088] As specific examples of such heterocycles, there can be
mentioned pyrrolyl (for example, 1-, 2- or 3-pyrrolyl), pyrazolyl
(for example, 1-, 3-,4- or 5-pyrazolyl), imidazolyl (for example,
1-, 2-, 4-, or 5-imidazolyl), triazolyl(for example,
1,2,3-triazol-1-,4- or 5-yl, 1,2,4-triazol-1-,3-,4-, or 5-yl),
tetrazolyl (for example, tetrazol-1-,2- or5-yl), furyl (for
example, 2- or3-furyl), thienyl (for example, 2- or 3-thienyl),
oxazolyl (for example,2-, 4- or, 5-oxazolyl), isooxazolyl (for
example, 3-, 4- or 5-isooxazolyl), oxadiazolyl (for example,
1,2,3-oxadiazol-4- or 5-yl, 1,2,4-oxadiazol-3- or 5-yl,
1,2,5-oxadiazol-3-yl, 1,3,4-oxadiazol-2-yl), thiazolyl (for
example, 2-, 4- or 5-thiazolyl), isothiazolyl(for example, 3-, 4-
or 5-isothiazolyl), thiadiazolyl (for example, 1,2,3-thiadiazol-4-
or 5-yl, 1,2,4-thiadiazol-3- or 5-yl, 1,2,5-thiadiazol-3-yl,
1,3,4-thiadiazol-2-yl), pyrrolidinyl (for example, 1-, 2- or
3-pyrrolidinyl), pyridyl (for example, 2-, 3- or 4-pyridyl),
pyridazinyl (for example, 3- or 4-pyridazinyl), pyrimidinyl (for
example, 2-, 4- or 5-pyrimidinyl), pyrazinyl, piperidinyl (for
example, 1-, 2-, 3- or 4-piperidinyl), piperazinyl (for example, 1-
or 2-piperazinyl), indolyl (for example, 3H-indol-2-,3-,4-, 5-, 6-
or 7-yl), pyranyl (for example, 2-, 3- or4-pyranyl), thiopyranyl
(for example, 2-, 3- or 4-thiopyranyl), morpholinyl(for example,
2-, 3- or 4-morpholinyl), thiomorpholinyl, quinolyl (for example,
2-, 3-, 4-, 5-,6-, 7- or 8-quinolyl), isoquinolyl,
pyrido[2,3-d]pyrimidinyl (for example,
pyrido[2,3-d]pyrimidin-2-yl), naphthyridinyl such as 1,5-, 1,6-,
1,7-, 1,8-, 2,6- or 2,7-naphthyridinyl (for example,
1,5-naphthyridin-2- or 3-yl), thieno[2,3-d]pyridyl (for example,
thieno[2,3-d]pyridin-3-yl), pyrazinoquinolyl (for example,
pyrazino[2,3-d]quinolin-2-yl), chromenyl (for example,
2H-chromen-2-, 3-, 4-, 5- or 6-yl), chromanyl (for example, 1-, 2-,
3-, 4-, 5-, 6-, 7- or 8-chromanyl), isochromanyl (for example, 1-,
3-, 4-, 5-, 6-, 7- or 8-isochromanyl), benzofuryl (for example, 2-,
3-, 4-, 5-, 6- or 7-benzofuryl), benzothienyl (for example, 2-, 3-,
4-, 5-,6-, or7-benzothienyl), benzoimidazolyl (for example, 2-,
4.-, 5-, 6- or 7-benzimidazolyl), indazolyl (for example,
1H-indazol-1-, 3-, 4-, 5-, 6- or 7-yl), benzooxazolyl (for example,
2-, 4-, 5-, 6- or 7-benzooxazolyl), benzoisooxazolyl (for example,
3-, 4-, 5-, 6- or 7-benzoisooxazolyl), benzothiazolyl (for example,
2-, 4-, 5-, 6- or7-benzothiazolyl), benzothiadiazolyl (for example,
benzo-1,2,3-thiadiazol-4-,5-, 6- or 7-yl,
benzo-1,2,4-thiadiazol-3-,4-, 5-, 6- or 7-yl,
benzo-1,2,5-thiadiazol-3-,4- -, 5-, 6- or 7-yl,
benzo-1,3,4-thiadiazol-2-,4-, 5-, 6- or 7-yl), benzoisothiazolyl
(for example, 3-, 4-,5-, 6- or 7-benzzoisothiazolyl),
benzotriazolyl (for example,4-, 5-, 6-, 7- or
8-benzo-1,2,3-triazolyl, 3-,5-,6-,7- or 8-benzo-1,2,4-triazolyl),
cinnolyl (for example, 3-, 4-, 5-, 6-, 7- or 8-cinnolyl),
phthalazinyl (for example, 1-, 5- or 6-phthalazinyl), quinazolinyl
(for example, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl), quinoxalinyl
(for example, 2-, 5- or 6-quinoxalinyl), imidazopyridyl (for
example, imidazo[1,2-a]pyridyl such as imidazo[1,2-a]pyridin-2-yl
and imidazo[1,2-a]pyridin-3-yl),imidazothiazol- yl (for example,
imidazo[2,1-b]thiazolyl such as imidazo[2,1-b]thiazol-5-y- l),
dioxaindanyl (for example, 1,3-dioxaindanyl such as
1,3-dioxaindan-2-,4-, 5-, 6- or 7-yl).
[0089] Among these heterocyclic groups, isoxazolyl, triazolyl,
pyridyl, quinolyl, thienyl, isoxazolyl, pyrazolyl, imidazolyl,
benzothiadiazolyl, imidazopyridyl, imidazothiazolyl are especially
preferable.
[0090] As the substituents on the said heterocyclic groups, those
which are in the substituent group (T) are preferable. The number
of the said substituents is 1 to 5 (preferably 1 to 3). As
preferable substituents on the aryl group in the "aryl group which
may be substituted" or on the heterocyclic group in the
"heterocyclic group which may be substituted", both represented as
A.sup.0, there can be mentioned:
[0091] C.sub.1-4 alkyl which may be substituted with 1 to 5
halogens, amino which may be substituted with one or two C.sub.1-4
alkyl-carbonyl,
[0092] (3) nitro,
[0093] (4) C.sub.1-4 alkoxy which may be substituted with 1 to 5
halogens,
[0094] (5) halogens,
[0095] (6) C.sub.1-4 alkoxy-carbonyl,
[0096] (7) cyano,
[0097] (8) mono- or di-C.sub.1-4 alkylcarbamoyl,
[0098] (9) C.sub.1-4 alkylsulfonyl,
[0099] (10) carbamoyl, and carboxyl.
[0100] As A.sup.0, phenyl groups which may be substituted with 1 to
3 substituents selected from C.sub.1-4 alkyl, halogens and cyano
are preferable, and phenyl groups which may be substituted with 1
to 3 substituents selected from C.sub.1-4 alkyl and halogens are
more preferable. The substituent can, most preferably, be at the
4-position of the phenyl group.
[0101] As the preferable substituents on the methylene group
regarding X.sup.0, there may be mentioned:
[0102] C.sub.1-4 alkyl (for example, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl), C.sub.1-4
alkoxy (for example, methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), C.sub.1-4 alkylthio
(for example, methylthio, ethylthio, n-propylthio, isopropylthio,
n-butylthio, isobutylthio, sec-butylthio, tert-butylthio),
[0103] (4) halogen atoms (for example, fluorine, chlorine, bromine,
iodine) and,
[0104] (5) cyano.
[0105] The number of the substituents is preferably one or two. As
the substituents on the vinylene group regarding X.sup.0, there can
be mentioned such substituents similar to those mentioned as the
substituents on the methylene group regarding X.sup.0. The number
of the said substituent is preferably one or two.
[0106] As X.sup.0, preferable are a chemical bond (a single bond or
a bond), a methylene group which may be substituted with one or two
C.sub.1-4 alkyl or a vinylene group which may be substituted with
one or two C.sub.1-4 alkyl, a chemical bond being especially
preferable. As the "heterocyclic group which may be substituted" in
B.sup.0, there can be mentioned those heterocyclic groups similar
to those described as the "heterocyclic group which may be
substituted" in A.sup.0.
[0107] The preferable heterocyclic groups is thienyl, pyrazolyl,
imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl,
pyridazinyl, pyrimidinyl, imidazopyridyl, dioxaindanyl. Prefered
substituents on the said heterocyclic group are nitro, halogens,
cyano, C.sub.1-4 alkyl which may be substituted with 1 to 5
halogens, C.sub.1-4 alkoxy, and C.sub.1-4 alkylthio.
[0108] As the "aryl group which may be substituted" in B.sup.0,
there can be mentioned those aryl groups similar to those described
as the "aryl group which may be substituted" in A.sup.0. As aryl
group, phenyl group is especially preferable. As preferable
substituents on the said aryl group, there can be mentioned (1)
halogens, (2) C.sub.1-4alkyl which may be substituted with 1 to 5
substituents selected from halogens, hydroxy, imino, hydroxyimino,
C.sub.1-4 alkoxyimino, hydrazono, mono- or di-C.sub.1-4
alkylhydrazono and C.sub.1-4 alkylthio, (3) C.sub.24 alkynyl,(4)
alkoxy which may be substituted with 1 to 5 substituents selected
from halogens and C.sub.1-4 alkoxy, (5) C.sub.1-4 alkylthio, (6)
C.sub.1-4 alkylsulfinyl, (7) C.sub.1-4 alkylsulfonyl, (8) C.sub.1-4
alkyl-carbonyloxy, (9) C.sub.1-4 alkoxy-carbonyl, (10) carboxyl,
(11) cyano, (12) nitro, (13) nitroso, (14) formyl, (15) carbamoyl,
(16) mono- or di-C.sub.1-4 alkylcarbamoyl, (17) thiocarbamoyl, (18)
hydroxy, (19) mono- or di-C.sub.1-4 alkylsulfamoyl, (20)
thiocyanato, (21) azoxycyano,(22) amino.
[0109] As the hydrocarbon group in the "hydrocarbon group which may
be substituted" in Z.sup.0, there may be mentioned:
[0110] (i) a C.sub.1-6 alkyl group (for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
n-pentyl, sec-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl),
[0111] (ii) a C.sub.2-6 alkenyl group (for example, a
straight-chain C.sub.2-6 alkenyl group such as vinyl, allyl,
propenyl, isopropenyl, 1-butenyl, 2-butenyl or 3-butenyl; a
branched C.sub.2-6 alkenyl group such as 2-methyl-propenyl,
2-methyl-2-propenyl, 1-methyl-2-propenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl,
1,1-dimethyl-2-propenyl, 1-methyl-2-butenyl, 3-methyl-2-butenyl,
2-methyl-2-butenyl, 1-methyl-3-butenyl, 1-ethyl-2-propenyl,
2-methyl-3-butenyl, 3-methyl-3-butenyl, 2-methyl-1-pentenyl
3-methyl-1-pentenyl, 4-methyl-1-pentenyl,1-methyl-2-pentenyl,
2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-3-pentenyl,
1,1-dimethyl-2-butenyl, 1,2-dimethyl-2-butenyl,
1,3-dimethyl-2-butenyl, 2,3-dimethyl-2-butenyl,
1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,
4-methyl-3-pentenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-3-butenyl,
1-methyl-4-pentenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,
1-ethyl-1-butenyl, and 1-ethyl-2-butenyl), (iii) a C.sub.2-6
alkynyl group (for example, ethynyl, 1-propynyl, 2-propynyl,
1-butynyl, 2-butynyl, 3-butynyl),
[0112] (iv) a C.sub.3-6 cycloalkyl group (for example, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl),
[0113] (v) a C.sub.3-6 alkadienyl group (for example,
1,2-propadienyl, 1,2-butadienyl, 1,3-butadienyl,
3-methyl-1,2-butadienyl, 1,2-pentadienyl, 2,4-pentadienyl,
1-methyl-1,2-pentadienyl, 1-methyl-1,3-pentadienyl), and
[0114] (vi) C.sub.6-14 aryl group (for example, phenyl, and
naphthyl such as 1-naphthyl, 2-naphthyl).
[0115] In cases where the said hydrocarbon group is alkyl group,
alkynyl group or alkadienyl group, as preferred substituents of the
said hydrocarbon group, there can be mentioned
[0116] (a) halogen atoms (for example, fluorine, chlorine, bromine,
iodine),
[0117] (b) an amino group,
[0118] (c) a mono- or di-C.sub.1-4 alkylamino group (for example,
methylamino, ethylamino, dimethylamino, methylethylamino),
[0119] (d) a hydroxyl group,
[0120] (e) a C.sub.1-4 alkoxy group (for example, methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,
tert-butoxy) which may be substituted with 1 to 5 (more preferably
1 to 3) halogens (for example, fluorine, chlorine,bromine,
iodine),
[0121] (f) mercapto,
[0122] (g) C.sub.1-4alkylthio (for example, methylthio, ethylthio,
n-propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio, tert-butylthio),
[0123] (h) C.sub.1-4 alkylsulfinyl (for example, methylsulfinyl,
ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl),
[0124] (i) C.sub.1-4 alkylsulfonyl (for example, methylsulfonyl,
ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl),
[0125] (j) cyano,
[0126] (k) C.sub.1-4 alkoxy-carbonyl (for example, methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl),
[0127] (l) carbamoyl and
[0128] (m) mono- or di-C.sub.1-4 alkyl-carbamoyl (for example,
methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl,
dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl).
[0129] The number of the said substituents is 1 to 5 (more
preferably 1 to 3).
[0130] In cases where the said hydrocarbon group is a cycloalkyl
group or an aryl group, as the substituents on the said hydrocarbon
group, there can be mentioned a C.sub.1-4 alkyl group which may be
substituted with 1 to 5 halogens (for example, fluorine, chlorine,
bromine, iodine) atoms (for example, methyl, ethyl, propyl,
isopropyl, tert-butyl, chloromethyl, trifluoromethyl),
[0131] (b) halogen atoms (for example, fluorine, chlorine, bromine,
iodine),
[0132] (c) an amino group,
[0133] (d) a mono- or di-C.sub.1-4 alkylamino group (for example,
methylamino, ethylamino, dimethylamino, methylethylamino),
[0134] (e) a hydroxyl group,
[0135] (f) a C.sub.1-4 alkoxy (for example, fluorine, chlorine,
bromine, iodine) (for example, methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy) which may
be substituted with 1 to 5 (more preferably 1 to 3) halogens,
[0136] (g) mercapto,
[0137] (h) C.sub.1-4 alkylthio (for example, methylthio, ethylthio,
n-propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio, tert-butylthio),
[0138] (i) C.sub.1-4 alkylsulfinyl (for example, methylsulfinyl,
ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl),
[0139] (j) C.sub.1-4 alkylsulfonyl (for example, methylsulfonyl,
ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl),
[0140] (k) cyano,
[0141] (l) C.sub.1-4 alkoxy-carbonyl (for example, methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl),
[0142] (m) carbamoyl and
[0143] (n) mono- or di-C.sub.1-4 alkyl-carbamoyl (for example,
methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl,
dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl).
[0144] The number of the said substituents is 1 to 5 (more
preferably 1 to 3).
[0145] As the "acyl group" in "an acyl group which may be
substituted" in Z.sup.0, there may be mentioned
[0146] (1) a C.sub.1-4 alkyl-carbonyl group (for example, acetyl,
propionyl, butyryl, isobutyryl),
[0147] (ii) a C.sub.1-4 alkoxy-carbonyl group (for example,
methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,
isopropoxycarbonyl),
[0148] (iii) a C.sub.1-4 alkylthio-carbonyl group (for example,
(methylthio)carbonyl, (ethylthio)carbonyl, (n-propylthio)carbonyl,
(isopropylthio)carbonyl, (n-butylthio)carbonyl,
(isobutylthio)carbonyl, (sec-butylthio)carbonyl,
(tert-butylthio)carbonyl),
[0149] (iv) a C.sub.1-4 alkoxy-thiocarbonyl group (for example,
(methoxy)thiocarbonyl, (ethoxy)thiocarbonyl,
(n-propoxy)thiocarbonyl, (isopropoxy)thiocarbonyl),
[0150] (v) a C.sub.1-4 alkylthio-thiocarbonyl (for example,
(methylthio)thiocarbonyl, (ethylthio)thiocarbonyl,
(n-propylthio)thiocarbonyl, (isopropylthio)thiocarbonyl,
(n-butylthio)thiocarbonyl, (isobutylthio)thiocarbonyl,
(sec-butylthio)thiocarbonyl, (tert-butylthio)thiocarbonyl),
[0151] (vi) a mono- or di-C.sub.1-4 alkyl-carbamoyl group (for
example, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl,
dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl), and
[0152] (vii) a mono- or di-C.sub.1-4 alkyl-thiocarbamoyl group (for
example, (methyl)thiocarbamoyl, (ethyl)thiocarbamoyl,
(n-propyl)thiocarbamoyl, (dimethyl)thiocarbamoyl,
(ethylmethyl)thiocarbam- oyl, (diethyl)thiocarbamoyl).
[0153] As the substituents on the said acyl group, halogens (for
example, fluorine, chlorine, bromine, iodine) are preferable. The
number of the said substituents is 1 to 5 (more preferably 1 to
3).
[0154] As the substituents on the "amino group which may be
substituted" in Z.sup.0, there may be mentioned
[0155] C.sub.1-4 alkyl (for example, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl),
[0156] C.sub.1-4 alkyl-carbonyl (for example, acetyl, propionyl,
butyryl, isobutyryl) which may be substituted with 1 to 5 (more
preferably 1 to 3) halogens (for example, fluorine, chlorine,
bromine, iodine),
[0157] C.sub.1-4 alkoxy-carbonyl (for example, methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl),
[0158] mono- or di-C.sub.1-4 alkyl-carbamoyl (for example,
methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl,
dimethylcarbamoyl, ethylmethylcarbamoyl, diethylcarbamoyl), and (e)
mono- or di-C.sub.1-4 alkyl-thiocarbamoyl (for example,
(methyl)thiocarbamoyl, (ethyl)thiocarbamoyl,
(n-propyl)thiocarbamoyl, (dimethyl)thiocarbamoyl,
(ethylmethyl)thiocarbamoyl, (diethyl)thiocarbamoyl).
[0159] The number of the said substituents is preferably 1 or
2.
[0160] As the "hydrocarbon groups which may be substituted" in
R.sup.1, R.sup.2, R.sup.3 and R.sup.4, there may be mentioned those
groups similar to those mentioned as the "hydrocarbon groups which
may be substituted" in Z.sup.0.
[0161] Among the "hydrocarbon groups which may be substituted" in
R.sup.1 and R.sup.2, C.sub.1-4 alkyl group (for example, methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl) are more preferable.
[0162] Among the "hydrocarbon groups which may be substituted" in
R.sup.3, C.sub.1-4 alkyl groups (for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl)
which may be substituted with 1 to 5 (more preferably 1 to 3)
halogens (fluorine, chlorine, bromine, iodine) are preferable.
[0163] Among the "hydrocarbon groups which may be substituted" in
R.sup.4, (1) C.sub.1-4 alkyl groups (for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl)
which may be substituted with 1 to 5 (more preferably 1 to 3)
halogens (fluorine, chlorine, bromine, iodine), and (2) C.sub.6-14
aryl groups (for example, phenyl and naphthyl such as 1-naphthyl
and 2-naphthyl) which may be substituted with 1 to 5 (more
preferably 1 to 3) C.sub.1-4 alkyl (for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl) are
preferable.
[0164] As the cyclic amino groups in Z.sup.0, there may be
mentioned three- to six-membered cyclic amino groups (for example,
aziridino, azetidino, pyrrolidino, piperidino, morpholino,
thiomorpholino).
[0165] As the "acyl group which may be substituted" in R.sup.3,
there may be mentioned those groups similar to those mentioned
above regarding the "acyl group which may be substituted" in
Z.sup.0. Among them, C.sub.1-4 alkyl-carbonyl groups (for example,
acetyl, propionyl, butyryl, isobutyryl) which may be substituted
with 1 to 5 (more preferably 1 to 3) halogens (for example,
fluorine, chlorine, bromine, iodine), and C.sub.1-4 alkoxy-carbonyl
groups (for example, methoxycarbonyl, ethoxycarbonyl,
n-propoxycarbonyl, isopropoxycarbonyl) which may be substituted
with 1 to 5 (more preferably 1 to 3)halogens (for example,
fluorine, chlorine, bromine, iodine) are more preferable.
[0166] As the "alkylsulfonyl" in the "alkylsulfonyl groups which
may be substituted" in R.sup.3, there may be mentioned C.sub.1-4
alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl,
n-propylsulfonyl, isopropylsulfonyl, and so on. As the substituents
on the said alkylsulfonyl groups, halogens (for example, fluorine,
chlorine, bromine, iodine) are preferable. The number of the said
substituents is 1 to 5 (more preferably 1 to 3).
[0167] Z.sup.0 is more preferably, among those mentioned above,
[0168] C.sub.1-6 alkyl group which may be substituted with 1 to 3
substituents selected from hydroxy, halogens, cyano, C.sub.1-4
alkylthio, C.sub.1-4 alkoxy, C.sub.1-4 alkoxy-carbonyl and mono- or
di-C.sub.1-4 alkylamino,
[0169] (2) C.sub.2-6 alkenyl group,
[0170] (3) C.sub.2-6 alkynyl group which may be substituted with 1
to 3 halogens,
[0171] (4) C.sub.3-6 cycloalkyl group,
[0172] (5) C.sub.3-6 alkadienyl group,
[0173] (6) phenyl group,
[0174] (7) C.sub.1-4 alkyl-carbonyl group which may be substituted
with 1 to 3 halogens,
[0175] (8) amino group which may be substituted with one or two
substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkyl-carbonyl and C.sub.1-4 alkoxy-carbonyl,
[0176] (9) a group represented by --N.dbd.CR.sup.1R.sup.2 (where
R.sup.1 and R.sup.2 are the same or different, and are a hydrogen
atom or a C.sub.1-4 alkyl group),
[0177] (10) C.sub.1-4 alkoxy group,
[0178] (11) C.sub.1-4 alkyl-carbonyloxy group,
[0179] (12) C.sub.1-4 alkylthio group which may be substituted with
1 to 5 halogens,
[0180] (13) C.sub.1-4 alkylsulfinyl group which may be substituted
with 1 to 5 halogens,
[0181] (14) C.sub.1-4 alkylsulfonyl group,
[0182] (15) phenylsulfonyl group which may be substituted with 1 to
3 C.sub.1-4 alkyl.
[0183] As the salt of compound (I.sup.0), there may be mentioned
any salts which are acceptable agrochemically. In the cases where
the compound (I.sup.0) is of basic nature, there may be mentioned
salts with inorganic acids such as hydrofluoric acid, hydrochloric
acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric
acid, and perchloric acid, and those with organic acids such as
formic acid, acetic acid, propionic acid, tartaric acid, malic
acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric
acid, methanesulfonic acid, p-toluenesulfonic acid and so on. In
the cases where the compound (I.sup.0) is of acidic nature, there
may be mentioned salts, alkali metals such as lithium, sodium,
potassium and so on, salts with alkaline earth metals such as
magnesium, calcium and so on, ammonium salts such as ammonia,
methylamine, dimethylamine, trimethylamine, triethylamine,
ethylenediamine, TMEDA (tetramethylethylenediamine), aniline,
N,N-dimethylaniline, pyridine, lutidine, collidine, hydrazine, and
so on, and salts with, for example, urea and guanidine, and so
on.
[0184] Among compound (I.sup.0) or salts thereof, those represented
by compound (I), compound (II), compound (III), compound (IV) and
compound (V) or salts thereof are more preferable.
[0185] [1] Compound (I) or salts thereof are those compounds
represented by the Formula (I) or salts thereof, 33
[0186] [wherein, A.sup.1 is (1) an aryl group which may be
substituted, or (2) a heterocyclic group which may be
substituted,
[0187] X.sup.1is (1) a chemical bond, (2) a methylene group which
may be substituted, (3) a vinylene group which may be
substituted,
[0188] B.sup.1 is a 5 membered heterocyclic group which may be
substituted (except for an isoxazolyl group) or a condensed
heterocyclic group which may be substituted,
[0189] Z.sup.1 is (1) a hydrocarbon group which may be substituted,
(2) an acyl group which may be substituted, (3) formyl group, (4)
an amino group which may be substituted, (5) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the same
or different, and are a hydrogen atom or a hydrocarbon group which
may be substituted, (6) a cyclic amino group, (7) a group
represented by --OR.sup.3 (wherein R.sup.3 is a hydrogen atom, a
hydrocarbon group which may be substituted, an acyl group which may
be substituted, formyl group or an alkylsulfonyl group which may be
substituted, or (8) a group represented by --S(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, R.sup.4 a hydrogen atom or
hydrocarbon group which may be substituted).
[0190] As the substituents on A.sup.1, X.sup.1 and Z.sup.1, there
may be mentioned those on A.sup.0, X.sup.0 and Z.sup.0, mentioned
above.
[0191] As the five-membered heterocylic group in the "five-membered
heterocyclic group which may be substituted" in B.sup.1, there may
be mentioned, a five-membered heterocyclic group, for example,
those heterocyclic groups which contain, nitrogen and/or sulfur
atoms as the ring constructing atoms besides carbon atoms, and
especially those which contain 1 to 4 (more preferably 1 to 3)
heteroatoms selected from nitrogen and sulfur atoms, exemplified by
pyrolyl (for example, 1-, 2- or 3-pyrolyl), pyrazolyl (for example
1-, 3-, 4- or 5-pyrazolyl), imidazolyl (for example, 1-, 2-, 4- or
5-imidazolyl), triazolyl (for example, 1,2,3-triazol-1-, 4- or5-yl,
1,2,4-triazol-1-,3-,4- or 5-yl), tetrazolyl (for example,
tetrazol-1-, 2- or 5-yl), thienyl (for example, 2- or 3-thienyl),
thiazolyl (for example, 2-, 4- or 5-thiazolyl), isothiazolyl (for
example, 3-, 4- or 5-isothiazolyl), thiadiazolyl (for example,
1,2,3-thiadiazol-4- or 5-yl, 1,2,4-thiadiazol-3- or 5-yl,
1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-2-yl), pyrrolidinyl (for
example, 1-, 2- or 3-pyrrolidinyl), and so on. Especially
preferable are thienyl, pyrazolyl, isothiazolyl, imidazolyl,
thiazolyl and thiadiazolyl.
[0192] As the substituents on the said five-membered heterocyclic
groups, those selected from the group of substituents (T) described
above are preferable. The number of the substituents is 1 to 5
(more preferably 1 to 3). The most preferable substituents are
halogens, nitro, cyano, and C.sub.1-4 alkyl, C.sub.1-4 alkoxy, and
C.sub.1-4 alkylthio substituted with 1 to 5 (more preferably 1 to
3) halogens.
[0193] As the "condensed heterocyclic groups" in the "condensed
heterocyclic groups which may be substituted" in B.sup.1, those
condensed heterocyclic groups which are composed of five- to
six-membered heterocycles and benzene rings or five- to
six-membered heterocycles and five- to six-membered heterocycles
are preferable. As specific examples of such preferable condensed
heterocycles, there can be mentioned indolyl (for example,
3H-indol-2-, 3-, 4-, 5-, 6- or 7-yl), quinolyl (for example, 2-,
3-, 4-, 5-, 6-, 7- or 8-quinolyl), isoquinolyl,
pyrido[2,3-d]pyrimidinyl (for example,
pyrido[2,3-d]pyrimidin-2-yl), naphthyridinyl such as 1,5-, 1,6-,
1,7-, 1,8-, 2,6- or 2,7-naphthyridinyl (for example,
1,5-naphthyridin-2- or 3-yl), thieno[2,3-d]pyridyl (for example,
thieno[2,3-d]pyridin-2-yl), pyrazinoquinolyl (for example,
pyrazino[2,3-d]quinolin-2-yl), chromenyl (for example,
2H-chromen-2-, 3-, 4-, 5- or 6-yl), chromanyl (for example, 1-, 2-,
3-, 4-, 5-, 6-, 7- or 8-chromanyl), isochromanyl (for example, 1-,
3-, 4-, 5-, 6-, 7- or 8-isochromanyl), benzofuryl (for example, 2-,
3-, 4-, 5-, 6- or 7-benzofuryl), benzothienyl (for example, 2-, 3-,
4-, 5-, 6- or 7-benzothienyl), benzoimidazolyl (for example, 2-,
4-, 5-, 6- or 7-benzimidazolyl), indazolyl (for example,
1H-indazol-1-, 3-, 4-, 5-, 6- or 7-yl), benzooxazolyl (for example,
2-, 4-, 5-, 6- or 7-benzooxazolyl), benzoisooxazolyl (for example,
3-, 4-, 5-, 6- or 7-benzoisooxazolyl), benzothiazolyl (for example,
2-, 4-, 5-, 6- or 7-benzothiazolyl), benzothiadiazolyl (for
example, benzo-1,2,3-thiadiazol-4-, 5-, 6- or 7-yl,
benzo-1,2,4-thiadiazol-3-, 4-, 5-, 6- or 7-yl),
benzo-1,2,5-thiadiazol-3-, 4-, 5-, 6- or 7-yl,
benzo-1,3,4-thiadiazol-2-, 4-, 5-, 6- or 7-yl), benzoisothiazolyl
(for example, 3-, 4-, 5-,6- or 7-benzoisothiazolyl), benzotriazolyl
(for example, 4-, 5-, 6-, 7- or 8-benzo-1,2,3-triazolyl, 3-, 5-,
6-, 7- or 8-benzo-1,2,4-triazolyl), cinnolyl (for example, 3-, 4-,
5-, 6-, 7- or 8-cinnolyl), phthalazinyl (for example, 1-, 5- or
6-phthalazinyl), quinazolynyl (for example, 2-, 4-, 5-, 6-, 7- or
8-quinazolynyl), quinoxalinyl (for example, 2-, 5- or
6-quinoxalinyl), imidazopyridyl (for example, imidazo[1,2-a]pyridyl
such as imidazo[1,2-a]pyridin-2-yl, imidazo[1,2-a]pyridin-3-yl, and
so on) imidazothiazolyl (for example, imidazo[2,1-b]thiazolyl such
as imidazo[2,1-b]thiazol-5-yl), dioxaindanyl (for example,
1,3-dioxaindanyl such as 1,3-dioxaindan-2-, 4-, 5-, 6- or 7-yl, and
so on). Among these, imidazopyridyl and dioxaindanyl are more
preferable.
[0194] As the substituents on the "condensed heterocyclic groups",
those selected from the group of substituents (T) described above
are preferable. The number of the substituents is 1 to 5 (more
preferably 1 to 3). Among those substituents, nitro is especially
preferable.
[0195] Among compounds included in compound (I), preferable are the
compounds represented by the Formula (I) above or salts thereof. In
the Formula(I), A.sup.1 is a C.sub.6-14 aryl group which may be
substituted with 1 to 3 C.sub.1-4 alkyl groups,
[0196] X.sup.1 is a chemical bond, B.sup.1 is a thienyl group,
pyrazolyl group, isothiazolyl group, imidazolyl group, thiazolyl
group, thiadiazolyl group, dioxaindanyl group or imidazopyridyl
group, each of which may be substituted with 1 to 5 substituents
selected from C.sub.1-4 alkyl which may be substituted with 1 to 5
halogens, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio,
cyano, halogens and nitro, Z.sup.1 is a C.sub.16 alkyl group or
C.sub.1-4 alkoxy group.
[0197] Hereinafter, the more preferable embodiments of the compound
(I) and the salts thereof are described:
[0198] As A.sup.1, a phenyl which may be substituted with 1 to 3
C.sub.1-4 alkyl is preferable, and the 4-methylphenyl group is
especially preferable.
[0199] (2) As B.sup.1, either (i) a thienyl group, a pyrazolyl
group, an isothiazolyl group, an imidazolyl group, a thiazolyl
group or a thiadiazolyl group, each of which may be substituted
with 1 to 5 substitutents selected from C.sub.1-4 alkyl substituted
with 1 to 5 halogens, C.sub.1-4 alkoxy, C.sub.1-4 alkylthio, cyano,
halogens and nitro, or (ii) a dioxaindanyl group or an
imidazopyridyl group which may be substituted with 1 to 3 nitros
are preferable. The more preferable B.sup.1 are:
[0200] (i) the thienyl group which may be substituted with 1 to 3
substituents selected from halogens and nitro,
[0201] (ii) the pyrazolyl group which may be substituted with 1 to
3 substituents selected from C.sub.1-4 alkyl, nitro and cyano,
[0202] (iii) the imidazolyl group which may be substituted with 1
to 3 substituents selected from C.sub.1-4 alkyl and nitro,
[0203] (iv) the thiazolyl group which may be substituted with 1 to
3 substituents selected from C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, C.sub.1-4 alkylthio, halogens,
nitro and cyano, (v) the thiadiazolyl group (more preferably a
1,3,4-thiadiazolyl group) which may be substituted with C.sub.1-4
alkyl which may be substituted with 1 to 5 halogens,
[0204] (vi) the isothiazolyl group which may be substituted with 1
to 3 substituents selected from C.sub.1-4 alkyl which may be
substituted with 1 to 5 halogens, C.sub.1-4 alkoxy, nitro and
cyano,
[0205] (vii) the 1,3-dioxaindanyl group which may be substituted
with 1 to 3 nitro, and
[0206] (viii) the imidazo[1,2-a]pyridyl group which may be
substituted with 1 to 3 nitro,
[0207] (3) As Z.sup.1, a C.sub.1-6 alkyl group or a C.sub.1-4
alkoxy group is preferable,
[0208] (4) As X.sup.1, a chemical bond (a single bond or a bond) is
preferable.
[0209] The preferable embodiments regarding A.sup.1, B.sup.1,
Z.sup.1 and X.sup.1 described in (1) to (4) above can be combined
together arbitrarily.
[0210] [2] Compound (II) or salts thereof are the compounds
represented by the Formula (II) 34
[0211] or salts thereof,
[0212] [where A.sup.2 is (1) an aryl group or a heterocyclic group
or (2) heterocyclic group, which may be substituted with 1 to 5
(more preferably 1 to 3) substituents selected from the substituent
group (T') described above,
[0213] X.sup.2 is (1) a chemical bond, (2) a methylene group which
may be substituted, or (3) a vinylene group which may be
substituted,
[0214] B.sup.2 is an aryl group which may be substituted,
[0215] Z.sup.2 is (1) an alkyl group which may be substituted with
substituents selected from mono- or di-C.sub.1-6 alkylamino,
hydroxy, halogens, C.sub.1-6 alkoxy, C.sub.1-6 alkoxy-carbonyl,
C.sub.1-6 alkylthio and cyano,
[0216] (2) the vinyl group,
[0217] (3) the allyl group,
[0218] (4) the propadienyl group,
[0219] (5) the alkynyl group which may be substituted,
[0220] (6) the cycloalkyl group which may be substituted,
[0221] (7) the aryl group which may be substituted,
[0222] (8) the acyl group which may be substituted,
[0223] (9) the formyl group,
[0224] (10) the amino group which may be substituted,
[0225] (11) the group represented by --N.dbd.CR.sup.1R.sup.2
(wherein R.sup.1 and R.sup.2 are the same or different, and are a
hydrogen or a hydrocarbon group which may be substituted),
[0226] (12) the cyclic amino group,
[0227] (13) the group represented by --OR.sup.3 (wherein R.sup.3 is
a hydrogen atom, a hydrocarbon group which may be substituted, an
acyl group which may be substituted, formyl group, or a
alkylsulfonyl group which may be substituted), or
[0228] the group represented by --S(O).sub.nR.sup.4 (where n is an
integer from 0 to 2, R.sup.4 a hydrogen atom or hydrocarbon group
which may be substituted).
[0229] As an aryl group in A.sup.2, there may be mentioned a
C.sub.6-14 aryl groups such as phenyl, and naphthyl (for example,
1-naphthyl, 2-naphthyl). A phenyl group is especially
preferable.
[0230] As a heterocyclic group which may be substituted in A.sup.2,
there may be mentioned the same heterocyclic groups as those which
may be substituted in A.sup.0.
[0231] As the substituents on X.sup.2, there can be mentioned the
same ones as those on X.sup.0.
[0232] As the aryl group which may be substituted in B.sup.2, there
can be mentioned the same ones as those in B.sup.0. As the aryl
group, a phenyl group is especially preferable.
[0233] As the alkyl group in "an alkyl group which may be
substituted with substituents selected from mono- or di-C.sub.1-6
alkylamino, hydroxy, halogens, C.sub.1-6 alkoxy, C.sub.1-6
alkoxy-carbonyl, C.sub.1-6 alkylthio and cyano" in Z.sup.2, there
may be mentioned C.sub.1-6 alkyl groups such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
n-pentyl, sec-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl and
soon. The number of substituents on the said alkyl groups is 1 to
5, or more preferably 1 to 3., As the mono- or di-C.sub.1-6
alkylamino groups as the said substituent, there may be mentioned
methylamino, ethylamino, -n-propylamino, dimethylamino,
ethylmethylamino, diethylamino, and mono- or di-C.sub.1-4
alkylamino groups are especially preferable. As halogens, there may
be mentioned fluorine, chlorine, bromine, and iodine. As C.sub.1-6
alkoxy, there may be mentioned methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and so
on, the C.sub.1-4 alkoxy groups being especially preferable. As
C.sub.1-6 alkoxy-carbonyl, there may be mentioned methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, and so on,
the C.sub.1-4 alkoxy-carbonyl groups being especially preferable.
As C.sub.1-6 alkylthio, there may be mentioned methylthio,
ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio, tert-butylthio, and so on, the C.sub.1-4 alkylthio
groups being especially preferable. As alkynyl in "alkynyl which
may be substituted" in Z.sup.2 there may be mentioned C.sub.2-6
alkynyl group such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,
2-butynyl, 3-butynyl and so on. As cycloalkyl in "cycloalkyl which
may be substituted", there may be mentioned C.sub.3-6 cycloalkyl
such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and so on.
As aryl in "the aryl group which may be substituted", there may be
mentioned C.sub.6-14 aryl such as phenyl, naphthyl, (for example,
1-naphthyl, 2-naphthyl) and so on. As the substituents on alkynyl
group, cycloalkyl group or aryl group described above, there may be
mentioned the same substituents as those on alkynyl group,
cycloalkyl group or aryl group exemplified in hydrocarbon group in
"hydrocarbon group which may be substituted" regarding Z.sup.0
mentioned above, the number of the substituent or substituents on
the said alkyl group, cycloalkyl group or aryl group being 1 to 5,
preferably 1 to 3 respectively. Each of "an acyl group which may be
substituted", "an amino group which may be substituted", "a group
represented by --N.dbd.CR.sup.1R.sup.2", "a cyclic amino group", "a
group represented by --OR.sup.3" and "a group represented by
--S(O).sub.nR.sup.4" in Z.sup.2 has the same meaning as that of "an
acyl group which maybe substituted", "an amino group which may be
substituted", "a group represented by --N.dbd.CR.sup.1R.sup.2", "a
cyclic amino group", "a group represented by --OR.sup.3" and "a
group represented by --S(O).sub.nR.sup.4" in Z.sup.0 mentioned
above.
[0234] Among compounds included in compound (II), preferable are
the compounds represented by the Formula (II) above or salts
thereof. In the Formula, [where A.sup.2 is (1) a C.sub.6-14 aryl
group which may be substituted with 1 to 5 substituents selected
from (i) a C.sub.1-4 alkyl group which may be substituted with 1 to
5 halogens,
[0235] (ii) the C.sub.1-4 alkoxy group which may be substituted
with 1 to 5 halogens,
[0236] (iii) the amino group which may be substituted with 1 or 2
C.sub.1-4 alkyl-carbonyl,
[0237] (iv) the C.sub.1-4 alkoxy-carbonyl group,
[0238] (v) halogen atoms,
[0239] (vi) the cyano group, and
[0240] (vii) the nitro group, or
[0241] the thienyl group, the triazolyl group, the imidazolyl
group, the isooxazolyl group, the pyrazolyl group, the pyridyl
group, the quinolyl group, the benzothiadiazolyl group, the
imidazothiazolyl group or the imidazopyridyl group, each of which
may be substituted with 1 to 5 substitutents selected from
[0242] (i) the C.sub.1-4 alkyl group,
[0243] (ii) the C.sub.1-4 alkoxy-carbonyl group,
[0244] (iii) the carbamoyl group,
[0245] (iv) the mono- or di-C.sub.1-4 alkylcarbamoyl group,
[0246] (v) C.sub.1-4 alkylsulfonyl group,
[0247] (vi) halogen atoms,
[0248] (vii) the carboxyl group and
[0249] (viii) the cyano group,
[0250] X.sup.2 is (1) the chemical bond,
[0251] (2) the methylene group which may be substituted with 1 or 2
C.sub.1-4 alkyl,
[0252] (3) the vinylene group which may be substituted with 1 or 2
C.sub.1-4 alkyl,
[0253] B.sup.2 is a C.sub.6-14 aryl group which may be substituted
with 1 to 5 substituents selected from
[0254] (1) a C.sub.1-4 alkyl group which may be substituted with 1
to 5 substituents selected from halogens, hydroxy, imino,
hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono, mono- or
di-C.sub.1-4 alkylhydrazono and C.sub.1-4 alkylthio,
[0255] (2) a C.sub.2-4 alkynyl group,
[0256] (3) the hydroxy group,
[0257] (4) the C.sub.1-4 alkoxy group which may be substituted with
1 to 5 substituents selected from halogens and C.sub.1-4 alkoxy
groups, (5) a C.sub.1-4 alkyl-carbonyloxy group,
[0258] (6) the C.sub.1-4 alkylthio group,
[0259] (7) the C.sub.1-4 alkylsulfinyl group,
[0260] (8) the C.sub.1-4 alkylsulfonyl group,
[0261] (9) the mono or di-C.sub.1-4 alkylsulfamoyl group,
[0262] (10) the amino group,
[0263] (11) the formyl group,
[0264] (12) the C.sub.1-4 alkoxy-carbonyl group,
[0265] the carbamoyl group,
[0266] the mono- or di-C.sub.1-4 alkylcarbamoyl group,
[0267] the thiocarbamoyl group,
[0268] halogen atoms,
[0269] the carboxyl group,
[0270] the thiocyanato group,
[0271] the cyano group,
[0272] the nitroso group, and
[0273] the nitro group,
[0274] Z.sup.2 is (1) the C.sub.1-6 alkyl group which may be
substituted with 1 to 5 substituents selected from mono- or
di-C.sub.1-4 alkylamino, hydroxy, halogens, C.sub.1-4 alkoxy,
C.sub.1-4 alkoxy-carbonyl, C.sub.1-4 alkylthio and cyano,
[0275] (2) the vinyl group,
[0276] (3) the allyl group,
[0277] (4) the propadienyl group,
[0278] (5) the C.sub.2-6 alkynyl group which may be substituted
with 1 to 5 halogens,
[0279] (6) the C.sub.3-6 cycloalkyl group,
[0280] (7) the C.sub.6-14 aryl group,
[0281] (8) the C.sub.1-4 alkyl-carbonyl which may be substituted
with 1 to 5 halogens,
[0282] (9) the amino group which may be substituted with 1 or 2
substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkyl-carbonyl and C.sub.1-4 alkoxy-carbonyl,
[0283] (10) the group represented by --N.dbd.CR.sup.1R.sup.2 (where
R.sup.1 and R.sup.2 are a C.sub.1-4 alkyl group, respectively),
[0284] (11) the group represented by --OR.sup.3 (where R.sup.3 is a
C.sub.1-4 alkyl group or a C.sub.1-4 alkyl-carbonyl group) or
[0285] (12) the group represented by --S(O).sub.nR.sup.4 (wherein,
n is an integer from 0 to 2, R.sup.4 is (a) the C.sub.1-4 alkyl
group which may be substituted with 1 to 5 halogens, or (b) the
C.sub.6-14 aryl group which may be substituted with 1 to 5
C.sub.1-4 alkyl groups).
[0286] Hereinafter, the more preferable embodiments of the compound
(II) and the salts thereof are described:
[0287] A.sup.2 is (a) the phenyl group which may be substituted
with 1 to 3 substituents selected from C.sub.1-4 alkyl which may be
substituted with 1 to 3 halogens, halogens, nitro, cyano,
acetylamino, C.sub.1-4 alkoxy which may be substituted with 1 to 3
halogens and C.sub.1-4 alkoxy-carbonyl,
[0288] (b) the naphthyl group,
[0289] (c) the isoxazolyl group which may be substituted with 1 to
3 C.sub.1-4 alkyl groups,
[0290] (d) the triazolyl group which may be substituted with 1 to 3
mono- or di-C.sub.1-4
[0291] carbamoyl,
[0292] (e) the pyridyl group,
[0293] (f) the quinolyl group,
[0294] (g) the thienyl group which may be substituted with 1 to 3
substituents selected from C.sub.1-4 alkyl and halogens,
[0295] (h) the pyrazolyl group which may be substituted with 1 to 3
substituents selected from C.sub.1-4 alkyl, C.sub.1-4
alkoxy-carbonyl, carboxyl, carbamoyl, cyano and halogens,
[0296] (i) the imidazolyl group which may be substituted with 1 to
3 C.sub.1-4 alkyl,
[0297] (j) the benzothiadiazolyl group (preferably a
2,1,3-benzothiadiazolyl group),
[0298] (k) the imidazothiazolyl group (preferably an
imidazo[2,1-b]thiazolyl group) which may be substituted with 1 to 3
halogens,
[0299] (l) the imidazopyridyl group (preferably an
imidazo[1,2-a]pyridyl group) which may be substituted with 1 to 3
substituents selected from halogens and C.sub.1-4 alkylsufonyl.
More preferable is a phenyl or a thienyl group which may be
substituted with 1 to 3 substituents such as C.sub.1-4 alkyl
groups, C.sub.1-4 alkoxy groups, halogens or cyano group is more
preferable. Among these, a phenyl group which may be substituted
with 1 to 3 substituents selected from C.sub.1-4 alkyl and halogens
is much more preferable. And the phenyl group which is substituted
at the 4-position with a methyl group or a chlorine atom is the
most preferable.
[0300] (2) As B.sup.2, preferable is a phenyl group which is
substituted at the 2- or 4-position with substituent selected from
(a) the C.sub.1-4 alkyl group which may be substituted with 1 to 5
substituents selected from halogens, hydroxy, imino, hydroxyimino,
C.sub.1-4 alkoxyimino, hydrazono, mono- or di-C.sub.1-4
alkylhydrazono and C.sub.1-4 alkylthio,
[0301] (b) the C.sub.2-4 alkynyl group,
[0302] (c) the hydroxy group,
[0303] (d) the C.sub.1-4 alkoxy group which may be substituted with
1 to 5 substituents selected from halogens and C.sub.1-4
alkoxy,
[0304] (e) a C.sub.1-4 alkyl-carbonyloxy group,
[0305] (f) a C.sub.1-4 alkylthio group,
[0306] (g) a C.sub.1-4 alkylsulfinyl group,
[0307] (h) a C.sub.1-4 alkylsulfonyl group,
[0308] (i) a mono- or di-C.sub.1-4 alkylsulfamoyl group,
[0309] (j) formyl group,
[0310] (k) a C.sub.1-4 alkoxy-carbonyl group,
[0311] (l) a carbamoyl group,
[0312] (m) a mono- or di-C.sub.1-4 alkylcarbamoyl group,
[0313] (n) a thiocarbamoyl group,
[0314] (o) halogen atoms,
[0315] (p) a carboxyl group,
[0316] (q) a thicyanato group,
[0317] (r) a cyano group,
[0318] s a nitroso group, and
[0319] (t) a nitro group.
[0320] As B.sup.2, a group represented by 35
[0321] (wherein, M.sup.1 is a nitro group, a cyano group, a
trifluoromethyl group or a thiocarbamoyl group, and M.sup.2 is
halogen atoms, a cyano group, a nitro group or a trifluoromethyl
group) is especially preferable.
[0322] (3) As Z.sup.2, preferable are (a) a C.sub.1-6 alkyl group
which may be substituted with 1 to 5 substituents selected from
mono- or di-C.sub.1-4 alkylamino, hydroxy, halogens, C.sub.1-4
alkoxy, C.sub.1-4 alkoxy-carbony, C.sub.1-4 alkylthio and
cyano,
[0323] (b) a vinyl group,
[0324] (c) an allyl group,
[0325] (d) a propadienyl group,
[0326] (e) a C.sub.2-6 alkynyl group which may be substituted with
1 to 5 halogens, or
[0327] (f) a C.sub.3-6 cycloalkyl group, or
[0328] (g) a C.sub.1-4 alkoxy group. Among these, a C.sub.1-6 alkyl
group, a C.sub.3-6 cycloalkyl group, a vinyl group, an allyl group,
a C.sub.2-6 alkynyl group or a C.sub.1-4 alkoxy group is especially
preferable.
[0329] (4) X.sup.2 is preferably a chemical bond (a single bond or
a bond). The preferable embodiments of A.sup.2, B.sup.2, Z.sup.2
and X.sup.2 described in (1) to (4) above, can be combined
arbitrarily.
[0330] Another preferable embodiments of compounds (II) or salts
thereof are preferably the compounds or salts thereof described the
following:
[0331] A.sup.2is a phenyl group which may be substituted with 1 to
3 substituents selected from C.sub.1-4 alkyl groups, halogens and
cyano,
[0332] X.sup.2 is a chemical bond,
[0333] B.sup.2is a phenyl group which may be substituted with 1 to
5 substituents selected from
[0334] (1) a C.sub.1-4 alkyl group which may be substituted with 1
to 3 halogens,
[0335] (2) a C.sub.1-4 alkoxy group,
[0336] (3) a C.sub.1-4 alkylthio group,
[0337] (4) a thiocarbamoyl,
[0338] (5) halogen atoms,
[0339] (6) a cyano group, and
[0340] (7) a nitro group,
[0341] Z.sup.2 is (1) a C.sub.1-6 alkyl group which may be
substituted with 1 to 3 C.sub.1-4 alkoxy, (2) a C.sub.3-6
cycloalkyl group, (3) an allyl group or (4) a C.sub.1-4 alkoxy
group.
[0342] [3] Compound (III) or salts thereof are preferably the
compounds represented
[0343] by the Formula (III): 36
[0344] or a salt thereof,
[0345] [where A.sup.3 is (1) an aryl group which may be substituted
or (2) a heterocyclic group which may be substituted,
[0346] X.sup.3 is (1) a chemical bond, (2) a methylene group which
may be substituted or (3) a vinylene group which may be
substituted,
[0347] B.sup.3 is a six-membered heterocyclic group containing
sucstituents,
[0348] Z.sup.3 is (1) a hydrocarbon group which may be substituted,
(2) an acyl group which may be substituted, (3) formyl group, (4)
an amino group which may be substituted, (5) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein, R.sup.1 and R.sup.2 are the same
or different, and are a hydrogen atom or hydrocarbon group which
may be substituted), (6) a cyclic amino group, (7) a group
represented by --OR.sup.3(wherein R.sup.3is a hydrogen atom, a
hydrocarbon group which may be substituted, an acyl group which may
be substituted, formyl group or a sulfonyl group which may be
substituted), or (8) a group represented by--S(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, R.sup.4 is a hydrogen atom or
a hydrocarbon group which may be substituted)].
[0349] The substituents on A.sup.3, X.sup.3 and Z.sup.3 are the
same as those on A.sup.0, X.sup.0 and Z.sup.0, respectively.
[0350] As the "six-membered heterocyclic group" in the
"six-membered heterocyclic group with substituents" in B.sup.3,
there can be mentioned six-membered heterocyclic groups comprising
1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur atoms.
As the specific examples, there can be mentioned pyridyl (for
example, 2-, 3- or 4-pyridyl), pyridazinyl (for example, 3- or
4-pyridazinyl), pyrimidinyl (for example, 2-, 4-, or
5-pyrimidinyl), pyrazinyl, piperidinyl (for example, 1-, 2-, 3- or
4-piperidinyl), piperazinyl (for example, 1- or 2-piperazinyl), and
so on. Among these six-membered heterocyclic groups, pyridyl,
pyridazinyl and pyrimidinyl are especially preferable.
[0351] As substituents on the said six-membered heterocyclic
groups, those included in the substituents group (T) mentioned
above are preferable. The number of the said substituents is 1 to 5
(more preferably 1 to 3).
[0352] Among the compounds included in compound (III), preferable
are those represented by the Formula (III)or salts thereof. In the
Formula (III), wherein A.sup.3 is a phenyl group which may be
substituted with 1 to 5 C.sub.1-4 alkyl or an imidazolyl group
which may be substituted with one or two C.sub.1-4 alkyl,
[0353] x.sup.3 is a chemical bond,
[0354] B.sup.3 is a pyridyl group, a pyridazinyl group or a
pyrimidinyl group which may be substituted with 1 to 5 substituents
selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy, halogens and
nitro,
[0355] Z.sup.3 is a C.sub.1-6 alkyl group or C.sub.3-6 cycloalkyl
group or salts thereof.
[0356] As for A.sup.3 above, a phenyl group which may be
substituted with 1 to 5 C.sub.1-4 alkyl is more preferable, and
furthermore a 4-methylphenyl group is the most preferable.
[0357] [4] Compounds (IV) or salts thereof are the compounds
represented by the Formula (IV): 37
[0358] or salts thereof,
[0359] [wherein A.sup.4 is (1) an aryl group which may be
substituted or (2) a heterocyclic group which may be
substituted,
[0360] X.sup.4 is (1) a chemical bond, (2) a methylene group which
may be substituted or (3) a vinylene group which may be
substituted,
[0361] B.sup.4 is a pyridazinyl group or a pyradinyl group,
[0362] Z.sup.4 is (1) a hydrocarbon group which may be substituted,
(2) an acyl group which may be substituted, (3) formyl group, (4)
an amino group which may be substituted, (5) a group represented by
--N.dbd.CR.sup.1R.sup.2 (wherein R.sup.1 and R.sup.2 are the same
or different, and are a hydrogen atom or a hydrocarbon group which
may be substituted), (6) a cyclic amino group, (7) a group
represented by --OR.sup.3 (wherein R.sup.3is a hydrogen atom, a
hydrocarbon group which may be substituted an acyl group which may
be substituted with hormyl group or sulfonyl group which may be
substituted, (8) a group represented by --S(O).sub.nR.sup.4
(wherein n is an integer from 0 to 2, R.sup.4 is a hydrogen atom or
a hydrocarbon group which may be substituted].
[0363] Substituents on A.sup.4, X.sup.4 and Z.sup.4 are the same as
those on A.sup.0, X.sup.0 and Z.sup.0 described above,
respectively.
[0364] [5] Compounds (V) or salts thereof are the compounds
represented by the Formula (V): 38
[0365] or salts thereof,
[0366] [wherein A.sup.5 is a 4-methylphenyl group, X.sup.5 is a
chemical bond (a single bond or a bond), B.sup.5 is a pyridyl group
or a pyrimidinyl group, Z.sup.5 is a C.sub.1-4 alkyl group (for
example, methyl, ethyl, n-propyl, isopropyl)].
[0367] Among the compound (1) to (V) stated above, compound (I) to
(III) or salts thereof are more preferable, and compound (II) or
salts thereof are especially preferable.
[0368] Among the compound (I.sup.0) or salts thereof, the compound
(VI) shown below or salts thereof are novel compounds and can be
used especially preferably. The said comound (VI) or salts thereof
are compounds included in the compound (II) or salts thereof
mentioned above. Compounds represented by the Formul (VI) and
saltys thereof, 39
[0369] [wherein, A.sup.6 is a phenyl group which may be substituted
with substituents selected from C.sub.1-4 alkyl (for example,
methyl, ethyl, n-propyl, isopropyl), halogens (for example,
fluorine, chlorine, bromine, iodine) and cyano, X.sup.6 is a
chemical bond ( a single bond or a bond), B.sup.6 is a
2-nitrophenyl group (or 6-nitrophenyl group) or 2-cyanophenyl group
(or 6-cyanophenyl group) which may be substituted with substituents
selected from halogen atoms (for example, fluorine, chlorine,
bromine, iodine), nitro and cyano, Z.sup.6 is an ethyl group, an
isopropyl group, a cyclopropyl group, a methoxy group, an ethoxy
group or an isopropoxy group].
[0370] Especially preferable are the compounds or salts thereof
which have as A.sup.6 a phenyl group which may be substituted with
substituents selected from C.sub.1-4 alkyl, halogens and cyano, as
X.sup.6 a chemical bond, as B.sup.6 a 2-nitrophenyl group which may
be substituted with substituents selected from halogen atoms, nitro
and cyano, and as Z.sup.6 an ethyl group, an isopropyl group or a
cyclopropyl group.
[0371] The number of the substituents on the phenyl group as
A.sup.6 is 1 to 3. As the said substituent, methyl and chlorine
atom are especially preferable. The substitutent of the said phenyl
group is preferably at position 4 of the said phenyl group.
[0372] The number of substituents on the 2-nitrophenyl group (or
6-nitrophenyl group) or the 2-cyanophenyl group (or 6-cyanophenyl
group) as B.sup.6 is 1 to 3. As the said substituent, halogens and
cyano are especially preferable. The said substituents are
preferably at the 4 position of the 2-nitrophenyl (or
6-nitrophneyl) group or 2-cyanophenyl (or 6-cyanophenyl) group.
[0373] When compound (I.sup.0), (I), (II), (III), (IV), (V) or (VI)
or salts thereof mentioned above (hereinafter, they may be called
as "compound (I.sup.0) or the salts thereof" for short) are used as
microbicidal compositions, they can be applied in the per se known
forms for general use of agrochemical compositions. Namely,
depending on the objects one or more than two kinds (preferably not
less than one nor more than three) of compound (I.sup.0) or salts
thereof are taken as the effective constituents and mixed with or
dispersed in some appropriate liquid carrier, or mixed with or
adsorbed on some appropriate solid carrier to get various forms of
compositions, for example, emulsions, oils, aqueous suspensions,
liquids, ULV preparations, hydrates, powders, DL (driftless)
powders, granules, fine granules, fine granules F, flowable
preparations, dry-flowable preparations, tablets, Jumbo
preparations, sprays, ointments, pastes, foams, aerosols,
micocapsules, seed coating agents, fumigants, and stick
preparations for infusing the crops. These preparations may be
further admixtured, if necessary, for example, with emulsifiers,
suspending agents, spreading agents, permeating agents, moistening
agents, dispersing agents, mucilage, stabilizers, binders,
fluidization auxiliaries, hardening preventives, flocculants,
antioxidants, floating agents, antifoaming agents, antifreeze
agents, antiseptics, moisture removers, ultraviolet absorbers,
ultraviolet scattering agents, coloring agents and
suspension-stabilizers, to prepare microbicidal compositions of the
present invention by the per se known methods. Namely, by mixing
comound (I.sup.0) or salts thereof, liquid carriers or solid
carriers, if necessary, various additives mentioned above, and
other active ingredients of pesticides uniformly.
[0374] Emulsions of the present invention, for example, can be
prepared by mixing and dissolving uniformly compound (I.sup.0) or
salts thereof, emulsifiers, organic solvents, and so on. Granules
and wettable granules of the present invention, for example, can be
manufactured by mixing uniformly compound (I.sup.0) or salts
thereof, dispersing agents (surfactants), binders, fillers (or
solid carriers) and so on, uniformly, and then granulating.
[0375] Powders (DL powders and so on) of the present invention, for
example, can be manufactured by mixing compound (I.sup.0) or salts
thereof with fillers (or solid carriers) uniformly and pulverizing
the resulting mixture. Flowable preparations of the present
invention can be manufactured by mixing, dispersing compound
(I.sup.0) or salts thereof, dispersing agents and so on with a
mixer, and then by wet-pulverizing the resulting mixture by means
of dynomill, and so on. Jumbo preparations, for example, can be
manufactured by mixing compound (I.sup.0) or salts thereof with
dispersing agents (surfactants), binders, floating agents, fillers
(or solid carriers) uniformly, and by granulating the resulting
mixture. Jambo formulations, powders, granules, wettable granules,
hydrates and so on can be packed into water-soluble film-packages
of 20 to 200 g each, for the sake of convenience in spraying. As
the water-soluble films, there may be mentioned those of polyvinyl
alcohol, carboxymethyl cellulose, starch, gelatin,
polyvinylpyrrolidone, polyacrylic acid or salts thereof, pullulan
(trade name: polysaccharide of a kind of starch), PAOGEN (Trade
Name: a thermoelastic water soluble polymer), and so on.
[0376] As liquid carriers (solvents) appropriate for use, there may
be mentioned, for example, water, alcohols such as methanol,
ethanol, propanol, isopropanol, ethylene glycol, and so on, ketones
such as acetone and methyl ethyl ketone, and so on, ethers such as
1,4-dioxane, tetrahydrofuran, ethylene glycol monomethyl ether,
diethylene glycol monomethyl ether, propylene glycol monomethyl
ether, and soon, aliphatic hydrocarobons such as kerosene,
paraffin, fuel oil, machine oil, and edible oil, and so on,
aromatic hydrocarbons such as benzene, toluene, xylene, solvent
naphtha, methylnaphthalene, and so on, halogenated hydrocarbons
such as dichloromethane, chloroform, carbon tetrachloride, and so
on, acid amides such as N,N-dimethylformamide,
N,N-dimethylacetamide, and so on, esters such as ethyl acetate,
butyl acetate, fatty acid glycerol esters, and so on, and nitriles
such as acetonitrile, propionitrile,and so on. These solvents can
be used by mixing one or more than two (preferably not less than
one nor more than three) of them in appropriate ratios. As solid
carriers (diluents, fillers), there may be mentioned, for example,
vegetable powders such as soybean powder, tobacco powder, wheat
flour,wood flour, and so on, mineral powder, for example, clays
such as kaolin, bentonite, acid clay, and so on, talcs such as
talcum powder, agalmatolite powder, and so on, silicate minerals
such as diatomaceous earth, mica, and soon, calcium carbonate,
alumina, sulfur powder, activated carbon, and so on. These fillers
can be used by mixing one or more than two (preferably not less
than one nor more than three) of them in appropriate ratios.
Further, as the ointment bases, there may be used, for example, one
or more than two (preferably not less than one nor more than three)
of polyethylene glycol, pectin, polyol higher fatty acid esters
such as glycerol mono-stearic acid ester, and so on, cellulose
derivatives such as methyl cellulose, and so on, sodium alginate,
bentonite, higher alcohols, polyols such as glycerol, and so on,
vaseline, white Vaseline, liquid paraffin, lard, various vegetable
oils, lanoline, dehydrated lanoline, hydrogenated oil, resins, or
mixtures of these substances with various surfactants described
below appropriately.
[0377] As surfactants which may be used as emulsifiers, spreading
agents, penetrants, moistening agents, dispersing agents, there may
be mentioned nonionic surfactants such as soaps, polyoxyethylene
alkylethers (NEWKALGEN FS4.TM. (TM means trade mark.), NOIGEN
EA-177.TM., NOIGEN ET83.TM., NOIGEN ET157.TM. and so on),
polyoxyethylene alkylphenyl ethers, polyoxyethylene nonylphenyl
ethers (NONIPOL20.TM., NONIPOL100.TM. and so on), polyoxyethylene
alkylaryl ethers [for example, NOIGEN EA142.TM., NOIGEN EA92.TM.;
manufacured by Dai-ichi Kogyo Seiyaku Co., Ltd., NONAL.TM.;
manufactured by Toho Chemical Industry Co., Ltd.],
polyethyleneglycol ethers [for example, NONIPOL 85.TM.,
NONIPOL160.TM. manufactured by Sanyo Chemical Industries Ltd.,
polyol esters [for example, Tween 20.TM., Tween 80.TM.;
manufactured by KAO Corp.], polyoxyethylene polyoxypropylene
ethers, polyoxyethylene distylenated phenylether (NOIGEN EA87.TM.,
NOIGEN EA177.TM. and so on), polyoxyethylene alkylesters
(ionetMO20TM, ionetMO600TM, and so on), sorbitan fatty acid esters
(LEODOL SP-S10.TM., LEODOL TW-S20.TM. and so on), polyoxyethylene
sorbitan fatty acid esters, block copolymer of ethylene oxide with
propylene oxide (NEWPOL PE64.TM.), higher fatty acid alkanol
amides, alkylmaleic acid copolymer (DEMOL EP.TM. and so on);
cationic surfactants such as alkylamine salts and tert-ammonium
salts, and so on; anionic surfactants such as alkylsulfuric acid
salts [for example, EMAL10.TM., EMAL40.TM.; manufactured by KAO
Corp.], alkylsulfonic acid salts such as [for example, NEOGEN.TM.,
NEOGEN T.TM. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.,
NEOPEREX; manufactured by KAO Corp.), polymeric compounds such as
naphtahlenesulfonic acid polycondensation product metal salts,
formalin condensate of naphthalenesulfonic acid salts (NEWKALGEN
FS4.TM. and so on), alkylnaphthalene sulfonic acid salts
(SOLPOL5115.TM. and so on), ligninsulfonic acid metal salts, alkyl
aryl sulfonic acid salts, alkyl arylsulfonate sulfate, and so on,
anionic surfactant such as polynaphthylmethanesulfonic acid salts,
polystyrenesulfonic acid sodium salt, polycarboxylic acid metal
salts, polyoxyethylen histhylyl phenylether sulfate ammonium,
higher alcohol sulfonic acid salts, higher alcohol ether sulfonic
acid salts, dialkylsulfosuccinate (NEWKALGEN EP70P.TM. and so on),
and higher fatty acid alkali metal salts, and so on.
[0378] As salts, sodium salts, potassium salts, ammonium salts,
diethanolamine salts, triethanolamine salts, monoisopropanolamin e
salts, diisopropanolamine salts, triisopropanolamine salts, other
tertiary amine salts such as dialkyldimethylammonium salts, and so
on can be used (applied, employed), in an extent where the function
of the surfactants is not influenced.
[0379] As spreading agents, anionic surfactants, among surfactants
mentioned above, which contain tert-amines as cationic part [for
example, dialkyl dimethyl ammonium salts of
polynaphthylmethanesulfonic acid such as Needs.TM. (marketed by
KUMIAI Chemical, The material is manufactured by KAO Corp.)] can be
used preferable.
[0380] As stabilizers, compounds having epoxy groups, antioxidants
[for example, dibutylhydroxytoluene (BHT), butylhydroxy anisole
(BHA),
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane
(Irganox 1010), DL-tocopherol, propyl gallate, erythorbic acid,
sodiumerythorbate, isopropylcitrate, and so on], phosphoric acid,
PAP auxiliary agents (isopropyl acid phosphate), cyclodextrin
(TOYODELLINE P), tall oil (Hartall fatty acids), and so on, can be
used. One or more than two (preferably not less than one nor more
than three) of these compounds can be admixed in appropriate ratios
when used.
[0381] As binders, dextrin, pregelatinized starch, polyvinyl
alcohol, Arabic gum, sodium alginate, polyvinylpyrrolidone,
glucose, saccharose, mannitol, sorbitol, and so on, can be used.
One or more than two (preferably not less than one nor more than
three) of these compounds can be admixed in appropriate ratios when
used.
[0382] As fluidization auxiliaries, PAP auxiliaries (for example,
isopropyl acidphosphate) and talc, and so on can be used. One or
more than two (preferably not less than one nor more than three) of
these compounds can be admixed in appropriate ratios when used.
[0383] As hardening preventives, white carbon, diatomaceous earth,
magnecium stearate, aluminum oxide, titanium dioxide, and so on,
can be used. One or more than two (preferably not less than one nor
more than three) of these compounds can be admixed in appropriate
ratios when used.
[0384] As flocculants, liquid paraffin, ethylene glycol, diethylene
glycol, triethylene glycol, isobutylene polymers (for example, IP
Solvent), and so on,be used. One or more than two (preferably not
less than one nor more than three) of these compounds can be
admixed in appropriate ratios when used.
[0385] As antioxidants, dibutylhydroxytoluene,
4,4-thiobis-6-tert-butyl-3-- methylphenol, butylhydroxyanisole,
paraoctylphenol, mono- (or di- or tri-)
(.alpha.-methylbenzyl)phenol, 2,6-di-tert-butyl-4-methylphenol,
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane,
and so on, can be used. One or more than two (preferably not less
than one nor more than three) of these compounds can be admixed in
appropriate ratios when used.
[0386] As floating agents, used especially for manufactureing jambo
formulation, powder bases which have the specific gravity of 1 or
less than 1 (preferably 1 to 0.5) and the particle diameter of 600
.mu.m or less, more preferably from 600m to 10 .mu.m, are
preferably used. As inorganic floating agents, there can be
mentioned those which can be obtained by calcinating natural
glass-like materials and consist of glass particles with one or
several air bubbles in them, for example perlite made from pearlite
and orobsidian, Shirasu-balloon (Trade Name) made from Shirasu,
vermiculite made from Hiru-ishi and phyllite (Trade Name) which is
one of aluminosilicates and can be obtained by calcination, and so
on, and as organic floating agents, there can be mentioned such
substances called in general wax-like materials, for example,
higher fatty acids such as stearic acid and palmitic acid which are
solid at room temperatures, higher alcohols such as stearyl
alcohols, and paraffin wax, and so on. However, as these wax-like
materials are water-repellant, they have tendency to prevent water
from penetrating into them and to prevent the agrochemical active
constituents which are confined in them from leaking and spreading
into surrounding water, thus making it reasonable to make use of
such wax-like organic floating agents in a mixture with the glass
hollow bodies mentioned above.
[0387] As antifoaming agents, silicone antifoaming agents (for
example, Antifoam E20), and so on, can be preferably used. One or
more than two (preferably not less than one nor more than three) of
these compounds can be admixed in appropriate ratios when used.
[0388] As antifreezing agents, ethylene glycol, diethylene glycol,
polyethylene glycol, glycerol, and so on, can be used. One or more
than two (preferably not less than one nor more than three) of
these compounds can be admixed in appropriate ratios when used.
[0389] As antiseptic agents, butylparaben and potassium sorbate,
and so on, can be used. One or more than two (preferably not less
than one nor more than three) of these compounds can be admixed in
appropriate ratios when used.
[0390] As moisture removers, anhydrous gypsum and silica gel
powder, and so on, can be used. One or more than two (preferably
not less than one nor more than three) of these compounds can be
admixed in appropriate ratios when used.
[0391] As ultraviolet absorbers,
2-(2'-hydroxy-5'-methylphenyl)benzotriazo- le,
2-ethoxy-2'-methyloxalic acid bisanilide, dimethyl
succinate-l-(2-hydroxyethyl)-4-hydroxy-2',2,6,6-tetramethylpiperidine
polycondensates and so on, can be used preferably. One or more than
two (preferably not less than one nor more than three) of these
compounds can be admixed in appropriate ratios when used.
[0392] As ultraviolet scattering agents, titanium dioxide, and so
on, can be used. One or more than two (preferably not less than one
nor more than three) of these compounds can be admixed in
appropriate ratios when used.
[0393] As coloring agents, CYANINEGREEN G, ERIOGREEN B400, and so
on, can be used. One or more than two (preferably not less than one
nor more than three) of these compounds can be admixed in
appropriate ratios when used.
[0394] As suspension stabilizers, polyvinyl alcohol (GOHSENOL GH17
and so on), clay minerals (Kunipia F, VEEGUM R, and so on),
silicone dioxide (AEROSIL COK84, and so on), and so on, can be
used. One or more than two (preferably not less than one nor more
than three) of these compounds can be admixed in appropriate ratios
when used. Jumbo preparations, powders, granules wettable granules,
hydrates and so on can be packed into water-soluble film-packages
of 20 to 200 g each, for convenience in spraying. As the said
water-soluble film, there may be mentioned polyvinyl alcohol,
carboxymethyl cellulose, starch, gelatin, polyvinylpyrrolidone,
polyacrylic acid or salts thereof, Pullulan (Trade Name:
polysaccharide of a kind of starch), PAOGEN (trade name: a
thermoelastic water soluble polymer), and so on.
[0395] Furthermore, compound (I.sup.0) or salts thereof can be
combined and used with, for example, insecticides, acaricide,
nematocides, herbicides, plant hormones, plant growth regulators,
antimicrobials, synergists, attractants, repellants, pigments,
fertilizers, and so on.
[0396] Thus, the present invention includes also microbiocides for
agricultural or horticultural use which contain both the compound
(I.sup.0) or salts thereof and other active agrochmical
constituents. The said other agrochemical constituents may be
contained in the same preparation with compound (I.sup.0) or salts
thereof or may be formulated into separate preparations which can
be mixed just before use.
[0397] Representative insecticides, acaricide and nematocides which
can be used by admixing with compound (I.sup.0) or salts thereof
are as follows: acephate, acetamiprid, acrinathrin, alanycarb,
aldrin, allethrin, Aluminium phosphide, amitraz, Arsenic acid,
avermectin-B, bendiocarb, benfuracarb, bensultap, benzoximate,
bifenthrin, bromopropylate, buprofezin, Calcium cyanamide, Calcium
polysulfide, carbaryl:NAC, carbofuran, carbosulfan, cartap,
chlordane, chlorfenvinphos:CVP, chlorfluazuron, chlorphenapyr,
chlorpyrifos-methyl, chromafenozide, clofentezine, clothianidin,
cyanophos:CYAP, cycloprothrin, cyfluthrin, cyhalothrin,
cypermethrin, cyromazine, dichlorodiisopropyl ether, D-D(1,
3-Dichloropropene), DDT, deltamethrin, diafenthiuron, diazinon,
dichlofenthion, dichlorvos:DDVP, dicofol, dieldrin, dienochlor,
diflubenzuron, dimethoate, dimethylvinphos, disulfoton, DSP ,
endosulfan, EPN , esfenvalerate, ethion, ethofenprox, ethoprophos,
etoxazole, fenbutatin oxide, fenitrothion:MEP, fenobucarb,
fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate,
fenvalerate, fipronil, fluazinam, flucythrinate, flufenoxuron,
flupyrazofos, fluvalinate, formetanate, formothion, fosthiazate,
furathiocarb, halfenprox, hexaflumuron, hexythiazox, Hydrogen
phosphide, imidacloprid, isofenphos, isoprocarb, isoxathion,
malathion, mesulfenfos, metam-ammonium, metam-sodium, methidathion,
methiocarb, methomyl, methoxychlor, methoxyfenozide, Methyl
bromide, metolcarb:MTMC, milbemycin-A, monocrotophos, naled:BRP,
nicotine-sulfate, nidinotefuran, nitenpyram, oxamyl,
oxydeprofos:ESP, parathion, permethrin, phenthoate:PAP, phosalone,
phosmet:PMP, pirimicarb, pirimiphos-methyl, Potassium oleate,
profenofos, propaphos, propargite:BPPS, propoxur, prothiofos,
protrifenbute, pymetrozine, pyraclofos, pyrethrins, pyridaben,
pyridafenthion, pyrimidifen, pyriproxyfen, quinalphos, resmethrin,
salithion, silafluofen, Sulfur, sulprofos, tebufenozide,
tebufenpyrad, teflubenzuron, tefluthrin, temephos,
tetrachlorvinphos, tetradifon, thiacloprid, thiamethoxam,
thiocyclam, thiodicarb, thiometon, tolfenpyrad, tralomethrin,
trichlorfon:DEP, triflumuron, vamidothion, XMC.
[0398] Representative antimicrobials which can be used by admixing
with compound (I.sup.0) or salts thereof are as follows: for
example, acetic acid, acibenzolar-S-methyl, amobam, anilazine,
azoxystrobin, benomyl, benthiazole, bitertanol, blasticidin-S,
Bordeaux mixture, bromuconazole, buthiobate, Calcium hypochlorite,
Calcium polysulfide, captan, carbendazol, carpropamid,
IKF-916(4-chloro-2-cyano-N,N-dimethyl-5-p-tolyl-
imidazole-1-sulfonamide), chloroneb, chloropicrin,
chlorothalonil:TPN, Cinnamaldehyde,
RH-7281(3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopr-
opyl)4-methylbenzamide), CNA(2,6-Dichloro-4-nitroaniline), Copper
hydroxide, Copper sulfate,
AC382042(N-(1-cyano-1,2-dimethylpropyl)-2-(2,4- -dichlorophenoxy)
propionamide(R,S)-and(R,R)-and(S,R)-and(S,S)), cymo X anil,
cyproconazole, cyprodinil, dazomet, dichlofluanid,
D-D(1,3-Dichloropropene), diclocymet, diclomezine, diethofencarb,
difenoconazole, diflumetorim, dimethirimol, dimethomorph,
diniconazole-M, dinocap, Nickel dimethyldithiocarbamate,
etridiazole, famoxadone, fenarimol, fenbuconazole, Fendazosulam,
fenhexamid, NNF-9425:fenoxanil, fenpiclonil, fentiazon, fentin
hydroxide, ferimzone, fluazinam, fludioxonil,
RPA-403397:flumetover, fluoroimide, fluquinconazole, flusulfamide,
flutolanil, fosetyl-Al, fthalide, furametpyr, hexaconazole,
hymexazol, imazalil, imibenconazole, iminoctadine-albesilate,
iminoctadinetriacetate, iodocarb, ipconazole, iprodione,
isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb,
mepanipyrim, mepronil, metalaxyl, metalaxyl-M, metam-sodium,
methasulfocarb, Methyl bromide,
RPA407213(s-5-methyl-2-methylthio-5-phenyl-3-phenylamino-3,5-dihydroimida-
zol-4-one), metominostrobin, mildiomycin, milneb, myclobutanil,
nabam, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin,
oxytetracycline, pefurazoate, penconazole, pencycuron,
picoxystrobin, polycarbamate, polyoxin, Potassium hydrogen
carbonate, probenazole, prochloraz, procymidone,
propamocarb-hydrochloride, propiconaole, propineb, pyrazophos,
pyributicarb, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen,
quintozene:PCNB, MON65500:silthiopham, sipconazole, Sodium
bicarbonate, sodium hypochlorite,
SSF-129((E)-2[2-(2,5-dimethylphenoxymet-
hyl)phenyl]-2-methoxyimino-N-methylacetamide), streptomycin,
Sulfur, tebuconazole, tecloftalam, tetraconazole, thiabendazole,
thiram:TMTD, thifluzamide, thiophanate-methyl, triadimefon,
triadimenol, tricyclazole, tridemorph, triflumizole,
trifloxystrobin, triforine, validamycin, vinclozolin, zineb,
ziram.
[0399] Representative herbicides, plant hormones, and plant growth
regulators which can be used by admixing with compound (I.sup.0) or
salts thereof are as follows: Abscisic acid, acetochlor,
acifluorfen-sodium, alachlor, alloxydim, ametryn, amidosulfuron,
amiprofos-methyl, ancymidol, asulam, atrazine, azimsulfuron,
benfluralin, benfuresate, bensulfuron-methyl, bensulide:SAP,
bentazone, benthiocarb, benzamizole, benzfendizone, benzofenap,
Benzyl adenine, bialaphos, bifenox, Brassinolide, bromacil,
bromobutide, butachlor, butafenacil, butamifos, butylate,
cafenstrole, Calcium carbonate, Calcium peroxide, carbaryl,
chlomethoxynil, chloridazon, chlorimuron-ethyl, chlorphthlim,
chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid:DCBN,
choline chloride, cinmethylin, cinosulfuron, clethodim, clomeprop,
cloxyfonac-sodium, 4-CPA(4-chlorophenoxyacetic acid), cumyluron,
cyanazine, cyclosulfamron, cyhalofop-butyl, 2,4-D
salts(2,4-Dichloropheno- xyacetic acid salts), dichlorprop:2,4-DP,
daimuron, dalapon:DPA, daminozide, dazomet, n-Decyl alcohol,
dicambasodium:MDBA, dichlobenil:DBN, diflufenican, dimepiperate,
dimethametryn, dimethenamid, diquat, dithiopyr, diuron, endothal,
esprocarb, ethephon, ethidimuron, ethoxysulfuron, ethychlozate,
etobenzanid, fenarimol, fenoxaprop-ethyl, fentrazamide,
flazasulfuron, florasulam, fluazifop-butyl, flumioxazin,
flupropanate-sodium, flurprimidol, fluthiacet-methyl,
forchlorfenuron, formesafen, gibberellin, glufosinate, glyphosate,
halosulfuron-methyl, hexazinone, imazamox, imazapyr, imazaquin,
imazosulfuron, inabenfide, Indole acetic acid:IAA, Indole butyric
acid, ioxynil-octanoate, isouron, karbutilate, lactofen, lenacil,
linuron, Maleic hydrazide, mecoprop:MCPP, MCP
salts(2-Methyl-4-chlorophenoxyacetic acid salts),
MCPA.multidot.thioethyl(MCPA-thioethyl),
MCPB(2-Methyl-4-chlorophenoxybut- anoic acid ethyl ester),
mefenacet, mefluidide, mepiquat, methyl daimuron, metolachlor,
metribuzin, metsulfuron-methyl, molinate,
NAD(1-naphthaleneacetamide), naproanilide, napropamide,
nicosulfuron, orbencarb, oxadiazon, oxaziclomefone, oxine-sulfate,
paclobutrazol, paraquat, Pelargonic acid, pendimethalin,
pentoxazone, pethoxamide, phenmedipham, picloram, piperonyl
butoxide, piperophos, pretilachlor, primisulfuronmethyl,
procarbazone, prodiamine, prohexadione-calcium, prometryn,
propanil, propyzamide, pyraflufen-ethyl, pyrazolate,
pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate,
pyriminobac-methyl, pyrithiobac, quiclorac, quinoclamine,
quizalofop-ethy, rimsulfuron, sethoxydim, siduron, simazine,
simetryn, Sodium chlorate, sulfosulfuron, swep:MCC, tebuthiuron,
terbacil, terbucarb:MBPMC, thenylchlor, thiazafluron,
thifensulfuron-methyl, triaziflam, triclopyr, tridiphane,
trifluralin, trinexapac-ethyl, tritosulfuron, uniconazole-P,
vemolate:PPTC.
[0400] Among "other active agrochemical constituents" mentioned
above, antimicrobial active constituents and insecticidal active
constituents are especially preferable.
[0401] Furthermore, as the said antimicrobial active constituents,
in addition to azoxystrobin, chlorothalonil, hexaconazole,
iminoctadine, mepanipyrim, kresoxim-methyl and iprodione, there may
be mentioned carpropamid, diclocymet, probenazole, tricyclazole,
pyroquilon, isoprothiolane, acibenzolar-S-methyl, as agents for
treating the soil, seed of rice and for spraying on the water
surface of the rice cultivation. And as agents for spraying on the
leaves and stems of the rice plant, carpropamid, diclocymet,
probenazole, tricyclazole, pyroquilon, isoprothiolane,
acibenzolar-S-methyl, validamycin A, ferimzone, fthalide and so on,
can be used more preferably, and among said agents, validamycin A,
ferimzone and fthalide can be used most preferably.
[0402] Futhermore, as the said inscticidal active constituents,
clothianidin
[0403] [1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguanidine],
nitenpyram
[0404]
[(E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N'-methyl-2-nitrovinylyde-
neamine], cartap hydrochloride
[0405]
[1,3-bis(carbamoylthio)-2-(N,N-di-methylamino)propanehydrochloride]-
, bensultap
[0406]
[S,S'-2-dimethyl-amminotrimethylene=di(benzenethiosulfonate)],
pyraclofos
[0407]
[(RS)-[O-1-(4-chlorophenyl)pyrazol-4-yl]=O-ethyl=S-propyl=phosphoro-
thioate], and so on, can be used especially preferably. Thus, the
present invention includes
[0408] [1] A microbicide for agricultural or horticultural use
which contains compound (I) or salts thereof and other
agrochemically active constituents,
[0409] [2] A microbicide for agricultural or horticultural use
which contains compound (II) or salts thereof and other
agrochemically active constituents,
[0410] [3] A microbicide for agricultural or horticultural use
which contains compound (III) or salts thereof and other
agrochemical active constituents,
[0411] [4] A microbicide for agricultural or horticultural use
which contains compound (IV) or salts thereof and other
agrochemical active constituents,
[0412] [5] A microbicide for agricultural or horticultural use
which contains compound (V) or salts thereof and other agrochemical
active constituents,
[0413] [6] A microbicide for agricultural or horticultural use
which contains compound (VI) or salts thereof and other
agrochemical active constituents,
[0414] [7] A microbicide for agricultural or horticultural use
which contains compound (II') which will be described below or
salts thereof and other agrochemically active constituents,
[0415] [8] A microbicide for agricultural or horticultural use
described in [1] to [7] above, wherein the other agrochemical
active constituents are insecticides,
[0416] [9] A microbicide for agricultural or horticultural use
described in [8], wherein the other agrochemical active
constituents are more than one of those selected from bensultap,
cartap, clothianidin, nitenpyram and pyraclofos,
[0417] [10] A microbicide described in [1] to [7] above, wherein
the other agrochemical active constituents are antimicrobial active
constituents,
[0418] [11] A microbicide for agricultural or horticultural use
described in [10] above, wherein the other agrochemical active
constituents are more than one of those selected from azoxystrobin,
chlorothalonil, hexaconazole, iminoctadine, mepanipyrim,
kresoxim-methyl, iprodione, ferimzone, fthalide and validamycin,
and
[0419] [12] A method to increment the microbicidal action of
compound (I), (II), (III), (IV), (V), (VI) or (II') described
below, or salts thereof which comprises using them in combination
with other agrochemically active constituents.
[0420] Among the said compound (I), (II), (III), (IV), (V), (VI)
which may be used in combination with other agrochemical active
constituents or (II') which will be described below, or salts
thereof, compound (I), (II), (III), (VI) or (II') or salts thereof
are more preferable, and compound (II), (VI) or (II') or salts
thereof are especially preferable.
[0421] Specific examples of the more preferable compound are
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide,
2',4'-dinitro-N-ethyl-p-toluenesulfonanilide,
2',4'-dicyano-N-ethyl-p-tol- uensulfonanilide,
4'-chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-fluoro-N-isopropyl-2'-nitro-p-toluene-sulfonanilide,
4'-cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide,
4'-chloro-N-isopropyl-2'-cyano-p-toluenesulfonanilide,
2',4'-dinitro-N-iso-propyl-p-toluenesulfoanilide,
4'-nitro-N-isopropyl-2'- -cyano-p-toluenesulfonanilide,
2'-cyano-N-methoxy-4'-nitro-p-toluenesulfon- anilide, or
2',4'-dinitro-N-methoxy-p-toluenesufonanilide or salts thereof.
[0422] In those compositions which contain compound (I.sup.0) [for
example, compound (I), (II), (III), (IV), (V), (VI) or (II') which
will be described below] or salts thereof and nitenpyram, it may be
advantageous to make first an inclusion compound of nitenpyram with
cyclodextrin, for example, TOYODERIN (commercial product name), and
then the resulting inclusion compound come into the composition in
order to enhance stability of the composition.
[0423] These compositions may further contain not less than one
kind (more preferably not less than one nor more than three kinds)
of other agrochemical active constituents,(for example,
insecticidal, acaricidal, antimicrobial active components, and so
on). As such compositions, there can be mentioned compositions
which contain compound (I.sup.0) [for example, compound (I), (II),
(III), (IV), (V), (VI) or (II') which will be described below] or
salts thereof, ferimzone and fthalide, and compositions which
contain compound (I.sup.0) [compound (I), (II), (III), (IV), (V),
(VI) or (II') which will be described below] or salts thereof,
validamycin, ferimzone and fthalide and so on.
[0424] More preferable embodiments of composition which contain
other agrochemically active constituents are as follows:
[0425] (i) A microbicide for agricultural or horticultural use
which contains 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or
salts thereof and ferimzone.
[0426] (ii) A microbicide for agricultural or horticultural use
which contains 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or
salts thereof and fthalide.
[0427] (iii) A microbicide for agricultural or horticultural use
which contains 4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or
salts thereof and validamycin.
[0428] (iv) An insecticide/microbicide for agricultural or
horticultural use which contains
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or salts thereof
and bensultap.
[0429] (v) An insecticide/microbicide for agricultural or
horticultural use which contains
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or salts thereof
and cartap.
[0430] (vi) An insecticide/microbicide for agricultural or
horticultural use which contains
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or salts thereof
and clothianidin.
[0431] (vii) An insecticide/microbicide for agricultural or
horticultural use which contains
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or salts thereof
and nitenpyram.
[0432] (viii) An insecticide/microbicide for agricultural or
horticultural use which contains
4'-chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide or salts thereof
and pyraclofos.
[0433] (ix) A microbicide for agricultural or horticultural use
which contains 2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or
salts thereof and ferimzone.
[0434] (x) A microbicide for agricultural or horticultural use
which contains 2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or
salts thereof and fthalide.
[0435] (xi) A microbicide for agricultural or horticultural use
which contains 2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or
salts thereof and validamycin.
[0436] (xii) An insecticide/microbicide for agricultural or
horticultural use which contains
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or salts thereof and
bensultap.
[0437] (xiii) An insecticide/microbicide for agricultural or
horticultural use which contains
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or salts thereof and
cartap.
[0438] (xiv) An insecticide/microbicide for agricultural or
horticultural use which contains
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or salts thereof and
chlothianidin.
[0439] (xv) An insecticide/microbicide for agricultural or
horticultural use which contains
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or salts thereof and
nitenpyram.
[0440] (xvi) An insecticide/microbicide for agricultural or
horticultural use which contains
2',4'-dinitro-N-methoxy-p-toluenesulfonanilide or salts thereof and
pyraclofos.
[0441] Regarding [12] mentioned above, the present inventors have
found that using the compound (I), (II), (III), (IV), (V), (VI) or
(II') which will be described below, or salts thereof of the
present invention in combination with other agrochemical active
constituents may give an increased effectiveness in their
microbicidal action over that which may be obtained when each of
those agents is used singly.
[0442] Those microbiocides obtained by combining the sulfonamide
derivatives of the present invention described above [for example,
compound (I), (II), (III), (IV), (V), (VI) or compound (II') which
will be described below] and other agrochemical active constituents
can exert excellent effectiveness in that (1) the
antimicrobial/insecticidal/acaric- idal/nematocidal effectiveness
may be increased relative to the cases where each agent is used
separately, (2) an immediate
antimicrobial/insecticidal/acaricidal/nematocidal effect is gained,
(3) a wide antimicrobial/insecticidal/acaricidal/nematocidal
spectrum and a sustained effectiveness are gained, which has not
been realized with known
antimicrobicide/insecticide/acaricide/nematocide, (4) the amounts
of agents needed can be decreased compared to the cases where each
agents is used singly, and (5) a more reliable protective effect
can be expected compared to the cases where each agent is used
singly against each harmful organism.
[0443] As the diseases protected using compound (I.sup.0) or salts
are, there may be mentioned, for example, diseases of rice plant
such as rice blast (Pyricularia oryzae), Helminthosporium leaf
blight (Helminthosporium oryzae, Cochliobolus miyabeanus), Bakanae
disease (Gibberella fujikuroi), seedling blight (Rhizopus oryzae),
sheath blight (Rhizoctonia solani), and so on, those of oat such as
crown rust (Puccinia coronata), and so on, those of barley such as
powdery mildew (Erysiphe graminis), scald (Rhynchsporium secalis),
spot-blotch (Cochliobolus sativus), yellow mottleleaf
(Helminthosporium gramineum, Pyrenophora gramineum), net blotch
(Pyrenophra teres), stinking smut (Tilletia caries), loose smut
(Ustilago nuda), and so on, those of wheat such as powdery mildew
(Erysiphe graminis), glume-blotch (Leptosphaeria nodorum, Septoria
nodorum), stripe rust (Puccinia striiformis), Typhula snow blight
(Typhula incarnata), eye spot (Pseudocercosporella
herpotrichoides), snow mold (Calonectria graminicola, Fusarium
nivale), stem rust (Puccinia graminis), black snow blight (Typhula
ishikariensis), scab (Gibberella zeae), leaf rust (Puccinia
recondita, Puccinia triticina), stripe (Helminthosporium
gramineum), stinking smut (Tilletia caries), speckled leaf blight
(Septoria tritici), loose smut (Ustilago tritici), and so on, those
of corn such as damping-off (Pythium debaryanum), and so on, those
of rye such as purple snow mold (Fusarium nivale), and so on, those
of potato such as foot rot (Phytophthora infestans), and so on,
those of tabacco plant such as downy mildew (Peronospora tabacina),
foot rot (Phytophthora parasitica var), septoria blight (Cercospora
nicotianae), mosaic disease (tobacco mosaic virus), and so on,
those of sugar beet such as leaf spot (Cercospora beticola),
damping-off (Pythium debaryanum, Rhizoctonia solani), take-all
(Pythium aphanidermatum), and so on, those of paprika such as gray
mold (Botrytis cinerea), and so on, those of kidney bean such as
gray mold (Botrytis cinerea), sclerotinia seed rot (sclerotial rot)
(Sclerotinia sclerotiorum), southern blight (Corticium rolfsii),
and so on, those of broad bean such as powdery mildew (Erysiphe
polygoni, Sphaerotheca fuliginea), rust (Uromyces fabae, Uromyces
phaseoli), gray mold (Botrytis cinerea), and so on, those of peanut
such as Ascochyta spot (Mycosphaerella arachidicola), and so on,
those of cabbage such as damping blight (Rhizoctonia solani), and
so on, those of cucumber such as powdery mildew (Sphaerotheca
fuliginea), stem rot (Fusarium oxysporum), gummy stem blight
(Mycosphaerella melonis), downy mildew (Pseudoperonospora
cubensis), gray mold (Botrytis cinerea), sclerotial seed rot
(Sclerotinia sclerotiorum), anthracnose (Colletotrichum
lagenarium), damping blight (Fusarium oxysporum, Pythium
aphanidermatum, Rhizoctonia solani), mosaic disease (Cucumber
mosaic virus), and so on, those of KOMATSUNA such as Alternaria
sooty spot (Alternaria brassicicola), club root (Plasmodiophora
brassicae), and so on, those of celery such as speckled leaf blotch
(Septoria apii), and soon, those of radish such as yellows
(Fusarium oxysporum), and so on, those of tomato such as Fusarium
wilt (Fusarium oxysporum), foot rot (Phytophthora infestans), ring
leaf-spot (Alternaria solani), gray mold (Botrytis cinerea), leaf
blight (Phytophthora capsici), black rot (Alternaria tomato), and
so on, those of eggplant such as brown rot (Phytophthora capsici),
Verticillium wilt (Verticillium albo-atrum), and so on, those of
Chinese cabbage such as black rot (Alternaria japonica), club root
(Plasmodiophora brassicae), and so on, those of sweet pepper such
as foot rot (Phytophthora capsici), gray mold (Botrytis cinerea),
and so on, those of lettuce such as gray mold (Botrytis cinerea),
and so on, those of citrus fruits such as pod and stem blight
(Diaporthe citri), and so on, those of pear such as scab (Venturia
nashicola), black rot (Alternaria kikuchiana), brown-spot
(Gymnosporangium haraeanum), and so on, those of grape such as
downy mildew (Plasmopara viticola), gray mold (Botrytis cinerea),
Sphaceloma scab (Elsinoe ampelina), and so on, those of peach such
as leaf curl (Taphrina deformans), shot hole (Mycosphaerella
cerasella), and so on, those of apple such as powdery mildew
(Podosphaera leucotria), scab (Cladsporium carpophilum), gray mold
(Botrytis cinerea), black rot (Venturia inaegualis), brown spot
(Gymnosporangium yamadae), white root rot (Rosellinia nectrix),
Alternaria leaf spot (Alternaria mali), and so on, and other
deseases of grains, fruits and vegetables such as oil-seed rape,
sunflower, carrot, pepper, strawberry, melon, kiwi fruit, onion,
leek, sweet potato, fig, ume, asparagus, persimmon, soybean,
adzukibean, watermelon, crown daisy, spinach,tea and so on. Thus,
compound (I.sup.0) or salts thereof show high activities against
deseases caused by microorganisms of, especially, the genus
Pyricularia, Cochliobolus, Curvularia, Pyrenophora, Alternaria, and
others akin to them. As for examples of deseases caused by those
microbes, there may be mentioned rice blast, Helminthosporium leaf
spot, and discolored rice grains of rice plant, spot-blotch,
stripe, and net blotch of barley, stripe and spot-blotch of wheat,
Helminthosporium leaf spot of corn, early blight of potato,
Alternaria sooty spot of HAKUSAI, ring leaf-spot and black rot of
tomato, black rot of Chinese cabbage, black rot of pear, and
Alternaria leaf spot of apple, and so on.
[0444] Among compound (I.sup.0) or salts thereof mentioned above,
those which have, as Z.sup.0, a group represented by --OR.sup.3 or
salts thereof show excellent protective effectiveness against
clubroot disease in the plants of Brassica family (for example,
canola, turnip, cauliflower, cabbage, KOMATSUNA, rape seed, and
Chinese cabbage.
[0445] Among them, compound (I), (II) and (III) mentioned-above or
salts thereof, which have , as Z.sup.1, Z.sup.2 and Z.sup.3, a
group represented by --OR.sup.3, respectively, are more preferable,
especially preferable being compound (II') below or salts
thereof.
[0446] Compound (II') are compounds represented by the Formula
(II'): 40
[0447] or salts thereof,
[0448] [where A.sup.2, X.sup.2 and B.sup.2 have the same meanings
as A.sup.2, X.sup.2 and B.sup.2 mentioned above, respectively,
Z.sup.2 is a group represented by --OR.sup.3 (R.sup.3 has the same
meaning as that mentioned above)].
[0449] Among the compounds included in compound (II'), preferable
compounds or salts thereof are those which have, as A.sup.2, either
(1) a C.sub.6-14 aryl group which may substituted with 1 to 5
substituents selected from
[0450] (i) a C.sub.1-4 alkyl group which may be substituted with 1
to 5 halogens,
[0451] (ii) a C.sub.1-4 alkoxy group which may be substituted with
1 to 5 halogens,(iii) an amino group which may be substituted with
1 or 2 C.sub.1-4 alkyl-carbonyl,
[0452] (iv) the C.sub.1-4 alkoxy-carbonyl group,
[0453] (v) halogen atoms,
[0454] (vi) the cyano group, and
[0455] (vii) the nitro group, or
[0456] (2) the thenyl group, the triazolyl group, the imidazolyl
group, the isooxazolyl group, the pyrazolyl group, the pyridyl
group, the quinolyl group, the benzothiadiazolyl group, the
imidazothiazolyl group or the imidazopyridyl group, each of which
may be substituted with 1 to 5 substituents selected from (i) the
C.sub.1-4 alkyl group,
[0457] (ii) the C.sub.1-4 alkoxy-carbonyl group,
[0458] (iii) the carbamoyl group,
[0459] (iv) mono- or di-C.sub.1-4 alkylcarbamoyl group,
[0460] (v) the C.sub.1-4 alkylsulfonyl group,
[0461] (vi) halogen atoms,
[0462] (vii) the carboxyl group and
[0463] (viii) the cyano group, as X.sup.2 is (1) the chemical
bond,
[0464] (2) the methylene group which may be substituted with 1 or 2
C.sub.1-4 alkyl, or
[0465] (3) the vinylene group which may be substituted with 1 or 2
C.sub.1-4 alkyl,
[0466] B.sup.2 is a C.sub.6-14 aryl group which may be substituted
with 1 to 5 Substituents selected from (1) a C.sub.1-4 alkyl group
which may be substituted with 1 to 5 substituents such as halogen,
hydroxy, imino, hydroxyimino, C.sub.1-4 alkoxyimino, hydrazono,
mono- or di-C.sub.1-4 alkyl-hydrazono and C.sub.1-4 alkylthio,
[0467] (2) the C.sub.2-4 alkynyl group,
[0468] (3) the hydroxy group,
[0469] (4) the C.sub.1-4 alkoxy group which may be substituted with
1 to 5 substituents selected from halogens and C.sub.1-4
alkoxy,
[0470] (5) the C.sub.1-4 alkyl-carbonyloxy group,
[0471] (6) the C.sub.1-4 alkylthio group,
[0472] (7) the C.sub.1-4 alkylsulfinyl group,
[0473] (8) the C.sub.1-4 alkylsulfonyl group,
[0474] (9) mono- or di-C.sub.1-4 alkylsulfamoyl group,
[0475] (10) the amino group,
[0476] (11) the formyl group,
[0477] (12) the C.sub.1-4 alkoxy-carbonyl group,
[0478] (13) the carbamoyl group,
[0479] (14) mono- or di-C.sub.1-4 alkylcarbamoyl group,
[0480] (15) the thiocarbamoyl group,
[0481] (16) halogen atoms,
[0482] (17) the carboxyl group,
[0483] (18) the thiocyanato group,
[0484] (19) the cyano group,
[0485] (20) the nitroso group and
[0486] (21) the nitro group,
[0487] Z.sup.2 is a group which is represented by --OR.sup.3
(wherein R.sup.3 is a C.sub.1-4 alkyl group or a C.sub.1-4
alkyl-carbonyl group) or salts thereof.
[0488] More preferable embodiments of compound (II') or salts
thereof are as follows:
[0489] Preferably, A.sup.2 is (a) a phenyl group which may be
substituted with 1 to 3 substituents selected from C.sub.1-4 alkyl
which may be substituted with 1 to 3 halogens, halogens and
nitro,
[0490] (b) a thienyl group which may be substituted with 1 to 3
halogens, or
[0491] (c) a pyrazolyl group which may be substituted with 1 to 3
substituents selected from C.sub.1-4 alkyl and halogens, a phenyl
group substituted with a methyl group at 4-position being
especially preferable.
[0492] Preferably, B.sup.2 is a phenyl group which may be
substituted with substituents selected from
[0493] (a) the C.sub.1-4 alkyl group which may be substituted with
1 to 5 (preferably with 1 to 3) halogen atoms,
[0494] (b) halogen atoms
[0495] (c) the cyano group and
[0496] (d) the nitro group, especially preferable being phenyl
groups which have substituents at the 2- or 4-position.
[0497] Z.sup.2 should preferably be a C.sub.1-4 alkoxy group or a
C.sub.1-4 alkyl-carbonyloxy group, especially preferable being
methoxy and ethoxy groups.
[0498] Preferably, X.sup.2 is a chemical bond (a single bond or a
bond).
[0499] Those preferable features of A.sup.2', B.sup.2', Z.sup.2'
and X.sup.2' mentioned in (1) to (4) above, may be combined
together arbitrarily.
[0500] Since compound (I.sup.0) or salts thereof have microbicidal
action and are of very low toxicity and safe to handle, they can be
used as excellent microbicidal compositions. The compositions of
the present invention can be used in a manner similar to the known
microbicidal compositions, and can exert superior effect to the
previously known compositions. The compositions of the present
invention can be used by spraying them on the irrigated rice field,
a field, an orchard, and non-cultivated land, and so on, by the per
se known method. More specifically, they can be used, for example,
by treating a seed bed with them, spraying them on the stem/leaves
of the plants, spraying them in the water of the irrigated field,
by treating seeds or the soil with them, and applying them directly
on the stem of fluit trees. And, the amount used may be, in
general, 0.3 g to 3000 g effective constituents per 1 hectare, or
more preferably 50 g to 1000 g effective
constituents(compound(I.sup.0) or salts thereof) per 1 hectare,
although it can be altered within a wide range according to the
time, place, and method of applying. Furthermore, in cases where
the compositions of the present invention are wettable powders,
they can be used by diluting them to adjust the final concentration
of the effective constituents to a range of 0.1 to 1000 ppm, or
more preferably to 10 to 500 ppm. The contents of compound
(I.sup.0) or salts thereof to the whole amount of the composition
can usually be about 0.1 to 80 wt %, or more preferably about 1 to
20 wt % or so. More specifically, when they are used as an
emulsion, liquids, wettable powders (for example wettable
granules), aqueous suspensions, microemulsions and so on, they can
be used in a ratio, in general, of about 1 to 80 wt % or so, or
more preferably of about 1 to 20 wt % or so, and when they are used
as ointments or powders and so on, they can be used usually in a
ratio of about 0.1 to 50 wt % or so, or more preferably in that of
about 1 to 20 wt % or so. When they are used as granules, tablets,
Jumbo agents and so on, they can be used usually in a ratio of
about 5 to 50 wt % or so, or more preferably of about 1 to 20 wt %
or so. The other agrochemical active constituents (for example,
insecticides, acgaricides, herbicides and (or) microbicides) which
may be mixed to prepare compositions of the present invention, can
be used usually in a ratio of about 1 to 80 wt % or so, or more
preferably in that of about 1 to 20 wt % or so to the whole amount
of the compositions. The contents of the additives other than the
active constituents mentioned above are in general about 0.001 to
99.9 wt % or so, or more preferably about 1 to 99 wt % or so,
although they vary depending upon the kinds, contents or
preparation form of the agrochemical active.
[0501] More specifically, it is preferable to add, to the total
amount of the compositions, usually about 1-20 wt % or so, or more
preferably about 1-15 wt % of surfactants, about 1-20 wt % or so
fluidization auxiliaries, about 1-90 wt % or so, or more preferably
about 1-70 wt % or so of carriers. To give more specific examples,
in the cases where liquids are to be prepared, it is usually
preferable to add about 1-20 wt % or so , or more preferably 1-10
wt % or so of surfactants, and 20-90 wt % or so of water. It is
preferable to dilute emulsions or wettable powders (for example
wettable granules) and so on to an appropriate volume (for example,
to about 100 to 5000 times of volume), for example, with water and
so on before use, and to spray it(them).
[0502] Compound (I.sup.0) or salts thereof can be manufactured, for
example, according to the reaction equations (A), (B), (C) or by
means of the synthetic method (D) given below: 41
[0503] Compound (I.sup.0) or salts thereof can be manufactured by
making compounds XI which are obtainable
[0504] by the reaction of sulfonylating agents represented by
Formula (VII)
A.sup.0-X.sup.0--SO.sub.2-L
[0505] (wherein A.sup.0 and X.sup.0 have the same meanings as those
mentioned above, and L is a leaving group) with amines represented
by Formula (VIII)
H.sub.2N--B.sup.0
[0506] (wherein B.sup.0 has the same meaning as mentioned above),
or salts thereof or
[0507] {circle over (2)} by the reaction of sulfonamides
represented by Formula (IX)
A.sup.0-X.sup.0--SO.sub.2--NH.sub.2
[0508] (wherein the symbols have the same meanings as those
mentioned above) or salts thereof,
[0509] with the compounds represented by Formula (X)
L'-B.sup.0
[0510] (wherein L' is a leaving group and B.sup.0 has the same
meaning as mentioned above) or salts thereof to give the compounds
represented by Formula(XI), (wherein each symbol has the same
meaning as mentioned above) and
[0511] Formula(XI): 42
[0512] react with electrophiles of Formula (XII)
Z.sup.0-L"
[0513] (wherein L' is a leaving group, and Z.sup.0 has the same
meaning as mentioned above).
[0514] As the sulfonylating agent represented by Formula (VII),
there can be mentioned, for example, sulfonyl chloride, sulfonyl
bromide, and sulfonic anhydride, and so on.
[0515] As the leaving group represented by L, L' or L", there can
be mentioned, for example, halogen atoms such as fluorine,
chlorine, bromine, and iodine, a lower alkoxy (preferably a
C.sub.1-4 alkoxy) group such as methoxy, ethoxy, propoxy, and so
on, a phenoxy group, a lower alkylthio (preferably a C.sub.1-4
alkylthio) group such as methylthio, ethylthio, propylthio,and so
on, a lower alkylsulfinyl (preferably a C.sub.1-4 alkylsulfinyl)
group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, a
lower alkylsulfonyl (preferably a C.sub.1-4 alkylsulfonyl) group
such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, and so on, a
lower alkylsulfonyloxy (preferably a C.sub.1-4 alkylsulfonyloxy)
group such as methylsulfonyloxy, ethylsulfonyloxy,
propylsulfonyloxy group, and so on, a trifluoromethylsulfonyloxy
group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group,
and so on.
[0516] {circle over (1)} The reaction of sulfonylating agents (VII)
with amines (VIII) can be carried out according to the method
described in, for example, The Journal of Pesticide Science Society
of Japan 21, p31(1996), Japanese Patent Publication for Opposition
6836/1970, and so on. Japanese Publication Patent for Opposition
19199/1965, Japanese Patent for Laid-Open 31655/1982, Japanese
Patent Application Laid-Open 219159/1983, Japanese Patent
Application Laid-Open 197553/1986, Japanese Patent Application
Laid-Open 271270/1986, Japanese Patent Application Laid-Open
57565/1988, Japanese Patent Application Laid-Open 272566/1989,
Japanese Patent for Laid-Open 156953/1989, Japanese Patent
Application Laid-Open 72151/1990, Japanese Patent Application
Laid-Open 96560/1990, Japanese Patent Application Laid-Open
231465/1990, Japanese Patent Application Laid-Open 212467/1990,
Japanese Patent Application Laid-Open 54161/1992, Japanese Patent
Application Laid-Open 145060/1992.
[0517] The reaction of sulfonamide bodies (IX) with compounds (X)
are usually carried out both with or without solvent.
[0518] As the solvent, in cases where it is used, there can be
mentioned, for example, hydrocarobons such as petrol ether,
pentane, hexane, cyclohexane, benzene, toluene, xylene, and so on,
halogenated hydrocarbons such as dichloromethane, chloroform,
carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene,
trichloroethylene, chlorobenzene, and so on, ethers such as diethyl
ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane,
dimethoxyethane, ethyleneglycol monomethylether, diethyleneglycol
dimethylether, and so on, esters such as ethyl acetate, butyl
acetate, and so on, ketones such as acetone, methyl ethyl ketone,
and so on, nitriles such as acetonitrile, propionitrile, and so on,
amides such as N,N-dimethylformamide, N,N-dimethylacetamide,
N-methylpyrrolidone, and so on, sulfoxides such as
dimethylsulfoxide, and so on, sulfones such as sulfolan, and so on,
nitro compounds such as nitromethane, nitrobenzene, and so on,
alcohols such as methanol, ethanol, isopropanol, 1-butanol,
ethylene glycol, and so on, carbon disulfide, water, and so on.
[0519] The reaction can be carried out at temperatures selected
from -100 to 300.degree. C., or more preferably from -50 to
200.degree. C. The reaction time is 1 minute to 1 week, or more
preferably 5 minutes to 24 hours.
[0520] Acids or bases may be added to promote the reaction. As the
acids employable for that purpose, there can be mentioned, for
example, hydrofluoric acid, hydrochloric acid, hydrobromic acid,
hydroiodic acid, phosphoric acid, sulfuric acid, nitric acid,
perchloric acid, and organic acids such as formic acid, acetic
acid, propionic acid, trifluoroacetic acid, tartaric acid, malic
acid, oxalic acid, succinic acid, benzoic acid, picric acid,
methanesulfonic acid, p-toluenesulfonic acid,
trifluoromethanesulfonic acid, and so on.
[0521] As the bases employable, there can be mentioned, for
example, metal hydroxides such as lithium hydroxide, sodium
hydroxide, potassium hydroxide, calcium hydroxide, and so on, metal
carbonates such as sodium carbonate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate, and so on, metal hydrides such
as sodium hydride, potassium hydride, carcium hydride, and so on,
metal amides such as lithium diisopropylamide, sodium amide,
potassium amide, and so on, organolithium reagents such as
methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium,
phenyllithium, and so on, organo-magnesium reagents (Grignard
reagent) such as methylmagnesium bromide, ethylmagnesium chloride,
and so on, metals such as lithium metal, sodium metal, potassium
methal, and so on, organic bases such as trimethylamine,
triethylamine, diisopropylamine, N,N-dimethyaniline, pyridine,
lutidine, collidine, DMAP(4-dimethylaminopyridine),
TMEDA(tetramethylethylenediamin- e),
DBU(1,8-diazacyclo[5.4.0]undec-7-ene), and so on.
[0522] Further, in order to promote the reaction, metal salts (for
example, oxides, fluorides, chlorides, bromides, iodides, sulfides,
sulfates, nitrates, phosphates, perchlorate, and so on) or metal
elements of titanium, vanadium, chromium, manganum, iron, cobalt,
nickel, copper, zinc, zilconium, niobium, molybdenum, ruthenium,
rhodium, palladium, silver, cadmium, tungsten, platinum, gold,
mercury, and so on, can be used as catalyst in an amount of
0.000001 to 1000 equivalents, or more preferably 0.001 to 10
equivalents. The reactions of sulfonamide bodies (XI) with
electrophiles are usually carried out with or without solvent.
[0523] As the solvent, in cases where it is employed, there can be
mentioned those solvents which can be employed in reaction {circle
over (2)} above. The reactions can be carried out at temperatures
of -100 to 300.degree. C., or more preferably at -50 to 200.degree.
C. And the reaction time is from 1 minutes to 1 week, or more
preferably from 5 minutes to 24 hours. Acids and bases may be added
to promote the reaction, and as such acids and bases, there can be
mentioned the same ones as mentioned in reaction {circle over (2)}
above also here.
[0524] Further, in order to promote the reaction, metal salts (for
example, oxides, fluorides, chlorides, bromides, iodides, sulfides,
sulfates, nitrates, phosphates, perchlorate, and so on) or metal
elements of titanium, vanadium, chromium, manganum, iron, cobalt,
nickel, copper, zinc, zilconium, niobium, molybdenum, ruthenium,
rhodium, palladium, silver, cadmium, tungsten (wolfram), platinum,
gold, mercury, and so on, can be used as catalyst in an amount of
0.000001 to 1000 equivalents, or more preferably 0.001 to 10
equivalents. The electrophiles (XII) can be used even in a large
excess, unless they have an effect wrongly on the reaction of
sulfonamides (XI). However, it is usually preferable to use 1.0 to
10 equivalents of them. As such electrophiles, there can be
mentioned, for example, halogenides such as methyl iodide, ethyl
iodide, propyl bromide, propyl iodide, isopropyl idodide,
cyclopropyl bromide, butyl bromide, isobutyl bromide, allyl
chloride, allyl bromide, propargyl bromide, 1,2-dibromoethane,
acetyl chloride, propargyl chloride, methyl chloro-formate, ethyl
chloroformate, methanesulfonyl chloride, benzene-sulfonyl chloride,
p-toluenesulfonyl chloride, and so on, sulfuric acid esters such as
dimethyl sulfate, diethyl sulfate, and so on, sulfuric acid esters
such as dimethyl sulfate, diethyl sulfate, and so on, sulfonates
such as methyl methanesulfonate, ethyl benzenesulfonate, isopropyl
p-toluenesulfonate, and soon, and acid anhydrides such as acetic
anhydride, trifluoroacetic acid anhydride,
trifluoromethane-sulfonic acid anhydride, mixed anhydride of acetic
acid-formic acid, and so on. 43
[0525] Compound (I.sup.0) or salts thereof can be obtained by
reacting sulfonylating agents represented by Formula (VII)
mentioned above, with amines represented by the Formula (XIII)
(wherein symbols have the same meanings as mentioned above) or
salts thereof.
[0526] The reactions of this type are usually carried out with or
without solvent. As the solvent which is employable in reactions
with solvent, there can be mentioned those mentioned in (A) {circle
over (2)} above. The reaction temperature is -100 to 300.degree.
C., or more preferably -50 to 200.degree. C., and the reaction time
is from 1 minutes to 1 week, or, more preferably from 5 minutes to
24 hours. Acids and bases may be added to promote the reaction, and
as those acids and bases, there can be mentioned the same ones as
those mentioned above regarding the reaction equation (A) {circle
over (2)} described above. Furthermore, in order to promote the
reaction, metal salts (for example, oxides, fluorides, chlorides,
bromides, iodides, sulfides, sulfates, nitrates, phosphates,
perchlorate, and so on) or metal elements of titanium, vanadium,
chromium, manganum, iron, cobalt, nickel, copper, zinc, zilconium,
niobium, molybdenum, ruthenium, rhodium, palladium, silver,
cadmium, tungsten, platinum, gold, mercury, and so on, can be added
as catalyst in an amount of 0.000001 to 1000 equivalents, or more
preferably 0.001 to 10 equivalents. 44
[0527] Compound (I.sup.0) or salts thereof can be obtained by
reacting sulfonamides represented by Formula XIV (wherein each
symbol has the same meaning as mentioned before) or salts thereof,
with compounds represented by the Formula (X) above or salts
thereof.
A.sup.0-X.sup.0--SO.sub.2--NHZ.sup.0 (XIV):
[0528] This kind of reaction is carried out usually with or without
solvent. As the solvent which is employable in reactions using
solvent, there can be mentioned those described in (A) {circle over
(2)} above. The reaction temperature is -100 to 300.degree. C., or
more preferably at -50 to 200.degree. C., and the reaction time is
from 1 minutes to 1 week, or more preferably from 5 minutes to 24
hours. Acids and bases may be added to promote the reaction, and as
for those acids and bases, there may be mentioned the same ones as
those mentioned above regarding the reaction equation (A) {circle
over (2)}. Further, in order to promote the reaction, metal salts
(for example, oxides, fluorides, chlorides, bromides, iodides,
sulfides, sulfates, nitrates, phosphates, perchlorate, and so on)
or metal elements of titanium, vanadium, chromium, manganum, iron,
cobalt, nickel, copper, zinc, zilconium, niobium, molybdenum,
ruthenium, rhodium, palladium, silver, cadmium, tungsten, platinum,
gold, mercury, and so on, can be added as catalyst in an amount of
0.000001 to 1000 equivalents, or more preferably 0.001 to 10
equivalents.
[0529] When compounds (VII) to (XIV) are in the forms of salts,
they can be in the types of the salt similar to those mentioned
concerning compound (I.sup.0).
[0530] [Synthetic Method (D)]
[0531] When compound (I.sup.0) or salts thereof have nitro groups
as the substituent in B.sup.0, they can be obtained by nitrating
the corresponding raw-material (compounds which have no
substituents at the positions where the nitro substitution will be
introduced) with nitrating agents [synthetic method (D)]. As
nitrating agents, 30 to 100% nitric acids and fuming nitric acids
are commonly used. However, other nitrating agents such as alkali
metal nitrates, for example, sodium nitrate, potassium nitrate, and
so on, alkyl ester nitrates such as ethyl nitrate, amyl nitrate,
and so on, nitronium tetrafluoroborate (NO.sub.2BF.sub.4),
nitronium trifluoromethanesulfonate (NO.sub.2CF.sub.3SO.sub.3),
nitrogen oxides (for example, NO.sub.2, N.sub.2O.sub.3,
N.sub.2O.sub.4, N.sub.2O.sub.5), and so on. Fifty to 100% nitric
acids are especially preferable. The nitrating agents may be used
about in 1.0 to 20 equivalents to the raw-material which is not
substituted at positions where nitro substitution will occur. More
preferably, the ratio of nitrating agent to the raw material is 1.0
to 10 equivalents, or about 1.0 to 3.0 equivalents in cases where
nitric acid of 90% or so is used.
[0532] Although the nitration reaction may be carried out in the
absence of solvent, it is usually done in the presence of acidic
solvents such as sulfuric acid, acetic acid, acetic anhydride,
trifluoroacetic acid anhydride, trifluoromethane sulfonic acid, and
so on. If it is desirable, any solvents or mixtures of solvents
which do not affect wrongly to the reaction can be used. As such
solvents, there can be mentioned, in addition to the acidic
solvents mentioned above, those solvents described regarding the
reaction (A) {circle over (2)} above. Those solvents can either be
used singly, or, if necessary, as mixtures of two or more
(preferably 2 to 3) species of them together, in appropriate ratios
of, for example, about 1:1 to 1:10 (v/v ratios).
[0533] In the cases where the reaction solvent is not homogeneous,
the reaction may be made in the presence of
phase-transfer-catalysts, for example, quaternary ammonium salts
such as triethylbenzyl-ammonium chloride, tri-n-octylmethylammonium
chloride, trimethyl-decylammonium chloride, tetramethylammonium
bromide, cetyl-pyridinium bromide, and so on, and crown ethers, and
so on.
[0534] The most preferable solvents are acetic acid and acetic
anhydride. The reaction temperature is usually about -50 to
200.degree. C., more preferably about -20 to 130.degree. C., and
the reaction time is from about 1 mimute to 24 hours, more
preferably from about 15 minutes to 3 hours.
[0535] Here, the compound (VI) or salts thereof can be prepared
according to the method (D) above, thus, for example, by nitrating
the compounds which may be represented by the Formula 45
[0536] (where B7 is a phenyl group which is substituted with
substituents selected from halogen atoms (for example, fluorine,
chlorine, bromine, iodine), nitro, and cyano, but at least one of
the 2- and 6-positions is remained unsubstituted), and other
symbols have the same meanings as mentioned above) or satls
thereof.
[0537] The "phenyl group of which at least one of the 2- and
6-positions is remained unsubstituted" in B.sup.6 can be
substituted with substituents selected from halogen atoms, nitro,
and cyano, and the number of substituents can be 1 to 3.
[0538] In the cases where compound (I.sup.0) or salts thereof have
substituents, those substituents can either be introduced in
advance at the stage of the raw material or the intermediates (VII)
to (XIV), or necessary sabstituents can be introduced or converted
into afterward, after synthesizing compound (I.sup.0) or salts
thereof, by means of known methods for converting functional groups
following the methods described in, for example, Organic Reactions,
Organic Syntheses, Synthetic Methods of Organic Chemistry,
Compendium of Organic Synthetic Methods), and so on.
[0539] As such substituent convertion reactions, there may be
mentioned, for example, the synthetic methods of (E) to (T) which
will be followed, but these are only examples and the methods
applicable, and should not be considered to be restricted to
them.
[0540] [Synthetic Method (E)]
[0541] Those compounds which have alkylthio groups and can be
prepared from known raw materials according to the reaction
equations (A), (B) or (C), may be converted into compounds which
have alkylsulfinyl groups by reacting them with 0.5 to 2.0
equivalents, or more preferably with 0.8 to 1.5 equivalents of
appropriate oxidating agent (for example, hydrogen peroxide,
peracetic acid, perbenzoic acid, meta-chloroperbenzoic acid,
potassium permanganate). Similarly, but with 1.5 or more
equivalents, or more preferably, with 2.0 to 3.0 equivalents of
oxidating agents, the compounds which have alkylthio groups which
have alkylsulfonyl groups can be converted into the corresponding
alkylsulfonyl compounds.
[0542] [Synthetic Method (F)]
[0543] Those compounds which have alkoxycarbonyl groups and can be
prepared from known raw materials according to the reaction
equations (A), (B) or (C), may be converted into compounds having
carboxyl groups by subjecting them to hydrolysis reaction in the
presence of bases (for example, sodium hydroxide, potassium
hydroxide, and so on) or acids (for example, sulfuric acid,
hydrochloric acid, and so on).
[0544] [Synthetic Method (G)]
[0545] Those compounds which have carboxyl groups, can be
esterified by reacting them with alcohols (for example, methanol,
ethanol, and so on), in the presence of appropriate acids, (for
example, sulfuric acid, p-toluenesulfonic acid, and so on).
Further, the carboxyl groups can be converted into compounds which
have esters or amides by first activating the carboxyl groups (for
example, by converting it (them) into acid chloride with thionyl
chloride or phosphorus oxychloride, by converting it (them) into
acid anhydride with carboxylic chloride, chlorofolmic ester by
activating it (them) with dicyclohexylcarbodiimide,
methylpyridinium chloride, and so on), and then by reacting the
products with alcohols or amines, respectively.
[0546] [Synthetic Method (H)]
[0547] Compounds having amide (CONH.sub.2) groups can be converted
into compounds having cyano groups by reacting the former compounds
with dehydrating agents (for example, acetic anhydride,
trifluoroacetic acid anhydride, thionyl chloride, phosphorus
oxychloride, phosphorus pentoxide, and so on) in the presence or
absence of bases (for example, pyridine, triethylamine, and so
on).
[0548] [Synthetic Method (I)]
[0549] Compounds having amide groups can be converted into
compounds with thioamide groups by reacting the amide compounds
with Lawesson's Reagent
(2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-di-phosphetane-2,4-disulfide)
or with phosphorus pentasulfide, those compounds having cayno
groups can be converted into compounds having thioamide groups by
adding hydrogen sulfide to the cyano groups.
[0550] [Synthetic Method (J)]
[0551] Compounds with carboxyl groups prepared by the synthetic
method (F), and so on, compounds with ester groups or amide groups
prepared by the synthetic method (G), and so on, or compounds with
cyano groups prepared by the synthetic method (H), and so on, can
be converted to compounds with formyl groups by subjecting them to
reduction reaction with appropriate reducing agents (for example,
catalytic hydrogenation, diborane, silanes, sodium borbhydride,
lithium aluminum hydride, diisobutyl aluminum, and so on), or
compounds with methyl groups or hydroxymethyl groups prepared by
the synthetic methods of (A) to (C) can be converted into compounds
with formyl groups by oxidizing them with oxidizing agents (for
example, chromic acids, dichromates, manganum dioxide, potassium
permanganate, selenium dioxide, dimethylsulfoxide-oxalyl
chloride-triethylamine [Swern oxidation], and so on).
[0552] [Synthetic Method (K)]
[0553] Compounds (compounds unsubstituted at positions where formyl
group can be Introduced) which can be prepared from known raw
material accoding to the methods shown by the reaction equations
(A), (B) or (C) can be converted into compounds with formyl groups
by formylating them with formulating agents (for example,
phosphorus oxychloride-N,N-dimethylforma- mide [Vilsmeier
reaction], zinc chloride-hydrogen cyanide-hydrogen chloride
[Gattermann reaction], chloroform-sodium hydroxide [Reimer-Tiemann
reaction] and dichloromethoxyethane-aluminum chloride, and so
on).
[0554] [Synthetic Method (L)]
[0555] Oximes and hydrazones can be prepared from compounds with
formyl groups which can be prepared by the synthetic methods (J) or
(K), by reacting them with hydroxylamines or hydrazines,
respectively.
[0556] [Synthetic Method (M)]
[0557] Compounds with haloalkyl groups can be converted to
compounds with various functional group by making them to react
with appropriate nucleophiles (for example, mercaptanes such as
methyl mercaptane, ethyl mercaptane, and so on, amines such as
ammonia, methylamine, dimethylamine, and so on, alcohols such as
methanol, ethanol, and so on) in the presence of appropriate bases
(for example, sodium hydroxide sodium hydride, sodium carbonate,
potassium carbonate, and so on).
[0558] [Synthetic Method (N)]
[0559] Compounds with haloethyl group which can be prepared from
known raw material accoding to the methods shown by the reaction
equations (A), (B) or (C) can be converted into compounds with
vinyl groups by subjecting them to dehydrohalogenation reaction
with bases.
[0560] [Synthetic Method (O)]
[0561] Compounds with terminal acetylene group which can be
prepared from known raw material accoding to the methods shown by
the reaction equations (A), (B) or (C) can be converted into
compounds with haloacetylene groups by making them to react with
halogen sorces (for example, N-chlorosuccinimide,
N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine,iodine,
and so on) in the presence of appropriate bases (for example,
sodium hydroxide, sodium hydride, sodium carbonate, potassium
carbonate, n-butyllithium, and so on).
[0562] [Synthetic Method (P)]
[0563] Compounds with nitro groups which can be obtained according
to the reaction equation (A), (B), or (C), or the synthetic method
(D), can be converted into compounds with amino groups by making
them to react with reducing agents (for example, catalytic
hydrogenation, iron, tin, zinc, ferrous chloride, stannous
chloride, and so on).
[0564] [Synthetic Method (Q)]
[0565] Compounds with amino groups which can be synthesized by the
synthetic method (P), and so on, may be converted to compounds with
nitroso groups by making them to react with oxidizing agents (for
example, hydrogen peroxide, peracetic acid, perbenzoic acid,
meta-chloro-perbenzoic acid, potassium permanganate, and so
on).
[0566] [Synthetic Method (R)]
[0567] Compounds with nitroso groups which can be prepared by the
synthetic method (Q), and so on, may be converted to compounds with
azoxycyano groups by making them to react first with N-oxidizing
agents (for example, N-chlorosuccinimide, N-bromosuccinimide,
iodobenzene diacetate, and so on), and then with cyanamide in the
presence of bases (for example, sodium carbonate, potassium
carbonate, sodium hydroxide, and so on).
[0568] [Synthetic Method s]
[0569] Compounds with hydroxy groups protected with a protecting
group (for example, methoxymethyl group, dihydropyranyl group,
acetyl group, methoxycarbonyl group, benzyl group,
tert-butylmethylsilyl group, and so on) which can be produced from
known raw materials according to the reaction equation (A), (B), or
(C), can be converted into compounds with hydroxyl groups by
subjecting them to deprotection reactions according to the method
described in, for example, "Protective Groups in Organic
Synthesis", and so on.
[0570] [Synthetic Method (T)]
[0571] Compounds with hydroxy groups which can be prepared by the
synthetic method s, and so on, may be converted to compounds with
various substituents by making them to react with electrophiles
(for example, methyl iodide, dimethyl sulfate, ethyl iodide,
isopropyl iodide, propyl bromide, 1,2-dibromo ethane, acetic
anhydride, acetyl chloride, methyl chloroformate, trifluoroacetic
anhydride, methanesulfonyl chloride, p-toluenesulfonyl chloride,
and soon), e.g., by means of substitution reactions, in the
presence of appropriate bases (for example, sodium hydroxide,
sodium hydride, sodium carbonate, potassium carbonate, and so
on).
[0572] Hereunder, the present invention is illustrated in more
detail by reference to the following Examples, Formulation
Examples, and Test Examples. However, the scope of the compound
(I.sup.0) or salts thereof is not to be considered to be restricted
to the present embodiment.
[0573] In the synthesis examples, elution in silica gel column
chromatography was carried out under observation by means of TLC
(Thin Layer Chromatography). In the TLC-observation, the Kieselgel
60F.sub.254 (70-230 mesh) plates manufactured by Merck & Co.,
were used as the TLC-plate, and as the eluents used were the same
solvent as that used in the column chromatography as eluent, and as
the detection method, either the UV-detector or coloration method
with iodine was adopted. As silica gel for the column
chromatography, Kieselgel 60 (70-230 mesh) manufactured by Merck
& Co. was used.
[0574] When a mixed solvent was used as eluent, the ratio shown in
the ( ) indicates the volume to volume ratio of the solvents mixed.
NMR (Nuclear Magnetic Resonance) spectrum means the proton NMR, and
was measured by a Bruker AC-200P type (200 MHz) spectrometer, using
tetramethylsilane as internal standard. All .delta. values are in
ppm. Abbreviations used in the Reference Examples, Examples and
Tables below have the meanings which follow,
[0575] s: singlet, d: doublet, t: triplet, q: quartet, m:
multiplet, dd: double doublet, dt: double triplet, dq: double
quartet, septet: septet (a set of seven lines), br: broad, brs:
broad singlet, ddd: double double doublet, ddt: double double
triplet, brd: broad doublet, brq: broad quartet, J: coupling
constant, J.sub.HF: coupling constant of the coupling between
hydrogen atom and fluorine atom, Hz: Heltz, CDCl.sub.3:
deutero-chloroform(chloroform-d), DMSO-d.sub.6: dimethyl
sulfoxide-d.sub.6, DMF: N,N-dimethylformamide, %: wt %, and mp:
melting point. In addition, room temperature means a temperature or
temperatures within 15-25.degree. C.
EXAMPLES
Example 1
[0576] Synthesis of
2',4'-Dichloro-N-methyl-p-toluenesulfonanilide
[0577] (Compound No. 51)
[0578] To a suspension of sodium hydride(60%, 0.07g (1.75 mmol)) in
DMF (2.0 ml), 2',4'-dichloro-p-toluenesulfonanilide(0.50 g (1.58
mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate(0.17 ml (1.80 mmol)) was added dropwise. After 15
hours' stirring at room temperature, the reaction mixture was
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The crystals separated were
filtered and washed with diisopropyl ether to give 0.38 g (73%) of
the title compound.
[0579] mp: 86.0-87.0.degree. C.
[0580] NMR(CDl.sub.3) .delta.: 2.44(3H,s), 3.17(3H,s),
7.13(1H,d,J=8.6 Hz), 7.22(1H,dd,J=8.6& 2.3 Hz), 7.30(2H,d,J=8.4
Hz), 7.42(1H,d,J=2.3 Hz), 7.65(2H,d,J=8.4 Hz).
Example 2
[0581] Synthesis of
N,4'-Dimethyl-3'-nitro-p-toluenesulfonanilide
[0582] (Compound No. 126)
[0583] To a suspension of sodium hydride (60%, 0.14g (3.50 mmol))
in DMF (3.0 ml), 4'-methyl-3'-nitro-p-toluenesulfonanilide (1.00 g
(3.26 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate (0.34 ml (3.56 mmol)) was added dropwise. After
one hours' stirring at room temperature, the reaction mixture was
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. Diethyl ether was added to the
residue, and the solid separated was filtered and washed to give
0.79 g (76%) of the title compound as pale yellow crystals.
[0584] mp: 103.5-106.0.degree. C.
[0585] NMR(CDCl.sub.3) .delta.: 2.43(3H,s), 2.59(3H,s), 3.17(3H,s),
7.27(2H,d,J=8.3 Hz), 7.31(1H,d,J=8.2 Hz), 7.43(2H,d,J=8.3 Hz),
7.45(1H,dd,J=8.2 & 2.3 Hz), 7.58(1H,d,J=2.3 Hz).
Example 3
[0586] Synthesis of
N-Ethyl-4'-fluoro-2'-nitro-p-toluenesulfonanilide
[0587] (Compound No. 263)
[0588] To a suspension of sodium hydride (60%, 0.05 g (1.25 mmol))
in DMF (2.0 ml), 4'-fluoro-2'-nitro-p-toluenesulfonanilide (0.31 g
(1.00 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
ethyl iodide (0.30 ml (3.75 mmol)) was added dropwise. After 30
minutes' heating at 100.degree. C. with stirring, the reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with water and saturated sodium chloride
solution, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure. Diisopropyl ether was
added to the residue and the solid separated was filtered and
washed to give 0.25 g (74%) of the title compound as pale yellow
crystals.
[0589] mp: 93.0-94.5.degree. C.
[0590] NMR(CDCl.sub.3) .delta.: 1.18(3H,s), 2.44(3H,s),
3.67(2H,brq,J=7.2 Hz), 7.10(1H,dd,J=8.9 Hz,J.sub.HF=5.1 Hz),
7.23(1H,ddd,J=8.9 & 2.9 Hz,J.sub.HF=7.2 Hz), 7.27(2H,d,J=8.4
Hz), 7.53(2H,d,J=8.4 Hz), 7.60(1H,dd,J=2.9 Hz,J.sub.HF=7.7 Hz).
Example 4
[0591] Synthesis of
4'-Chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide
[0592] (Compound No. 289)
[0593] To a suspension of sodium hydride(60%, 0.05 g (1.25 mmol))
in DMF (2.0 ml), 4'-chloro-2'-nitro-p-toluenesulfonanilide(0.30 g
(0.92 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
ethyl iodide (0.50 ml (6.25 mmol)) was added dropwise. After one
hour's heating at 100.degree. C. with stirring, the reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with water and saturated sodium chloride
solution, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure. The residue was subjected
to silica gel column chromatography with ethyl acetate-hexane (1:3)
as eluent, giving 0.24 g (74%) of the title compound as pale yellow
crystals.
[0594] mp: 132.5-134.0.degree. C.
[0595] NMR(CDCl.sub.3) .delta.: 1.18(3H,t,J=7.2 Hz), 2.44(3H,s),
3.66(2H,q,J=7.2 Hz), 7.05(1H,d,J=8.6 Hz), 7.28(2H,d,J=8.2 Hz),
7.50(1H,dd,J=8.6 & 2.5 Hz), 7.53(2H,d,J=8.2 Hz);
7.86(1H,d,J=2.5 Hz).
Example 5
[0596] Synthesis of
[0597] 4'-Methoxy-2'-nitro-N-isopropyl-p-toluenesulfonanilide
[0598] (Compound No. 207)
[0599] To a suspension of sodium hydride (60%, 0.10 g (2.50 mmol))
in DMF (2.0 ml), 4'-methoxy-2'-nitro-p-toluenesulfonanilide (0.65 g
(2.02 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
isopropyl iodide (1.00 g (5.88 mmol)) was added dropwise. After
five hours' heating at 130.degree. C. with stirring, the reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with water and saturated sodium chloride
solution, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure. The residue was subjected
to silica gel column chromatography with ethyl acetate-hexane (1:2)
as eluent, giving 0.21 g (28.5%) of the title compound as pale
brown crystals.
[0600] mp: 148.0-149.5.degree. C.
[0601] NMR(CDCl.sub.3) .delta.: 1.04(3H,d,J=6.7 Hz),
1.11(3H,d,J=6.7 Hz), 2.43(3H,s), 3.89(3H,s), 4.36(1H,septet,J=6.7
Hz), 7.06(1H,dd,J=8.8 & 2.8 Hz), 7.16(1H,d,J=8.8 Hz),
7.28(2H,d,J=8.3 Hz), 7.38(1H,d,J=2.8 Hz), 7.67(2H,d,J=8.3 Hz).
Example 6
[0602] Synthesis of
[0603]
4-Chloro-4'-cyano-2'-nitro-N-(isopropyl)-benzenesulfonanilide
[0604] (Compound No. 413)
[0605] (1) To a solution of 4-aminobenzonitrile (2.36 g (20.0
mmol))in pyridine (10 ml), 4-chlorobenzenesulfonyl chloride (4.35 g
(20.6 mmol)) was added under cooling in a water bath(15.degree.
C.). After 18 hours' stirring at room temperature, water (100 ml)
was added to the reaction mixture and the stirring was continued to
bring about separation of crystals, which were then collected by
filtration and washed with water to give 4.45 g (76%) of
4-chloro-4'-cyanobenzenesulfonanilide as pale orange crystals.
[0606] mp: 182.5-184.0.degree. C.
[0607] NMR(CDCl.sub.3) .delta.: 7.11(1H.s), 7.18(2H,d,J=8.8 Hz),
7.47(2H,d,J=8.8 Hz), 7.56(2H,d,J=8.8 Hz), 7.78(2H,d,J=8.8 Hz).
[0608] (2) To a suspension of 4-chloro-4'-cyanobenzenesulfonanilide
(4.03 g (13.8 mmol)) in 15 ml of acetic anhydride, 97% fuming
nitric acid (0.61 ml (14.3 mmol)) was added dropwise with stirring
at room temperature. After one hour's stirring at 50.degree. C.,
the reaction mixture was poured into water to give crystals, which
were then collected by filtration and washed with water to give
4.30 g (93%) of 4-chloro-4'-cyano-2'-nitrobenzenesulfonanilide as
pale yellow crystals.
[0609] mp: 193.0-195.0.degree. C.
[0610] NMR(CDCl.sub.3) .delta.: 7.53(2H,d,J=8.8 Hz),
7.81(1H,dd,J=8.8 & 1.9 Hz), 7.88(2H,d,J=8.8 Hz),
7.95(1H,d,J=8.8 Hz), 8.50(1H,d,J=1.9 Hz), 10.28(1H,brs).
[0611] (3) To a suspension of sodium hydride (60%, 0.10 g (2.50
mmol)) in 4.0 ml of DMF,
4-chloro-4'-cyano-2'-nitrobenzenesulfonanilide (0.70 g (2.07 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 15 minutes' stirring at room temperature, isopropyl
iodide (0.50 ml (5.01 mmol)) was added dropwise. After three hours'
heating at 130C with stirring, the reaction mixture was poured into
water and extracted with ethyl acetate. The extract was washed with
water and saturated sodium chloride solution, successively, dried
over anhydrous magnesium sulfate, and then concentrated under
reduced pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:2) as eluent, giving
0.11 g (14%) of the title compound as pale yellow crystals.
[0612] mp: 167.5-168.5.degree. C.
[0613] NMR(CDCl.sub.3) .delta.: 1.07(3H,d,J=6.7 Hz),
1.19(3H,d,J=6.7 Hz), 4.39(1H,septet,J=6.7 Hz), 7.46(1H,d,J=8.3 Hz),
7.50(2H,d,J=8.8 Hz), 7.72(2H,d,J=8.8 Hz), 7.89(1H,dd,J=8.3 &
2.0 Hz), 8.20(1H,d,J=2.0 Hz).
Example 7
[0614] Synthesis of
N-Allyl-4'-chloro-2'-nitro-p-toluenesulfonanilide
[0615] (compound No.299)
[0616] To a suspension of sodium hydride (60%, 0.05 g (1.25 mmol))
in DMF (2.0 ml), 4'-chloro-2'-nitro-p-toluenesulfonanilide (0.30 g
(0.92 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
allyl bromide (0.50 ml (5.78 mmol)) was added dropwise. After being
stirred for 30 minutes' at 50.degree. C., and for 15 hours at room
temperature, the reaction mixture was poured into water and
extracted with ethyl acetate. The extract was washed with water and
saturated sodium chloride solution, successively, dried over
anhydrous magnesium sulfate, and then concentrated under reduced
pressure. Diisopropyl ether was added to the residue, and the
crystals separated was filtered and washed to give 0.21 g (62%) of
the title compound as pale yellow crystals.
[0617] mp: 77.0-78.0.degree. C.
[0618] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 4.22(2H,dt,J=6.9 &
1.2 Hz), 5.05(1H,ddt,J=17.0 & 2.5 & 1.2 Hz),
5.11(1H,ddt,J=10.1 & 2.5& 1.2 Hz), 5.89(2H,ddt,J=17.0 &
10.1 & 6.9 Hz), 7.05(1H,d,J=8.5 Hz), 7.28(2H,d,J=8.4 Hz),
7.48(1H,dd,J=8.5 & 2.4 Hz), 7.54(2H,d,J=8.4 Hz),
7.84(1H,d,J=2.4 Hz).
Example 8
[0619] Synthesis of
N-Acetyl-4'-methoxy-2'-nitro-p-toluenesulfonanilide
[0620] (compound No.213)
[0621] To a suspension of sodium hydride (60%, 0.08 g (2.00 mmol))
in DMF (3.0 ml), 4'-methoxy-2'-nitro-p-toluenesulfonanilide (0.50 g
(1.55 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
acetic anhydride (0.20 ml (2.12 mmol)) was added dropwise. After
one hour's stirring at room temperature, water was poured into the
reaction mixture and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. Crystals separated was added
to diethyl ether, filtered and washed to give 0.51 g (90%) of the
title compound as pale yellow crystals.
[0622] mp: 172.5-174.0.degree. C.
[0623] NMR(CDCl.sub.3) .delta.: 2.08(3H,s), 2.45(3H,s),
3.94(3H,s),7.22(1H,dd,J=8.8 & 2.9 Hz), 7.32(2H,d,J=8.5 Hz),
7.37(1H,d,J=8.8 Hz), 7.56(1H,d,J=2.9 Hz), 7.82(2H,d,J=8.5 Hz).
Example 9
[0624] Synthesis of
N,N-Bis(p-toluenesulfonyl)-4-methoxy-2-nitroaniline
[0625] (Compound No. 214)
[0626] To a solution of 4'-Methoxy-2'-nitro-p-toluenesulfonanilide
(0.32 g (1.00 mmol)) in pyridine (1,0 ml), p-toluenesulfonyl
chloride (0.20 g (1.05 mmol)) was added with stirring at room
temperature. After 15 hours' stirring at room temperature, the
reaction mixture was poured into water and crystals separated was
filtered and washed to give 0.34 g (83%) of the title compound as
pale yellow crystals.
[0627] mp: 180.5-182.0.degree. C.
[0628] NMR(CDCl.sub.3) .delta.: 2.46(6H,s), 3.90(3H,s),
6.95-7.15(2H,m), 7.33(4H,d,J=8.4 Hz), 7.45-7.55(1H,m),
7.83(4H,d,J=8.4 Hz).
Example 10
[0629] Synthesis of
4-Chloro-2-nitro-N-methyl-N-[(trans)-.beta.-styrenesul-
fonyl]aniline (Compound No. 282)
[0630] To a suspension of sodium hydride (60%, 0.13 g (3.25 mmol))
in DMF (7.0 ml),
4-chloro-2-nitro-N-[(trans)-.beta.-styrenesulfonyl]aniline (1.00 g
(2,95 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate (0.32 ml (3.38 mmol)) was added. The resulting
mixture was stirred at 80.degree. C. for 3 hours, and then poured
into water, extracted with diethyl ether. The extract was washed
with 1% sodium hydroxide solution, water and saturated sodium
chloride solution, successively, dried over anhydrous magnesium
sulfate, and then concentrated under reduced pressure. Small amount
of diethyl ether was added to the residue and crystals separated
was filtered and washed to give 0.99 g (95%) of the title compound
as pale yellow crystals.
[0631] mp: 162.0-164.0.degree. C.
[0632] NMR(CDCl.sub.3) .delta.: 3.28(3H,s), 6.74(1H,d,J=15.4 Hz),
7.35-7.60(7H,m), 7.60(1H,dd,J=8.6 & 2.3 Hz), 7.87(1H,d,J=2.3
Hz).
Example 11
[0633] Synthesis of 2',4-Dinitro-N-methylbenzenesulfonanilide
[0634] (Compound No. 425)
[0635] To a suspension of sodium hydride (60%, 0.12 g (3.00 mmol))
in DMF (4.0 ml), N-methyl-2,4-dinitroaniline (0.39 g (1.98 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 15 minutes' stirring at room temperature,
benzenesulfonyl chloride (0.38 ml (2.98 mmol)) was added dropwise.
After two hours' stirring at room temperature, the reaction mixture
was poured into water and extracted with diethyl ether. The extract
was washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel chromatography with ethyl acetate-hexane (1:2) as
eluent, to give 0.52 g (78%) of the title compound as pale yellow
crystals.
[0636] mp: 151.5-153.0.degree. C.
[0637] NMR(CDCl.sub.3) .delta.: 3.28(3H,s), 7.38(1H,d,J=8.8 Hz),
7.45-7.75(5H,m), 8.39(1H,dd,J=8.8 & 2.6 Hz), 8.73(1H,d,J=2.6
Hz).
Example 12
[0638] Synthesis of 2',4-Dinitro-N-ethyl-p-toluenesulfonanilide
[0639] (Compound No. 435)
[0640] To a suspension of sodium hydride (60%, 0.12 g (3.00 mmol))
in DMF (4.0 ml), 2,4-dinitro-N-ethylaniline (0.42 g (1.99 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 15 minutes' stirring at room temperature,
p-toluenesulfonyl chloride (0.57 g (2.99 mmol)) was added. After
two hours' stirring at room temperature, the reaction mixture was
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel chromatography with ethyl acetate-hexane (1:2) as
eluent, to give 0.47 g (65%) of the title compound as pale yellow
crystals.
[0641] mp: 135.0-136.5.degree. C.
[0642] NMR(CDCl.sub.3) .delta.: 1.21(3H,t,J=7.2 Hz), 2.45(3H,s),
3.69(2H,q,J=7.2 Hz), 7.30(2H,d,J=8.4 Hz), 7.30(1H,d,J=8.8 Hz),
7.52(2H,d,J=8.4 Hz), 8.38(1H,dd,J=8.8 & 2.6 Hz),
8.74(1H,d,J=2.6 Hz).
Example 13
[0643] Synthesis of
[0644] 4'-chloro-N-cyclopropyl-2'-nitro-p-toluenesulfonanilide
[0645] (Compound No. 292)
[0646] (1) A mixture of 2,5-dichloronitrobenzene (2.00 g (10.4
mmol)) and cyclopropylamine (2.0 ml) was heated under reflux for 60
hours, and the excess cyclopropylamine was removed by concentration
under reduced pressure. The residue was dissolved in ethyl acetate
and the resulting solution was washed with aqueous 1% sodium
hydroxide, saturated sodium chloride solution. The organic layer
was dried over anhydrous magnesium sulfate and then concentrated
under reduced pressure. The residue was subjected to silica gel
column chromatography with ethyl acetate-hexane (1:10) as eluent to
give 1.30 g (59%) of 4-chloro-N-cyclopropyl-2-nitroan- iline as
orange crystals.
[0647] mp: 65.0-66.0.degree. C.
[0648] NMR(CDCl.sub.3) .delta.: 0.60-0.75(2H,m), 0.85-1.00(2H,m),
2.50-2.65(1H,m), 7.29(1H,d,J=9.5 Hz), 7.42(1H,dd,J=9.5 & 2.4
Hz), 8.05(1H,brs), 8.15(1H,d,J=2.4 Hz).
[0649] (2) To a suspension of sodium hydride (60%, 0.10 g (2.50
mmol)) in DMF (3.0 ml), 4-chloro-N-cyclopropyl-2-nitroaniline (0.40
g (1.88 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
p-toluenesulfonyl chloride (0.38 g (1.99 mmol)) was added. After
one hour's stirring at room temperature, the reaction mixture was
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel chromatography with ethyl acetate-hexane (1:3) as
eluent, to give 0.42 g (61%) of the title compound as yellow
crystals
[0650] mp: 98.5-100.0.degree. C.
[0651] NMR(CDCl.sub.3) .delta.: 0.55-0.85(2H,m), 0.85-1.20(2H,m),
2.45(3H,s), 2.60-2.80(1H,m), 7.02(1H,d,J=8.6 Hz), 7.32(2H,d,J=8.2
Hz), 7.48(1H,dd,J=8.6 & 2.4 Hz), 7.60(2H,d,J=8.2 Hz),
7.81(1H,d,J=2.4 Hz).
Example 14
[0652] Synthesis of
2',4'-Dinitro-N-methoxy-p-toluenesulfonanilide
[0653] (Compound No. 545)
[0654] (1) 2,4-Dinitrochlorobenzene (4.05 g (20.0mmol)) and
methoxylamine hydrochloride (2.00 g (23.9 mmol)) were dissolved in
15 ml of acetonitrile. To this mixture, under ice cooling and with
stirring, triethylamine (7.00 ml (50.2 mmol))was added. After being
stirred for 24 hours at room temperature, the resulting black
solution was concentrated under reduced pressure. Water and dilute
hydrochloric acid were added to the residue and the mixture was
extracted with ethyl acetate. The extract was dried over anhydrous
magnesium sulfate and then concentrated under reduced pressure. The
residue was then subjected to silica gel column chromatography with
ethyl acetate-hexane (1:5) as eluent, to give 2.26 g (53%) of
N-(2,4-dinitrophenyl)-O-methylhydroxylamine as yellow crystals.
[0655] mp: 109.5-111.5.degree. C.
[0656] NMR(CDCl.sub.3) .delta.: 3.92(3H,s), 7.47(1H,d,J=9.5 Hz),
8.38(1H,dd,J=9.5 & 2.6 Hz), 9.11(1H,d,J=2.6 Hz),
10.23(1H,brs).
[0657] (2) To a suspension of sodium hydride (60%, 0.24 g (6.00
mmol)) in DMF (8.0 ml), N-(2,4-dinitrophenyl)-O-methylhydroxylamine
(0.85 g (3.99 mmol)) was added under ice-cooling with stirring.
After 15 minutes' stirring under ice-cooling, p-toluenesulfonyl
chloride (1.15 g (6.03 mmol)) was added. Then, the temperature of
the reaction mixture was brought to room temperature and stirred at
the same temperature for 18 hours. The reaction mixture was then
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel chromatography with ethyl acetate-hexane (1:3) as
eluent, to give 0.30 g (21%) of the title compound as orange
crystals.
[0658] mp: 146.0-148.0.degree. C.
[0659] NMR(CDCl.sub.3) .delta.: 2.47(3H,s), 3.90(3H,s),
7.31(1H,d,J=9.0 Hz), 7.32(2H,d,J=8.3 Hz), 7.54(2H,d,J=8.3 Hz),
8.28(1H,dd,J=9.0 & 2.5 Hz), 8.71(1H,d,J=2.5 Hz).
Example 15
[0660] Synthesis of
[0661]
N-(5-Chloro-3-nitropyridin-2-yl)-N-methyl-p-toluenesulfonamide
[0662] (Compound No. 494)
[0663] To a suspension of sodium hydride (60%, 0.05 g (1.25 mmol))
in 2.0 ml of DMF, 5-chloro-2-methylamino-3-nitropyridine (0.20 g
(1.07 mmol)) was added under cooling with ice and with stirring. To
the resulting mixture, after 15 minutes' stirring under cooling
with ice, p-toluenesulfonyl chloride (0.23 g (1.21 mmol)) was
added. The reaction mixture was stirred under cooling with ice for
30 minutes and then at room temperature for 30 minutes, poured into
water and extracted with ethyl acetate. The extract was washed with
water and saturated sodium chloride solution, successively, dried
over anhydrous magnesium sulfate, and then concentrated under
reduced pressure. The residue was then subjected to silica gel
column chromatography with ethyl acetate-hexane (1:3) as eluent, to
give 0.16 g (44%) of the title compound as pale yellow
crystals.
[0664] mp: 141.0-143.0.degree. C.
[0665] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 3.22(3H,s),
7.29(2H,d,J=8.3 Hz), 7.48(2H,d,J=8.3 Hz), 8.28(1H,d,J=2.4 Hz),
8.48(1H,d,J=2.4 Hz).
Example 16
[0666] Synthesis of
[0667] 4',5-Dichloro-N-methyl-2'-nitro-2-thiophenesulfonanilide
[0668] (Compound No. 370)
[0669] To a suspension of sodium hydride (60%, 0.15 g (3.75 mmol))
in DMF (5.0 ml),4-chloro-N-methyl-2-nitroaniline(0.34g (1.82mmol))
was added with stirring at room temperature. To the resulting
mixture, after 30 minutes' stirring at room temperature,
5-chloro-2-thiophenesulfonyl chloride (0.67 g (3.11 mmol)) was
added. The reaction mixture was stirred at room temperature for 24
hours and then poured into water and extracted with chloroform. The
extract was washed with water and saturated sodium chloride
solution, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure. The residue was then
subjected to silica gel column chromatography with acetone-hexane
(1:4) as eluent, to give 0.11 g (16%) of the title compound as pale
yellow crystals.
[0670] mp: 85.0-86.0.degree. C.
[0671] NMR(CDCl.sub.3) .delta.: 3.31(3H,s), 6.96(1H,d,J=4.0 Hz),
7.17(1H,d,J=8.5 Hz), 7.26(1H,d,J=4.0 Hz), 7.56(1H,dd,J=8.5 &
2.5 Hz), 7.90(1H,d,J=2.5 Hz).
Example 17
[0672] Synthesis of
[0673] N-(6-Chloro-3-pyridazinyl)-N-methyl-p-toluenesulfonamide
[0674] (Compound No. 420)
[0675] To a suspension of sodium hydride (60%, 0.42 g (10.5 mmol))
in 10.0 ml of DMF, N-methyl-p-toluenesulfonamide (1.85 g (9.99
mmol)) was added under ice-cooling and with stirring. To the
resulting mixture, after 15 minutes' stirring under cooling with
ice, 3,6-dichloropyridazine(1.49g(10- .0 mmol))was added. The
reaction mixture was stirred at room temperature for one hour,
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was then subjected
to silica gel column chromatography with ethyl acetate-hexane (1:3)
as eluent, to give 1.41 g (47%) of the title compound as white
crystals.
[0676] mp: 80.0-81.0.degree. C.
[0677] NMR(CDCl.sub.3) .delta.: 2.41(3H,s), 3.38(3H,s),
7.27(2H,d,J=8.4 Hz), 7.47(2H,d,J=8.4 Hz), 7.48(1H,d,J=9.3 Hz),
8.02(1H,d,J=9.3 Hz).
Example 18
[0678] Synthesis of
N,2'-Dimethyl-4'-nitro-p-toluenesulfonanilide
[0679] (Compound No. 125)
[0680] To a suspension of sodium hydride (60%, 0.08 g (2.00 mmol))
in 2.0 ml of DMF, N-methyl-p-toluenesulfonamide (0.37 g (2.00
mmol)) was added at room temperature with stirring. To the
resulting mixture, after 15 minutes' stirring at room temperature,
2-fluoro-5-nitrotoluene (0.31 g (2.00 mmol)) was added. The
reaction mixture was stirred at room temperature for 2 hours,
poured into water and extracted with ethyl acetate. The extract was
washed with water and saturated sodium chloride solution,
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. Diisopropyl ether was added to
the residue and crystals separated was filtered and washed to give
0.22 g (36%) of the title compound as pale yellow crystals.
[0681] mp: 103.0-104.0.degree. C.
[0682] NMR(CDCl.sub.3) .delta.: 2.47(3H,s), 2.51(3H,s), 3.13(3H,s),
6.77(1H,d,J=8.7 Hz), 7.34(2H,d,J=8.3 Hz), 7.58(2H,d,J=8.3 Hz),
7.92(1H,dd,J=8.7 & 2.6 Hz), 8.17(1H,d,J=2.6 Hz).
Example 19
[0683] Synthesis of 5-Chloro-N-methyl-N-(p-toluenesulfonyl)
[0684] anthranilic acid (Compound No. 71)
[0685] (1) To a solution of methyl 5-chloroanthranilate (10.50 g
(56.6 mmol) in pyridine (30 ml), p-toluenesulfonyl chloride (12.00
g (62.9 mmol)) was added with stirring at 5.degree. C. The mixture
was stirred at room temperature for 18 hours, and then, 200 ml of
water was added to the resulting mixture. The crystals separated
were filtered and washed to give 18.20 g (95%) of
4'-chloro-2'-methoxycarbonyl-p-toluenesulfonanilide as white
crystals.
[0686] mp: 112.5-113.5.degree. C.
[0687] NMR(CDCl.sub.3) .delta.: 2.37(3H,s), 3.88(3H,s),
7.23(2H,d,J=8.4 Hz), 7.40(1H,dd, J=9.0 & 2.6 Hz),
7.67(1H,d,J=9.0 Hz), 7.72(2H,d,J=8.4 Hz), 7.88(1H,d,J=2.6 Hz),
10.48(1H,s).
[0688] (2) To a suspension of sodium hydride (60%, 0.43 g (10.8
mmol)) in DMF (10.0 ml),
4'-chloro-2'-methoxycarbonyl-p-toluenesulfonanilide (3.33 g (9.80
mmol)) was added under cooling with ice and with stirring. After 15
minutes' stirring under cooling with ice, dimethyl sulfate (1.02 g
(10.8 mmol)) was added dropwise, and the reaction mixture was
stirred at room temperature for 16 hours. Then, resulting reaction
mixture was poured into water and extracted with ethyl acetate, and
the extract was washed with water, dried over anhydrous magnesium
sulfate, and then concentrated under reduced pressure. The residue
was subjected to silica gel column chromatography with ethyl
acetate-hexane (1:3) as eluent, to give 2.95 g (85%) of
4'-chloro-2'-methoxycarbonyl-N-methyl-p-toluenesulfo- nanilide as
white crystals.
[0689] mp: 65.5-67.0.degree. C.
[0690] NMR(CDCl.sub.3) .delta.: 2.43(3H,s), 3.23(3H,s), 3.85(3H,s),
6.85(1H,d,J=8.5 Hz), 7.27(2H,d,J=8.3 Hz), 7.37(1H,dd,J=8.5 &
2.6 Hz), 7.52(2H,d,J=8.3 Hz), 7.82(1H,d,J=2.6 Hz).
[0691] (3) To a suspension of
4'-chloro-2'-methoxycarbonyl-N-methyl-p-tolu- enesulfonanilide
(13.3 g (37.5 mmol)) in methanol (30.0 ml), 10% aqueous sodium
hydroxide solution (30.0 ml) was added dropwise with stirring at
room temperature. The mixture was stirred at room temperature for
48 hours, and then concentrated under reduced pressure. Water was
added to the residue to get a homogeneous solution, followed by
addition of concentrated hydrochloric acid (10.0 ml) to bring about
precipitation of crystals. To this, ethyl acetate was added to
extract the product. The extract was then washed with water, dried
over anhydrous magnesium sulfate, and concentrated under reduced
pressure. Diethyl ether was added to the crystals. The crystals
were collected by filtration and washed to give 10.4 g (82%) of the
title compound as white crystals.
[0692] mp: 175.0-177.0.degree. C.
[0693] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 3.25(3H,s),
5.70-6.60(1H,br), 6.86(1H,d,J=8.5 Hz), 7.31(2H,d,J=8.3 Hz),
7.42(1H,dd,J=8.5 & 2.6 Hz), 7.55(2H,d,J=8.3 Hz),
7.98(1H,d,J=2.6 Hz).
Example 20
[0694] Synthesis of
[0695] 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide
[0696] (Compound No. 79)
[0697] 5-Chloro-N-methyl-N-(p-toluenesulfonyl)anthranilic acid
(5.00 g (14.7 mmol)) and pyridine (1.33 ml (16.4 mmol)) were
dissolved in 70.0 ml of acetonitrile. To this, under cooling with
ice and with stirring, isopropyl chloroformate (2.00g (16.3 mmol))
was added dropwise. After 30 minutes' stirring under ice-cooling,
ammonia gas (ca. 1.25 g (73.4 mmol)) was bubbled into the reaction
mixture. The resulting mixture was stirred under cooling with ice
for 30 minutes and at room temperature for 20 hours, and then
concentrated under reduced pressure. Water was added to the
residue, and the mixture was extracted with ethyl acetate. The
extract was washed with water, dilute sodium hydroxide solution and
water, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure to give crude crystals.
Diethyl ether was added to these crystals, followed by filtration
and washing, to give 1.70 g (34%) of the title compound.
[0698] mp: 176.5-178.0.degree. C.
[0699] NMR(CDCl.sub.3) .delta.: 2.49(3H,s), 3.17(3H,s),
5.92(1H,brs), 6.44(1H,d,J=8.5 Hz), 7.24(1H,dd,J=8.5& 2.6 Hz),
7.37(2H,d,J=8.4 Hz), 7.44(1H,br), 7.61(2H,d,J=8.4 Hz),
7.84(1H,d,J=2.6 Hz).
Example 21
[0700] Synthesis of
4'-Chloro-2'-cyano-N-methyl-p-toluenesulfonanilide
[0701] (Compound No.94)
[0702] To a solution of
4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonani- lide (0.70 g
(2.07 mmol)) in pyridine (3.0 ml), under cooling with ice and with
stirring, trifluoroacetic anhydride (0.40 ml (2.83 mmol)) was added
dropwise. The temperature of the reaction mixture was brought to
room temperature and the mixture was stirred at the same
temperature for 2 hours. Then, the mixture was poured into water
and extracted with ethyl acetate. The extract was washed with
dilute hydrochloric acid, water and saturated sodium chloride
solution, successively, dried over anhydrous magnesium sulfate and
concentrated under reduced pressure. Diisopropyl ether was added to
the residue and crystals separated was filtered and washed to give
0.63 g (95%) of the title compound as white crystals.
[0703] mp: 145.0-147.0.degree. C.
[0704] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 3.22(3H,s),
7.24(1H,d,J=8.7 Hz), 7.33(2H,d,J=8.3 Hz), 7.54(1H,dd,J=8.7 &
2.5 Hz), 7.63(1H,d,J=2.5 Hz), 7.64(2H,d,J=8.3 Hz).
Example 22
[0705] Synthesis of
[0706]
4'-Chloro-N-methyl-2'-thiocarbamoyl-p-toluenesulfonanilide
[0707] (Compound No. 83)
[0708] 4'-Chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide (1.05
g (3.10mmol)) and 95% Lawsone reagent
(2,4-bis(4-methoxyphenyl)-1,3-dithia--
2,4-diphosphetane-2,4-disulfide) (1.70 g (3.99 mmol)) were heated
in 1,4-dioxane (10.0 ml) at 100.degree. C. for one hour with
stirring. The reaction mixture was then concentrated under reduced
pressure and the residue was subjected to silica gel column
chromatography with chloroform as eluent to give 0.51 g (46%) of
the title compound as pale yellow crystals.
[0709] mp: 180.5-182.5.degree. C.
[0710] NMR(CDCl.sub.3) .delta.: 2.50(3H,s), 3.17(3H,s),
6.34(1H,d,J=8.5 Hz), 7.16(1H,dd,J=8.5 & 2.5 Hz),
7.38(2H,d,J=8.3 Hz), 7.64(2H,d,J=8.3 Hz), 7.74(1H,d,J=2.5 Hz),
8.04(1H,brs), 8.68(1H,brs).
Example 23
[0711] Synthesis of
[0712]
4'-Chloro-N-methyl-2'-methanesulfinyl-p-toluenesulfonanilide
[0713] (Compound No. 63)
[0714] To a suspension of
4'-chloro-N-methyl-2'-methylthio-p-toluenesulfon- anilide (0.35 g
(1.02 mmol)) in acetic acid (2.0 ml), 30% hydrogen peroxide water
(0.12 g (1.06 mmol)) was added dropwise with stirring at room
temperature. The mixture was stirred at 50.degree. C. for 15
minutes to get a homogeneous solution, and then stirring was
continued at room temperature for 18 hours. Then, the resulting
solution was dissolved in ethyl acetate, washed with aqueous sodium
hydroxide solution, and water, dried over anhydrous magnesium
sulfate and concentrated under reduced pressure to give a crude
crystals. Diisopropyl ether was added to these crystals. The
crystals were filtered and washed to give 0.27 g (74%) of the title
compound as white crystals.
[0715] mp: 142.0-143.5.degree. C.
[0716] NMR(CDCl.sub.3) .delta.: 2.49(3H,s), 2.98(3H,s), 3.12(3H,s),
6.59(1H,d,J=8.5 Hz), 7.33(1H,dd,J=8.5 & 2.3 Hz),
7.37(2H,d,J=8.3 Hz),7.60(2H,d,J=8.3 Hz),8.06(1H,d,J=2.3 Hz).
Example 24
[0717] Synthesis of
4'-Fluoro-N-methyl-2'-nitro-p-toluenesulfonanilide
[0718] (Compound No.262)
[0719] (1) To a suspension of sodium hydride (60%, 0.31 g (7.75
mmol)) in DMF (10.0 ml), 4'-fluoro-p-toluenesulfonanilide (2.00 g
(7.54 mmol)) was added with stirring at room temperature. To the
mixture, after 15 minutes' stirring at room temperature, dimethyl
sulfate (0.75 ml (7.93 mmol)) was added dropwise and stirring was
continued at room temperature for another one hour. Then, the
reaction mixture was poured into water, extracted with ethyl
acetate. The extract was washed with water, saturated sodium
chloride solution successively, dried over anhydrous magnesium
sulfate and concentrated under reduced pressure. Diisopropyl ether
was added to the residue and the crystals separated were filtered
and washed to 1.96 g (93%) of
4'-fluoro-N-methyl-p-toluenesulfonanilide as pale yellowish gray
crystals.
[0720] mp: 92.0-94.5.degree. C.
[0721] NMR(CDCl.sub.3) .delta.: 2.43(3H,s), 3.14(3H,s),
6.90-7.15(4H,m), 7.25(2H,dt,J=8.3 & 0.6 Hz), 7.43(2H,dt,J=8.3
& 1.8 Hz).
[0722] (2) 4'-Fluoro-N-methyl-p-toluenesulfonanilide (1.00 g (3.58
mmol) was dissolved in 5.0 ml of acetic acid. To this, was added
with stirring at room temperature, 97% fuming nitric acid (0.35 ml
(8.19 mmol)) dropwise, and the mixture was stirred at 100.degree.
C. for one hour, poured into water and extracted with ethyl
acetate. The extract was washed with saturated aqueous solution of
sodium bicarbonate, dried over anhydrous magnesium sulfate and
concentrated under reduced pressure to give crude crystals. Diethyl
ether was added to these crystals. The crystals were filtered and
washed to give 0.81 g (70%) of the title compound as yellow
crystals.
[0723] mp: 93.5-94.5.degree. C.
[0724] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.25(3H,s),
7.11(1H,dd,J=8.8 Hz,J.sub.HF=4.9 Hz), 7.15-7.40(3H,m),
7.50-7.65(3H,m).
Example 25
[0725] Synthesis of
[0726]
N-(2-Bromoethyl)-4'-chloro-2'-nitro-p-toluenesulfonanilide
[0727] (Compound No. 305)
[0728] To a suspension of sodium hydride (60%, 0.20 g (5.00 mmol))
in DMF (7.0 ml), 4'-chloro-2'-nitro-p-toluenesulfonanilide (1.20 g
(3.67 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
1,2-dibromoethane (2.00 ml (23.2 mmol)) was added and the mixture
was heated at 130.degree. C. for one hour with stirring. The
reaction mixture was cooled to room temperature, poured into water
and extracted with diethyl ether. The extract was washed with 1%
aqueous sodium hydroxide solution, a saturated sodium chloride
solution successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure to make the residue
crystalline. Hexane was added to the crystals and the crystals were
collected while washing to give 1.12 g (70%) of the title compound
as pale yellow crystals.
[0729] mp: 70.0-72.0.degree. C.
[0730] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 3.61(2H,t,J=8.1 Hz),
3.97(2H,t,J=8.1 Hz), 7.15(1H,d,J=8.6 Hz), 7.28(2H,d,J=8.4 Hz),
7.50(2H,d,J=8.4 Hz), 7.54(1H,dd,J=8.6 & 2.5 Hz),
7.89(1H,d,J=2.5 Hz).
Example 26
[0731] Synthesis of
4'-Chloro-N-(2-methylthioethyl)-2'-nitro-p-toluenesulf-
onanilide
[0732] (Compound No.307)
[0733]
N-(2-Bromoethyl)-4'-chloro-2'-nitro-p-toluenesulfonanilide(0.30 g
(0.69 mmol) was dissolved in 3.0 ml of acetonitrile. To this, 15%
aqueous methylmercaptane sodium salt solution (0.50 g (1.07 mmol))
was added dropwise with stirring at room temperature. The mixture
was stirred at room temperature for 15 hours and concentrated under
reduced pressure. Water was added to the residue and the resulting
mixture was extracted with ethyl acetate. The extract was washed
with water and saturated sodium chloride solution, dried over
anhydrous magnesium sulfate and concentrated under reduced
pressure. Diisopropyl ether was added to the residue to bring about
separation of crystals. These crystals were filtered and washed to
give 0.22 g (79%) of the title compound as pale yellow
crystals.
[0734] mp: 94.5-95.5.degree. C.
[0735] NMR(CDCl.sub.3) .delta.: 2.09(3H,s), 2.44(3H,s),
2.77(2H,dd,J=7.9 & 5.9 Hz), 3.78(2H,dd,J=7.9 & 7.5 Hz),
7.13(1H,d,J=8.6 Hz), 7.28(2H,d,J=8.3 Hz), 7.51(2H,d,J=8.3 Hz),
7.52(1H,dd,J=8.6 & 2.5 Hz), 7.87(1H,d,J=2.5 Hz).
Example 27
[0736] Synthesis of
4'-Chloro-2'-nitro-N-vinyl-p-toluenesulfonanilide
[0737] (Compound No. 298)
[0738] To a suspension of sodium hydride (60%, 0.04 g (1.00 mmol))
in DMF (5.0 ml), 1,2,4-triazole (0.08 g (1.16 mmol)) was added with
stirring at room temperature. To the resulting mixture, after 15
minutes' stirring at room temperature,
N-(2-bromoethyl)-4'-chloro-2'-nitro-p-toluenesulfonanil- ide (0.35
g (0.81 mmol)) was added and the mixture was stirred at room
temperature for 18 hours. The reaction mixture was poured into
water and extracted with ethyl acetate. The extract was washed with
water and saturated sodium chloride solution, dried over anhydrous
magnesium sulfate, and then concentrated under reduced pressure.
The residue was subjected to silica gel column chromatography with
ethyl acetate-hexane (1:3) as eluent, to give 0.052 g (18%) of the
title compound as pale yellow crystals.
[0739] mp: >108.0.degree. C. (dec.)
[0740] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.88(1H,dd,J=15.5 &
1.7 Hz), 4.40(1H,dd,J=8.9 & 1.7 Hz), 6.96(1H,d,J=8.5 Hz),
7.12(1H,dd,J=15.5 & 8.9 Hz), 7.30(2H,d,J=8.3 Hz),
7.54(1H,dd,J=8.5 & 2.4 Hz), 7.57(2H,d,J=8.3 Hz),
7.99(1H,d,J=2.4 Hz).
Example 28
[0741] Synthesis of
[0742]
4'-Methoxymethoxy-N-methyl-2'-nitro-p-toluenesulfonanilide
[0743] (Compound No. 219)
[0744] (1) To a suspension of sodium hydride (60%, 2.70 g (67.5
mmol)) in THF (100.0 ml), under cooling with ice and with stirring,
4-amino-3-nitrophenol (10.0 g (64.9 mmol)) was added. To the
resulting mixture, after 10 minutes' stirring under cooling with
ice, chloromethyl methyl ether (5.50 g (68.3 mmol)) was added
dropwise and the mixture was stirred at 5.degree. C. for one hour
and at room temperature for one hour, and then concentrated under
reduced pressure. The residue was dissolved in ethyl acetate,
washed with water and saturated aqueous solution of sodium
bicarbonate successively, dried over anhydrous magnesium sulfate,
and then concentrated under reduced pressure. Then the residue was
subjected to silica gel column chromatography with
chloroform-ethanol (100:1) as eluent to give 7.69 g (60%) of
4-methoxymethoxy-2-nitroaniline as red oil.
[0745] NMR(CDCl.sub.3) .delta.: 3.48(3H,s), 5.12(2H,s),
5.92(2H,brs), 6.77(1H,d,J=9.0 Hz), 7.15(1H,dd,J=9.0 & 2.9 Hz),
7.78(1H,d,J=2.9 Hz).
[0746] (2) 4-Methoxymethoxy-2-nitroaniline (7.69 g (38.8 mmol)) was
dissolved in 19.0 ml of pyridine. To this, p-toluenesulfonyl
chloride (8.14 g (42.7 mmol)) was added with stirring at room
temperature and the mixture was stirred at room temperature for 18
hours. Then, water (200.0 ml) was added to the reaction mixture,
and the resulting mixture was extracted with chloroform. The
extract was washed with water, dried over anhydrous magnesium
sulfate, and concentrated under reduced pressure. The residue was
then subjected to silica gel column chromatography with
chloroform-ethanol (100:1) as eluent, to give 9.46 g (63%) of
4'-methoxymethoxy-2'-nitro-p-toluenesulfonanilide as a yellow
oil.
[0747] NMR(CDCl.sub.3) .delta.: 2.38(3H,s), 3.46(3H,s), 5.16(2H,s),
7.23(2H,d,J=8.4 Hz), 7.29(1H,dd,J=9.1 Hz & 2.7 Hz),
7.64(2H,dt,J=8.4 & 2.0 Hz), 7.70(1H,d,J=2.7 Hz),
7.79(1H,d,J=9.1 Hz), 9.34(1H,brs).
[0748] (3) To a suspension of sodium hydride (60%, 0.40 g (10.0
mmol)) in 15.0 ml of DMF,
4'-methoxymethoxy-2'-nitro-p-toluenesulfonanilide (3.00 g (8.51
mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate (1.0 ml (10.6 mmol)) was added and the mixture was
stirred for 15 hours at room temperature. The reaction mixture was
poured into water and extracted with ethyl acetate. The extract was
washed with water and dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure. The residue was then
subjected to silica gel column chromatography with ethyl
acetate-hexane (1:2) to give 2.91 g (93%) of the title compound as
yellow crystals.
[0749] mp: 110.5-112.0.degree. C.
[0750] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 3.24(3H,s), 3.49(3H,s),
5.21(2H,s), 7.01(1H,d,J=8.8 Hz), 7.15(1H,dd,J=8.8 & 2.8 Hz),
7.29(2H,d,J=8.3 Hz), 7.50(1H,d,J=2.8 Hz), 7.57(2H,d,J=8.3 Hz).
Example 29
[0751] Synthesis
of4'-Hydroxy-N-methyl-2'-nitro-p-toluenesulfonanilide
[0752] (Compound No. 156)
[0753] 4'-Methoxymethoxy-N-methyl-2'-nitro-p-toluenesulfonanilide
(2.70 g (7.37 mmol) was suspended in 20.0 ml of methanol. To this,
35% hydrochloric acid (5.0 ml) was added with stirring at room
temperature. The mixture was stirred at room temperature for 15
hours and then concentrated under reduced pressure. Diethyl ether
was added to the residual solid. The solid was filtered and washed
to give 2.30 g (97%) of the title compound as pale red
crystals.
[0754] mp: 173.0-174.0.degree. C.
[0755] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.22(3H,s),
6.37(1H,brs), 6.90-7.05(2H,m), 7.25(1H,d,J=2.3 Hz), 7.31(2H,d,J=8.4
Hz), 7.59(2H,d,J=8.4 Hz).
Example 30
[0756] Synthesis of
[0757] N-Methyl-2'-nitro-4'-(n-propoxy)-p-toluenesulfonanilide
[0758] (Compound No. 216)
[0759] To a suspension of sodium hydride (60%, 0.05 g (1.25 mmol))
in 1.0 ml of DMF,
4'-hydroxy-N-methyl-2'-nitro-p-toluenesulfonanilide (0.32 g (0.99
mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
n-propyl bromide (0.20 g (2.20 mmol)) was added dropwise and the
mixture was stirred at room temperature for 15 hours. The reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with water and saturated sodium chloride
solution, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. Diisopropyl ether was added to
the residue and crystals separated were filtered and washed to give
0.15 g (42%) of the title compound as pale yellow crystals.
[0760] mp: 93.0-94.0.degree. C.
[0761] NMR(CDCl.sub.3) .delta.: 1.05(3H,t,J=7.3 Hz),
1.83(2H,tq,J=6.5 & 7.3 Hz), 2.44(3H,s), 3.24(3H,s),
3.96(2H,t,J=6.5 Hz), 6.90-7.10(2H,m), 7.20-7.35(3H,m),
7.56(2H,d,J=8.3 Hz).
Example 31
[0762] Synthesis of
4'-Bromo-N-methyl-2'-nitro-p-toluenesulfonanilide
[0763] (Compound No. 398)
[0764] (1) To a suspension of sodium hydride (60%, 0.18 g (4.50
mmol)) in 5.0 ml of DMF, 4'-bromo-p-toluenesulfonanilide (1.30 g
(3.99 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate (0.40 g (4.23 mmol)) was added dropwise and the
mixture was stirred at room temperature for 24 hours. The reaction
mixture was then poured into water and extracted with ethyl
acetate. The extract was washed with water, dried over anhydrous
magnesium sulfate, and then concentrated under reduced pressure to
make the residue crystalline. The crystals were collected by
filtration, while washing them with diisopropyl ether, giving 1.17
g (86%) of the title compound as white crystals.
[0765] mp: 82.5-83.5.degree. C.
[0766] NMR(CDCl.sub.3) .delta.: 2.42(3H,s), 3.13(3H,s),
6.98(2H,d,J=8.9 Hz), 7.25(2H,d,J=8.4 Hz), 7.42(2H,d,J=8.9 Hz),
7.42(2H,d,J=8.4 Hz).
[0767] (2) 4'-Bromo-N-methyl-p-toluenesulfonanilide (0.90 g (2.65
mmol)) was dissolved in 5.0 ml of acetic acid. To this, 97% fuming
nitric acid (0.64 ml (15.0 mmol)) was added dropwise, and the
mixture was heated at 100.degree. C. for 1.5 hours with stirring,
followed by cooling to room temperature. Then, the reaction mixture
was poured into water and extracted with ethyl acetate. The extract
was washed with saturated aqueous solution of sodium bicarbonate,
dried over anhydrous magnesium sulfate, and concentrated under
reduced pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:3) as eluent, to give
0.64 g (63%) of the title compound as pale yellow crystals.
[0768] mp: 108.0-110.5.degree. C.
[0769] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.24(3H,s),
7.00(1H,d,J=8.5 Hz), 7.31(2H,d,J=8.4 Hz), 7.56(2H,d,J=8.4 Hz),
7.65(1H,dd,J=8.5 & 2.3 Hz), 7.99(1H,d,J=2.3 Hz).
Example 32
[0770] Synthesis of
[0771]
4'-Chloro-N-ethyl-2'-methoxycarbonyl-p-toluenesulfnanilide
[0772] (Compound No.76)
[0773] In a manner similar to that in Example 19-(2), but diethyl
sulfate was used instead of dimethyl sulfate and the reaction was
carried out at 80.degree. C. for one hour, the title compound was
obtained as white crystals in a yield of 72%.
[0774] mp: 105.0-107.0.degree. C.
[0775] NMR(CDCl.sub.3) .delta.: 1.15(3H,t,J=7.1 Hz), 2.42(3H,s),
3.67(2H,q,J=7.1 Hz), 3.81(3H,s), 6.86(1H,d,J=8.5 Hz),
7.25(2H,d,J=8.4 Hz), 7.38(1H,dd,J=8.5 & 2.6 Hz),
7.50(2H,d,J=8.4 Hz), 7.84(1H,d,J=2.6 Hz).
Example 33
[0776] Synthesis of
4'-Chloro-N-isopropyl-2'-methoxycarbonyl-p-toluenesulf-
onanilide
[0777] (Compound No. 77)
[0778] In a manner similar to that in Example 19-(2), but isopropyl
iodide was used instead of dimethyl sulfate and the reaction was
carried out at 130.degree. C. for one hour, the title compound was
obtained as white crystals in a yield of 19%.
[0779] mp: 113.5-115.5.degree. C.
[0780] NMR(CDCl.sub.3) .delta.: 1.04(3H,d,J=6.7 Hz),
1.06(3H,d,J=6.7 Hz), 2.42(3H,s), 3.87(3H,s), 4.49(1H,septet,J=6.7
Hz), 6.94(1H,d,J=8.5 Hz), 7.26(2H,d,J=8.4 Hz), 7.41(1H,dd,J=8.5
& 2.6 Hz), 7.60(2H,d,J=8.4 Hz), 7.89(1H,d,J=2.6 Hz).
Example 34
[0781] Synthesis of
5-Chloro-N-ethyl-N-(p-toluenesulfonyl)-anthranilic
[0782] acid (Compound No. 72)
[0783] In a manner similar to that in Example 19-(3), but
4'-chloro-N-ethyl-2'-methoxycarbonyl-p-toluenesulfonanilide was
used instead of
4'-chloro-2'-methoxycarbonyl-N-methyl-p-toluenesulfonanilide, the
title compound was obtained as white crystals in a yield of
68%.
[0784] mp: 163.0-165.0.degree. C.
[0785] NMR(CDCl.sub.3) .delta.: 1.12(3H,t,J=7.2 Hz), 2.44(3H,s),
3.20-3.80(1H,br), 3.50-4.10(1H,br), 4.00-5.20(1H,br),
6.77(1H,d,J=8.6 Hz), 7.30(2H,d,J=8.3 Hz), 7.41(1H,dd,J=8.6 &
2.6 Hz), 7.55(2H,d,J=8.3 Hz), 7.99(1H,d,J=2.6 Hz).
Example 35
[0786] Synthesis of
[0787] 5-Chloro-N-isopropyl-N-(p-toluenesulfonyl)-anthranilic
acid
[0788] (Compound No. 73)
[0789] In a manner similar to that in Example 19-(3), but
4'-chloro-N-isopropyl-2'-methoxycarbonyl-p-toluenesulfonanilide was
used instead of
4'-chloro-2'-methoxycarbonyl-N-methyl-p-toluenesulfonanilide, the
title compound was obtained as white crystals in a yield of
90%.
[0790] mp: 175.0-176.5.degree. C.
[0791] NMR(CDCl.sub.3) .delta.: 1.02(3H,d,J=6.7 Hz),
1.10(3H,d,J=6.7 Hz),2.46(3H,s), 4.67(1H,septet,J=6.7 Hz),
6.61(1H,d,J=8.6 Hz), 7.32(2H,d,J=8.3 Hz), 7.36(1H,dd,J=8.6 &
2.6 Hz), 7.61(2H,d,J=8.3 Hz), 7.91(1H,d,J=2.6 Hz).
Example 36
[0792] Synthesis of
[0793] 4'-Chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide
(Compound
[0794] No. 80)
[0795] 5-Chloro-N-ethyl-N-(p-toluenesulfonyl)anthranilic acid (3.40
g (9.61mmol)), thionyl chloride (5.00 ml (68.5mmol)) and chloroform
(50.0 ml) were mixed and heated at 70.degree. C. for one hour with
stirring. The reaction mixture was left to cool to room
temperature, followed by concentration under reduced pressure, to
give crude crystals of the corresponding acid chloride. The whole
product (acid chloride) was dissolved in 25.0 ml of acetonitrile.
To this, under cooling with ice, a solution made by dissolving 5.00
g (73.4 mmol) of 25% aqueous ammonia in 25.0 ml of acetonitrile was
added dropwise. After 30 minutes' stirring under cooling with ice,
the reaction mixture was concentrated under reduced pressure. Water
was added to the residue to bring about separation of crystals,
which were filtered and washed to give 3.14 g (93%) of the title
compound as white crystals.
[0796] mp: 148.5-150.0.degree. C.
[0797] NMR(CDCl.sub.3) .delta.: 1.05(3H,t,J=7.2 Hz), 2.49(3H,s),
2.90-3.70(1H,br), 3.60-4.40(1H,br), 5.93(1H,brs), 6.37(1H,d,J=8.5
Hz), 7.24(1H,dd,J=8.5 & 2.6 Hz), 7.36(2H,d,J=8.3 Hz),
7.61(2H,d,J=8.3 Hz), 7.63(1H,brs), 7.82(1H,d,J=2.6 Hz).
Example 37
[0798] Synthesis of
[0799]
4'-Chloro-2'-carbamoyl-N-isopropyl-p-toluenesulfonanilide
[0800] (Compound No. 81)
[0801] In a manner similar to that in Example 36, but
5-chloro-N-isopropyl-N-(p-toluenesulfonyl)anthranilic acid was used
instead of 5-chloro-N-ethyl-N-(p-toluenesulfonyl)anthranilic acid,
the title compound was obtained as white crystals in a yield of
94%.
[0802] mp: 177.0-178.5.degree. C.
[0803] NMR(CDCl.sub.3) .delta.: 0.84(3H,d,J=6.7 Hz),
1.14(3H,d,J=6.7 Hz), 2.48(3H,s), 4.65(1H,septet,J=6.7 Hz),
5.87(1H,brs), 6.43(1H,d,J=8.6 Hz), 7.25(1H,dd,J=8.6 & 2.6 Hz),
7.35(2H,d,J=8.3 Hz), 7.67(2H,d,J=8.3 Hz), 7.78(1H,d,J=2.6 Hz),
7.82(1H,brs).
Example 38
[0804] Synthesis of
4'-Chloro-2'-cyano-N-ethyl-p-toluenesulfonanilide
[0805] (Compound No. 95)
[0806] In a manner similar to that in Example 21, but
4'-chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide was used
instead of 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide,
the title compound was obtained as white crystals in a yield of
84%.
[0807] mp: 138.5-140.5.degree. C.
[0808] NMR(CDCl.sub.3) .delta.: 1.10(3H,t,J=7.2 Hz), 2.45(3H,s),
3.64(2H,q,J=7.2 Hz), 7.20(1H,d,J=8.6 Hz), 7.32(2H,d,J=8.4 Hz),
7.55(1H,dd,J=8.6 & 2.5 Hz), 7.60-7.75(3H,m).
Example 39
[0809] Synthesis of
[0810] 4'-Chloro-2'-cyano-N-isopropyl-p-toluenesulfonanilide
(Compound No. 97)
[0811] In a manner similar to that in Example 21, but
4'-chloro-2'-carbamoyl-N-isopropyl-p-toluenesulfonanilide was used
instead of 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide,
the title compound was obtained as white crystals in a yield of
90%.
[0812] mp: 129.5-130.5.degree. C.
[0813] NMR(CDCl.sub.3) .delta.: 1.14(6H,d,J=6.7 Hz), 2.44(3H,s),
4.49(1H,septet,J=6.7 Hz), 7.26(1H,d,J=8.6 Hz), 7.31(2H,d,J=8.5 Hz),
7.57(1H,dd,J=8.6 & 2.5 Hz), 7.68(1H,d,J=2.5 Hz),
7.74(2H,d,J=8.5 Hz).
Example 40
[0814] Synthesis of
[0815]
4'-Chloro-N-ethyl-2'-thiocarbamoyl-p-toluenesulfonanilide
[0816] (Compound No. 84)
[0817] In a manner similar to that in Example 22, but
4'-chloro-2'-carbamoyl-N-ethyl-p-toluenesulfonanilide was used
instead of 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide,
the title compound was obtained as pale yellow crystals in a yield
of 91%.
[0818] mp: 180.0-182.0.degree. C.
[0819] NMR(CDCl.sub.3) .delta.: 1.06(3H,t,J=7.2 Hz), 2.49(3H,s),
3.21(1H,dq,J=7.0 & 7.2 Hz), 3.88(1H,dq,J=7.0 & 7.2 Hz),
6.29(1H,d,J=8.6 Hz), 7.17(1H,dd,J=8.6 & 2.5 Hz),
7.37(2H,d,J=8.4 Hz), 7.63(2H,d,J=8.4 Hz), 7.84(1H,d,J=2.5 Hz),
8.01(1H,brs), 9.04(1H,brs).
Example 41
[0820] Synthesis of
[0821]
4'-Chloro-N-isopropyl-2'-thiocarbamoyl-p-toluenesulfonanilide
[0822] (Compound No. 85)
[0823] In a manner similar to that in Example 22, but
4'-chloro-2'-carbamoyl-N-isopropyl-p-toluenesulfonanilide was used
instead of 4'-chloro-2'-carbamoyl-N-methyl-p-toluenesulfonanilide,
the title compound was obtained as pale yellow crystals in a yield
of 34%.
[0824] mp: 189.0-191.0.degree. C.
[0825] NMR(CDCl.sub.3) .delta.: 0.85(3H,d,J=6.8 Hz),
1.23(3H,d,J=6.8 Hz), 2.48(3H,s), 4.59(1H,septet,J=6.8 Hz),
6.36(1H,d,J=8.6 Hz), 7.19(1H,dd,J=8.6 & 2.6 Hz),
7.35(2H,d,J=8.4 Hz), 7.65(2H,d,J=8.4 Hz), 7.98(1H,d,J=2.6 Hz),
7.99(1H,brs), 9.29(1H,brs).
Example 42
[0826] Synthesis of
2'-Cyano-N-methoxy-4'-nitro-p-toluenesulfonanilide
[0827] (Compound No. 535)
[0828] (1) Methoxylamine (9.00 g (108 mmol) was suspended in
pyridine (30.0 ml). To this, under cooling with ice and with
stirring, p-toluenesulfonyl chloride (19.07 g (100 mmol)) was added
and the mixture was stirred under cooling with ice for 30 minutes
and at room temperature for 2 hours. Water (200.0 ml) was added to
the reaction mixture to bring about separation of crystals. After
30 minutes' stirring, the crystals were filtered and washed to give
20.26 g (99%) of N-methoxy-p-toluenesulf- onamide as white
crystals.
[0829] mp: 116.0-117.0.degree. C.
[0830] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.79(3H,s), 7.14(1H,s),
7.35(2H,d,J=8.3 Hz), 7.84(2H,d,J=8.3 Hz).
[0831] (2) To a suspension of sodium hydride (60%, 0.09 g (2.25
mmol)) in 3.0 ml of DMF, N-methoxy-p-toluenesulfonamide (0.45 g
(2.20 mmol)) was added under cooling with ice and with stirring. To
the resulting mixture, after 15 minutes' stirring under cooling
with ice, 2-chloro-5-nitrobenzonitrile (0.37 g (2.03 mmol)) was
added and the mixture was stirred under cooling with ice for one
hour and at room temperature for 18 hours. The reaction mixture was
then poured into water and extracted with diethyl ether. The
extract was washed twice with water, dried over anhydrous sodium
sulfate, and then concentrated under reduced pressure. The residue
was subjected to silica gel column chromatography with ethyl
acetate-hexane (1:5) as eluent to give 0.48 g (68%) of the title
compound as pale yellow crystals.
[0832] mp: 148.0-149.5.degree. C.
[0833] NMR(CDCl.sub.3) .delta.: 2.48(3H,s), 3.84(3H,s),
7.32(1H,d,J=9.0 Hz), 7.35(2H,d,J=8.3 Hz), 7.62(2H,d,J=8.3 Hz),
8.32(1H,dd,J=9.0 & 2.5 Hz), 8.54(1H,d,J=2.5 Hz).
Example 43
[0834] Synthesis of
2'-Chloro-N-ethoxy-4'-nitro-p-toluenesulfonanilide
[0835] (Compound No. 533)
[0836] (1) In a manner similar to that in Example 42-(1), except
for that ethoxylamine hydrochloride was used instead of
methoxylamine hydrochloride, N-ethoxy-p-toluenesulfonamide was
obtained as white crystals in a yield of 91%.
[0837] mp: 94.0-95.0.degree. C.
[0838] NMR(CDCl.sub.3) .delta.: 1.20(3H,t,J=7.0 Hz), 2.45(3H,s),
4.03(2H,q,J=7.0 Hz), 6.89(1H,s), 7.35(2H,d,J=8.3 Hz),
7.82(2H,d,J=8.3 Hz).
[0839] (2) To a suspension of sodium hydride (60%, 0.18 g (4.50
mmol)) in 6.0 ml of DMF, N-ethoxy-p-toluenesulfonamide (0.90 g
(4.18 mmol)) was added under cooling with ice and with stirring. To
the resulting mixture, after 15 minutes' stirring under cooling
with ice, 3-chloro-4-fluoronitrobenzene (0.70 g (3.99 mmol)) was
added and the mixture was stirred under cooling with ice for one
hour and at room temperature for 18 hours. The reaction mixture was
then poured into water and extracted with diethyl ether. The
extract was washed twice with water, dried over anhydrous magnesium
sulfate, and then concentrated under reduced pressure to give crude
crystals. These crystals were filtered while washing with
diisopropyl ether to give 1.06 g (72%) of the title compound as
pale yellow crystals.
[0840] mp: 133.5-135.0.degree. C.
[0841] NMR(CDCl.sub.3) .delta.: 1.15(3H,t,J=7.0 Hz), 2.49(3H,s),
4.10(2H,q,J=7.0 Hz), 6.89(1H,d,J=8.9 Hz), 7.34(2H,d,J=8.4 Hz),
7.62(2H,d,J=8.4 Hz), 7.95(1H,dd,J=8.9 & 2.5 Hz),
8.35(1H,d,J=2.5 Hz).
Example 44
[0842] Synthesis of
[0843] 2'-Chloro-N-isopropoxy-4'-nitro-p-toluenesulfonanilide
[0844] (Compound No. 534)
[0845] (1) In a manner similar to that in Example 42-(1), except
for that isopropoxylamine hydrochloride was used instead of
methoxylamine hydrochloride, N-isopropoxy-p-toluenesulfonamide was
obtained as pale yellow crystals in a yield of 96%.
[0846] mp: 103.5-104.5.degree. C.
[0847] NMR(CDCl.sub.3) .delta.: 1.18(6H,d,J=6.2 Hz), 2.45(3H,s),
4.24(1H,septet,J=6.2 Hz), 6.75(1H,s), 7.34(2H,d,J=8.3 Hz),
7.81(2H,d,J=8.3 Hz).
[0848] (2) In a manner similar to that in Example 43-(2), except
for that N-isopropoxy-p-toluenesulfonamide was used instead of
N-ethoxy-p-toluenesulfonamide was used to give the title compound
as pale yellow crystals in a yield of 80%.
[0849] mp: 160.5-162.0.degree. C.
[0850] NMR(CDCl.sub.3) .delta.: 1.14(6H,d,J=6.2 Hz), 2.49(3H,s),
4.42(1H,septet,J=6.2 Hz), 6.86(1H,d,J=9.0 Hz), 7.34(2H,d,J=8.3 Hz),
7.59(2H,d,J=8.3 Hz), 7.94(1H,dd,J=9.0 & 2.5 Hz),
8.35(1H,d,J=2.5 Hz).
Example 45
[0851] Synthesis of
2',4-Dichloro-N-methoxy-4'-nitrobenzenesulfonamide
[0852] (Compound No. 526)
[0853] (1) In a manner similar to that in Example 42-(1), but
4-chlorobenzenesulfonyl chloride was used instead of
p-toluenesulfonyl chloride to give
4-chloro-N-methoxybenzenesulfonamide as pale yellow crystals in a
yield of 97%.
[0854] mp: 81.0-82.5.degree. C.
[0855] NMR(CDCl.sub.3) .delta.: 3.81(3H,s), 7.23(1H,s),
7.53(2H,dt,J=8.7 & 2.5 Hz), 7.87(2H,dt,J=8.7 & 2.5 Hz).
[0856] (2) In a manner similar to that in Example 43-(2), except
for that 4-chloro-N-methoxybenzenesulfonamide was used instead of
N-ethoxy-p-toluenesulfonamide to give the title compound as pale
yellow crystals in a yield of 49%.
[0857] NMR(CDCl.sub.3) .delta.: 3.84(3H,s), 6.91(1H,d,J=8.9 Hz),
7.54(2H,d,J=8.5 Hz), 7.70(2H,d,J=8.5 Hz), 8.00(1H,dd,J=8.9 &
2.5 Hz), 8.37(1H,d,J=2.5 Hz).
Example 46
[0858] Synthesis of
2',4'-Dicyano-N-isopropyl-p-toluenesulfonanilide
[0859] (Compound No. 114)
[0860] (1) To a solution of potassium permanganate (47.5 g (0.30
mol) in 500.0 ml of water, 3-methyl-4-nitrobenzoic acid (20.0 g
(0.13 mol) was added and the resulting mixture was stirred at
70.degree. C. overnight. Then, porassium permanganate (24.5 g (0.16
mol) was further added and the mixture was stirred at 70.degree. C.
for another two days. The insolubles were removed by filtrering
while hot, and the filtrate was made, after being cooled, acidic
with concentrated hydrochloric acid to have crystals separated. The
resulting crystals were filtered and washed with water to give 11.9
g (51%) of 4-nitroisophthalic acid as white crystals.
[0861] mp: 256.8-258.5.degree. C.
[0862] NMR(DMSO-d.sub.6) .delta.: 8.07(1H,dd,J=8.3 & 0.3 Hz),
8.27(1H,dd,J=8.3 & 1.9 Hz), 8.34(1H,dd,J=1.9 & 0.3 Hz),
13.80(2H,brs).
[0863] (2) A mixture of 4-nitroisophthalic acid (11.9 g (56.4 mmol)
and thionyl chloride (20.0 ml) was heated at 70.degree. C. for two
days with stirring, and then concentrated under reduced pressure.
The residue was diluted with 30.0 ml of acetonitrile and, to this,
ice-cooled 25% aqueous ammonia (30.0 ml) was added dropwise. The
crystals separated were filtered and washed with water to give 11.9
g (100%) of 4-nitroisophthalamide as white crystals.
[0864] mp: 287.0-289.0.degree. C.
[0865] NMR(DMSO-d.sub.6) .delta.: 7.77(2H,br), 8.00-8.20(3H,m),
8.25(2H,br).
[0866] (3) To a solution of 4-nitroisophthalamide (6.0 g (28.7
mmol) in ethanol (150.0 ml), stannous chloride (20.02 g (86.1 mmol)
was added and the mixture was stirred at 70.degree. C. overnight.
After cooling, the reaction mixture was neutralized with a
saturated aqueous sodium bicarbonate solution, and insolubles
formed were removed by filtration. The filtrate was extracted with
ethyl acetate and the extract was dried over anhydrous magnesium
sulfate and concentrated under reduced pressure to give 2.59 g
(50%) of 4-aminoisophthalamide as pale yellow crystals.
[0867] mp: 177.0-197.5.degree. C.
[0868] NMR(DMSO-d.sub.6) .delta.: 6.68(1H,d,J=8.6 Hz),
6.90-7.30(4H,m), 7.40-7.80(2H,m), 7.65(1H,dd,J=8.6 & 1.9 Hz),
8.11(1H,d,J=1.9 Hz).
[0869] (4) To a solution of 4-aminoisophthalamide (1.00 g (5.58
mmol) in pyridine (10.0 ml), p-toluenesulfonyl chloride (1.06 g
(5.58 mmol) was added with stirring at room temperature. After 3
hours' stirring at room temperature, water was added to the
reaction mixture to separate crystals. The crystals were filtered
and washed with water and ethyl acetate to give 0.94 g (51%) of
2',4'-dicarbamoyl-p-toluenesulfonanilide as white crystals.
[0870] mp: 212.0-215.0.degree. C.
[0871] NMR(DMSO-d.sub.6) .delta.: 2.33(3H,s), 7.35(2H,d,J=8.3 Hz),
7.40(1H,brs), 7.53(1H,d,J=8.6 Hz), 7.70(2H,d,J=8.3 Hz),
7.79(1H,brs), 7.90(1H,dd,J=8.6 & 1.8 Hz), 7.97(1H,brs),
8.26(1H,d,J=1.8 Hz), 8.38(1H,brs), 12.30(1H,s).
[0872] (5) Phosphorus oxychloride (5.00 g) was added to
2',4'-dicarbamoyl-p-toluenesulfonanilide (0.30 g (0.90 mmol), and
the mixture was heated at 50.degree. C. for 4 hours with stirring.
After cooling, addition of water, and stirring brought about
precipitation of an insoluble solid. These crystals were filtered,
washed with water and recrystallized from ethyl acetate-hexane to
give 0.16 g (60%) of 2',4'-dicyano-p-toluenesulfonanilide as pale
brown crystals.
[0873] mp: 200.0-206.0.degree. C.
[0874] NMR(DMSO-d.sub.6) .delta.: 2.38(3H,s), 7.31(1H,d,J=8.7 Hz),
7.41(2H,d,J=8.3 Hz), 7.73(2H,d,J=8.3 Hz), 8.01(1H,dd,J=8.7 &
2.0 Hz), 8.40(1H,d,J=2.0 Hz).
[0875] (6) To a suspension of sodium hydride (65%, 0.12 g (3.30
mmol)) in 6.0 ml of DMF, 2',4'-dicyano-p-toluenesulfonanilide (0.49
g (1.65 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 10 minutes' stirring at room temperature,
isopropyl iodide (0.50 ml (4.94 mmol)) was added and the mixture
was heated at 130.degree. C. for 6 hours with stirring. The
reaction mixture was then cooled to room temperature, poured into
water and extracted with diethyl ether. The extract was washed with
1% aqueous sodium hydroxide solution and with a saturated aqueous
solution of sodium chloride, dried over anhydrous magnesium
sulfate, and concentrated under reduced pressure. The residue was
subjected to silica gel column chromatography with ethyl
acetate-hexane (3:7) as eluent, to give 0.07 g (13%) of the title
compound as white crystals.
[0876] mp: 157.2-157.7.degree. C.
[0877] NMR(CDCl.sub.3) .delta.: 1.16(6H,d,J=6.7 Hz), 2.45(3H,s),
4.48(1H,q,J=6.7 Hz), 7.33(2H,d,J=8.4 Hz), 7.49(1H,d,J=8.3 Hz),
7.74(2H,d,J=8.4 Hz), 7.89(1H,dd,J=8.3 & 2.0 Hz),
8.01(1H,d,J=2.0 Hz).
Example 47
[0878] Synthesis of
2'-Cyano-N-ethyl-4'-nitro-p-toluenesulfonanilide
[0879] (Compound No. 420)
[0880] (1) To a solution of 2-aminobenzonitrile (2.36 g (20.0 mmol
in pyridine (10.0 ml), p-toluenesulfonyl chloride (4.20 g (22.0
mmol) was added with stirring at room temperature. After 15 hours'
stirring at room temperature, water (100 ml) was added to the
reaction mixture and stirring was continued for another 30 minutes.
The crystals separated were filtered, washed with water and
re-dissolved in chloroform. The soluble part in 1% aqueous sodium
hydroxide solution was extracted from the chloroform solution. The
extract was made acidic with hydrochloric acid and re-extracted
with chloroform. The chloroform extract was dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give a
product which then crystallized. The crystals were washed with
diisopropyl ether and filtered to give 4.83 g (89%) of
2'-cyano-p-toluenesulfonanilide as white crystals.
[0881] mp: 134.5-136.5.degree. C.
[0882] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 7.06(1H,brs),
7.10-7.35(3H,m), 7.40-7.60(2H,m), 7.60-7.80(3H,m).
[0883] (2) To a suspension of 2'-cyano-p-toluenesulfonanilide (2.67
g (9.80 mmol) in acetic anhydride (7.0 ml), 97% fuming nitric acid
(0.45 ml (10.5 mmol) was added with stirring at room temperature.
After stirring for one hour at 50.degree. C., crystals began to
separate. Water was added to decompose excess acetic anhydride, and
the crystals were filtered, washed with water, dried in the air and
then, washed with diethyl ether and collected by filtration to give
3.05 g (98%) of 2'-cyano-4'-nitro-p-toluenesulfonanilide as pale
yellow crystals.
[0884] mp: 165.5-167.0.degree. C.
[0885] NMR(CDCl.sub.3) .delta.: 2.43(3H,s), 7.34(2H,d,J=8.4 Hz),
7.62(1H,s), 7.81(2H,d,J=8.4 Hz), 7.80-7.95(1H,m),
8.25-8.45(2H,m).
[0886] (3) To a suspension of sodium hydride (60%, 0.12 g (3.00
mmol)) in 3.0 ml of DMF, 2'-cyano-4'-nitro-p-toluenesulfonanilide
(0.80 g (2.52 mmol)) was added with stirring at room temperature.
To the resulting mixture, after 15 minutes' stirring at room
temperature, diethyl sulfate (0.40 ml (3.05 mmol)) was added
dropwise and the mixture was heated at 80.degree. C. for 2 hours
and at 100.degree. C. for 2 hours with stirring. The reaction
mixture was then cooled to room temperature, poured into water and
extracted with diethyl ether. The extract was washed three times
with 1% aqueous sodium hydroxide solution, dried over anhydrous
magnesium sulfate, and concentrated under reduced pressure. The
residue was subjected to silica gel column chromatography with
ethyl acetate-hexane (1:2) as eluent, to give 0.23 g (26%) of the
title compound as white crystals.
[0887] mp: 135.0-136.5.degree. C.
[0888] NMR(CDCl.sub.3) .delta.: 1.13(3H,t,J=7.2 Hz), 2.46(3H,s),
3.72(2H,q,J=7.2 Hz), 7.34(2H,d,J=8.4 Hz), 7.50(1H,d,J=8.8 Hz),
7.65(2H,d,J=8.4 Hz), 8.43(1H,dd,J=8.8 & 2.2 Hz),
8.54(1H,d,J=2.2 Hz).
Example 48
[0889] Synthesis of
4'-Chloro-N-ethyl-2'-nitro-p-toluenesulfonanilide
[0890] (Compound No. 289)
[0891] (1) To a solution of 4-chloroaniline (98%, 500 g (3.84 mol)
in pyridine (338 ml) and acetonitrile (800 ml), p-toluenesulfonyl
chloride (807.8 g (4.11 mol)) was added with stirring at
temperature below 15.degree. C. After stirring for 16 hours at room
temperature, water (4000 ml) was added to the reaction mixture and
stirring was continued for 3 hours to have crystals separated. The
crystals were then filtered and washed with water to give 1100 g
(102%) of 4'-chloro-p-toluenesulfona- nilide as pale red crude
crystals.
[0892] mp: 122.0-123.0.degree. C.
[0893] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 6.73(1H,brs),
7.00(2H,d,J=8.8 Hz), 7.20(2H,d,J=8.8 Hz), 7.24(2H,d,J=8.3 Hz),
7.64(2H,d,J=8.3 Hz).
[0894] (2) To a suspension of 4'-chloro-p-toluenesulfonanilide
(1100 g (3.90 mol) in acetic acid (2200 ml), fuming nitric acid
(273.9 g (4.22 mol) was added dropwise over a period of 40 minutes
with stirring at 50.degree. C. After completion of the addition,
the reaction mixture was stirred at the same temperature to
complete the reaction. After being left to cool to room
temperature, the reaction mixture was treated with 7000 ml of water
to bring about precipitation of crystals. The crystals were
filtered and washed with water to give 1261 g (99%) of
4'-chloro-2'-nitro-p-toluenesulfonanilide as yellow crystals.
[0895] mp: 110.0-111.0.degree. C.
[0896] NMR(CDCl.sub.3) .delta.: 2.40(3H,s), 7.27(2H,d,J=8.4 Hz),
7.54(1H,dd,J=9.0 & 2.4 Hz), 7.71(2H,d,J=8.4 Hz),
7.83(1H,d,J=9.0 Hz), 8.09(1H,d,J=2.4 Hz), 9.72(1H,s).
[0897] (3) Sodium hydroxide (96%, 164.0 g (3.94 mol)) was dissolved
in a mixed solvent of water (390 ml) and ethanol (1600 ml). To
this, 4'-chloro-2'-nitro-p-toluenesulfonanilide (1261 g (3.86 mol))
was added, while being stirred at temperatures of 10 to 25.degree.
C. After being stirred at room temperature for 4 hours, the
reaction mixture was cooled and crystals formed were filtered and
washed with ethanol to give 1253 g (93%) of
4'-chloro-2'-nitro-p-toluenesulfonanilide sodium salt as orange
crystals.
[0898] mp: 267.0-284.0.degree. C.
[0899] NMR(DMSO-d.sub.6) .delta.: 2.29(3H,s), 7.06(1H,dd,J=9.1
& 2.7 Hz), 7.17(2H,d,J=8.3 Hz), 7.25(1H,d,J=9.1 Hz),
7.42(1H,d,J=2.7 Hz), 7.59(2H,d,J=8.3 Hz).
[0900] (4) To a mixture of
4'-chloro-2'-nitro-p-toluenesulfonanilide sodium salt (1046 g (3.00
mol)) and DMF (1100 ml), heated in an oil bath kept at 100.degree.
C., was added diethyl sulfate (733.8 g (4.50 mol)) over a period of
one hour. The resulting mixture was further stirred for 1.5 hours
at the same temperature to complete the reaction, and then left to
cool to room temperature. A 1.5% aqueous sodium hydroxide solution
was added and the mixture was stirred for one hour. The resulting
solid was then filtered, washed with water, dried and
recrystallized from 1450 ml of ethyl acetate to give 858 g (81%) of
the title compound as pale yellow crystals.
[0901] mp: 132.5-134.0.degree. C.
[0902] NMR(CDCl.sub.3) .delta.: 1.18(3H,t,J=7.2 Hz), 2.44(3H,s),
3.66(2H,q,J=7.2 Hz), 7.05(1H,d,J=8.6 Hz), 7.28(2H,d,J=8.2 Hz),
7.50(1H,dd,J=8.6 & 2.5 Hz), 7.53(2H,d,J=8.2 Hz),
7.86(1H,d,J=2.5 Hz).
Example 49
[0903] Synthesis of
[0904] 4'-Chloro-N-isopropyl-2'-nitro-p-toluenesulfonanilide
(Compound No. 291)
[0905] In a manner similar to that of Example48-(4), but isopropyl
iodide was used instead of diethyl sulfate, and the reaction was
carried out by heating for three hours in an oil bath kept at the
temperature of 120.degree. C. to give the title compound as pale
yellow crystals in a yield of 48%.
[0906] Mp: 112.0-114.0.degree. C.
[0907] NMR(CDCl.sub.3) .delta.: 1.06(3H,d,J=6.7 Hz),
1.13(3H,d,J=6.7 Hz), 2.44(3H,s), 4.38(1H,septet,J=6.7 Hz),
7.22(1H,d,J=8.5 Hz), 7.29(2H,d,J=8.4 Hz), 7.54(1H,dd,J=8.5 &
2.5 Hz), 7.66(2H,d,J=8.4 Hz), 7.88(1H,d,J=2.5 Hz).
Example 50
[0908] Synthesis of
[0909] 4'-Fluoro-N-isopropyl-2'-nitro-p-toluenesulfonanilide
(Compound No. 265)
[0910] (1) To a solution of 4-fluoroaniline (200.0 g (1.80 mol) in
pyridine (155.0 g (1.96 mol)) and acetonitrile (155 ml), under
cooling with ice and with stirring, p-toluenesulfonyl chloride
(360.3 g (1.89 mol)) was added. After stirring for 20 hours at room
temperature, water (1500 ml) was added to the reaction mixture to
bring about separation of crystals. The crystals were filtered and
washed with water to give 486.6 g (102%) of
4'-fluoro-p-toluenesulfonanilide as pale red crude crystals.
[0911] mp : 78.0-79.5.degree. C.
[0912] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 6.61(1H,brs),
6.85-7.10(4H,m), 7.23(2H,dt,J=8.3 & 0.6 Hz), 7.60(2H,dt,J=8.3
& 1.8 Hz). (2) To a suspension of
4'-fluoro-p-toluenesulfonanilide (486.6 g (1.80 mol) in acetic acid
(955 ml), 97% fuming nitric acid (128.6 g (1.98 mol) was added
dropwise, keeping the inner temperature at 45.degree. C., over a
period of 40 minutes. After completion of the addition, the
reaction mixture was stirred at 50.degree. C. for 2 hours and left
to cool to room temperature. Water (2000 ml) was then added and the
mixture was stirred for 30 minutes. The crystals separated were
filtered and washed with water to give 543.5 g (97%) of
4'-fluoro-2'-nitro-p-toluenesulfonanilide as yellow crystals.
[0913] mp: 117.5-118.5.degree. C.
[0914] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 7.25(2H,d,J=8.4 Hz),
7.35(1H,ddd,J=9.3 & 3.0 Hz,J.sub.HF=6.9 Hz), 7.66(2H,d,J=8.4
Hz), 7.79(1H,dd,J=3.0 Hz,J.sub.HF=8.2 Hz), 7.89(1H,dd,J=9.3
Hz,J.sub.HF=4.9 Hz), 9.51(1H,s).
[0915] (3) Sodium hydroxide (97%, 12.0 g (291 mmol)) was dissolved
in a mixed solvent of water (24 ml) and methanol (89 ml). To this,
4'-fluoro-2'-nitro-p-toluenesulfonanilide (89.16 g (287 mmol)) was
added with stirring at room temperature. After being stirred at
room temperature for 30 minutes, the mixed suspension obtained was
cooled with ice, and crystals formed were filtered and washed with
methanol to give 79.31 g (83%) of
4'-fluoro-2'-nitro-p-toluenesulfonanilide sodium salt as orange
crystals.
[0916] mp: 276.0-278.0.degree. C.
[0917] NMR(DMSO-d.sub.6) .delta.: 2.29(3H,s), 6.97(1H,ddd,J=9.3
& 3.2 Hz,J.sub.HF=8.3 Hz), 7.16(2H,d,J=8.3 Hz),
7.20-7.40(2H,m), 7.58(2H,d,J=8.3 Hz).
[0918] (4) 4'-Fluoro-2'-nitro-p-toluenesulfonanilide sodium salt
(66.46 g (200 mmol)) was dissolved in DMF (66 ml). To this, under
heating in an oil bath kept at 120.degree. C., isopropyl iodide
(102.0 g (600 mmol)) was added over a period of 20 minutes. The
resulting mixture was left to cool to room temperature, mixed with
1% aqueous sodium hydroxide solution and stirred. The resulting
crystals were filtered, washed with water and ethanol,
successively. The crude crystals thus obtained were recrystallized
from ethyl acetate to give 30.58 g (43%) of the title compound as
pale yellow crystals.
[0919] mp: 129.0-130.degree. C.
[0920] NMR(CDCl.sub.3) .delta.: 1.05(3H,d,J=6.7 Hz),
1.13(3H,d,J=6.7 Hz), 2.44(3H,s), 4.38(1H,septet,J=6.7 Hz),
7.20-7.40(4H,m), 7.55-7.75(3H,m).
Example 51
[0921] Synthesis of
[0922] 4'-Cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide
(Compound No. 409)
[0923] (1) 4-Aminobenzonitrile (98%, 500.0 g (4.15 mol) was
dissolved in a mixed solvent of pyridine (360 ml) and acetonitrile
(900 ml). To this, p-toluenesulfonyl chloride (872.3 g (4.44 mol))
was added with stirring at room temperature. After stirring for 16
hours at room temperature, water (4000 ml) was added to the
reaction mixture to bring about separation of crystals. The
crystals were filtered and washed with water to give 1153 g (98%)
of 4'-cyano-p-toluenesulfonanilide as pale red crude crystals.
[0924] mp: 182.0-184.0.degree. C.
[0925] NMR(CDCl.sub.3) .delta.: 2.40(3H,s), 7.18(2H,dt,J=8.8 &
2.3 Hz), 7.28(2H,d,J=8.4 Hz), 7.52(2H,dt,J=8.8 & 2.0 Hz),
7.59(1H,s), 7.75(2H,dt,J=8.4 & 1.7 Hz).
[0926] (2) To a suspension of 4'-cyano-p-toluenesulfonanilide (1153
g (4.23 mol) in acetic anhydride (2306 ml), fuming nitric acid
(294.3 g (4.53 mol) was added dropwise, keeping the temperature at
50.degree. C. with stirring, over a period of 100 minutes. After
completion of the addition, the reaction mixture was stirred at
50.degree. C. for 1.5 hours. Then, 1.75 ml (0.042 mol) of fuming
nitric acid was further added and stirring was continued for
another one hour at 50.degree. C. To the resulting mixture, after
being left to cool to room temperature, water (7000 ml) was then
added to make crystals to deposite. After stirring under cooling
with ice for one hour, the crystals were filtered and washed with
water to give 1305 g (97%) of 4'-cyano-2'-nitro-p-toluenesulf-
onanilide as yellow crystals.
[0927] mp: 150.0-152.0.degree. C.
[0928] NMR(CDCl.sub.3) .delta.: 2.42(3H,s), 7.33(2H,d,J=8.5 Hz),
7.78(1H,dd,J=8.8 & 2.3 Hz), 7.82(2H,d,J=8.5 Hz),
7.95(1H,d,J=8.8 Hz), 8.46(1H,d,J=2.3 Hz), 10.60(1H,brs).
[0929] (3) Sodium hydroxide (96%, 174.8 g (4.20 mol)) was dissolved
in a mixed solvent of water (420 ml) and methanol (1950 ml). To
this, under cooling with ice and with stirring,
4'-cyano-2'-nitro-p-toluenesulfonanil- ide (1305 g (4.11 mol)) was
added. After stirring at 5 to 12.degree. C. for 75 minutes,
crystals formed were filtered and washed with methanol to give 1330
g (95%) of 4'-cyano-2'-nitro-p-toluenesulfonanilide sodium salt as
yellow crystals.
[0930] mp: higher than 300.degree. C.
[0931] NMR(DMSO-d.sub.6) .delta.: 2.31(3H,s), 7.22(2H,d,J=8.1 Hz),
7.29(1H,d,J=8.9 Hz), 7.39(1H,dd,J=8.9 & 2.0 Hz),
7.61(2H,d,J=8.1 Hz), 7.85(1H,d,J=2.0 Hz).
[0932] (4) To a mixture of 4'-cyano-2'-nitro-p-toluenesulfonanilide
sodium salt (1330 g (3.92 mol)) and DMF (3000 ml), under heating in
an oil bath kept at 110.degree. C., isopropyl iodide (2019 g (11.8
mol)) was added over a period of 1.5 hours. After completion of the
addition, the mixture was further heated at the same temperature
with stirring for 3 hours, and then left to cool to room
temperature. Water (1500 ml) was added to bring about separation of
crystals. The crystals were filtered, washed with water, dried, and
then suspended in diethyl ether. The suspension was stirred for 4
hours, and the insolubles were removed by filtration, the diethyl
ether solution was washed with 0.1% aqueous sodium hydroxide
solution to remove the remaining starting material,
4'-cyano-2'-nitro-p-toluenesulfonanilide. The diethyl ether layer
was dried over anhydrous magnesium sulfate, filtered, and
concentrated under reduced pressure to give crude crystals which
were, after washing with ethanol, recrystallized from ethyl acetate
to give 124 g (8.8%) of the title compound as pale yellow
crystals.
[0933] mp: 125.0-126.0.degree. C.
[0934] NMR(CDCl.sub.3) .delta.: 1.07(3H,d,J=6.7 Hz),
1.15(3H,d,J=6.7 Hz), 2.45(3H,s), 4.40(1H,septet,J=6.7 Hz),
7.31(2H,d,J=8.4 Hz), 7.44(1H,d,J=8.3 Hz), 7.66(2H,d,J=8.4 Hz),
7.86(1H,dd,J=8.3 & 1.9 Hz), 8.19(1H,d,J=1.9 Hz).
Example 52
[0935] Synthesis of N-methyl-2'-nitro-p-toluenesulfonanilide
(Compound No. 38) and N,N-bis(p-toluenesulfonyl)-2'-nitroaniline
(Compound No. 39)
[0936] (1) 2-Nitroaniline (2.15 g (15.6 mmol)) was dissolved in
10.0 ml of pyridine. To this, p-toluenesulfonyl chloride (3.55 g
(18.6 mmol)) was added with stirring at room temperature. After
stirring for 15 hours at room temperature, water (100 ml) was added
to the reaction mixture to bring about separation of crystals. The
crystals were filtered, washed with water, dried and then subjected
to silica gel column chromatography with ethyl acetate-hexane (2:3)
as eluent to give 2.88 g (53%) of 2'-nitro-p-toluenesulfonanilide
as yellow crystals, and 1.17 g (17%) of
N,N-bis(p-toluenesulfonyl)-2'-nitroaniline (Compound No. 39) as
pale yellow crystals.
[0937] Physical Constants of 2'-nitro-p-toluenesulfonanilide
[0938] mp: 115.0-116.5.degree. C.
[0939] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 7.15(1H,dt,J=1.3 &
8.5 Hz), 7.26(2H,d,J=8.3 Hz), 7.58(1H,dt,J=1.5 & 8.5 Hz),
7.73(2H,d,J=8.3 Hz), 7.85(1H,dd,J=8.5 & 1.3 Hz),
8.11(1H,dd,J=8.5 & 1.5 Hz), 9.85(1H,s).
[0940] Physical Constants of Compound No. 39
[0941] mp: 184.5-186.5.degree. C.
[0942] NMR(CDCl.sub.3) .delta.: 2.47(6H,s), 7.15(1H,dd,J=7.6 &
2.0 Hz), 7.33(4H,d,J=8.5 Hz), 7.56(1H,dt,J=2.0 & 7.5 Hz),
7.62(1H,dt,J=1.9 & 7.6 Hz), 7.84(4H,dt,J=8.5 & 1.9 Hz),
8.02(1H,dd,J=7.5 & 1.9 Hz).
[0943] (2) To a suspension of sodium hydride (60%, 0.15 g (3.75
mmol)) in 3.0 ml of DMF, 2'-nitro-p-toluenesulfonanilide (1.00 g
(3.42 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 15 minutes' stirring at room temperature,
dimethyl sulfate (0.4 ml (4.22 mmol)) was added dropwise. After 2
hour's stirring, water was added to bring about separation of
crystals. The resulting crystals were filtered, washed with water,
dried and subjected to silica gel column chromatography with ethyl
acetate-hexane (1:2 to 1:1) as eluent to give 0.93 g (89%) of
N-methyl-2'-nitro-p-toluenesulfonanilide (Compound No. 38) as pale
yellow crystals.
[0944] mp: 131.5-132.5.degree. C.
[0945] NMR(CDCl.sub.3) .delta.: 2.44(3H,s), 3.26(3H,s),
7.11(1H,dd,J=7.1 & 2.2 Hz), 7.29(2H,d,J=8.5 Hz),
7.40-7.60(2H,m), 7.55(2H,d,J=8.5 Hz), 7.85(1H,dd,J=7.5 & 2.3
Hz).
Example 53
[0946] Synthesis of
2'-Chloro-N-ethyl-4'nitro-p-toluenesulfonanilide
[0947] (Compound No. 275)
[0948] (1) 2-Chloro-4-nitroaniline (1.73 g (10.0 mmol)) was
dissolved in 5.0 ml of pyridine. To this, p-toluenesulfonyl
chloride (1.91 g (10.0 mmol)) was added with stirring at room
temperature. After stirring for 18 hours at room temperature, water
(50 ml) was added to the reaction mixture to bring about separation
of crystals. The crystals were filtered, washed with water and then
dissolved in an aqueous solution of sodium hydroxide. The resulting
solution was washed with diethyl ether, and the water layer was
made acidic again with hydrochloric acid and extracted with ethyl
acetate. The extract was dried over anhydrous magnesium sulfate and
concentrated under reduced pressure to give 2.61 g (80%) of
2'-chloro-4'-nitro-p-toluenesulfonanilide as pale yellow
crystals.
[0949] mp: 167.0-168.5.degree. C.
[0950] NMR(CDCl.sub.3) .delta.: 2.41(3H,s), 7.30(2H,d,J=8.4 Hz),
7.41(1H,s), 7.77(1H,d,J=9.0 Hz), 7.77(2H,d,J=8.4 Hz),
8.09(1H,dd,J=9.0 & 2.5 Hz), 8.21(1H,d,J=2.5 Hz).
[0951] (2) To a suspension of sodium hydride (60%, 0.07 g (1.75
mmol)) in 3.0 ml of DMF, 2'-chloro-4'-nitro-p-toluenesulfonanilide
(0.50 g (1.53 mmol)) was added under cooling with ice and with
stirring. To the resulting mixture, after 15 minutes' stirring
under cooling with ice, dimethyl sulfate (0.23 ml (1.76 mmol)) was
added dropwise and the mixture heated at 100.degree. C. for 2 hours
with stirring. Then, after being left to cool to room temperature,
water was added and the mixture was extracted with diethyl ether.
The extract was washed with water and 1% aqueous solution of sodium
hydroxide, dried over anhydrous magnesium sulfate, filtered and
concentrated under reduced pressure. The residue was purified by
subjecting it to silica gel column chromatography with ethyl
acetate-hexane (1:3) as eluent and the crystals obtained were
recrystallized from ethyl acetate to give 0.31 g (57%) of the title
compound as pale yellow crystals.
[0952] mp: 118.0-119.0.degree. C.
[0953] NMR(CDCl.sub.3) .delta.: 1.10(3H,t,J=7.2 Hz), 2.45(3H,s),
3.67(2H,q,J=7.2 Hz), 7.30(2H,d,J=8.3 Hz), 7.39(1H,d,J=8.7 Hz),
7.64(2H,d,J=8.3 Hz), 8.11(1H,dd,J=8.7 & 2.6 Hz),
8.31(1H,d,J=2.6 Hz).
Example 54
[0954] Synthesis of
[0955] 2'-Chloro-N-isopropyl-4'nitro-p-toluenesulfonanilide
(Compound No. 272)
[0956] In a manner similar to that of Example 53-(2), but isopropyl
iodide was used instead of dimethyl sulfate, and the reaction was
carried out by heating at 130.degree. C. for 2 hours, to give the
title compound as pale yellow crystals in a yield of 24%.
[0957] mp: 154.0-157.0.degree. C.
[0958] NMR(CDCl.sub.3) .delta.: 1.09(3H,d,J=6.7 Hz),
1.14(3H,d,J=6.7 Hz), 2.45(3H,s), 4.46(1H,septet,J=6.7 Hz),
7.31(2H,d,J=8.4 Hz), 7.33(1H,d,J=8.7 Hz), 7.69(2H,d,J=8.4 Hz),
8.11(1H,dd,J=8.7 & 2.6 Hz), 8.38(1H,d,J=2.6 Hz).
Example 55
[0959] Synthesis of
2'-Chloro-4'-cyano-N-ethyl-p-toluenesulfonanilide
[0960] (Compound No. 92)
[0961] (1) 4-Amino-3-chlorobenzonitrile (1.50 g (9.83mmol))was
dissolved in 5.0 ml of pyridine. To this, p-toluenesulfonyl
chloride (1.90 g (9.97 mmol)) was added under cooling with ice and
with stirring. After stirring for 18 hours at room temperature,
water (100 ml) was added to the reaction mixture to bring about
separation of crystals. The crystals were filtered, washed with
water and then dissolved in an aqueous solution of sodium
hydroxide. The resulting solution was washed with diethyl ether,
and the water layer was made acidic again with hydrochloric acid
and extracted with chloroform. The extract was dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give
1.65 g (55%) of 2'-chloro-4'-cyano-p-toluenesulfonanilide as white
crystals.
[0962] mp: 186.0-187.0.degree. C.
[0963] NMR(CDCl.sub.3) .delta.: 2.41(3H,s), 7.20-7.40(1H,br),
7.29(2H,d,J=8.4 Hz), 7.49(1H,dd,J=8.7 & 1.7 Hz),
7.58(1H,d,J=1.7 Hz), 7.72(1H,d,J=8.7 Hz), 7.75(2H,d,J=8.4 Hz).
[0964] (2) To a suspension of sodium hydride (60%, 0.07 g (1.75
mmol)) in 3.0 ml of DMF, 2'-chloro-4'-cyano-p-toluenesulfonanilide
(0.50 g (1.63 mmol)) was added under cooling with ice and with
stirring. To the resulting mixture, after 15 minutes' stirring
under cooling with ice, diethyl sulfate (0.25 ml (1.91 mmol)) was
added dropwise and the mixture heated at 100.degree.C. for 2 hours
with stirring. Then, after being left to cool to room temperature,
water was added and the mixture was extracted with diethyl ether.
The extract was washed with water and 1% aqueous solution of sodium
hydroxide, dried over anhydrous magnesium sulfate, filtered and
concentrated under reduced pressure. The resulting crystals were
recrystallized from diethyl ether to give 0.33 g (61%) of the title
compound as white crystals.
[0965] mp:112.0-114.0.degree. C.
[0966] NMR(CDCl.sub.3) .delta.: 1.08(3H,t,J=7.1 Hz), 2.44(3H,s),
3.64(2H,q,J=7.1 Hz), 7.29(2H,d,J=8.4 Hz), 7.31(1H,d,J=8.3 Hz),
7.55(1H,dd,J=8.3 & 1.9 Hz), 7.63(2H,d,J=8.4 Hz),
7.73(1H,d,J=1.9 Hz).
Example 56
[0967] Synthesis of
[0968] 2'-Chloro-4'-cyano-N-isopropyl-p-toluenesulfonanilide
(Compound No. 93)
[0969] In a manner similar to that of Example 55-(2), but isopropyl
iodide was used instead of diethyl sulfate, and the reaction was
carried out by heating at 130.degree. C. for 2 hours, to give the
title compound as pale yellow crystals in a yield of 19%.
[0970] mp: 118.0-119.0.degree. C.
[0971] NMR(CDCl.sub.3) .delta.: 1.06(3H,d,J=6.7 Hz),
1.12(3H,d,J=6.7 Hz), 2.45(3H,s), 4.45(1H,septet,J=6.7 Hz),
7.26(1H,d,J=8.3 Hz), 7.30(2H,d,J=8.4 Hz), 7.56(1H,dd,J=8.3 &
1.9 Hz), 7.68(2H,d,J=8.4 Hz), 7.81(1H,d,J=1.9 Hz).
Example 57
[0972] Synthesis of Methyl
[0973] 5-chloro-2-(N-ethyl-N-p-toluenesulfonyl)aminobenzthioimidate
hydroiodic acid salt (Compound No. 87)
[0974] A mixture of
4'-chloro-N-ethyl-2'-thiocarbamoyl-p-toluenesulfonanil- ide (0.30 g
(0.81 mmol)), methyl iodide (1.0 ml (16.1 mmol)) and chloroform
(3.0 ml) was heated under reflux for 5 hours. After being left to
cool to room temperature, the reaction mixture was concentrated
under reduced pressure to give crude crystals. Diethyl ether was
added to the crystals and stirred, and then the crystals were
filtered and washed with diethyl ether to give 0.41 g (99%) of the
title compound as pale yellow crystals.
[0975] mp: >160.degree. C. (dec.)
[0976] NMR(CDCl.sub.3) .delta.: 1.03(3H,t,J=7.2 Hz), 2.47(3H,s),
3.30(3H,s), 3.00-3.50(1H,br), 3.50-4.10(1H,br), 6.72(1H,d,J=8.6
Hz), 7.38(2H,d,J=8.3 Hz), 7.49(1H,dd,J=8.6 & 2.4 Hz),
7.62(2H,d,J=8.3 Hz), 7.82(1H,d,J=2.4 Hz), 10.50-12.50(2H,br).
Example 58
[0977] Synthesis of Ethyl
[0978] 5-chloro-2-(N-ethyl-N-p-toluenesulfonyl)aminobenzthioimidate
hydroiodic acid salt (Compound No. 88)
[0979] In a manner similar to that of Example 57, but ethyl iodide
was used instead of methyl iodide, and the reaction was carried out
by heating under reflux for 6 hours, to give the title compound as
pale yellow crystals in a yield of 94%.
[0980] mp: >161.degree. C. (dec.)
[0981] NMR(CDCl.sub.3) .delta.: 1.03(3H,t,J=7.1 Hz),
1.56(3H,t,J=7.5 Hz), 2.47(3H,s), 2.90-3.50(1H,br),
3.50-4.00(1H,br), 3.93(2H,q,J=7.5 Hz), 6.74(1H,d,J=8.6 Hz),
7.38(2H,q,J=8.4 Hz), 7.49(1H,dd,J=8.6 & 2.4 Hz),
7.63(2H,d,J=8.4 Hz), 7.79(1H,d,J=2.4 Hz), 10.50-12.50(2H,br).
Example 59
[0982] Synthesis of
[0983] N-ethyl-4'-methylthio-2'-nitro-p-toluenesulfonanilide
(Compound No. 227)
[0984] (1) To a solution of 4-Aminophenyl thiocyanate (10.0 g (66.6
mmol)) in pyridine (70 ml), p-toluenesulfonyl chloride (12.7 g
(66.6 mmol)) was added with stirring at room temperature, and the
mixture was stirred at room temperature for 16 hours. Then, water
was added to the reaction mixture and the resulting mixture was
extracted with ethyl acetate. The extract was washed with dilute
hydrochloric acid and a saturated aqueous solution of sodium
chloride, dried over magnesium sulfate, filtered and concentrated
under reduced pressure to give 19.4 g (98%) of
4'-thiocyano-p-toluenesulfonanilide as pale yellow crystals.
[0985] mp: 122.0-123.5.degree. C.
[0986] NMR(CDCl.sub.3) .delta.: 2.40(3H,s), 7.16(2H,dt,J=8.7 &
2.0 Hz), 7.20-7.30(2H,m), 7.37(1H,brs), 7.40(2H,dt,J=8.7 & 2.0
Hz), 7.71(2H,d,J=8.3 Hz).
[0987] (2) 4'-Thiocyano-p-toluenesulfonanilide (19.2 g (63.2 mmol))
was dissolved in acetic acid (60 ml). To this, fuming nitric acid
(3.04 ml (75.9 mmol)) was added dropwise with stirring at room
temperature. Then, the mixture was stirred at 50.degree. C. for 4
hours, poured into water, and the crystals separated were filtered
and washed with water. The resulting crystals were dissolved in
ethyl acetate, and the solution was dried over anhydrous magnesium
sulfate and then concentrated under reduced pressure to give 21.8 g
(99%) of 2'-nitro-4'-thiocyano-p-toluenes- ulfonanilide as pale
yellow crystals.
[0988] mp: 121.0-122.5.degree. C.
[0989] NMR(CDCl.sub.3) .delta.:2.42(3H,s), 7.32(2H,d,J=8.6 Hz),
7.73(1H,dd,J=9.0 & 2.3 Hz), 7.78(2H,d,J=8.6 Hz),
7.95(1H,d,J=9.0 Hz), 8.33(1H,d,J=2.3 Hz).
[0990] (3) To a solution of
2'-Nitro-4'-thiocyano-p-toluenesulfonanilide (5.0 g (14.3 mmol) in
methanol (20 ml), sodium borohydride (2.80 g (66.7 mmol)) was added
under cooling with ice and with stirring. After 30 minutes'
stirring, to the resulting mixture, methyl iodide (3.67 ml (59.0
mmol)) was added dropwise under cooling with ice and the mixture
was then stirred at room temperature for 20 hours. Then, water was
added to the reaction mixture and the resulting mixture was
extracted with ethyl acetate. The extract was washed with a
saturated aqueous solution of sodium chloride, dried over anhydrous
magnesium sulfate, filtered and concentrated. The residue was then
subjected to silica gel column chromatography with ethyl
acetate-hexane (1:4) as eluent. The resulting crystals were
recrystallized from ethyl acetate to give 2.27 g (47%) of
2'-nitro-4'-methylthio-p-toluenesulfonanilide as orange
crystals.
[0991] mp: 116.0-117.0.degree. C.
[0992] NMR(CDCl.sub.3) .delta.: 2.39(3H,s), 2.48(3H,s),
7.25(2H,d,J=8.4 Hz), 7.44(1H,dd,J=8.8 & 2.3 Hz),
7.68(2H,d,J=8.4 Hz), 7.78(1H,d,J=8.8 Hz), 7.88(1H,d,J=2.3 Hz).
[0993] (4) To a suspension of sodium hydride (65%, 0.21 g (5.76
mmol)) in 4.0 ml of DMF,
2'-nitro-4'-methylthio-p-toluenesulfonanilide (1.50 g (4.43 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 30 minutes' stirring at room temperature, ethyl
iodide (0.52 ml (6.21 mmol)) was added dropwise and the mixture was
stirred at room temperature for 16 hours. Then, the reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with a saturated aqueous solution of sodium
bicarbonate, dilute hydrochloric acid, and saturated aqueous
solution of sodium chloride successively. The ethyl acetate layer
was dried over anhydrous magnesium sulfate, filtered and
concentrated under reduced pressure. The resulting residue was then
subjected to silica gel column chromatography with chloroform as
eluent to give 1.04 g (64%) of the title compound as pale yellow
crystals.
[0994] mp: 135.0-136.5.degree. C.
[0995] NMR(CDCl.sub.3) .delta.: 1.18(3H,t,J=7.2 Hz), 2.43(3H,s),
2.53(3H,s), 3.50-3.80(2H,m), 6.96(1H,d,J=8.5 Hz), 7.20-7.40(3H,m),
7.53(2H,d,J=8.3 Hz), 7.62(1H,d,J=2.3 Hz).
Example 60
[0996] Synthesis of
[0997]
N-isopropyl-4'-methylthio-2'-nitro-p-toluenesulfonanilide
[0998] (Compound No. 229)
[0999] In a manner similar to that of Example 59-(4), but isopropyl
iodide was used instead of ethyl iodide, and the reaction was
carried out by heating at 80.degree. C. for 7 hours with stirring,
to give the title compound as pale yellow crystals in a yield of
31%.
[1000] mp: 124.5-126.0.degree. C.
[1001] NMR(CDCl.sub.3) .delta.: 1.05(3H,d,J=6.7 Hz),
1.11(3H,d,J=6.7 Hz), 2.43(3H,s), 2.54(3H,s), 4.37(1H,septet,J=6.7
Hz), 7.14(1H,d,J=8.5 Hz), 7.28(2H,d,J=8.2 Hz), 7.36(1H,dd,J=8.5
& 2.3 Hz), 7.60-7.70(3H,m).
Example 61
[1002] Synthesis of
[1003] 2'-cyano-N-methyl-4'-methylthio-p-toluenesulfonanilide
[1004] (Compound No. 99)
[1005] (1) To a solution of 2-aminobenzonitrile (4.00 g (33.9
mmol)) and sodium thiocyanate (3.00 g (37.0 mmol)) in methanol (20
ml), a solution of bromine (5.50 g (34.4 mmol)) in methanol (5.0
ml) was added dropwise over a period of 40 minutes under cooling
with ice and with stirring. The mixture was then stirred under
cooling with ice for 30 mitutes, and then neutralized with a
saturated aqueous solution of sodium bicarbonate and extracted with
ethyl acetate. The extract was washed with water, dried over
anhydrous magnesium sulfate, and concentrated under reduced
pressure. The resulting residue was subjected to silica gel column
chromatography with chloroform as eluent to give 4.21 g (71%) of
2-amino-5-thiocyanobenzonitrile as pale yellow-white crystals.
[1006] mp: 123.5-125.0.degree. C.
[1007] NMR(CDCl.sub.3) .delta.: 4.77(2H,br), 6.81(1H,d,J=8.8 Hz),
7.54(1H,dd,J=8.8 & 2.2 Hz), 7.64(1H,d,J=2.2 Hz).
[1008] (2) Sodium hydroxide (97%, 1.20 g (29.1 mmol)) was dissolved
in a mixed solvent of water (4.0 ml) and methanol (20.0 ml). To
this, 2-amino-5-thiocyanobenzonitrile (5.03 g (28.7 mmol) was added
with stirring. To the resulting mixture, after 30 minutes' stirring
under cooling with ice, sodium borohydride (90%, 0.60 g (14.3
mmol)) was added and further stirred for 30 minutes under cooling
with ice. Then, dimethyl sulfate (95%, 3.0 ml (30.0 mmol)) was
added dropwise. The resulting mixture was further stirred under
cooling with ice for 30 minutes and at room temperature for 30
minutes, and then concentrated under reduced pressure. Water was
added to the residue and the mixture was extracted with diethyl
ether. The extract was washed twice with water, dried over
anhydrous magnesium sulfate and then concentrated under reduced
pressure to give 4.73 g (100%) of 2-amino-5-methylthiobenzonitrile
as yellow crystals.
[1009] mp: 50.0-54.0.degree. C.
[1010] NMR(CDCl.sub.3) .delta.: 2.41(3H,s), 3.20-4.60(2H,br),
6.70(1H,ddd,J=9.1 & 2.2 & 1.1 Hz), 7.30-7.45(2H,m).
[1011] (3) To a solution of 2-amino-5-methylthiobenzonitrile (4.60
g (28.0 mmol)) in pyridine (20.0 ml), p-toluenesulfonyl chloride
(5.60 g (29.4 mmol)) was added under cooling with ice and with
stirring. The mixture was further stirred for 30 minutes under
cooling with ice and for one hour at room temperature. Water (200
ml) was then added to the reaction mixture and the mixture was
stirred for 30 minutes to separate crystals. The crystals were
filtered and washed with water to give 8.33 g (93%) of
2'-cyano-4'-thiomethyl-p-toluenesulfonanilide as pale yellow
crystals.
[1012] mp: 170.0-173.0.degree. C.
[1013] NMR(CDCl.sub.3) .delta.: 2.40(3H,s), 2.45(3H,s),
7.20-7.35(3H,m), 7.40(1H,dd,J=8.9 & 2.3 Hz), 7.64(1H,d,J=8.9
Hz), 7.67(2H,d,J=8.3 Hz).
[1014] (4) To a suspension of sodium hydride (60%, 0.27 g (6.75
mmol)) in 7.0 ml of DMF,
2'-cyano-4'-thiomethyl-p-toluenesulfonanilide (2.00 g (6.28 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 15 minutes' stirring at room temperature, dimethyl
sulfate (0.70 ml (7.38 mmol)) was added dropwise and the mixture
was stirred at room temperature for 18 hours. Then, the reaction
mixture was poured into water and extracted with ethyl acetate. The
extract was washed with water and a saturated aqueous solution of
sodium chloride, dried over anhydrous magnesium sulfate, and
concentrated under reduced pressure. The resulting residue was then
subjected to silica gel column chromatography with chloroform as
eluent to give 1.63 g (78%) of the title compound as white
crystals.
[1015] mp: 139.0-140.0.degree. C.
[1016] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 2.51(3H,s), 3.22(3H,s),
7.17(1H,d,J=8.4 Hz), 7.25-7.45(4H,m), 7.65(2H,d,J=8.3 Hz).
Example 62
[1017] Synthesis of
[1018] 2'-cyano-N-ethyl-4'-methylthio-p-toluenesulfonanilide
(Compound No. 100)
[1019] In a manner similar to that of Example 61-(4), but diethyl
sulfate was used instead of dimethyl sulfate, and the reaction was
carried out by heating at 100.degree. C. for one hour with
stirring, to give the title compound as white crystals in a yield
of 43%.
[1020] mp: 136.0-137.0.degree. C.
[1021] NMR(CDCl.sub.3) .delta.: 1.10(3H,t,J=7.2 Hz), 2.44(3H,s),
2.51(3H,s), 3.63(2H,q,J=7.2 Hz), 7.12(1H,d,J=8.5 Hz),
7.31(2H,d,J=8.4 Hz), 7.38(1H,dd,J=8.5 & 2.3 Hz),
7.44(1H,d,J=2.3 Hz), 7.66(2H,d,J=8.4 Hz).
Example 63
[1022] Synthesis of
[1023]
2'-cyano-4'-methanesulfonyl-N-methyl-p-toluenesulfonanilide
[1024] (Compound No. 105)
[1025] To a solution of
2'-cyano-N-methyl-4'-methylthio-p-toluenesulfonani- lide (0.29 g
(0.87 mmol)) in chloroform (2.0 ml), 70% mCPBA (m-chloro-perbenzoic
acid) (0.43 g (1.74 mmol) was added with stirring under cooling
with ice. The mixture was stirred under cooling with ice for 30
minutes and at room temperature for 2 hours, diluted with
chloroform, washed with aqueous sodium hydrogen sulfite solution,
and 1% aqueous solution of sodium hydroxide, successively. The
chloroform layer was dried with anhydrous magnesium sulfate and
concentrated under reduced pressure to give 0.31 g (97.5%) of the
title compound as white crystals.
[1026] mp: 179.0-180.5.degree. C.
[1027] NMR(CDCl.sub.3) .delta.: 2.47(3H,s), 3.12(3H,s), 3.26(3H,s),
7.36(2H,d,J=8.3 Hz), 7.56(1H,d,J=8.5 Hz), 7.67(2H,d,J=8.3 Hz),
8.13(1H,dd,J=8.5 & 2.2 Hz), 8.23(1H,d,J=2.2 Hz).
Example 64
[1028] Synthesis of
[1029] N-methoxy-4'-nitro-2',3,4-trichlorobenzenesulfonanilide
[1030] (Compound No. 527)
[1031] (1) To a suspension of methoxylamine hydrochloride (0.93 g
(11.1 mmol)) in pyridine (5.0 ml), 3,4-dichlorobenzenesulfonyl
chloride (2.73 g (11.1 mmol)) was added with stirring under cooling
with ice and the resulting mixture was stirred for one hour under
cooling with ice, and at room temperature for 18 hours. Water (50.0
ml) was then added to the reaction mixture to bring about
separation of crystals. The crystals were filtered and washed with
water to give 2.69 g (95%) of
3,4-dichloro-N-methoxybenzenesulfonamide as pale yellow
crystals.
[1032] mp: 146.0-147.0.degree. C.
[1033] NMR(CDCl.sub.3) .delta.: 3.82(3H,s), 7.63(1H,dd,J=8.4 &
0.3 Hz), 7.76(1H,dd,J=8.4 & 2.1 Hz), 7.86(1H,s),
8.02(1H,dd,J=2.1 & 0.3 Hz).
[1034] (2) To a suspension of sodium hydride (60%, 0.09 g (2.25
mmol)) in 3.0 ml of DMF, 3,4-dichloro-N-methoxybenzenesulfonamide
(0.56 g (2.19 mmol)) was added with stirring under cooling with
ice. To the resulting mixture, after 15 minutes' stirring under
cooling with ice, 3-chloro-4-fluoronitrobenzene (0.35 ml (1.99
mmol)) was added and the mixture was stirred for one hour under
cooling with ice and 3 hours at room temperature. Then, water was
added to the reaction mixture and the resulting mixture was
extracted with diethyl ether. The extract was washed twice with
water and the ether layer was dried over anhydrous magnesium
sulfate, and concentrated under reduced pressure to give 0.56 g
(68%) of the title compound as pale yellow-white crystals.
[1035] mp: 132.0-133.0.degree. C.
[1036] NMR(CDCl.sub.3) .delta.: 3.87(3H,s), 6.95(1H,d,J=8.8 Hz),
7.53(1H,dd,J=8.4 & 2.1 Hz), 7.64(1H,dd,J=8.4 & 0.3 Hz),
7.88(1H,dd,J=2.1 & 0.3 Hz), 8.03(1H,dd,J=8.8 & 2.5 Hz),
8.39(1H,d,J=2.5 Hz).
Example 65
[1037] Synthesis of
[1038] N-methoxy-4'-nitro-2,2',5-trichlorobenzenesulfonanilide
[1039] (Compound No. 528)
[1040] (1) In a manner similar to that of Example 64-(1), but
2,5-dichlorobenzenesulfonyl chloride was used instead of
3,4-dichlorobenzenesulfonyl chloride to give
2,5-dichloro-N-methoxybenzen- esulfonamide as pale yellow crystals
in a yield of 93%.
[1041] mp: 127.0-128.5.degree. C.
[1042] NMR(CDCl.sub.3) .delta.: 3.80(3H,s), 7.48(1H,dd,J=8.5 &
0.4 Hz), 7.55(1H,dd,J=8.5 & 2.3 Hz), 8.14(1H,dd,J=2.3 & 0.4
Hz), 8.14(1H,s).
[1043] (2) In a manner similar to that of Example 64-(2), but
2,5-dichloro-N-methoxybenzenesulfonamide was used instead of
3,4-dichloro-N-methoxybenzenesulfonamide to give the title compound
as pale yellow-white crystals in a yield of 68%.
[1044] mp: 132.0-133.0.degree. C.
[1045] NMR(CDCl.sub.3) .delta.: 3.83(3H,s), 7.23(1H,d,J=9.0 Hz),
7.50(1H,dd,J=8.6 & 0.3 Hz), 7.59(1H,dd,J=8.6 & 2.4 Hz),
7.96(1H,dd,J=2.4 & 0.3 Hz), 8.06(1H,dd,J=9.0 & 2.5 Hz),
8.37(1H,d,J=2.5 Hz).
Example 66
[1046] Synthesis of
2'-chloro-N-methoxy-4'-nitro-3-trifluoromethylbenzenes-
ulfonanilide (Compound No. 529)
[1047] (1) In a manner similar to that of Example 64-(1), but
3-trifluoromethylbenzenesulfonyl chloride was used instead of
3,4-dichlorobenzenesulfonyl chloride to give
N-methoxy-3-trifluoromethylb- enzenesulfonamide as pale yellow
crystals in a yield of 97%.
[1048] mp: 78.0-81.0.degree. C.
[1049] NMR(CDCl.sub.3) .delta.: 3.83(3H,s), 7.27(1H,s),
7.72(1H,t,J=7.8 Hz), 7.92(1H,dt,J=7.8 & 0.6 Hz),
8.13(1H,dt,J=7.8 & 0.6 Hz), 8.20(1H,t,J=0.6 Hz).
[1050] (2) In a manner similar to that of Example 64-(2), but
N-methoxy-3-trifluoromethylbenzenesulfonamide was used instead of
3,4-dichloro-N-methoxybenzenesulfonamide to give the title compound
as white crystals in a yield of 57%.
[1051] mp: 95.5-96.5.degree. C.
[1052] NMR(CDCl.sub.3) .delta.: 3.86(3H,s), 6.86(1H,d,J=9.0 Hz),
7.73(1H,t,J=7.9 Hz), 7.90-8.10(4H,m), 8.39(1H,d,J=2.5 Hz).
Example 67
[1053] Synthesis of
[1054] 2'-chloro-3,4'-dinitro-N-methoxybenzenesulfonanilide
(Compound No. 530)
[1055] (1) In a manner similar to that of Example 64-(1), but
3-nitrobenzenesulfonyl chloride was used instead of
3,4-dichlorobenzenesulfonyl chloride to give
N-methoxy-3-nitrobenzenesulf- onamide as pale yellow crystals in a
yield of 85%.
[1056] mp: 111.0-113.0.degree. C.
[1057] NMR(CDCl.sub.3) .delta.: 3.86(3H,s), 7.28(1H,s),
7.80(1H,t,J=8.3 Hz), 8.26(1H,ddd,J=8.3 & 1.8 & 1.1 Hz),
8.52(1H,ddd,J=8.3 & 2.2 & 1.1 Hz), 8.77(1H,dd,J=2.2 &
1.8 Hz).
[1058] (2) In a manner similar to that of Example 64-(2), but
N-methoxy-3-nitrobenzenesulfonamide was used instead of
3,4-dichloro-N-methoxybenzenesulfonamide to give the title compound
as pale yellow crystals in a yield of 80%.
[1059] mp: 167.5-169.0.degree. C.
[1060] NMR(CDCl.sub.3) .delta.: 3.89(3H,s), 6.90(1H,d,J=8.8 Hz),
7.80(1H,t,J=8.2 Hz), 7.95-8.10(2H,m), 8.40(1H,d,J=2.5 Hz),
8.55-8.70(2H,m).
Example 68
[1061] Synthesis of
[1062] 2',4-Dichloro-3,4'-dinitro-N-methoxybenzenesulfonanilide
[1063] (Compound No. 531)
[1064] (1) Methoxylamine hydrochloride (0.90 g (10.8 mmol) was
suspended in pyridine (3.0 ml). To this, under cooling with ice and
with stirring, 4-chloro-3-nitrobenzenesulfonylchloride (2.56 g
(10.8 mmol)) was added and the mixture was stirred under cooling
with ice for one hour and at room temperature for 3 hours. Water
(50.0 ml) was added to the reaction mixture and the mixture was
extracted with ethyl acetate. The extract was washed with dilute
hydrochloric acid and water successively, dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give
2.02 g (76%) of 4-chloro-N-methoxy-3-nitrobenzenesulfonamide as
pale yellow-white crystals.
[1065] mp: 69.5-71.0.degree. C.
[1066] NMR(CDCl.sub.3) .delta.: 3.86(3H,s), 7.29(1H,s),
7.77(1H,d,J=8.4 Hz), 8.05(1H,dd,J=8.4 & 2.1 Hz),
8.41(1H,d,J=2.1 Hz).
[1067] (2) To a solution of
4-chloro-N-methoxy-3-nitrobenzenesulfonamide (0.53 g (1.99 mmol))
and 3-chloro-4-fluoronitrobenzene (1.05 g (5.98 mmol) in 5.0 ml of
DMF, sodium hydride (60%, 0.09 g (2.25 mmol)) was added bit by bit
with stirring under cooling with ice, and the mixture was stirred
under cooling with ice for one hour and at room temperature for 2
hours. Water and diethyl ether were added to the resulting mixture
and insolubles were removed by filtration. The filtrate was allowed
to stand somewhile and then, the organic layer was separated and
washed with water, dried over anhydrous magnesium sulfate and
concentrated under reduced pressure. The residue was subjected to
silica gel column chromatography with ethyl acetate-hexane (1:5) as
eluent to give 0.10 g (12%) of the title compound as pale
yellow-white crystals.
[1068] mp: 138.0-139.0.degree. C.
[1069] NMR(CDCl.sub.3) .delta.: 3.89(3H,s), 6.96(1H,d,J=8.9 Hz),
7.70-7.90(2H,m), 8.05(1H,dd,J=8.9 & 2.5 Hz), 8.26(1H,d,J=1.5
Hz), 8.40(1H,d,J=2.5 Hz).
Example 69
[1070] Synthesis of
4-chloro-2'-fluoro-N-methoxy-4'-nitro-3-(trifluorometh-
yl)benzenesulfonanilide (Compound No. 524)
[1071] (1) In a manner similar to that of Example 68-(1), but
4-chloro-3-(trifluoromethyl)benzenesulfonyl chloride was used
instead of 4-chloro-3-nitrobenzenesulfonyl chloride to give
4-chloro-N-methoxy-3-(tr- ifluoromethyl)benzenesulfonamide as white
crystals in a yield of 92%.
[1072] mp: 88.0-90.5.degree. C.
[1073] NMR(CDCl.sub.3) .delta.: 3.84(3H,s), 7.20(1H,s),
7.72(1H,d,J=8.4 Hz), 8.03(1H,dd,J=8.4 & 2.2 Hz),
8.23(1H,d,J=2.2 Hz).
[1074] (2) To a solution of
4-chloro-N-methoxy-3-(trifluoromethyl)benzenes- ulfonamide (0.58 g
(2.00 mmol)) and 3,4-difluoronitrobenzene (0.66 ml (5.96 mmol)) in
5.0 ml of DMF, sodium hydride (60%, 0.09 g (2.25 mmol)) was added
bit by bit with stirring under cooling with ice. The resulting
mixture was stirred under cooling with ice for one hour and allowed
to warm-up to room temperature. Water was added to the reaction
mixture and the resulting mixture was extracted with diethyl ether.
The extract was washed with water, and dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give
0.32 g (37%) of the title compound as pale yellow crystals.
[1075] mp: 104.5-105.5.degree. C.
[1076] NMR(CDCl.sub.3) .delta.: 3.92(3H,s), 7.03(1H,dd,J=9.0
Hz,J.sub.HF=7.0 Hz), 7.60-7.85(2H,m), 7.90-8.15(3H,m).
Example 70
[1077] Synthesis of
4-Chloro-2'-cyano-N-methoxy-4'-nitro-3-(trifluoromethy-
l)benzenesulfonanilide (Compound No. 536)
[1078] (1) In a manner similar to that of Example 69-(2), but
2-chloro-5-nitrobenzonitrile was used instead of
3,4-difluoronitrobenzene to give the title compound as pale
yellow-white crystals in a yield of 38%.
[1079] mp: 140.5-142.0.degree. C.
[1080] NMR(CDCl.sub.3) .delta.: 3.88(3H,s), 7.36(1H,d,J=9.0 Hz),
7.72(1H,d,J=8.4 Hz), 7.82(1H,dd,J=8.4 & 2.1 Hz),
8.07(1H,d,J=2.1 Hz), 8.39(1H,dd,J=9.0 & 2.5 Hz),
8.58(1H,d,J=2.5 Hz).
Example 71
[1081] Synthesis of
5-chloro-1,3-dimethyl-N-(2,4-dinitrophenyl)-N-methoxy--
4-pyrazolesulfonamide (Compound No. 552)
[1082] (1) Methoxylamine hydrochloride (0.90 g (10.8 mmol) was
suspended in pyridine (2.0 ml). To this, under cooling with ice and
with stirring, a solution of
5-chloro-1,3-dimethyl-4-pyrazolesulfonyl chloride (2.29 g (10.0
mmol)) in acetonitrile (2.0 ml) was added dropwise, and the mixture
was stirred under cooling with ice for one hour and at room
temperature for one hour. Water (50.0 ml) was added to bring about
separation of crystals. The crystals were filtered and washed with
water, dried, and subjected to silica gel column chromatography
with ethyl acetate-hexane (1:1) as eluent to give 1.72 g (72%) of
5-chloro-1,3-dimethyl-N-methoxy-4- -pyrazolesulfonamide as white
crystals.
[1083] mp: 120.0-122.5.degree. C.
[1084] NMR(CDCl.sub.3) .delta.: 2.43(3H,s), 3.82(3H,s), 3.83(3H,s),
7.09(1H,s).
[1085] (2) To a solution of
5-chloro-1,3-dimethyl-N-methoxy-4-pyrazolesulf- onamide (0.48 g
(2.00 mmol)) and 2,4-dinitrochlorobenzene (0.49 g (2.42 mmol)) in
DMF (3.0 ml), sodium hydride (60%, 0.09 g (2.25 mmol)) was added
dropwise under cooling with ice and with stirring and the mixture
was stirred under cooling with ice for one hour and at room
temperature for one hour. Water was added to the reaction mixture
and the resulting mixture was extracted with ethyl acetate. The
extract was washed with water, dried over anhydrous magnesium
sulfate, and then concentrated under reduced pressure. The residue
was subjected to silica gel column chromatography with
chloroform-hexane (10:1) as eluent to give 0.65 g (87%) of the
title compound as pale yellow crystals.
[1086] mp: 189.0-191.0.degree. C. (dec.)
[1087] NMR(CDCl.sub.3) .delta.: 2.14(3H,s), 3.81(3H,s), 3.99(3H,s),
7.59(1H,d,J=9.0 Hz), 8.35(1H,dd,J=9.0 & 2.5 Hz),
8.67(1H,d,J=2.5 Hz).
Example 72
[1088] Synthesis of
5-chloro-N-(2-cyano-4-nitrophenyl)-N-methoxy-2-thiophe-
nesulfonamide (Compound No. 537)
[1089] (1) In a manner similar to that of Example 71-(1), but
5-chloro-2-thiophenesulfonyl chloride was used instead of
5-chloro-1,3-dimethyl-4-pyrazolesulfonyl chloride to give
5-chloro-N-methoxy-2-thiophenesulfonamide as white crystals in a
yield of 69%.
[1090] mp: 65.5-66.5.degree. C.
[1091] NMR(CDCl.sub.3) .delta.: 3.86(3H,s), 6.99(1H,d,J=4.1 Hz),
7.08(1H,s), 7.53(1H,d,J=4.1 Hz).
[1092] (2) To a solution of
5-chloro-N-methoxy-2-thiophenesulfonamide (0.46 g (2.02 mmol))
and2-chloro-5-nitrobenzonitrile (0.45 g (2.46 mmol)) in DMF (3.0
ml), sodium hydride (60%, 0.09 g (2.25 mmol)) was added bit by bit
under cooling with ice and with stirring and the mixture was
stirred under cooling with ice for one hour and at room temperature
for one hour. Water was added to the reaction mixture and the
resulting mixture was extracted with ethyl acetate. The extract was
washed with water, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel chromatography with ethyl acetate-hexane (1:3) as eluent
to give 0.41 g (54%) of the title compound as pale yellow
crystals.
[1093] mp: 144.0-146.0.degree. C.
[1094] NMR(CDCl.sub.3) .delta.: 3.99(3H,s), 7.03(1H,d,J=4.1 Hz),
7.29(1H,d,J=4.1 Hz), 7.37(1H,d,J=9.0 Hz), 8.37(1H,dd,J=9.0 &
2.5 Hz), 8.57(1H,d,J=2.5 Hz).
Example 73
[1095] Synthesis of
2'-chloro-4'-cyano-N-methoxy-p-toluenesulfonanilide
[1096] (Compound No. 566)
[1097] To a suspension of sodium hydride (60%, 0.09 g (2.25 mmol))
in DMF (3.0 ml), N-methoxy-p-toluenesulfonamide (0.45 g (2.20
mmol)) was added with stirring under cooling with ice. To the
resulting mixture, after 15 minutes' stirring under cooling with
ice, 3-chloro-4-fluorobenzonitrile (0.31 g (1.99 mmol)) was added.
The resulting mixture was then stirred under cooling with ice for
one hour and at 50.degree. C. for 18 hours.
[1098] Water was added to the reaction mixture and extracted with
diethyl ether. The extract was washed with water and a saturated
aqueous solution of sodium chloride, successively, dried over
anhydrous magnesium sulfate, and then concentrated under reduced
pressure, to give 0.54 g (81%) of the title compound as white
crystals.
[1099] mp: 145.0-147.0.degree. C.
[1100] NMR(CDCl.sub.3) .delta.: 2.49(3H,s), 3.81(3H,s),
6.82(1H,d,J=8.3 Hz), 7.34(2H,d,J=8.3 Hz), 7.39(1H,dd,J=8.3 &
1.8 Hz), 7.63(2H,d,J=8.3 Hz), 7.77(1H,d,J=1.8 Hz).
Example 74
[1101] Synthesis of
[1102] 2-Chloro-2',4'-dinitro-N-methoxybenzenesulfonanilide
(Compound No. 563)
[1103] (1) Methoxylamine hydrochloride (0.95 g (11.4 mmol)) was
suspended in pyridine (4.0 ml). To this, under cooling with ice and
with stirring, 2-chlorobenzenesulfonyl chloride (2.11 g (10.0
mmol)) was added and the mixture was stirred under cooling with ice
for one hour and at room temperature for one hour. Water (50.0 ml)
was added to the reaction mixture and the resulting mixture was
extracted with ethyl acetate. The extract was washed with water,
dilute hydrochloric acid and a saturated aqueous solution of sodium
chloride, successively, dried over anhydrous magnesium sulfate and
concentrated under reduced pressure to give 1.41 g (64%) of
2-chloro-N-methoxybenzenesulfonamide as pale yellow crystals.
[1104] mp: 92.5-94.0.degree. C.
[1105] NMR(CDCl.sub.3) .delta.: 3.80(3H,s), 7.40-7.70(3H,m),
7.86(1H,s), 8.17(1H,ddd,J=7.7 & 1.6 & 0.8 Hz).
[1106] (2) To a suspension of sodium hydride (60%, 0.09 g (2.25
mmol)) in DMF (3.0 ml), 2-chloro-N-methoxybenzenesulfonamide (0.48
g (2.17 mmol)) was added with stirring under cooling with ice. To
the resulting mixture, after 15 minutes' stirring under cooling
with ice, 2,4-dinitrochlorobenzene (0.41 g (2.02 mmol)) was added.
The resulting mixture was then stirred under cooling with ice for
one hour and at room temperature for one hour. Water was added to
the reaction mixture and the resulting mixture was extracted with
diethyl ether. The extract was washed with water, dilute
hydrochloric acid and a saturated aqueous solution of sodium
chloride, successively, dried over anhydrous magnesium sulfate, and
then concentrated under reduced pressure, to give 0.49 g (62%) of
the title compound as pale yellow crystals.
[1107] mp: 112.5-114.0.degree. C.
[1108] NMR(CDCl.sub.3) .delta.: 3.93(3H,s), 7.40-7.70(4H,m),
7.96(1H,dd,J=7.9 & 1.7 Hz), 8.34(1H,dd,J=8.9 & 2.5 Hz),
8.67(1H,d,J=2.5 Hz).
Example 75
[1109] Synthesis of
[1110] 3-chloro-2',4'-dinitro-N-methoxybenzenesulfonanilide
(Compound No. 564)
[1111] (1) In a manner similar to that of Example 74-(1), but
3-chlorobenzenesulfonyl chloride was used instead of
2-chlorobenzenesulfonyl chloride to give
3-chloro-N-methoxybenzenesulfona- mide as pale yellow crystals in a
yield of 38%.
[1112] mp: 72.0-74.5.degree. C.
[1113] NMR(CDCl.sub.3) .delta.: 3.83(3H,s), 7.10(1H,s),
7.50(1H,dd,J=8.0 & 7.7 Hz), 7.63(1H,ddd,J=8.0 & 2.0 &
1.2 Hz), 7.82(1H,ddd,J=7.7 & 1.7 & 1.2 Hz),
7.92(1H,dd,J=2.0 & 1.7 Hz).
[1114] (2) In a manner similar to that of Example 74-(2), but
3-chloro-N-methoxybenzenesulfonamide was used instead of
2-chloro-N-methoxybenzenesulfonamide to give the title compound as
pale yellow crystals in a yield of 76%.
[1115] mp: 157.0-159.0.degree. C.
[1116] NMR(CDCl.sub.3) .delta.: 3.94(3H,s), 7.35(1H,d,J=8.9 Hz),
7.45-7.55(2H,m), 7.65-7.75(2H,m), 8.32(1H,dd,J=8.9 & 2.7 Hz),
8.73(1H,d,J=2.7 Hz).
Example 76
[1117] Synthesis of
2'-Cyano-N-methoxy-4'-nitro-4-(trifluoromethyl)-Benzen-
esulfonanilide (Compound No. 565)
[1118] (1) In a manner similar to that of Example 74-(1), but
4-(trifluoromethyl)benzenesulfonyl chloride was used instead of
2-chlorobenzenesulfonyl chloride to give
N-methoxy-4-(trifluoromethyl)ben- zenesulfonamide as pale
yellow-white crystals in a yield of 22%.
[1119] mp: 96.0-97.0.degree. C.
[1120] NMR(CDCl.sub.3) .delta.: 3.84(3H,s), 7.15(1H,s),
7.83(2H,d,J=8.2 Hz), 8.07(2H,d,J=8.2 Hz).
[1121] (2) To a suspension of sodium hydride (60%, 0.09 g (2.25
mmol)) in DMF (4.0 ml),
N-methoxy-4-(trifluoromethyl)benzenesulfonamide (0.55 g (2.16
mmol)) was added with stirring under cooling with ice. To the
resulting mixture, after 15 minutes' stirring under cooling with
ice,2-chloro-5-nitrobenzonitrile (0.37 g (2.03 mmol)) was added.
The resulting mixture was then stirred under cooling with ice for
one hour and at room temperature for one hour. Water was added to
the reaction mixture and the resulting mixture was extracted with
diethyl ether. The extract was washed with water, dilute
hydrochloric acid and a saturated aqueous solution of sodium
chloride, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel column chromatography with ethyl acetate-hexane (1:4) as
eluent to give 0.51 g (63%) of the title compound as white
crystals.
[1122] mp: 133.5-135.0.degree. C.
[1123] NMR(CDCl.sub.3) .delta.: 3.87(3H,s), 7.34(1H,d,J=9.0 Hz),
7.84(2H,d,J=8.6 Hz), 7.91(2H,d,J=8.6 Hz), 8.37(1H,dd,J=9.0 &
2.7 Hz), 8.57(1H,d,J=2.7 Hz).
Example 77
[1124] Synthesis of
[1125] 2',4'-dinitro-N-methoxy-3-methylbenzenesulfonanilide
(Compound No. 562)
[1126] (1) In a manner similar to that of Example 74-(1), but
3-methylbenzenesulfonyl chloride was used instead of
2-chlorobenzenesulfonyl chloride to give
N-methoxy-3-methylbenzenesulfona- mide as pale yellow crystals in a
yield of 53%.
[1127] mp: 90.0-92.0.degree. C.
[1128] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.80(3H,s), 7.05(1H,s),
7.40-7.55(2H,m), 7.70-7.80(2H,m).
[1129] (2) In a manner similar to that of Example 74-(2), but
N-methoxy-3-methylbenzenesulfonamide was used instead of
2-chloro-N-methoxybenzenesulfonamide to give the title compound as
pale yellow crystals in a yield of 77%.
[1130] mp: 147.5-149.5.degree. C.
[1131] NMR(CDCl.sub.3) .delta.: 2.42(3H,s), 3.90(3H,s),
7.32(1H,d,J=9.0 Hz), 7.35-7.45(2H,m), 7.45-7.60(2H,m),
8.29(1H,dd,J=9.0 & 2.5 Hz), 8.72(1H,d,J=2.5 Hz).
Example 78
[1132] Synthesis of N-methoxy-4'-methylthio-2'-nitro-p-toluene
sulfonanilide (Compound No. 572)
[1133] (1) To a suspension of dry potassium fluoride (0.57 g (9.79
mmol) in dimethylsulfoxide (10.0 ml),
2-chloro-5-(methylthio)nitrobenzene (1.88 g (9.23 mmol)) was added
and the mixture was stirred at 170.degree. C. for 3 hours. As the
reaction had not yet completed, dry potassium fluoride (0.68 g
(11.7 mmol)) was added further and the mixture was stirred at
170.degree. C. for another 3 hours. The reaction mixture was poured
into water and extracted with diethyl ether. The extract was washed
with water, dried over anhydrous magnesium sulfate and concentrated
under reduced pressure. The residue was then distilled by means of
a glass tube oven under reduced pressure, and a fraction which
boiled at 110-160.degree. C./0.8 mmHg was collcted to give 1.39 g
of a 3:2 mixture of 2-fluoro-5-(methylthio)nitrobenzene and
2-chloro-5-(methylthio)nitrobenzene as yellow oil.
[1134] (2) To a suspension of sodium hydride (60%, 0.33 g (8.17
mmol)) in DMF (10.0 ml), N-methoxy-p-toluenesulfonamide (1.63 g
(8.17 mmol)) was added with stirring under cooling with ice. To the
resulting mixture, after 15 minutes' stirring at room temperature,
a 3:2 mixture of 2-fluoro-5-(methylthio)nitrobenzene and
2-chloro-5-(methylthio)nitrobenze- ne (1.39 g) was added. The
mixture was stirred overnight at room temperature, poured into
water and extracted with diethyl ether. The extract was washed with
water, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The residue was subjected to
silica gel column chromatography with ethyl acetate-hexane (1:6 to
1:4) as eluent. The eluted substance was recrystallized from ethyl
acetate-hexane to give 0.60 g of the title compound as yellow
crystals.
[1135] mp: 110.3-110.8.degree. C.
[1136] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 2.52(3H,s), 3.82(3H,s),
6.89(1H,d,J=8.6 Hz), 7.23(1H, dd,J=8.6 & 2.2 Hz),
7.30(2H,d,J=8.0 Hz), 7.50-7.70(3H,m).
Example 79
[1137] Synthesis of
[1138]
2'-cyano-N-methoxy-4'-methylthio-p-toluenesulfonylanilide
[1139] (Compound No. 571)
[1140] (1) To a solution of 2-amino-5-(thiocyanato)benzonitrile
(2.00 g (11.4 mmol)) and 42% borofluoric acid (7.16 g (34.2 mmol))
in ethanol (10.0 ml), a solution of sodium nitrite (0.87 g (12.6
mmol)) in water (1.2 ml), was added dropwise under cooling with
ice. The mixture was stirred under cooling with ice for 2 hours and
crystals separated were filtered. The solid was washed with water,
methanol and then ether, successively, and dried under reduced
pressure to give 2.98 g (95%) of
2-cyano-4-(thiocyanato)benzenediazonium fluoroborate as white
crystals.
[1141] mp: 191.degree. C. (dec.)
[1142] NMR(DMSO-d.sub.6) .delta.: 8.47(1H,dd,J=8.9 & 2.1 Hz),
8.82(1H,d,J=2.1 Hz), 9.01(1H,d,J=8.9 Hz).
[1143] (2) 2-Cyano-4-(thiocyanato)benzenediazonium fluoroborate
(2.98 g (10.9 mmol)) was decomposed by first heating with a
heat-gun until until the whole mass became black and then by
heating to 200.degree. C. in an oil bath for 30 minutes. After
cooling, water was added and the resulting mixture was extracted
with ethyl acetate. The extract was washed with a saturated aqueous
solution of sodium chloride, dried over anhydrous magnesium sulfate
and concentrated under reduced pressure. The residue was then
distilled by means of a glass tube oven under reduced pressure, and
a fraction which boiled at 180-240.degree. C./0.2 mmHg was
collected to give 0.29 g (15%) of
2-fluoro-5-(thiocyanato)benzonitrile as a pale yellow-white
crystals.
[1144] mp: 39.0-41.0.degree. C.
[1145] NMR(CDCl.sub.3) .delta.: 8.36(1H,ddd,J=9.4 & 8.1 &
1.2 Hz), 7.7-7.9(2H,m), 7.67(1H,d,J=2.2 Hz).
[1146] (3) To a suspension of sodium borohydride (90%, 0.41 g (9.76
mmol)) in ethanol (10 ml), 2-fluoro-5-(thiocyanato)benzonitrile
(0.29 g (1.63 mmol)) was added with stirring under cooling with
ice. To the resulting mixture, after one hour's stirring at room
temperature, methyl iodide (0.11 ml (1.71 mmol)) was added and the
resulting mixture was stirred overnight at room temperature. Then,
the reaction mixture was poured into water and the resulting
mixture was extracted with ethyl acetate. The extract was washed
with a saturated aqueous solution of sodium chloride, dried over
anhydrous magnesium sulfate, and concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (3:7) as eluent, to give
0.25 g (92%) of 2-fluoro-5-(methylthio)benzonitrile as pale
yellow-white crystals.
[1147] mp: 61.7-62.7.degree. C.
[1148] NMR(CDCl.sub.3) .delta.: 2.50(3H,s), 7.05-7.2(1H,m),
7.4-7.55(2H,m).
[1149] (4) To a suspension of sodium hydride (60%, 0.07 g (1.64
mmol)) in DMF (5.0 ml), N-methoxy-p-toluenesulfonamide (0.33 g
(1.64 mmol)) was added with stirring under cooling with ice. To the
resulting mixture, after 15 minutes' stirring at room temperature,
2-fluoro-5-(methylthio)be- nzonitrile(0.25 g (1.50 mmol)) was added
and the mixture was stirred overnight at room temperature, without
any progress of reaction. So, the mixture was further heated at
50.degree. C. for 3 days and then allowed to cool. The reaction
mixture was poured into water and the resulting mixture was
extracted with diethyl ether. The extract was washed with water,
dried over anhydrous magnesium sulfate, and then concentrated under
reduced pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:4) as eluent. The
eluate was then purified by recrystallization from ethyl
acetate-hexane, giving 0.34 g (65%) of the title compound as white
crystals.
[1150] mp: 146.8-147.6.degree. C.
[1151] NMR(CDCl.sub.3) .delta.: 2.47(3H,s), 2.51(3H,s), 3.76(3H,s),
6.96(1H,d,J=8.7 Hz), 7.2-7.4(3H,m), 7.44(1H,d,J=2.2 Hz),
7.66(2H,d,J=8.3 Hz).
Example 80
[1152] Synthesis of
[1153]
N-(4-Cyano-3-methoxy-5-isothiazolyl)-N-methoxy-p-toluenesulfon
anilide (Compound No. 560)
[1154] To a suspension of sodium hydride (60%, 0.09 g (2.25 mmol))
in DMF (3.0 ml), N-methoxy-p-toluenesulfonamide (0.45 g (2.20
mmol)) was added with stirring under cooling with ice. To the
resulting mixture, after 15 minutes' stirring under cooling with
ice, 4-cyano-5-methanesulfonyl-3-met- hoxyisothiazole (0.44 ml
(2.02 mmol)) was added. After being stirred for 30 minutes under
cooling with ice and at room temperature for 30 minutes. Water was
added to the reaction mixture and the resulting mixture was
extracted with ethyl acetate. The extract was washed with water and
a saturated aqueous solution of sodium chloride, dried over
anhydrous magnesium sulfate, and then concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:3) as eluent, giving
0.44 g (64%) of the title compound as white crystals.
[1155] mp: 115.5-118.0.degree. C.
[1156] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 4.00(3H,s), 4.14(3H,s),
7.35(2H,d,J=8.3 Hz), 7.77(2H,d,J=8.3 Hz).
Example 81
[1157] Synthesis of
[1158]
4'-chloro-4-ethyl-N-isopropyl-2'-nitrobenzenesulfonanilide
[1159] (Compound No. 328)
[1160] (1) To a solution of 4-ethylbenzenesulfonyl chloride (90%,
4.25 g (20.8 mmol)) in pyridine (10 ml), 4-chloroaniline (2.55 g
(20.0 mmol)) was added with stirring at room temperature.
After18hours' stirring at room temperature, water (100.0 ml) was
added to the reaction mixture and the mixture was extracted with
ethyl acetate. The extract was washed with dilute hydrochloric
acid, water and a saturated aqueous solution of sodium chloride
successively, dried over anhydrous magnesium sulfate, and then
concentrated under reduced pressure to give 5.26 g (89%) of
4'-chloro-4-ethylbenzenesulfonanilide as white crystals.
[1161] mp: 119.5-121.5.degree. C.
[1162] NMR(CDCl.sub.3) .delta.: 1.23(3H,t,J=7.6 Hz),
2.68(2H,q,J=7.6 Hz), 6.90(1H,s), 7.02(2H,d,J=8.8 Hz),
7.20(2H,d,J=8.8 Hz), 7.26(2H,d,J=8.4 Hz), 7.68(2H,d,J=8.4 Hz).
[1163] (2) To a suspension of 4'-chloro-4-ethylbenzenesulfonanilide
(4.70 g (15.9 mmol)) in 15 ml of acetic acid, 97% fuming nitric
acid (0.69 ml (16.1 mmol)) was added dropwise with stirring at room
temperature. The resulting mixture was stirred at 50.degree. C. for
30 minutes and then allowed to cool to room temperature. Water
(100.0 ml) was added to the reaction mixture and the resulting
crystals were filtered and washed with water to give 5.35 g (99%)
of 4'-chloro-4-ethyl-2'-nitrobenzenesulfonanil- ide as pale yellow
crystals.
[1164] mp: 104.5-105.5.degree. 0.C
[1165] NMR(CDCl.sub.3) .delta.: 1.23(3H,t,J=7.6 Hz),
2.69(2H,q,J=7.6 Hz), 7.30(2H,d,J=8.4 Hz), 7.54(1H,dd,J=9.0 &
2.5 Hz), 7.74(2H,d,J=8.4 Hz), 7.84(1H,d,J=9.0 Hz), 8.10(1H,d,J=2.5
Hz), 9.73(1H,brs).
[1166] (3) To a suspension of sodium hydride (60%, 0.12 g (3.00
mmol)) in DMF (7.0 ml),
4'-chloro-4-ethyl-2'-nitrobenzenesulfonanilide (1.00 g (2.93 mmol))
was added with stirring at room temperature. To the resulting
mixture, after 15 minutes' stirring at room temperature, isopropyl
iodide (0.70 ml (7.01 mmol)) was added dropwise and heated at
130.degree. C. for 2 hours with stirring. After being allowed to
cool to room temperature, water was added to the reaction mixture
and the resulting mixture was extracted with diethyl ether. The
extract was washed with 1% aqueous solution of sodium hydroxide and
a saturated aqueous solution of sodium chloride, dried over
anhydrous magnesium sulfate, and then concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:3) as eluent to give
0.41 g (37%) of the title compound as pale red crystals.
[1167] mp: 117.0-118.5.degree. C.
[1168] NMR(CDCl.sub.3) .delta.: 1.06(3H,d,J=6.7 Hz),
1.13(3H,d,J=6.7 Hz), 1.27(3H,t,J=7.6 Hz), 2.74(2H,q,J=7.6 Hz),
4.37(1H,septet,J=6.7 Hz), 7.23(1H,d,J=8.6 Hz), 7.32(2H,d,J=8.4 Hz),
7.55(1H,dd,J=8.6 & 2.5 Hz), 7.69(2H,d,J=8.4 Hz),
7.89(1H,d,J=2.5 Hz).
Example 82
[1169] Synthesis of
4,4'-Dichloro-N-ethyl-2'-nitrobenzenesulfonanilide
[1170] (Compound No. 338)
[1171] (1) In a manner similar to that of Example 81-(1), but
4-chlorobenzenesulfonyl chloride was used instead of
4-ethylbenzenesulfonyl chloride to give
4,4'-dichlorobenzenesulfonanilide as pale red crystals in a yield
of 86%.
[1172] mp: 144.5-145.5.degree. C.
[1173] NMR(CDCl.sub.3) .delta.: 6.71(1H,s), 7.01(2H,d,J=8.9 Hz),
7.23(2H,d,J=8.9 Hz), 7.43(2H,d,J=8.8 Hz), 7.68(2H,d,J=8.8 Hz).
[1174] (2) In a manner similar to that of Example 81-(2), but
4,4'-dichlorobenzenesulfonanilide was used instead of
4'-chloro-4-ethylbenzenesulfonanilide to give
4,4'-dichloro-2'-nitrobenze- nesulfonanilide in a yield of 96%.
[1175] mp: 122.0-123.0.degree. C.
[1176] NMR(CDCl.sub.3) .delta.: 7.46(2H,d,J=8.8 Hz),
7.57(1H,dd,J=9.0 & 2.5 Hz), 7.77(2H,d,J=8.8 Hz),
7.83(1H,d,J=9.0 Hz), 8.12(1H,d,J=2.5 Hz), 9.74(1H,s).
[1177] (3) To a suspension of sodium hydride (60%, 0.13 g (3.25
mmol)) in DMF (7.0 ml), 4,4'-dichloro-2'-nitrobenzenesulfonanilide
(1.00 g (2.88 mmol)) was added with stirring at room temperature.
To the resulting mixture, after 15 minutes' stirring at room
temperature, diethyl sulfate (0.45 ml (3.44 mmol)) was added
dropwise and the mixture was heated at 100.degree. C. for 2 hours
with stirring. The reaction mixture was allowed to cool to room
temperature, poured into water and extracted with diethyl ether.
The extract was washed with 1% aqueous sodium hydroxide and
saturated aqueous solution of sodium chloride, dried over anhydrous
magnesium sulfate, and then concentrated under reduced pressure to
give 0.51 g (47%) of the title compound as pale yellow
crystals.
[1178] mp: 121.5-123.0.degree. C.
[1179] NMR(CDCl.sub.3) .delta.: 1.20(3H,t,J=7.2 Hz),
3.68(2H,q,J=7.2 Hz), 7.09(1H,d,J=8.6 Hz), 7.47(2H,d,J=8.7 Hz),
7.54(1H,dd,J=8.6 & 2.5 Hz), 7.60(2H,d,J=8.7 Hz),
7.88(1H,d,J=2.5 Hz).
Example 83
[1180] Synthesis of
[1181]
4'-Chloro-2'-hydroxymethyl-N-methyl-p-toluenesulfonanilide
[1182] (Compound No. 65)
[1183] To a solution of
5-chloro-N-methyl-N-(p-toluenesulfonyl)anthranilic acid (5.20 g
(15.3 mmol)) in chloroform (20.0 ml), thionyl chloride (2.00 g
(27.4 mmol)) was added with stirring at room temperature. The
resulting mixture was heated at 50.degree. C. for 2 hours with
stirring and then concentrated under reduced pressure. The residue
was dissolved in acetonitrile (20.0 ml) and added dropwise to a
solution of sodium borohydride (90%, 1.30 g (30.9mmol) in water
(20.0 ml) under cooling with ice. After one hour's stirring at room
temperature, water (100.0 ml) was added to the reaction mixture and
the resulting mixture was extracted with ethyl acetate. The extract
was washed with dilute hydrochloric acid, dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give
4.40 g (88%) of the title compound as white crystals.
[1184] mp: 130.0-132.0.degree. C.
[1185] NMR(CDCl.sub.3) .delta.: 2.47(3H,s), 2.70-3.20(1H,br),
3.12(3H,s), 4.61(1H,brs), 4.94(1H,brs), 6.37(1H,d,J=8.5 Hz),
7.10(1H,dd,J=8.5 & 2.5 Hz), 7.32(2H,d,J=8.3 Hz),
7.54(2H,d,J=8.3 Hz), 7.60(1H,d,J=2.5 Hz).
Example 84
[1186] Synthesis of
[1187]
5-Chloro-2-(N-methyl-N-p-toluenesulfonyl)aminobenzaldehyde
[1188] (Compound No. 66)
[1189] A mixture of
4'-chloro-2'-hydroxymethyl-N-methyl-p-toluenesulfonani- lide (3.83
g (11.8 mmol)), manganese dioxide (5.11 g (58.8 mmol) and
acetonitrile (30.0 ml) was stirred at room temperature for 3 hours.
Then, manganese dioxide (5.11 g (58.8 mmol)) was further added and
the mixture was stirred for 20 hours further. The insolubles were
filtered off, and the filtrate was concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with chloroform-ethanol (100:1) as eluent to give
2.33 g (61%) of the title compound as white crystals.
[1190] mp: 123.0-124.0.degree. C.
[1191] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 3.22(3H,s),
6.64(1H,d,J=8.6 Hz), 7.30(2H,d,J=8.4 Hz), 7.41(1H,dd,J=8.6 &
2.6 Hz), 7.44(2H,d,J=8.4 Hz), 7.97(1H,d,J=2.6 Hz), 10.39(1H,s).
Example 85
[1192] Synthesis of
[1193] 5-Chloro-2-(N-methyl-N-p-toluenesulfonyl)aminobenzaldehyde
methoxime (Compound No. 68)
[1194] A mixture of
5-chloro-2-(N-methyl-N-p-toluenesulfonyl)aminobenzalde- hyde (0.30
g (0.93 mmol)), methoxylamine hydrochloride (0.10 g (1.20 mmol) and
pyridine (0.50 ml) was stirred at room temperature for 18 hours.
The reaction mixture was concentrated under reduced pressure and
the residue was dissolved in diethyl ether, followed by washing
with water. The organic layer was separated, dried over anhydrous
magnesium sulfate and concentrated under reduced pressure to give
0.30 g (92%) of the title compound as white crystals.
[1195] mp: 123.5-124.5.degree. C.
[1196] NMR(CDCl.sub.3) .delta.: 2.45(3H,s), 3.11(3H,s), 3.99(3H,s),
6.56(1H,d,J=8.6 Hz), 7.18(1H,dd,J=8.6 & 2.5 Hz),
7.31(2H,d,J=8.4 Hz), 7.54(2H,d,J=8.4 Hz), 7.96(1H,d,J=2.5 Hz),
8.38(1H,s).
Example 86
[1197] Synthesis of
2'-Amino-4'-chloro-N-methyl-p-toluenesulfonanilide
[1198] (Compound No. 61)
[1199] A mixture of
4'-chloro-N-methyl-2'-nitro-p-toluenesulfonanilide (7.11 g (20.9
mmol)), stannous chloride (14.7 g (62.6 mmol)) and ethanol (100.0
ml) was stirred at room temperature for 45 minutes, and at
50.degree. C. for 16 hours. After being allowed to cool to room
temperature, the reaction mixture was neutralized with a saturated
aqueous solution of sodium bicarbonate and the insolubles were
removed by filtration. The filtrate was extracted with ethyl
acetate and the extract was dried over anhydrous magnesium sulfate
and concentrated under reduced pressure. The residue was subjected
to silica gel column chromatography with acetone-chloroform-hexane
(1:3:5) as eluent to give 5.22 g (81%) of the title compound as
white crystals.
[1200] mp: 101.5-102.5.degree. C.
[1201] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 3.10(3H,s),
3.65(2H,brs), 6.21(1H,d,J=8.5 Hz), 6.50(1H,dd,J=8.5 &2.3 Hz),
6.81(1H,d,J=2.3 Hz), 7.31(2H,d,J=8.3 Hz), 7.58(2H,d,J=8.3 Hz).
Example 87
[1202] Synthesis of
[1203] 4'-chloro-N-methyl-2'-nitroso-p-toluenesulfonanilide
(Compound No. 284)
[1204] To a solution of
2'-amino-4'-chloro-N-methyl-p-toluenesulfonanilide (1.50 g (4.83
mmol)) in chloroform (20.0 ml), 70% mCPBA (m-chloro-perbenzoic
acid) (2.38 g) was added with stirring at room temperature. After
being stirred for 3 days at room temperature, saturated aqueous
solution of sodium bicarbonate was added to the reaction mixture
and the resulting mixture was extracted with chloroform. The
extract was dried over anhydrous magnesium sulfate and concentrated
under reduced pressure. The residue was subjected to silica gel
column chromatography with ethyl acetate-hexane (1:6) as eluent to
give 1.15 g (73%) of the title compound as blue-green crystals.
[1205] mp: 113.0-114.5.degree. C.
[1206] NMR(CDCl.sub.3) .delta.: 2.40(3H,s), 3.63(3H,s),
6.09(1H,dd,J=1.8 & 1.1 Hz), 7.17(2H,m), 7.45(2H,d,J=8.3 Hz),
7.66(1H,d,J=1.8 Hz), 7.66(1H,d,J=1.1 Hz).
Example 88
[1207] Synthesis of
[1208] 2'-Azoxycyano-4'-chloro-N-methyl-p-toluenesulfonanilide
[1209] (Compound No. 393)
[1210] To a solution of
4'-chloro-N-methyl-2'-nitroso-p-toluenesulfonanili- de (0.50 g
(1.54 mmol)) in DMF (6.0 ml), NBS (N-bromosuccinimide) (0.28 g
(1.54 mmol)) was added with stirring at room temperature. To the
resulting mixture, after 20 minutes' stirring at room temperature,
a solution of cyanamide (0.10 g (2.31 mmol)) in water (1.0 ml) was
added dropwise and the mixture was stirred at room temperature for
2 days. Water was added to the reaction mixture and the mixture was
extracted with ethyl acetate. The extract was dried over anhydrous
magnesium sulfate and concentrated under reduced pressure. The
residue was subjected to silica gel column chromatography with
acetone-chloroform-hexane (1:3:8) as eluent to give 0.32 g (57%) of
the title compound as pale yellow-white crystals.
[1211] mp: 140.0-142.0.degree. C.
[1212] NMR(CDCl.sub.3) .delta.: 2.46(3H,s), 3.24(3H,s),
7.11(1H,d,J=8.6 Hz), 7.31(2H,d,J=8.4 Hz), 7.52(2H,d,J=8.4 Hz),
7.57(1H,d,J=8.6 Hz), 7.84(1H,d,J=2.5 Hz).
Example 89
[1213] Synthesis of 4'-Cyano-N-ethyl-p-toluenesulfonanilide
[1214] (Compound No. 29)
[1215] To a suspension of sodium hydride (65%, 3.39 g (91.8 mmol))
in DMF (60.0 ml), 4'-cyano-p-toluenesulfonanilide (10.0 g (36.7
mmol)) was added with stirring at room temperature. To the
resulting mixture, after stirring for an hour at room temperature,
diethyl sulfate (12.0 ml (91.8 mmol)) was added dropwise, and the
resulting mixture was heated with stirring at 75.degree. C. for 4
hours. Then, the reaction mixture was allowed to cool to room
temperature, poured into water and extracted with ethyl acetate.
The extract was washed with dilute hydrochloric acid and a
saturated aqueous solution of sodium chloride, dried over anhydrous
magnesium sulfate, and concentrated under reduced pressure. The
residue was subjected to silica gel column chromatography with
chloroform as eluent, to give 9.8 g (89%) of the title compound as
white crystals.
[1216] mp: 85.4-86.6.degree. C.
[1217] NMR(CDCl.sub.3) .delta.: 1.08(3H,t, J=7.1 Hz), 2.43(3H,s),
3.63(2H,q,J=7.1 Hz), 7.15-7.30(4H,m), 7.44(2H,dt,J=8.4 & 2.0
Hz), 7.62(2H,dt,J=8.4 & 2.0 Hz).
Example 90
[1218] Synthesis of
5-Chloro-N-(4-cyano-2-nitrophenyl)-N-ethyl-2-thiophene- sulfonamide
(Compound No. 415)
[1219] (1) 4'-Cyano-N-ethyl-p-toluenesulfonanilide (6.95 g (23.1
mmol) was dissolved in concentrated sulfuric acid (20.0 ml) under
cooling with ice. To this, 97% fuming nitric acid (1.00 ml (23.4
mmol)) was added dropwise and the mixture was stirred for 30
minutes under cooling with ice. The resulting mixture was poured
into ice-water, followed by extraction with ethyl acetate. The
extract was washed with water, dried over anhydrous magnesium
sulfate and concentrated under reduced pressure. The residue was
subjected to silica gel column chromatography with ethyl
acetate-hexane (1:3) as eluent, to give 1.25 g (28%) of
4-cyano-N-ethyl-2-nitroaniline as yellow crystals.
[1220] mp: 130.0-131.5.degree. C.
[1221] NMR(CDCl.sub.3) .delta.: 1.41(3H,t,J=7.2 Hz),
3.42(2H,dq,J=5.1 & 7.2 Hz), 6.91(1H,d,J=9.0 Hz),
7.61(1H,dd,J=9.0 & 2.0 Hz), 8.33(1H,br), 8.52(1H,d,J=2.0
Hz).
[1222] (2) To a suspension of sodium hydride (60%, 0.10 g (2.50
mmol)) in tetrahydrofuran (THF) (3.0 ml),
4-cyano-N-ethyl-2-nitroaniline (0.38 g (1.99 mmol)) was added with
stirring at room temperature. To the mixture, upon stirring for 15
minutes at room temperature and after the solution had turned deep
purple, 5-chloro-2-thiophenesulfonyl chloride (0.55 g (2.53 mmol))
was added and the resulting mixture was stirred at room temperature
for 18 hours. The reaction mixture was poured into water and the
resulting mixture was extracted with ethyl acetate. The extract was
washed with a saturated aqueous solution of sodium chloride, dried
over anhydrous magnesium sulfate and concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:3) as eluent, to give
0.22 g (30%) of the title compound as yellow crystals.
[1223] mp: 101.5-103.0.degree. C.
[1224] NMR(CDCl.sub.3) .delta.: 1.24(3H,t,J=7.2 Hz),
3.75(2H,q,J=7.2 Hz), 6.96(1H,d,J=4.1 Hz), 7.25(1H,d,J=4.1 Hz),
7.36(1H,d,J=8.3 Hz), 7.88(1H,dd,J=8.3 & 1.9 Hz),
8.22(1H,d,J=1.9 Hz).
Example 91
[1225] Synthesis of
5-Chloro-N-(4-chloro-2-nitrophenyl)-N,1,3-trimethyl-4--
pyrazolesulfonanilide (Compound No. 377)
[1226] To a suspension of sodium hydride (65%, 0.14 g (3.86 mmol)
in DMF (5.0 ml), 4-chloro-N-methyl-2-nitroaniline (0.48 g (2.57
mmol)) was added with stirring at room temperature. To the mixture,
upon stirring for one hour at room temperature and after the
solution had turned deep purple,
5-chloro-1,3-dimethyl-4-pyrazolesulfonyl chloride (0.70 g (3.06
mmol)) was added and the resulting mixture was stirred at room
temperature for 16 hours. Upon addition of water to the reaction
mixture, a solid separated. The solid was filtered and, after
washing with water and drying, subjected to silica gel column
chromatography with acetone-chloroform-hexane (1:3:8 to 1:0:5) as
eluent, to give 0.55 g (56%) of the title compound as white
crystals.
[1227] mp: 102.0-103.0.degree. C.
[1228] NMR(CDCl.sub.3) .delta.: 2.14(3H,s), 3.33(3H,s), 3.81(3H,s),
7.41(1H,d,J=8.6 Hz), 7.57(1H,dd,J=8.6 & 2.4 Hz),
7.82(1H,d,J=2.4 Hz).
Example 92
[1229] Synthesis of
N-(4-Chloro-2-nitrophenyl)-N,3,5-trimethyl-4-isoxazole- sulfonamide
(Compound No. 376)
[1230] (1) To a suspension of potassium carbonate (0.18 g (1.28
mmol)) in acetonitrile (5.0 ml), 4-chloroaniline (0.33 g (2.56
mmol)), 3,5-dimethyl-4-isoxazolesulfonyl chloride (0.50 g (2.56
mmol)), 18-crown-6 (0.20 g (0.77 mmol)), were added with stirring
at room temperature and the resulting mixture was stirred for 16
hours at the same temperature. Then, water (15.0 ml) was added to
the reaction mixture and the resulting mixture was extracted with
ethyl acetate. The extract was dried over anhydrous magnesium
sulfate and concentrated under reduced pressure. The residue was
subjected to silica gel column chromatography with chloroform as
eluent, to give 0.68 g (92%) of
N-(4-chlorophenyl)-3,5-dimethyl-4-isoxazolesulfonamide.
[1231] mp: 143.5-144.3.degree. C.
[1232] NMR(CDCl.sub.3) .delta.: 2.31(3H,s), 3.46(3H,s),
6.92(1H,brs), 7.04(2H,d,J=8.8 Hz), 7.29(2H,d,J=8.8 Hz).
[1233] (2) To a solution of
N-(4-Chlorophenyl)-3,5-dimethyl-4-isoxazolesul- fonamide (1.10 g
(3.84 mmol)) in acetic acid (4.0 ml), fuming nitric acid (0.20 ml
(4.68 mmol)) was added dropwise with stirring at room temperature,
and the mixture was heated at 50.degree. C. for one hour with
stirring. Water (20.0 ml) was added to the reaction mixture and the
resulting mixture was extracted with ethyl acetate. The extract was
washed with aqueous sodium hydroxide solution and a saturated
aqueous solution of sodium chloride, dried over anhydrous magnesium
sulfate and concentrated under reduced pressure. The residue was
subjected to silica gel column chromatography with
acetone-chloroform-hexane (1:3:8) as eluent, to give 0.82 g (64%)
of N-(4-chloro-2-nitrophenyl)-3,5 dimethyl-4-isoxazolesulfonamide
as yellow crystals.
[1234] mp: 129.5-130.7.degree. C.
[1235] NMR(CDCl.sub.3) .delta.: 2.18(3H,s), 2.35(3H,s),
7.44(1H,d,J=8.7 Hz), 7.81(1H,dd,J=8.7 & 2.5 Hz),
8.10(1H,d,J=2.5 Hz), 10.70(1H,brs).
[1236] (3) To a suspension of sodium hydride (65%, 0.05 g (1.36
mmol)) in DMF (3.0 ml),
N-(4-chloro-2-nitrophenyl)-3,5-dimethyl-4-isoxazolesulfonam- ide
(0.30 g (0.90 mmol)) was added with stirring at room temperature.
To the mixture, after stirring for one hour at room temperature,
dimethyl sulfate (0.13 ml (1.36 mmol)) was added dropwise, and the
mixture was stirred for 16 hours. Water (20.0 ml) was added to the
reaction mixture and the resulting mixture was extracted with ethyl
acetate. The extract was dried over anhydrous magnesium sulfate and
concentrated under reduced pressure. The residue was subjected to
silica gel column chromatography with acetone-hexane (1:4) as
eluent, to give 0.11 g (35%) of the title compound as white
crystals.
[1237] mp: 99.0-101.0.degree. C.
[1238] NMR(CDCl.sub.3) .delta.: 2.21(3H,s), 2.40(3H,s), 3.33(3H,s),
7.40(1H,d,J=8.6 Hz), 7.61(1H,dd,J=8.6 & 2.4 Hz),
7.86(1H,d,J=2.4 Hz).
Example 93
[1239] Synthesis of
[1240] 4'-Chloro-4-cyano-N-ethyl-2'-nitrobenzenesulfonanilide
(Compound No. 356)
[1241] To a suspension of sodium hydride (60%, 0.10 g (2.50 mmol))
in tetrahydrofuran (THF) (3.0 ml), 4-chloro-N-ethyl-2-nitroaniline
(0.40 g (1.99 mmol)) was added with stirring at room temperature.
To the mixture, after stirring for 30 minutes at room temperature,
4-cyanobenzenesulfonyl chloride (0.50 g (2.48 mmol)) was added and
the resulting mixture was stirred at room temperature for 3 hours.
The reaction mixture was poured into water and the resulting
mixture was extracted with ethyl acetate. The extract was washed
with a saturated aqueous solution of sodium chloride, dried over
anhydrous magnesium sulfate and concentrated under reduced
pressure. The residue was subjected to silica gel column
chromatography with ethyl acetate-hexane (1:2) as eluent, to give
0.47 g (64%) of the title compound as pale yellow crystals. mp:
146.0-148.0.degree. C.
[1242] NMR(CDCl.sub.3) .delta.: 1.22(3H,t,J=7.2 Hz),
3.71(2H,q,J=7.2 Hz), 7.16(1H,d,J=8.5 Hz), 7.58(1H,dd,J=8.5 &
2.5 Hz), 7.78(4H,s), 7.89(1H,d,J=2.5 Hz).
[1243] Table 1 shows the compound (I.sup.0) which can be prepared
by the methods similar to those in Examples 1 to 93 or based upon
them (for example according to the methods of reaction equations
from (A) to (D) and synthetic methods form (D) to (T)).
[1244] Abbreviations used in the Table have the meanings which
follow: Me: methyl group, Et: ethyl group, n-Pr: n-propyl group,
i-Pr: isopropyl group, c-Pr: cyclopropyl group, n-Bu: n-butyl
group, i-Bu: isobutyl group, s-Bu: s-butyl group, t-Bu: t-butyl
group, Ph: phenyl group, Ac: acetyl group.
1TABLE 1 46 Compound No. A.sup.0 X.sup.0 Z.sup.0 B.sup.0 Melting
point (.degree. C.) 4-Me-Ph -- Me 4-Me-Ph 2 4-Me-Ph -- Me 4-Et-Ph
an oil.sup.1) 3 4-Me-Ph -- Me 4-(n-Pr)-Ph 4 4-Me-Ph -- Me
4-(i-Pr)-Ph 92.5-93.5 5 4-Me-Ph -- Me 4-(n-Bu)-Ph 6 4-Me-Ph -- Me
2-F-Ph 7 4-Me-Ph -- Me 3-F-Ph 8 4-Me-Ph -- Me 4-F-Ph 92.0-94.5 9
4-Me-Ph -- Me 2-Cl-Ph 98.0-99.0 10 4-Me-Ph -- Me 3-Cl-Ph 11 4-Me-Ph
-- Me 4-Cl-Ph 12 4-NH.sub.2-Ph -- Me 4-Cl-Ph 170.0-174.0 13
4-AcNH-Ph -- Me 4-Cl-Ph 195.0-199.0 14 4-NO.sub.2-Ph -- Me 4-Cl-Ph
183.0-184.0 15 3,5-Me.sub.2-4-isoxazolyl -- Me 4-Cl-Ph 109.0-112.0
16 4-Me-Ph -- Et 4-Cl-Ph 17 4-Me-Ph -- Me 2-Br-Ph 18 4-Me-Ph -- Me
3-Br-Ph 19 4-Me-Ph -- Me 4-Br-Ph 82.5-83.5 20 4-Me-Ph -- Me
2-SMe-Ph 120.0-122.0 21 4-Me-Ph -- Me 2-SOMe-Ph 22 4-Me-Ph -- Me
2-SO.sub.2Me-Ph 191.0-194.0 23 4-Me-Ph -- Me 2-COOMe-Ph 91.0-94.0
24 4-Me-Ph -- Me 2-COOH-Ph 161.0-166.0 25 4-Me-Ph -- Me 2-CN-Ph
138.5-140.0 26 4-Me-Ph -- SO.sub.2-(4-MePh) 2-CN-Ph 179.5-181.0 27
4-Me-Ph -- Me 3-CN-Ph 112.0-114.5 28 4-Me-Ph -- Me 4-CN-Ph
117.0-120.0 29 4-Me-Ph -- Et 4-CN-Ph 85.4-86.6 30 4-Me-Ph -- Me
2-CF.sub.3-Ph 122.5-124.0 31 4-Me-Ph -- SO.sub.2-(4-Me-Ph)
2-CF.sub.3-Ph 176.0-177.5 32 4-Me-Ph -- Me 3-CF.sub.3-Ph
100.0-102.0 33 4-Me-Ph -- Me 4-CF.sub.3-Ph 75.0-76.0 34 4-Me-Ph --
Me 2-OCF.sub.3-Ph 35 4-Me-Ph -- Me 3-OCF.sub.3-Ph 36 4-Me-Ph -- Me
4-OCF.sub.3-Ph 61.5-63.0 37 Ph -- Me 2-NO.sub.2-Ph 38 4-Me-Ph -- Me
2-NO.sub.2-Ph 131.5-132.5 39 4-Me-Ph -- SO.sub.2-(4-Me-Ph)
2-NO.sub.2-Ph 184.5-186.5 40 4-Me-Ph -- Me 3-NO.sub.2-Ph
108.0-109.0 41 4-Me-Ph -- Me 4-NO.sub.2-Ph 179.0-181.0 42 4-Me-Ph
-- Me 3,4-(OMe).sub.2-Ph 108.5-109.5 43 4-Me-Ph -- Me
3,4-(OCH.sub.2O)-Ph 124.0-125.0 44 4-Me-Ph -- Me
3,4-(OCF.sub.2O)-Ph 45 4-Me-Ph -- Me 2-F-4-Cl-Ph 46 4-Me-Ph -- Et
2-F-4-Cl-Ph 47 4-Me-Ph -- n-Pr 2-F-4-Cl-Ph 48 4-Me-Ph -- Me
2,4-F.sub.2-Ph 49 4-Me-Ph -- Et 2,4-F.sub.2-Ph 50 4-Me-Ph -- n-Pr
2,4-F.sub.2-Ph 51 4-Me-Ph -- Me 2,4-Cl.sub.2-Ph 86.0-87.0 52
4-Me-Ph -- Et 2,4-Cl.sub.2-Ph 53 4-Me-Ph -- n-Pr 2,4-Cl.sub.2-Ph 54
4-Me-Ph -- Me 2,6-Cl.sub.2-Ph 55 4-Me-Ph -- Et 2,6-Cl.sub.2-Ph 56
4-Me-Ph -- n-Pr 2,6-Cl.sub.2-Ph 57 4-Me-Ph -- Me 3,4-Cl.sub.2-Ph
85.0-86.0 58 4-Me-Ph -- Et 3,4-Cl.sub.2-Ph 59 4-Me-Ph -- Me
3,5-Cl.sub.2-Ph 60 4-Me-Ph -- Et 3,5-Cl.sub.2-Ph 61 4-Me-Ph -- Me
2-NH.sub.2-4-Cl-Ph 101.5-102.5 62 4-Me-Ph -- Me 4-Cl-2-SMe-Ph
84.5-86.0 63 4-Me-Ph -- Me 4-Cl-2-SOMe-Ph 142.0-143.5 64 4-Me-Ph --
Me 4-Cl-2-SO.sub.2Me-Ph 189.5-191.0 65 4-Me-Ph -- Me
4-Cl-2-CH.sub.2OH-Ph 130.0-132.0 66 4-Me-Ph -- Me 4-Cl-2-CHO-Ph
123.0-124.0 67 4-Me-Ph -- Me 4-Cl-2-(CH.dbd.NOH)-Ph 160.5-162.0 68
4-Me-Ph -- Me 4-Cl-2-(CH.dbd.NOMe)-Ph 123.5-124.5 69 4-Me-Ph -- Me
4-Cl-2-(CH.dbd.N--NH.sub.2)-Ph 107.5-109.5 70 4-Me-Ph -- Me
4-Cl-2-(CH.dbd.N--NMe.sub.2)-Ph 114.0-115.5 71 4-Me-Ph -- Me
4-Cl-2-COOH-Ph 175.0-177.0 72 4-Me-Ph -- Et 4-Cl-2-COOH-Ph
163.0-165.0 73 4-Me-Ph -- i-Pr 4-Cl-2-COOH-Ph 175.0-176.5 74
4-Me-Ph -- Me 2-Cl-4-COOMe-Ph 75 4-Me-Ph -- Me 4-Cl-2-COOMe-Ph
65.5-67.0 76 4-Me-Ph -- Et 4-Cl-2-COOMe-Ph 105.0-107.0 77 4-Me-Ph
-- i-Pr 4-Cl-2-COOMe-Ph 113.5-115.5 78 4-Me-Ph -- Me
2-Cl-4-CONH.sub.2-Ph 79 4-Me-Ph -- Me 4-Cl-2-CONH.sub.2-Ph
176.5-178.0 80 4-Me-Ph -- Et 4-Cl-2-CONH.sub.2-Ph 148.5-150.0 81
4-Me-Ph -- i-Pr 4-Cl-2-CONH.sub.2-Ph 177.0-178.5 82 4-Me-Ph -- Me
2-Cl-4-CSNH.sub.2-Ph 83 4-Me-Ph -- Me 4-Cl-2-CSNH.sub.2-Ph
180.5-182.5 84 4-Me-Ph -- Et 4-Cl-2-CSNH.sub.2-Ph 180.0-182.0 85
4-Me-Ph -- i-Pr 4-Cl-2-CSNH.sub.2-Ph 189.0-191.0 86 4-Me-Ph -- Me
4-Cl-2-[C(SMe).dbd.NH]-Ph (*) amorphous.sup.2) 87 4-Me-Ph -- Et
4-Cl-2-[C(SMe).dbd.NH]-Ph (*) or >160 (dec.) 88 4-Me-Ph -- Et
4-Cl-2-[C(SEt).dbd.NH]-Ph (*) or >161 (dec.) 89 4-Me-Ph -- Et
4-Cl-2-[C(S(i-Pr)).dbd.NH]-Ph (*) or >155 (dec.) 90 4-Me-Ph --
Me 4-Cl-2-CONMe.sub.2-Ph an oil.sup.3) 91 4-Me-Ph -- Me
2-Cl-4-CN-Ph 92 4-Me-Ph -- Et 2-Cl-4-CN-Ph 93 4-Me-Ph -- i-Pr
2-Cl-4-CN-Ph 94 4-Me-Ph -- Me 4-Cl-2-CN-Ph 145.0-147.0 95 4-Me-Ph
-- Et 4-Cl-2-CN-Ph 138.5-140.5 96 4-Me-Ph -- n-Pr 4-Cl-2-CN-Ph 97
4-Me-Ph -- i-Pr 4-Cl-2-CN-Ph 129.5-130.5 98 4-Me-Ph -- c-Pr
4-Cl-2-CN-Ph 99 4-Me-Ph -- Me 2-CN-4-SMe-Ph 139.0-140.0 100 4-Me-Ph
-- Et 2-CN-4-SMe-Ph 136.0-137.0 101 4-Me-Ph -- i-Pr 2-CN-4-SMe-Ph
134.0-136.0 102 4-Me-Ph -- Me 2-CN-4-SOMe-Ph 103 4-Me-Ph -- Et
2-CN-4-SOMe-Ph 104 4-Me-Ph -- i-Pr 2-CN-4-SOMe-Ph 105 4-Me-Ph -- Me
2-CN-4-SO.sub.2Me-Ph 179.0-180.5 106 4-Me-Ph -- Et
2-CN-4-SO.sub.2Me-Ph 154.5-156.0 107 4-Me-Ph -- i-Pr
2-CN-4-SO.sub.2Me-Ph 184.0-186.0 108 4-Me-Ph -- Et 2-CN-4-COOH-Ph
178.5-181.5 109 4-Me-Ph -- Et 2-CN-4-COOMe-Ph 135.6-136.8 110
4-Me-Ph -- SO.sub.2-(4-Me-Ph) 2-CN-4-COOMe-Ph 166.5-167.5 111
4-Me-Ph -- Et 2-CN-4-CONH.sub.2-Ph 163.5-165.0 112 4-Me-Ph -- Me
2,4-(CN).sub.2-Ph 146.0-147.3 113 4-Me-Ph -- Et 2,4-(CN).sub.2-Ph
184.5-185.5 114 4-Me-Ph -- i-Pr 2,4-(CN).sub.2-Ph 157.2-157.7 115
4-Me-Ph -- SO.sub.2-(4-Me-Ph) 2,4-(CN).sub.2-Ph 195.0-196.5 116
4-Me-Ph -- Me 4-Cl-2-CF.sub.3-Ph 143.0-144.5 117 4-Me-Ph -- Et
4-Cl-2-CF.sub.3-Ph 118 4-Me-Ph -- Me 3,5-(CF.sub.3).sub.2-Ph
110.5-113.0 119 4-Me-Ph -- Me 4-Me-2-NO.sub.2-Ph 123.0-124.0 120
4-Me-Ph -- Et 4-Me-2-NO.sub.2-Ph 121 4-Me-Ph -- n-Pr
4-Me-2-NO.sub.2-Ph 122 4-Me-Ph -- i-Pr 4-Me-2-NO.sub.2-Ph 123
4-Me-Ph -- c-Pr 4-Me-2-NO.sub.2-Ph 124 4-Me-Ph -- n-Bu
4-Me-2-NO.sub.2-Ph 125 4-Me-Ph -- Me 2-Me-4-NO.sub.2-Ph 103.0-104.0
126 4-Me-Ph -- Me 4-Me-3-NO.sub.2-Ph 103.5-106.0 127 4-Me-Ph -- Me
4-Et-2-NO.sub.2-Ph 137.0-139.0 128 4-Me-Ph -- Me
4-(i-Pr)-2-NO.sub.2-Ph 135.0-136.0 129 4-Me-Ph -- Me
4-C.ident.CH-2-NO.sub.2-Ph 130 4-Me-Ph -- Et
4-C.ident.CH-2-NO.sub.2-Ph 131 4-Me-Ph -- n-Pr
4-C.ident.CH-2-NO.sub.2-Ph 132 4-Me-Ph -- Me 4-CHO-2-NO.sub.2-Ph
133 4-Me-Ph -- Et 4-CHO-2-NO.sub.2-Ph 134 4-Me-Ph -- n-Pr
4-CHO-2-NO.sub.2-Ph 135 4-Me-Ph -- Me 4-CH.dbd.NOMe-2-NO.sub.2-Ph
136 4-Me-Ph -- Et 4-CH.dbd.NOMe-2-NO.sub.2-Ph 137 4-Me-Ph -- n-Pr
4-CH.dbd.NOMe-2-NO.sub.2-Ph 138 4-Me-Ph -- Me 4-COOMe-2-NO.sub.2-Ph
139 4-Me-Ph -- Et 4-COOMe-2-NO.sub.2-Ph 140 4-Me-Ph -- n-Pr
4-COOMe-2-NO.sub.2-Ph 141 4-Me-Ph -- i-Pr 4-COOMe-2-NO.sub.2-Ph 142
4-Me-Ph -- c-Pr 4-COOMe-2-NO.sub.2-Ph 143 4-Me-Ph -- n-Bu
4-COOMe-2-NO.sub.2-Ph 144 4-Me-Ph -- Me 4-CONH.sub.2-2-NO.sub.2-Ph
145 4-Me-Ph -- Et 4-CONH.sub.2-2-NO.sub.2-Ph 146 4-Me-Ph -- n-Pr
4-CONH.sub.2-2-NO.sub.2-Ph 147 4-Me-Ph -- i-Pr
4-CONH.sub.2-2-NO.sub.2-Ph 148 4-Me-Ph -- c-Pr
4-CONH.sub.2-2-NO.sub.2-Ph 149 4-Me-Ph -- n-Bu
4-CONH.sub.2-2-NO.sub.2-Ph 150 4-Me-Ph -- Me
4-CSNH.sub.2-2-NO.sub.2-Ph 151 4-Me-Ph -- Et
4-CSNH.sub.2-2-NO.sub.2-Ph 152 4-Me-Ph -- n-Pr
4-CSNH.sub.2-2-NO.sub.2-Ph 153 4-Me-Ph -- i-Pr
4-CSNH.sub.2-2-NO.sub.2-Ph 154 4-Me-Ph -- c-Pr
4-CSNH.sub.2-2-NO.sub.2-Ph 155 4-Me-Ph -- n-Bu
4-CSNH.sub.2-2-NO.sub.2-Ph 156 4-Me-Ph -- Me 4-OH-2-NO.sub.2-Ph
173.0-174.0 157 4-Me-Ph -- Me 2-OMe-4-NO.sub.2-Ph 158 4-Me-Ph -- Et
2-OMe-4-NO.sub.2-Ph 159 4-Me-Ph -- n-Pr 2-OMe-4-NO.sub.2-Ph 160
4-Me-Ph -- i-Pr 2-OMe-4-NO.sub.2-Ph 161 4-Me-Ph -- c-Pr
2-OMe-4-NO.sub.2-Ph 162 4-Me-Ph -- n-Bu 2-OMe-4-NO.sub.2-Ph 163 Ph
-- Me 4-OMe-2-NO.sub.2-Ph 90.0-91.5 164 Ph -- Et
4-OMe-2-NO.sub.2-Ph 165 Ph -- n-Pr 4-OMe-2-NO.sub.2-Ph 166 Ph --
i-Pr 4-OMe-2-NO.sub.2-Ph 167 Ph -- c-Pr 4-OMe-2-NO.sub.2-Ph 168 Ph
-- n-Bu 4-OMe-2-NO.sub.2-Ph 169 2-Me-Ph -- Me 4-OMe-2-NO.sub.2-Ph
an oil.sup.4) 170 3-Me-Ph -- Me 4-OMe-2-NO.sub.2-Ph 171 4-Me-Ph --
Me 4-OMe-2-NO.sub.2-Ph 123.0-124.0 172 2,4,6-Me.sub.3-Ph -- Me
4-OMe-2-NO.sub.2-Ph 161.0-163.0 173 3-OMe-Ph -- Me
4-OMe-2-NO.sub.2-Ph 174 4-OMe-Ph -- Me 4-OMe-2-NO.sub.2-Ph
146.0-147.0 175 2-Cl-Ph -- Me 4-OMe-2-NO.sub.2-Ph 176 3-Cl-Ph -- Me
4-OMe-2-NO.sub.2-Ph 177 4-Cl-Ph -- Me 4-OMe-2-NO.sub.2-Ph
162.5-163.5 178 4-Cl-Ph -- Et 4-OMe-2-NO.sub.2-Ph 179 4-Cl-Ph --
n-Pr 4-OMe-2-NO.sub.2-Ph 180 4-Cl-Ph -- i-Pr 4-OMe-2-NO.sub.2-Ph
181 4-Cl-Ph -- c-Pr 4-OMe-2-NO.sub.2-Ph 182 4-Cl-Ph -- n-Bu
4-OMe-2-NO.sub.2-Ph 183 4-Br-Ph -- Me 4-OMe-2-NO.sub.2-Ph 184
2,5-Cl.sub.2-Ph -- Me 4-OMe-2-NO.sub.2-Ph 113.0-115.0 185
2-COOMe-Ph -- Me 4-OMe-2-NO.sub.2-Ph 186 3-COOMe-Ph -- Me
4-OMe-2-NO.sub.2-Ph 187 4-COOMe-Ph -- Me 4-OMe-2-NO.sub.2-Ph 188
2-CN-Ph -- Me 4-OMe-2-NO.sub.2-Ph 189 3-CN-Ph -- Me
4-OMe-2-NO.sub.2-Ph 190 4-CN-Ph -- Me 4-OMe-2-NO.sub.2-Ph 191
2-CF.sub.3-Ph -- Me 4-OMe-2-NO.sub.2-Ph 192 3-CF.sub.3-Ph -- Me
4-OMe-2-NO.sub.2-Ph 193 4-CF.sub.3-Ph -- Me 4-OMe-2-NO.sub.2-Ph 194
2-NO.sub.2-Ph -- Me 4-OMe-2-NO.sub.2-Ph 136.5-138.5 195
3-NO.sub.2-Ph -- Me 4-OMe-2-NO.sub.2-Ph 123.5-125.0 196
4-NO.sub.2-Ph -- Me 4-OMe-2-NO.sub.2-Ph 157.5-158.5 197
4-NO.sub.2-Ph -- Et 4-OMe-2-NO.sub.2-Ph 198 4-NO.sub.2-Ph -- n-Pr
4-OMe-2-NO.sub.2-Ph 199 4-NO.sub.2-Ph -- i-Pr 4-OMe-2-NO.sub.2-Ph
200 1-CONEt.sub.2-triazol-3-yl -- Me 4-OMe-2-NO.sub.2-Ph
119.5-120.5 201 1-naphthyl -- Me 4-OMe-2-NO.sub.2-Ph 123.0-124.0
202 2-naphthyl -- Me 4-OMe-2-NO.sub.2-Ph 180.0-182.0 203 2-pyridyl
-- Me 4-OMe-2-NO.sub.2-Ph 100.0-101.0 204 8-quinolyl -- Me
4-OMe-2-NO.sub.2-Ph 166.0-170.0 205 4-Me-Ph -- Et
4-OMe-2-NO.sub.2-Ph 91.0-92.0 206 4-Me-Ph -- n-Pr
4-OMe-2-NO.sub.2-Ph 85.0-86.0 207 4-Me-Ph -- i-Pr
4-OMe-2-NO.sub.2-Ph 148.0-149.5 208 4-Me-Ph -- c-Pr
4-OMe-2-NO.sub.2-Ph 209 4-Me-Ph -- n-Bu 4-OMe-2-NO.sub.2-Ph an
oil.sup.5) 210 4-Me-Ph -- CH.sub.2CH.dbd.CH.sub.2
4-OMe-2-NO.sub.2-Ph 116.5-117.5 211 4-Me-Ph -- CH.sub.2CH.ident.CH
4-OMe-2-NO.sub.2-Ph 84.0-85.0 212 4-Me-Ph -- CH.sub.2CH.ident.C--I
4-OMe-2-NO.sub.2-Ph 213 4-Me-Ph -- Ac 4-OMe-2-NO.sub.2-Ph
172.5-174.0 214 4-Me-Ph -- SO.sub.2-(4-Me-Ph) 4-OMe-2-NO.sub.2-Ph
180.5-182.0 215 4-Me-Ph -- Me 4-OEt-2-NO.sub.2-Ph 116.0-117.5 216
4-Me-Ph -- Me 4-O(n-Pr)-2-NO.sub.2-Ph 93.0-94.0 217 4-Me-Ph -- Me
4-O(i-Pr)-2-NO.sub.2-Ph 119.5-120.5 218 4-Me-Ph -- Me
4-OAc-2-NO.sub.2-Ph 122.5-123.5 219 4-Me-Ph -- Me
4-(OCH.sub.2OCH.sub.3)-2-NO.sub.2-Ph 110.5-112.0 220 Ph -- Me
4-SMe-2-NO.sub.2-Ph 221 Ph -- Et 4-SMe-2-NO.sub.2-Ph 222 Ph -- n-Pr
4-SMe-2-NO.sub.2-Ph 223 Ph -- i-Pr 4-SMe-2-NO.sub.2-Ph 224 Ph --
c-Pr 4-SMe-2-NO.sub.2-Ph 225 Ph -- n-Bu 4-SMe-2-NO.sub.2-Ph 226
4-Me-Ph -- Me 4-SMe-2-NO.sub.2-Ph 130.0-131.0 227 4-Me-Ph -- Et
4-SMe-2-NO.sub.2-Ph 135.0-136.0 228 4-Me-Ph -- n-Pr
4-SMe-2-NO.sub.2-Ph 229 4-Me-Ph -- i-Pr 4-SMe-2-NO.sub.2-Ph
124.5-126.0 230 4-Me-Ph -- c-Pr 4-SMe-2-NO.sub.2-Ph 231 4-Me-Ph --
n-Bu 4-SMe-2-NO.sub.2-Ph 232 4-Me-Ph -- Me 4-SOMe-2-NO.sub.2-Ph
168.5-170.5 233 4-Me-Ph -- Et 4-SOMe-2-NO.sub.2-Ph 115.0-117.0 234
4-Me-Ph -- n-Pr 4-SOMe-2-NO.sub.2-Ph 235 4-Me-Ph -- i-Pr
4-SOMe-2-NO.sub.2-Ph 157.5-158.5 236 4-Me-Ph -- c-Pr
4-SOMe-2-NO.sub.2-Ph 237 4-Me-Ph -- n-Bu 4-SOMe-2-NO.sub.2-Ph 238
4-Me-Ph -- Me 4-SO.sub.2Me-2-NO.sub.2-Ph 147.0-148.0 239 4-Me-Ph --
Et 4-SO.sub.2Me-2-NO.sub.2-Ph 184.0-184.5 240 4-Me-Ph -- n-Pr
4-SO.sub.2Me-2-NO.sub.2-Ph 241 4-Me-Ph -- i-Pr
4-SO.sub.2Me-2-NO.sub.2-Ph 178.7-179.3 242 4-Me-Ph -- c-Pr
4-SO.sub.2Me-2-NO.sub.2-Ph 243 4-Me-Ph -- n-Bu
4-SO.sub.2Me-2-NO.sub.2-Ph 244 4-Me-Ph -- Me
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 245 4-Me-Ph -- Et
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 246 4-Me-Ph -- n-Pr
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 247 4-Me-Ph -- i-Pr
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 248 4-Me-Ph -- c-Pr
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 249 4-Me-Ph -- n-Bu
4-SO.sub.2NMe.sub.2-2-NO.sub.2-Ph 250 4-Me-Ph -- Me
4-SCN-2-NO.sub.2-Ph 251 4-Me-Ph -- Et 4-SCN-2-NO.sub.2-Ph 252
4-Me-Ph -- n-Pr 4-SCN-2-NO.sub.2-Ph 253 4-Me-Ph -- i-Pr
4-SCN-2-NO.sub.2-Ph 254 4-Me-Ph -- c-Pr 4-SCN-2-NO.sub.2-Ph 255
4-Me-Ph -- n-Bu 4-SCN-2-NO.sub.2-Ph 256 Ph -- Me 4-F-2-NO.sub.2-Ph
257 Ph -- Et 4-F-2-NO.sub.2-Ph 258 Ph -- n-Pr 4-F-2-NO.sub.2-Ph 259
Ph -- i-Pr 4-F-2-NO.sub.2-Ph 260 Ph -- c-Pr 4-F-2-NO.sub.2-Ph 261
Ph -- n-Bu 4-F-2-NO.sub.2-Ph 262 4-Me-Ph -- Me 4-F-2-NO.sub.2-Ph
93.5-94.5 263 4-Me-Ph -- Et 4-F-2-NO.sub.2-Ph 93.0-94.5 264 4-Me-Ph
-- n-Pr 4-F-2-NO.sub.2-Ph 96.0-98.0 265 4-Me-Ph -- i-Pr
4-F-2-NO.sub.2-Ph 129.0-130.0 266 4-Me-Ph --
CH.sub.2CH.dbd.CH.sub.2 4-F-2-NO.sub.2-Ph 76.0-77.0 267 4-Cl-Ph --
Me 4-F-2-NO.sub.2-Ph 268 4-Cl-Ph -- Et 4-F-2-NO.sub.2-Ph 269
4-Cl-Ph -- n-Pr 4-F-2-NO.sub.2-Ph 270 4-Cl-Ph -- i-Pr
4-F-2-NO.sub.2-Ph 271 4-Cl-Ph -- c-Pr 4-F-2-NO.sub.2-Ph 272 4-Me-Ph
-- i-Pr 2-Cl-4-NO.sub.2-Ph 154.0-157.0 273 4-Me-Ph -- Me
4-F-3-NO.sub.2-Ph 119.0-121.0 274 4-Me-Ph -- Me 2-Cl-4-NO.sub.2-Ph
122.0-123.0 275 4-Me-Ph -- Et 2-Cl-4-NO.sub.2-Ph 276 Ph -- Me
4-Cl-2-NO.sub.2-Ph 102.5-103.5 277 Ph -- Et 4-Cl-2-NO.sub.2-Ph
108.0-109.0 278 Ph -- n-Pr 4-Cl-2-NO.sub.2-Ph 279 Ph -- i-Pr
4-Cl-2-NO.sub.2-Ph 129.0-130.5 280 Ph CH.sub.2 Me
4-Cl-2-NO.sub.2-Ph 153.5-155.0 281 Ph CHMe Me 4-Cl-2-NO.sub.2-Ph
282 Ph CH.dbd.CH Me 4-Cl-2-NO.sub.2-Ph 162.0-164.0 283 4-Me-Ph
CMe.dbd.CH Me 4-Cl-2-NO.sub.2Ph 284 4-Me-Ph -- Me 4-Cl-2-NO-Ph
113.0-114.5 285 4-Me-Ph -- Et 4-Cl-2-NO-Ph 286 4-Me-Ph -- i-Pr
4-Cl-2-NO-Ph 287 3-Me-Ph -- Me 4-Cl-2-NO.sub.2-Ph 115.5-117.0 288
4-Me-Ph -- Me 4-Cl-2-NO.sub.2-Ph 97.5-99.0 289 4-Me-Ph -- Et
4-Cl-2-NO.sub.2-Ph 132.5-134.0 290 4-Me-Ph -- n-Pr
4-Cl-2-NO.sub.2-Ph 88.0-89.5 291 4-Me-Ph -- i-Pr 4-Cl-2-NO.sub.2-Ph
112.0-114.0 292 4-Me-Ph -- c-Pr 4-Cl-2-NO.sub.2-Ph 98.5-100.0 293
4-Me-Ph -- n-Bu 4-Cl-2-NO.sub.2-Ph 294 4-Me-Ph -- s-Bu
4-Cl-2-NO.sub.2-Ph 295 4-Me-Ph -- i-Bu 4-Cl-2-NO.sub.2-Ph
127.5-130.0 296 4-Me-Ph -- t-Bu 4-Cl-2-NO.sub.2-Ph 297 4-Me-Ph --
CH.dbd.C.dbd.CH.sub.2 4-Cl-2-NO.sub.2-Ph 298 4-Me-Ph --
CH.dbd.CH.sub.2 4-Cl-2-NO.sub.2-Ph >108 (dec.) 299 4-Me-Ph --
CH.sub.2CH.dbd.CH.sub.2 4-Cl-2-NO.sub.2-Ph 77.0-78.0 300 4-Me-Ph --
CH.sub.2CH.ident.CH 4-Cl-2-NO.sub.2-Ph 122.0-124.5 301 4-Me-Ph --
CH.sub.2CH.ident.C--I 4-Cl-2-NO.sub.2-Ph 302 4-Me-Ph --
CH.sub.2NMe.sub.2 4-Cl-2-NO.sub.2-Ph 303 4-Me-Ph --
CH.sub.2CH.sub.2OH 4-Cl-2-NO.sub.2-Ph 102.0-103.5 304 4-Me-Ph --
CH.sub.2CH.sub.2F 4-Cl-2-NO.sub.2-Ph 305 4-Me-Ph --
CH.sub.2CH.sub.2Br 4-Cl-2-NO.sub.2-Ph 70.0-72.0 306 4-Me-Ph --
CH.sub.2CH.sub.2NMe.sub.2 4-Cl-2-NO.sub.2-Ph 108.0-109.0 307
4-Me-Ph -- CH.sub.2CH.sub.2SMe 4-Cl-2-NO.sub.2-Ph 94.5-95.5 308
4-Me-Ph -- CH.sub.2OCH.sub.3 4-Cl-2-NO.sub.2-Ph 61.0-62.0 309
4-Me-Ph -- CH.sub.2COOMe 4-Cl-2-NO.sub.2-Ph an oil.sup.6) 310
4-Me-Ph -- CH.sub.2CN 4-Cl-2-NO.sub.2-Ph 311 4-Me-Ph -- Ac
4-Cl-2-NO.sub.2-Ph 173.0-175.0 312 4-Me-Ph -- COCH.sub.2Cl
4-Cl-2-NO.sub.2-Ph 195.0-199.0 313 4-Me-Ph -- GOOF3
4-Cl-2-NO.sub.2-Ph 314 4-Me-Ph -- NMe2 4-Cl-2-NO.sub.2-Ph 315
4-Me-Ph -- NHAc 4-Cl-2-NO.sub.2-Ph 316 4-Me-Ph -- NHCOOMe
4-Cl-2-NO.sub.2-Ph 317 4-Me-Ph -- N.dbd.CMe.sub.2
4-Cl-2-NO.sub.2-Ph 318 4-Me-Ph -- SCCl.sub.2F 4-Cl-2-NO.sub.2-Ph
319 4-Me-Ph -- SCF.sub.3 4-Cl-2-NO.sub.2-Ph 320 4-Me-Ph --
SCCl.sub.3 4-Cl-2-NO.sub.2-Ph 321 4-Me-Ph -- SOCF.sub.3
4-Cl-2-NO.sub.2-Ph 322 4-Me-Ph -- SO.sub.2Me 4-Cl-2-NO.sub.2-Ph
163.5-165.5 323 4-Me-Ph -- SO.sub.2-(4-Me-Ph) 4-Cl-2-NO.sub.2-Ph
205.0-206.5 324 4-Me-Ph -- Ph 4-Cl-2-NO.sub.2-Ph 157.0-159.0 325
4-Et-Ph -- Me 4-Cl-2-NO.sub.2-Ph 100.0-101.5 326 4-Et-Ph -- Et
4-Cl-2-NO.sub.2-Ph 123.0-125.0 327 4-Et-Ph -- n-Pr
4-Cl-2-NO.sub.2-Ph 328 4-Et-Ph -- i-Pr 4-Cl-2-NO.sub.2-Ph
117.0-118.5 329 4-F-Ph -- Me 4-Cl-2-NO.sub.2-Ph 140.5-141.5 330
4-F-Ph -- Et 4-Cl-2-NO.sub.2-Ph 155.5-156.5 331 4-F-Ph -- n-Pr
4-Cl-2-NO.sub.2-Ph 332 4-F-Ph -- i-Pr 4-Cl-2-NO.sub.2-Ph
122.0-123.0 333 4-F-Ph -- c-Pr 4-Cl-2-NO.sub.2-Ph 334 4-F-Ph --
n-Bu 4-Cl-2-NO.sub.2-Ph 335 2-Cl-Ph -- Me 4-Cl-2-NO.sub.2-Ph
116.0-117.0 336 3-Cl-Ph -- Me 4-Cl-2-NO.sub.2-Ph 136.5-138.5 337
4-Cl-Ph -- Me 4-Cl-2-NO.sub.2-Ph 158.5-160.5 338 4-Cl-Ph -- Et
4-Cl-2-NO.sub.2-Ph 121.5-123.0 339 4-Cl-Ph -- n-Pr
4-Cl-2-NO.sub.2-Ph 340 4-Cl-Ph -- i-Pr 4-Cl-2-NO.sub.2-Ph
99.5-100.5 341 4-Cl-Ph -- c-Pr 4-Cl-2-NO.sub.2-Ph 342 4-Cl-Ph --
n-Bu 4-Cl-2-NO.sub.2-Ph 343 4-Cl-Ph -- CH.sub.2CH.dbd.CH.sub.2
4-Cl-2-NO.sub.2-Ph 344 4-Cl-Ph -- CH.sub.2C.ident.CH
4-Cl-2-NO.sub.2-Ph 345 4-Cl-Ph -- CH.sub.2C.ident.C--I
4-Cl-2-NO.sub.2-Ph 346 4-Cl-Ph -- Ph 4-Cl-2-NO.sub.2-Ph 347
3,4-Cl.sub.2-Ph -- Me 4-Cl-2-NO.sub.2-Ph 140.5-142.0 348 4-Br-Ph --
Me 4-Cl-2-NO.sub.2-Ph 155.5-157.5 349 4-Br-Ph -- Et
4-Cl-2-NO.sub.2-Ph 350 4-Br-Ph -- n-Pr 4-Cl-2-NO.sub.2-Ph 351
4-Br-Ph -- i-Pr 4-Cl-2-NO.sub.2-Ph 352 4-Br-Ph -- c-Pr
4-Cl-2-NO.sub.2-Ph 353 4-Br-Ph -- n-Bu 4-Cl-2-NO.sub.2-Ph 354
3-CN-Ph -- Et 4-Cl-2-NO.sub.2-Ph 165.0-166.5 355 4-CN-Ph -- Me
4-Cl-2-NO.sub.2-Ph 356 4-CN-Ph -- Et 4-Cl-2-NO.sub.2-Ph 146.0-148.0
357 4-CN-Ph -- n-Pr 4-Cl-2-NO.sub.2-Ph 358 4-CN-Ph -- i-Pr
4-Cl-2-NO.sub.2-Ph 359 4-CN-Ph -- c-Pr 4-Cl-2-NO.sub.2-Ph 360
4-CN-Ph -- n-Bu 4-Cl-2-NO.sub.2-Ph 361 3-CF.sub.3-Ph -- Me
4-Cl-2-NO.sub.2-Ph 120.5-122.0 362 4-CF.sub.3-Ph -- Et
4-Cl-2-NO.sub.2-Ph 105.0-106.0 363 4-OCF.sub.3-Ph -- Me
4-Cl-2-NO.sub.2-Ph 117.0-118.0 364 5-Me-2-thienyl -- Me
4-Cl-2-NO.sub.2-Ph 365 5-Me-2-thienyl -- Et 4-Cl-2-NO.sub.2-Ph 366
5-Me-2-thienyl -- n-Pr 4-Cl-2-NO.sub.2-Ph 367 5-Me-2-thienyl --
i-Pr 4-Cl-2-NO.sub.2-Ph 368 5-Me-2-thienyl -- c-Pr
4-Cl-2-NO.sub.2-Ph 369 5-Me-2-thienyl -- n-Bu 4-Cl-2-NO.sub.2-Ph
370 5-Cl-2-thienyl -- Me 4-Cl-2-NO.sub.2-Ph 85.0-86.0 371
5-Cl-2-thienyl -- Et 4-Cl-2-NO.sub.2-Ph 95.0-96.0 372
5-Cl-2-thienyl -- n-Pr 4-Cl-2-NO.sub.2-Ph 373 5-Cl-2-thienyl --
i-Pr 4-Cl-2-NO.sub.2-Ph 374 5-Cl-2-thienyl -- c-Pr
4-Cl-2-NO.sub.2-Ph 375 5-Cl-2-thienyl -- n-Bu 4-Cl-2-NO.sub.2-Ph
376 3,5-Me.sub.2-4-isoxazolyl -- Me 4-Cl-2-NO.sub.2-Ph 99.0-101.0
377 5-Cl-1,3-Me.sub.2-4-pyrazolyl -- Me 4-Cl-2-NO.sub.2-Ph
102.0-103.0 378 1-Me-4-COOMe-5-pyrazolyl -- Me 4-Cl-2-NO.sub.2-Ph
379 1,3-Me.sub.2-4-COOMe-5-pyrazolyl -- Me 4-Cl-2-NO.sub.2-Ph
236.5-237.5 380 1,3-Me.sub.2-4-COOH-5-pyrazolyl -- Me
4-Cl-2-NO.sub.2-Ph 129.0-130.5 381
1,3-Me.sub.2-4-CONH.sub.2-5-pyrazolyl -- Me 4-Cl-2-NO.sub.2-Ph
164.0-164.5 382 1,3-Me.sub.2-4-CN-5-pyrazolyl -- Me
4-Cl-2-NO.sub.2-Ph 109.0-110.5 383 3-Cl-1-Me-4-COOMe-5-pyraz- olyl
-- Me 4-Cl-2-NO.sub.2-Ph 384 1-Me-4-imidazolyl -- Me
4-Cl-2-NO.sub.2-Ph 199.0-201.5 385 1,2,4-triazol-3-yl -- Me
4-Cl-2-NO.sub.2-Ph 219.5-220.0 386 2-pyridyl -- Me
4-Cl-2-NO.sub.2-Ph 127.0-128.0 387 3-pyridyl -- Me
4-Cl-2-NO.sub.2-Ph 125.5-127.5 388 2,1,3-benzothiadiazol-4-yl -- Me
4-Cl-2-NO.sub.2-Ph 124.5-126.5 389 2-Cl-imidazo[1,2a]pyridin-3-- yl
-- Me 4-Cl-2-NO.sub.2-Ph 390 2-SO.sub.2Rt-imidazo[1,2-a]pyridin--
3-yl -- Me 4-Cl-2-NO.sub.2-Ph 391 2-Cl-imidazo[2,1-b]thiazol-5-yl
-- Me 4-Cl-2-NO.sub.2-Ph 168.0-172.0 392 8-quinolyl -- Me
4-Cl-2-NO.sub.2-Ph 177.0-178.5 393 4-Me-Ph -- Me
4-Cl-2-(NO.dbd.N--CN)-Ph 140.0-142.0 394 4-Me-Ph -- Et
4-Cl-2-(NO.dbd.N--CN)-Ph 395 4-Me-Ph -- i-Pr
4-Cl-2-(NO.dbd.N--CN)-Ph 396 4-Me-Ph -- Me 4-Cl-3-NO.sub.2-Ph
106.0-107.0 397 4-Me-Ph -- Me 5-Cl-2-NO.sub.2-Ph 118.0-120.0 398
4-Me-Ph -- Me 4-Br-2-NO.sub.2-Ph 108.0-110.5 399 4-Me-Ph -- Et
4-Br-2-NO.sub.2-Ph 400 4-Me-Ph -- n-Pr 4-Br-2-NO.sub.2-Ph 401
4-Me-Ph -- i-Pr 4-Br-2-NO.sub.2-Ph 402 4-Me-Ph -- c-Pr
4-Br-2-NO.sub.2-Ph 403 4-Me-Ph -- n-Bu 4-Br-2-NO.sub.2-Ph 404
4-Me-Ph -- Me 4-Br-3-NO.sub.2-Ph 93.0-94.5 405 4-Me-Ph -- Me
4-I-2-NO.sub.2-Ph 406 4-Me-Ph -- Me 4-CN-2-NO.sub.2-Ph 123.0-124.5
407 4-Me-Ph -- Et 4-CN-2-NO.sub.2-Ph 158.0-160.0 408 4-Me-Ph --
n-Pr 4-CN-2-NO.sub.2-Ph 409 4-Me-Ph -- i-Pr 4-CN-2-NO.sub.2-Ph
125.0-126.0 410 4-Me-Ph -- c-Pr 4-CN-2-NO.sub.2-Ph 411 4-Cl-Ph --
Me 4-CN-2-NO.sub.2-Ph 159.5-160.5 412 4-Cl-Ph -- Et
4-CN-2-NO.sub.2-Ph 172.5-174.5 413 4-Cl-Ph -- i-Pr
4-CN-2-NO.sub.2-Ph 167.5-168.5 414 4-CN-Ph -- Et 4-CN-2-NO.sub.2-Ph
171.0-172.0 415 5-Cl-2-thienyl -- Et 4-CN-2-NO.sub.2-Ph 101.5-103.0
416 Ph -- Me 2-CN-4-NO.sub.2-Ph 417 Ph -- Et 2-CN-4-NO.sub.2-Ph 418
Ph -- i-Pr 2-CN-4-NO.sub.2-Ph 419 4-Me-Ph -- Me 2-CN-4-NO.sub.2-Ph
165.0-167.0 420 4-Me-Ph -- Et 2-CN-4-NO.sub.2-Ph 135.0-136.5 421
4-Me-Ph -- i-Pr 2-CN-4-NO.sub.2-Ph 140.5-142.5 422 4-Me-Ph -- Me
2-NO.sub.2-4-OCF.sub.3-Ph 91.0-92.0 423 4-Me-Ph -- Me
2-NO.sub.2-4-CF.sub.3-Ph 145.5-147.0 424 4-Me-Ph -- Et
2-NO.sub.2-4-CF.sub.3-Ph 425 Ph -- Me 2,4-(NO.sub.2).sub.2-Ph
151.5-153.0 426 Ph -- Et 2,4-(NO.sub.2).sub.2-Ph 129.5-131.0 427 Ph
-- n-Pr 2,4-(NO.sub.2).sub.2-Ph 428 Ph -- i-Pr
2,4-(NO.sub.2).sub.2-Ph 429 Ph -- c-Pr 2,4-(NO.sub.2).sub.2-Ph
166.0-168.0 430 Ph -- n-Bu 2,4-(NO.sub.2).sub.2-Ph 431 Ph --
CH.sub.2CH.dbd.CH.sub.2 2,4-(NO.sub.2).sub.2-Ph 432 Ph -- Ph
2,4-(NO.sub.2).sub.2-Ph 433 Ph -- NMe.sub.2 2,4-(NO.sub.2).sub.2-Ph
434 4-Me-Ph -- Me 2,4-(NO.sub.2).sub.2-Ph 130.5-133.0 435 4-Me-Ph
-- Et 2,4-(NO.sub.2).sub.2-Ph 135.0-136.5 436 4-Me-Ph -- n-Pr
2,4-(NO.sub.2).sub.2-Ph 437 4-Me-Ph -- i-Pr 2,4-(NO.sub.2).sub.2-Ph
141.5-142.5 438 4-Me-Ph -- c-Pr 2,4-(NO.sub.2).sub.2-Ph 113.0-114.5
439 4-Me-Ph -- n-Bu 2,4-(NO.sub.2).sub.2-Ph 440 4-Me-Ph -- s-Bu
2,4-(NO.sub.2).sub.2-Ph 441 4-Me-Ph -- i-Bu 2,4-(NO.sub.2).sub.2-Ph
442 4-Me-Ph -- t-Bu 2,4-(NO.sub.2).sub.2-Ph 443 4-Me-Ph --
CH.sub.2CH.dbd.CH.sub.2 2,4-(NO.sub.2).sub.2-Ph 444 4-Me-Ph --
CH.sub.2C.ident.CH 2,4-(NO.sub.2).sub.2-Ph 445 4-Me-Ph --
CH.sub.2C.ident.C--I 2,4-(NO.sub.2).sub.2-Ph 446 4-Me-Ph --
NMe.sub.2 2,4-(NO.sub.2).sub.2-Ph 447 4-Me-Ph -- N.dbd.CMe.sub.2
2,4-(NO.sub.2).sub.2-Ph >175(dec) 448 4-F-Ph -- Me
2,4-(NO.sub.2).sub.2-Ph 172.0-173.5 449 4-Cl-Ph -- Me
2,4-(NO.sub.2).sub.2-Ph 135.0-137.0 450 4-Cl-Ph -- Et
2,4-(NO.sub.2).sub.2-Ph 451 4-Cl-Ph -- n-Pr 2,4-(NO.sub.2).sub.2-Ph
452 4-Cl-Ph -- i-Pr 2,4-(NO.sub.2).sub.2-Ph 453 4-Cl-Ph -- c-Pr
2,4-(NO.sub.2).sub.2-Ph 454 4-Cl-Ph -- n-Bu 2,4-(NO.sub.2).sub.2-Ph
455 4-CN-Ph -- Et 2,4-(NO.sub.2).sub.2-Ph 150.5-152.0 456
5-Cl-2-thienyl -- Me 2,4-(NO.sub.2).sub.2-Ph 156.0-157.5 457
5-Cl-2-thienyl -- Et 2,4-(NO.sub.2).sub.2-Ph 109.0-111.0 458
5-Cl-2-thienyl -- n-Pr 2,4-(NO.sub.2).sub.2-Ph 459 5-Cl-2-thienyl
-- i-Pr 2,4-(NO.sub.2).sub.2-Ph 460 5-Cl-2-thienyl -- n-Bu
2,4-(NO.sub.2).sub.2-Ph 461 4-Me-Ph -- Me
4,5-(OMe).sub.2-2-NO.sub.2-Ph 179.0-181.0 462 4-Me-Ph -- Me
4,5-(OCH.sub.2O)-2-NO.sub.2-Ph 181.0-182.0 463 4-Me-Ph -- Me
4,5-(OCF.sub.2O)-2-NO.sub.2-Ph 464 4-Me-Ph -- Me
4,5-Cl.sub.2-2-NO.sub.2-Ph 185.0-187.0 465 4-Me-Ph -- Me
4-Cl-2,6-(NO.sub.2).sub.2-Ph 168.5-169.5 466 4-Me-Ph -- Et
4-Cl-2,6-(NO.sub.2).sub.2-Ph 467 4-Me-Ph -- n-Pr
4-Cl-2,6-(NO.sub.2).sub.2-Ph 468 4-Me-Ph -- i-Pr
4-Cl-2,6-(NO.sub.2).sub.2-Ph 469 4-Me-Ph -- c-Pr
4-Cl-2,6-(NO.sub.2).sub.2-Ph 470 4-Me-Ph -- Me
2,6-(NO.sub.2).sub.2-4-CF.sub.3-Ph 176.5-177.5 471 4-Me-Ph -- Me
2-NO.sub.2-1-naphthyl 472 4-Me-Ph -- Me 1-NO.sub.2-2-naphthyl 473
4-Me-Ph -- Me 3,5-Cl.sub.2-2-thienyl 474 4-Me-Ph -- Et
3,5-Cl.sub.2-2-thienyl 475 4-Me-Ph -- i-Pr 3,5-Cl.sub.2-2-thienyl
476 4-Me-Ph -- Me 5-Cl-3-NO.sub.2-2-thienyl 477 4-Me-Ph -- Et
5-Cl-3-NO.sub.2-2-thienyl 478 4-Me-Ph -- i-Pr
5-Cl-3-NO.sub.2-2-thienyl 479 4-Me-Ph -- Me 1-Me-4-CN-5-pyrazolyl
480 4-Me-Ph -- Me 1,3-Me.sub.2-4-NO.sub.2-5-pyrazolyl 481 4-Me-Ph
-- Me 1-Me-5-NO.sub.2-4-imidazolyl 482 4-Me-Ph -- Me
2-Me-5-CN-4-thiazolyl 483 4-Me-Ph -- Me 2-SMe-5-CN-4-thiazolyl 484
4-Me-Ph -- Me 2-Cl-5-CN-4-thiazolyl 485 4-Me-Ph -- Me
2-Me-5-CF.sub.3-4-thiazolyl 486 4-Me-Ph -- Me
2-Me-5-NO.sub.2-4-thiazolyl 487 4-Me-Ph -- Me
2-Cl-5-NO.sub.2-4-thiazolyl 488 4-Me-Ph -- Me
3-OMe-4-CF.sub.3-5-isothiazolyl 489 4-Me-Ph -- Me
3-Me-4-CN-5-isothiazolyl 490 4-Me-Ph -- Me 3-Me-4-NO.sub.2-5-isoth-
iazolyl 491 4-Me-Ph -- Me 5-Cl-2-pyridyl 74.0-75.0 492 4-Me-Ph --
Me 6-Cl-3-pyridyl 493 4-Me-Ph -- Me 3-NO.sub.2-2-pyridyl
118.5-119.5 494 4-Me-Ph -- Me 5-Cl-3-NO.sub.2-2-pyridyl 141.0-143.0
495 4-Me-Ph -- Et 5-Cl-3-NO.sub.2-2-pyridyl 496 4-Me-Ph -- n-Pr
5-Cl-3-NO.sub.2-2-pyridyl 497 4-Me-Ph -- i-Pr
5-Cl-3-NO.sub.2-2-pyridyl 498 4-Me-Ph -- c-Pr
5-Cl-3-NO.sub.2-2-pyridyl 499 4-Me-Ph -- n-Bu
5-Cl-3-NO.sub.2-2-pyridyl 500 4-Me-Ph -- Me
6-Me-4-NO.sub.2-2-pyridyl 501 4-Me-Ph -- Me
6-OMe-4-NO.sub.2-2-pyridyl 502 4-Me-Ph -- Me
6-Cl-4-NO.sub.2-2-pyridyl 503 4-Me-Ph -- Me
3,5-(NO.sub.2).sub.2-2-pyridyl amorphous.sup.7) 504 4-Me-Ph -- Me
6-Cl-3-pyridazinyl 80.0-81.0 505 4-Me-Ph -- Et 6-Cl-3-pyridazinyl
506 4-Me-Ph -- n-Pr 6-Cl-3-pyridazinyl 507 4-Me-Ph -- i-Pr
6-Cl-3-pyridazinyl 508 4-Me-Ph -- c-Pr 6-Cl-3-pyridazinyl 509
4-Me-Ph -- n-Bu 6-Cl-3-pyridazinyl 510 1-Me-4-imidazolyl -- Me
6-Cl-3-pyridazinyl 183.5-184.5 511 4-Me-Ph -- Me 5-Cl-2-pyrimidinyl
136.0-139.0 512 4-Me-Ph -- Et 5-Cl-2-pyrimidinyl 513 4-Me-Ph --
n-Pr 5-Cl-2-pyrimidinyl 514 4-Me-Ph -- i-Pr 5-Cl-2-pyrimidinyl 515
4-Me-Ph -- c-Pr 5-Cl-2-pyrimidinyl 516 4-Me-Ph -- n-Bu
5-Cl-2-pyrimidinyl 517 4-Me-Ph -- Me 6-Cl-4-pyrimidinyl 99.5-100.5
518 4-Me-Ph -- Me 5-Cl-6-Me-4-pyrimidinyl 162.0-164.0 519 4-Me-Ph
-- Me 3-NO.sub.2-2-imidazo[1,2-a]pyridyl 169.5-171.0 520 4-Me-Ph --
Et 3-NO.sub.2-2-imidazo[1,2-a]pyridyl 521 4-Me-Ph -- OMe
4-NO.sub.2-Ph 142.5-144.5 522 4-Me-Ph -- OMe 2-Me-4-NO.sub.2-Ph
118.0-119.0 523 4-Me-Ph -- OMe 2-F-4-NO.sub.2-Ph 154.0-155.5 524
4-Cl-3-CF.sub.3-Ph -- OMe 2-F-4-NO.sub.2-Ph 104.5-105.5 525 4-Me-Ph
-- OMe 2-Cl-4-NO.sub.2-Ph 126.0-127.5 526 4-Cl-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 150.0-151.0 527 3,4-Cl.sub.2-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 132.0-133.0 528 2,5-Cl.sub.2-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 136.0-138.0 529 3-CF.sub.3-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 95.5-96.5 530 3-NO.sub.2-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 167.5-169.0 531 4-Cl-3-NO.sub.2-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 138.0-139.0 532 4-Cl-3-CF.sub.3-Ph -- OMe
2-Cl-4-NO.sub.2-Ph 111.5-113.0 533 4-Me-Ph -- OEt
2-Cl-4-NO.sub.2-Ph 133.5-135.0 534 4-Me-Ph -- O(i-Pr)
2-Cl-4-NO.sub.2-Ph 160.5-162.0 535 4-Me-Ph -- OMe
2-CN-4-NO.sub.2-Ph 148.0-149.5 536 4-Cl-3-CF.sub.3-Ph -- OMe
2-CN-4-NO.sub.2-Ph 140.5-142.0 537 5-Cl-2-thienyl -- OMe
2-CN-4-NO.sub.2-Ph 144.0-146.0 538 4-Me-Ph -- OMe
2-CF.sub.3-4-NO.sub.2-Ph 123.0-124.5 539 4-Me-Ph -- OMe
2-NO.sub.2-Ph 104.5-105.5 540 4-Me-Ph -- OMe 4-Cl-2-NO.sub.2-Ph
114.0-115.0 541 2,5-Cl.sub.2-Ph -- OMe 4-Cl-2-NO.sub.2-Ph
>180(dec.) 542 3-CF.sub.3-Ph -- OMe 4-Cl-2-NO.sub.2-Ph 84.5-85.5
543 4-Cl-3-CF.sub.3-Ph -- OMe 4-Cl-2-NO.sub.2-Ph 108.0-109.0 544
4-Me-Ph -- OMe 2-Cl-4-CF.sub.3-Ph 131.0-132.5 545 4-Me-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 146.0-148.0 546 4-Me-Ph -- OEt
2,4-(NO.sub.2).sub.2-Ph 547 4-Me-Ph -- OAc 2,4-(NO.sub.2).sub.2-Ph
548 4-Cl-Ph -- OMe 2,4-(NO.sub.2).sub.2-Ph 549 2,5-Cl.sub.2-Ph --
OMe 2,4-(NO.sub.2).sub.2-Ph 153.0-155.0 550 3-CF.sub.3-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 130.5-132.0 551 4-Cl-3-CF.sub.3-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 108.0-109.5 552
5-Cl-1,3-Me.sub.2-4-pyrazolyl -- OMe 2,4-(NO.sub.2).sub.2-Ph
189.0-191.0 553 4-Me-Ph -- OMe 3-Cl-5-CF.sub.3-2-pyridyl 99.0-100.0
554 4-Me-Ph -- OMe 5-NO.sub.2-2-pyridyl 96.0-97.0 555 4-Me-Ph --
OMe 6-Cl-3-pyridazinyl 91.5-92.5 556 4-Me-Ph -- OMe
6-CN-3-pyridazinyl 112.0-113.0 557 4-Me-Ph -- OMe
5-NO.sub.2-2-thiazolyl 135.0-138.5 558 4-Me-Ph -- OMe
4-CF.sub.3-2-thiazolyl 107.0-108.5 559 4-Me-Ph -- OMe
5-CF.sub.3-1,3,4-thiadiazol-2-yl 84.0-85.5 560 4-Me-Ph -- OMe
4-CN-3-OMe-5-isothiazolyl 115.5-118.0 561 Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 161.0-163.5 562 3-Me-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 147.5-149.5 563 2-Cl-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 112.5-114.0 564 3-Cl-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 157.0-159.0 565 4-CF.sub.3-Ph -- OMe
2-CN-4-NO.sub.2-Ph 133.5-135.0 566 4-Me-Ph -- OMe 2-Cl-4-CN-Ph
145.0-147.0 567 4-F-Ph -- OMe 2,4-(NO.sub.2).sub.2-Ph 118.0-119.5
568 4-Et-Ph -- OMe 2,4-(NO.sub.2).sub.2-Ph 90.0-92.0 569 4-Me-Ph --
OMe 4-CN-2-NO.sub.2-Ph 126.0-128.0 570 4-NO.sub.2-Ph -- OMe
2,4-(NO.sub.2).sub.2-Ph 117.0-119.0 571 4-Me-Ph -- OMe
2-CN-4-SMe-Ph 146.8-147.6 572 4-Me-Ph -- OMe 4-SMe-2-NO.sub.2-Ph
110.3-110.8 .sup.1)NMR(CDCl.sub.3) .delta.: 1.22(3H, t, J=7.6Hz),
2.42(3H, s), 2.63(2H, q, J=7.6Hz), 3.14(3H, s), 6.99(2H, d, J=8.6
& 2.3Hz), 7.12(2H, d, J=8.6 & 2.3Hz), 7.24(2H, d, J=8.3Hz),
7.45(2H, d, J=8.3Hz). .sup.2)NMR(CDCl.sub.3) .delta.: 2.46(3H, s),
3.17(3H, s), 3.27(3H, s), 6.68(1H, d, J=8.7Hz), 7.34(2H, d,
J=8.3Hz), 7.43(1H, dd, J=8.7 & 2.4Hz), 7.51(2H, d, J=8.3Hz),
7.77(1H, d, J=2.4Hz), 11.00-12.00(2H, br). .sup.3)NMR(CDCl.sub.3)
.delta.: 2.46(3H, s), 3.01(3H, s), 3.14(6H, s), 6.80(1H, d,
J=8.9Hz), 7.20-7.35(2H, m), 7.34(2H, d, J=8.3Hz), 7.66(2H, d,
J=8.3Hz). (*): Isolated as hydroiodide and measured the melting
point .sup.4)NMR(CDCl.sub.3) .delta.: 2.47(3H, s), 3.35(3H, s),
3.85(3H, s), 7.06(1H, dd, J=8.9 & 3.0Hz), 7.10-7.35(3H, m),
7.34(1H, dt, J=8.9Hz), 7.45(1H, dt, J=1.4 & 7.9Hz), 7.69(1H,
dd, J=7.9 & 1.4Hz). .sup.5)NMR(CDCl.sub.3) .delta.: 0.87(3H, t,
J=7.2Hz), 1.30(2H, brq, J=7.2Hz), 1.40-1.70(2H, br), 2.43(3H, s),
3.45-3.70(2H, br), 3.87(3H, s), 6.90-7.10(2H, m), 7.26(2H, d,
J=8.3Hz), 7.34(1H, d, J=2.2Hz), 7.51(2H, d, J=8.3Hz).
.sup.6)NMR(CDCl.sub.3) .delta.: 2.43(3H, s), 3.74(3H, s), 4.59(2H,
brs), 7.24(2H, d, J=8.4Hz), 7.40-7.60(3H, m), 7.71(1H, d, J=8.6Hz),
7.83(1H, d, J=2.3Hz). .sup.7)NMR(CDCl.sub.3) .delta.: 2.45(3H, s),
3.28(3H, s), 7.32(2H, d, J=8.3Hz), 7.48(2H, d, J=8.3Hz), 9.06(1H,
d, J=2.5Hz), 9.33(1H, d, J=2.5Hz).
Formulation Example 1
[1245] Compound No. 171 (20 wt %), xylene (75 wt %) and
polyoxyethyleneglycol ether (NONIPOL 85.TM.)(5 wt %) were mixed
intimately to produce an emulsion.
Formulation Example 2
[1246] Compound No. 226 (30 wt %), sodium ligninsulfonate (5 wt %),
polyoxyethyleneglycol ether (NONIPOL 85.TM.) (5 wt %), white carbon
(30 wt %) and clay (30 wt %) were mixed intimately to produce a
wettable powder.
Formulation Example 3
[1247] Compound No. 263 (3 wt %), white carbon (3 wt %) and clay
(94 wt %) were mixed intimately to produce a powder.
Formulation Example 4
[1248] Compound No. 291 (10 wt %), sodium ligninsulfonate (5 wt %)
and clay (85 wt %) were crushed finely, mixed intimately, then
kneaded with addition of water, granulated and dried to produce a
granule.
Formulation Example 5
[1249] Compound No. 289 (11 wt %), ethylene glycol (12 wt %),
Antifoam E20 (0.2 wt %), Butylparaben (0.1 wt %), NOIGENEA-177 (2
wt %), NEW KALGEN FS-7 (2 wt %), Kunipia F (1 wt %), polyvinyl
alcohol 224 (1 wt %) and water (70.7 wt %) were mixed intimately
and then wet ground using Dynomill KDL to produce a homogeneous
suspension (a flowable).
Formulation Example 6
[1250] Compound No. 409 (11 wt %), ethylene glycol (12 wt %),
Antifoam E20 (0.2 wt %), Butylparaben (0.1 wt %), NOIGENEA-177 (2
wt %), NEWKALGEN FS-7 (2 wt %), Kunipia F (1 wt %), CELLOGEN 7A(1.5
wt %) and water (70.2 wt %) were mixed intimately and then wet
ground using Dynomill KDL to produce a homogeneous suspension (a
flowable).
Formulation Example 7
[1251] Compound No. 292 (2 wt %), ferimzone (2 wt %), white carbon
(3 wt %), and clay (93 wt %) were mixed intimately to produce a
mixed powder.
Formulation Example 8
[1252] Compound No. 289 (11 parts), ferimzone (20 parts), ethylene
glycol (12 parts), Antifoam E20 (0.2 part), Butylparaben (0.1
part), NOIGEN EA-177 (2 parts), NEW KALGEN FS-7 (2 parts), Kunipia
F (1 part), polyvinyl alcohol (1 part), and water (50.7 parts) were
mixed and wet ground using Dynomill KDL to produce a homogeneous
suspension (a flowable).
Formulation Example 9
[1253] Compound No. 289 (11 parts), azoxystrobin (2 parts),
ethylene glycol (12 parts), Antifoam E20 (0.2 part), Butylparaben
(0.1 part), NOIGEN EA-177 (2 parts), NEW KALGEN FS-7 (2 parts),
Kunipia F (1 part), polyvinyl alcohol (1 part), water (68.7 parts)
were mixed and wet ground using Dynomill KDL to give a homogeneous
suspension (a flowable).
Formulation Example 10
[1254] Compound No. 289 (4 parts), ValidamycinA (0.3 part),
ferimzone (2 parts), fthalide (1.5 parts), IP solvent (0.2 part),
NEW KALGEN EP-60P (2 parts), white carbon (1.5 parts), Butylparaben
(0.05 part), NEW KALGEN D-1504 (3 parts), Hertall fatty acids (0.25
part) and calcium carbonate (85.2 parts) were mixed homogeneously
and then ground to produce a DL powder.
Formulation Example 11
[1255] Compound No. 421 (15 parts), chlorothalonil (15 parts),
sodium ligninsulfonate (5 parts), polyoxyethyleneglycol ether
(NONIPOL 85.TM.) (5 parts), white carbon (30 parts) and clay (30
parts) were blended intimately to produce a wettable powder.
Formulation Example 12
[1256] Compound No. 289 (17 parts), clothianidin (8 parts), xylene
(70 parts) and, polyoxyethyleneglycol ether (Nonipol 85.TM.) (5
parts) were mixed intimately to produce an emulsion.
Formulation Example 13
[1257] Compound No. 289 (17 parts), clothianidin (8 parts), NOIGEN
EA-177 (0.5 part), NEW KALGEN FS-4 (2 parts), Gosenol GH-17 (2
parts), Butylparaben (0.1 part) and water (70.4 parts) were mixed
and suspended well using a high-speed stirrer, and then wet ground
using Dynomill (Shinmaru enterprises Corporation, 1.0 mm glass
beads, ratio of filling 80%, rotation speed 15 m/s) to produce a
homogeneous suspension (a flowable).
Formulation Example 14
[1258] Compound No. 437 (5 parts), clothianidin (1 part), NEWPOL
PE-64 (0.5 parts), dextrin NDS (4 parts) and clay (89.5 parts) were
mixed homogeneously, kneaded with water (5-10 parts) and then
granulated by extruding through a screen of 0.8 mm.phi.. The
granules obtained were dried at 60.degree. C. for 1 hour to produce
a granule.
Formulation Example 15
[1259] A solution of Nitenpyram (20 parts) and TOYODELINE P (80
parts) in water (400 parts) was spray-died to give the cyclodextrin
inclusion compound of nitenpyram (cyclodextrin inclusion compound
A). Compound No. 274 (1 parts), cyclodextrin inclusion compound A
(5 parts), NEW KALGEN EP-70P (2 parts), dextrin NDS (10 parts) and
clay (82 parts) were mixed homogeneously, kneaded with water (5-10
parts), and then granulated by extruding through a screen of 0.8
mm.phi.. The granules obtained were dried at 60.degree. C. for 1
hour to produce a granule.
Formulation Example 16
[1260] Compound No. 545 (4 parts), clothianidin (0.15 part), NEW
KALGEN EP-70P (2 parts), IP solvent (0.2 part), white carbon (1
part) and clay (92.65 parts) were mixed and kneaded homogeneously
and then ground to produce a DL powder.
Formulation Example 17
[1261] Compound No. 409 (4 parts), cyclodextrin inclusion compound
A (1.25 parts), NEW KALGEN EP-70P (2 parts), IP solvent (0.2 part),
white carbon (1.5 parts) and clay (91.05 parts) were mixed and
kneaded homogeneously and then ground to produce a DL powder.
Formulation Example 18
[1262] Compound No. 545 (4 parts), cartap hydrochloride (2 parts),
Hertallfatty acids (1 part), IP solvent (0.2 part), white carbon
(1.5 parts) and clay (91.3 parts) were mixed and kneaded
homogeneously and then ground to produce a DL powder.
Formulation Example 19
[1263] Compound No. 525 (60 parts), clothianidin (15 parts),
HITENOL NE-15 (5 parts), VANILEX-N (10 parts), white carbon CARPLEX
#80D (10 parts) were mixed and ground homogeneously, and then
stirred, mixed and kneaded with small amount of water, and
granulated by using a granulater of an extruder type. The granules
obtained were then dried to produce a wettable granule (a dry
flowable).
Test Examples
Test Example 1
[1264] Protective Effects Against Rice Blast (Pyricularia
oryzae)
[1265] Each test compound (denoted by the compound No. in Table 1
above) was dissolved in dimethylformamide (final concentration was
1 wt %). Xylene (final concentration was 0.02 wt %) and Tween 20
(Trade Name) (final concentration was 0.02 wt %) were added to the
solution. The resulting mixture was diluted with water to give a
test solution which contained the effective constituent in a given
concentration (200 ppm). A spreader adjuvant SINDAIN (Trade name,
Manufactured by Takeda Chemical Industries, Ltd, and containing 20
wt % of polyoxyethylene nonylphenyl ether and 12 wt % of calcium
ligninsulfonate) was added to this solution in the final
concentration of 0.05 wt % to give a spray agent. The spray
solution was sprayed in an amount of 10 ml/pot on young rice plants
(cultural variety: Asahi No. 4) which were cultivated for 2 to 3
weeks in a greenhouse. After drying up in a romm, the treated rice
plants were inoculated with placing infected rice plants beside the
treated ones on the condition of natural inoculation. After 24
hours, the infected plants were removed and the treated rice plants
were cultivated for a week in a greenhouse kept at 25-35.degree. C.
(in humidity of more than 70%). Then, the ratio of the lesion area
on the treated rice plants to that on untreated plants was
investigated, and the protective effect of the compound was
evaluated as a protection score as follows.
[1266] Protection score 3: the lesion area ratio on the treated
plants relative to that on the untreated plants is less than
14%
[1267] Protection score 2: the ratio is from 15 to 29%
[1268] Protection score 1: the ratio is from 30 to 55%
[1269] Protection score 0: the ratio is more than 56%
[1270] Test Results: Compounds of the compound No. 43, 174, 201,
262, 305, 519, 276, 361, 362, 393, 538 showed the protection score
3.
Test Example 2
[1271] Protective Effects Against Rice Leaf Spot (Cochliobolus
miyabeanus)
[1272] Each spray solution was prepared in a manner similar to that
in the Test Example 1, and sprayed in an amount of 10 ml/pot on
young rice plants (cultural variety: Nihonbare or Asahi No. 4)
cultivated for 3 to 4 weeks in a greenhouse. After drying up in a
room, the treated rice plants were inoculated with Cochliobolus
miyabeanus spores by spraying suspension of 3 to 5.times.10.sup.5
spores/ml, and had been kept in a high-humidity-room at 28.degree.
C. for 2 days. After cultivation for 5 days further in a
greenhouse, the ratio of the lesion area on the treated rice plants
to that on untreated plants was investigated and the preventive
effect of the compound was evaluated as a protection score as
follows.
[1273] Protection score 3: the lesion area ratio on the treated
plants relative to that on the untreated plants is less than
10%:
[1274] Protection score 2: the ratio is from 11 to 20%
[1275] Protection score 1: the ratio is from 21 to 50%
[1276] Protection score 0: the ratio is more than 51%
[1277] Test Results: Compounds of the compound No. 171, 207, 262,
288, 289, 292 showed the protection score 3.
Test Example 3
[1278] Protective Effects Against Apple Alternaria leaf blotch
(Alternaria mali)
[1279] Each spray solution was prepared in a manner similar to that
in the Test Example 1, and sprayed in an amount of 10 ml/pot on
apple seedlings (cultural variety: Starking-Delicious) cultivated
for 3 to 4 weeks in a greenhouse. On the next day of the treatment,
the treated apple plants were inoculated with spraying a suspension
which contains 1% yeast extract, 1% sacchalose and 5.times.10.sup.5
spores/ml of the Alternaria mali spores in an amount of 1 ml/pot.
After inoculation, the treated plants were kept in a high-humidity
box maintained at 28.degree. C. for 4 days. The ratio of the lesion
area on the treated leaves relative to that on untreated ones was
investigated and the protective effect of the compound was
evaluated as a protection score as follows. Protection score 3: the
lesioned area ratio is less than 10%
[1280] Protection score 2: the ratio is from 11 to 20%
[1281] Protection score 1: the ratio is from 21 to 50%
[1282] Protection score 0: the ratio is more than 51%
[1283] Test Results: Compounds of the compound No. 12, 23, 25, 30,
40, 51, 84, 94, 116, 118, 119, 125, 126, 127, 163, 171, 172, 177,
194, 195, 205, 206, 207, 209, 210, 211, 213, 214, 216, 218, 219,
226, 262, 263, 264, 265, 266, 273, 274, 276, 277, 279, 282, 288,
289, 290, 291, 292, 295, 298, 299, 300, 305, 307, 308, 309, 311,
322, 324, 326, 332, 337, 338, 340, 370, 387, 396, 398, 404, 406,
407, 409, 411, 412, 413, 423, 425, 426, 429, 434, 435, 438, 545,
448, 449, 450, 456, 464, 494, 503, 504, 511, 517, 26, 61, 65, 67,
69, 80, 83, 85, 86, 87, 88, 89, 95, 97, 99, 100, 101, 105, 111,
112, 113, 114, 227, 229, 348, 354, 356, 414, 415, 419, 420, 421,
437, 455, 457, 522, 523, 525, 533, 535, 538, 539, 540, 554, 563,
565, 566, 567, 571, 572 showed protection score 3.
Test Example 4
[1284] Preventive Effects Against Club Root (Plasmodiophora
brassicae) of Brassica campestris L. subsp. napus Hook. f. et
Thoms, var. komatsuna Makino
[1285] Each test compound (denoted by the compound No. in Table 1
above) was dissolved in dimethylformamide (final concentration was
1 wt %). The resulting solution was admixed with xylene (final
concentration was 0.02 wt %), Tween 20 (Trade Name) (final
concentration was 0.02 wt %) and diluted with water further. This
solution was irrigated onto soil infected with club root disease in
an amount of 353.7 mg compound/m.sup.2, followed by a thorough
mixing the soil. Then, seeds of Chinese cabbage (cv. Komatsuna)
were sown in the soil and cultivated in a greenhouse for 4-6 weeks.
The roots of the plants were rinsed out and the degree of disease
development was investigated. The test results were shown in the
protection score as follows,
[1286] Protection score 3: degree of disease development is less
than 25%
[1287] Protection score 2: the degree is from 26 to 50%
[1288] Protection score 1: the degree is from 51 to 75%
[1289] Protection score 0: the degree is more than 76%
[1290] Test Results: Compounds of the compound No. 115, 312, 525,
528, 529, 535, 536, 537, 545, 552, 560 showed the protection score
3.
[1291] Hereunder, in the Test Examples 5 to 9, the evaluation of
each fungicide was carried out by converting the ratio into a
protection value after measuring the lesion area ratio (in
percentage). The protection value was calculated by means of the
equation as follows.
protection value=(1-(lesion area in the division treated with
fungicide)/lesion area in the division not treated with
fungicide)).times.100
[1292] An estimated protection value of a mixture of active
ingredients was calculated according to the Colby's formula [R. S.
Colby, Weeds 15, 20-22 (1967)] and compared with the experimental
protection value.
[1293] Colby's Equation:
E=x+y-xy/100
[1294] [wherein, E is the estimated protection value (additive
effect) which will be obtained when the active ingredients A and B
are used in a mixture in concentrations a and b, respectively x is
the protection value obtained when the active igredient A is used
in a concentration a, and y is the protection value obtained when
the active ingredient B is used in a concentration b. When an
experimental protection value is greater than the expected value E,
it shows the presence of synergism (potentiation). A protection
value equal 0 means that the lesion area ratio of the plants in the
test group is as large as that of the plants in the untreated
control group. A protection value equals 100 means that the plants
in the test group are free from the disease.
Test Example 5
[1295] Protective Effects Against Apple Alternaria Leaf Blotch
(Alternaria mali)
[1296] The test compounds (denoted by the compound No. in Table 1
above), chlorothalonil, hexaconazole and azoxystrobin, individually
or in combination, were dissolved in dimethylformamide (final
concentration was 1 wt %). Xylene (final concentration was 0.02 wt
%) and Tween 20 (Trade Name) (final concentration was 0.02 wt %)
were added to the solution. The resulting mixture was diluted with
water to give a test solution which contains the active ingredient
in a given concentration (ppm). A spreader adjuvant SINDAIN (Trade
name, Manufactured by Takeda Chemical Industries, Ltd, and
comprises 20 wt % of polyoxyethylene nonylphenyl ether and 12 wt %
of calcium ligninsulfonate) was added to this solution in the final
concentration of 0.05 wt % to give a spray agent. Each solution was
then sprayed in an amount of 10 ml/pot on the apple seedlings
(cultural variety: Starking-Delicious) cultivated for 3 to 4 weeks
in a greenhouse. After one day, the treated apple plants were
inoculated with spraying in an amount of 1 ml/pot suspension which
contain 1% yeast extract, 1% sacchalose and 5.times.10.sup.5
spores/ml of the Alternaria mali spores. After inoculation, the
treated plants were kept in a high-humidity box maintained at
28.degree. C. for 4 days, and then, the lesion area ratio on the
treated leaves was investigated and the protective effect of the
compound was evaluated as a protection score mentioned above. The
results are shown in Table 2.
[1297] Compounds No. 289 and No. 421 showed a higher protection
effect when used in combination with chlorothalonil, hexaconazole
and azoxystrobin than the estimated protection effect which was
obtained when each compound was used individually, thus Synergy
effects were shown by the results.
2TABLE 2 Concentration of the active Lesion ingredient area
Protection E Test substances (ppm) ratio (%) value value Compound
No. 289 25 4.3 93 -- 6.3 3.8 94 -- 1.6 20.8 65 -- 0.4 36.9 38 --
Compound No. 21 25 0.3 99 -- 6.3 2.3 96 -- 1.6 20.0 66 -- 0.4 24.7
58 -- Chlorothalonil 100 16.8 72 -- 25 60.0 0 -- 6.3 43.5 27 --
Azoxystrobin 25 25.0 58 -- 6.3 25.8 56 -- Hexaconazole 6.3 21.7 63
-- 1.6 66.7 0 -- 0.4 70.0 0 -- Compound No. 421 + 1.6 + 6.3 2.2 96
75 Chlorothalonil 1.6 + 25 1.5 97 66 Compound No. 421 + 1.6 + 6.3
1.5 97 91 Azoxystrobin Compound No. 289 + 0.4 + 6.3 10.7 82 73
Azoxystrobin Compound No. 289 + 0.4 + 0.4 31.0 48 38 Hexaconazole
1.6 + 0.4 16.5 72 65 0.4 + 1.6 31.7 47 38 Untreated plot -- 59.3 --
--
Test Example 6
[1298] Protective Effects Against Apple Alternaria Leaf Blotch
(Alternaria mali)
[1299] The test compounds (denoted by the compound No. in Table 1
above), iminoctadine, mepanipyrim and kresoxim-methyl, individually
or in combination, were tested by similar way to test example 4.
The lesion area ratios on the treated leaves were investigated and
the results are shown as protection value above. Table 3 shows the
results.
[1300] Compounds No. 289 and No. 97 showed a higher protection
effect when used in combination with mepanipyrim and iminoctadine,
respectively, than the estimated protection effect which was
obtainable when each compound was used individually, thus Synergy
effects were shown by the results.
3TABLE 3 Concentration of the active Lesion ingredient area
Protection E Test substances (ppm) ratio (%) value value Compound
No. 289 6.3 9.3 87 -- 1.6 13.7 81 -- 0.4 18.3 74 -- Compound No. 97
6.3 8.0 89 -- 1.6 19.2 73 -- 0.4 25.0 65 -- Iminoctadine 6.3 35.0
51 -- 1.6 33.8 52 -- 0.4 66.7 6 -- Mepanipyrim 6.3 19.3 73 -- 1.6
73.3 0 -- 0.4 68.3 4 -- Compound No. 97 + 0.4 + 0.4 16.3 77 67
Iminoctadine Compound No. 289 + 1.6 + 0.4 5.3 93 82 Mepanipyrim 1.6
+ 1.6 4.3 94 81 Untreated plot -- 70.8 -- --
Test Example 7
[1301] Protective Effect Against Rice Blast (Pyricularia
oryzae)
[1302] The test compound (denoted by the compound No. in Table 1
above) and azoxystrobin, individually or in combination, were
dissolved in dimethylformamide (final concentration was 1 wt %).
Xylene (final concentration was 0.02 wt %) and Tween 20 (Trade
Name) (final concentration was 0.02 wt %) were added to the
solution. The resulting mixture was diluted with water to give a
test solution which contains (contained a given concentration (ppm)
of the active ingredient in a given concentration (ppm). A spreader
adjuvant SINDAIN (Trade name, Manufactured by Takeda Chemical
Industries, Ltd, and comprises 20 wt % of polyoxyethylene
nonylphenyl ether and 12 wt % of calcium ligninsulfonate) was added
to this solution in the final concentration of 0.05 wt % to give a
spray agent.
[1303] The spray agent above was sprayed in an amount of 10 ml/pot
on rice plants (cultural variety: Asahi No. 4) cultivated for 2 to
3 weeks in a greenhouse. After drying up in a room, the treated
rice plants were inoculated with placing infected rice plants
beside the treated ones on the condition of natural inoculation.
After 24 hours, the infected plants were removed and the treated
rice plants were cultivated for a week in a greenhouse kept at
25-35.degree. C. (in humidity more than 70%). Then, the ratio of
the lesion area on the rice plants treated with the sulfonamide
(test compounds) and that on the plants treated with another
substance to that on untreated plants was investigated and the
results are shown as protection value above. Table 4 shows the
results. Compounds No. 289 showed a higher protection effect when
used in combination with azoxystrobin than the estimated protection
effect which was obtainable when each compound was used
individually, thus Synergy effects were shown by the results.
4TABLE 4 Concentration of the active Lesion ingredient area
Protection E Test substances (ppm) ratio (%) value value Compound
No. 289 200 25.0 0 -- 100 25.0 0 -- Azoxystrobin 0.5 5.0 80 -- 0.1
11.0 56 -- Compound No. 289 + 200 + 0.5 0.8 97 80 Azoxystrobin 200
+ 0.1 3.5 86 56 100 + 0.5 0.8 97 80 100 + 0.1 5.0 80 56 Untreated
plot -- 25.0 -- --
Test Example 8
[1304] Protective Effect Against Rice Helminthosporium Leaf Spot
(Cochliobolus miyabeanus)
[1305] The test compound (denoted by the compound No. in Table 1
above) and ferimzone, individually or in combination, were
dissolved in dimethylformamide (final concentration was 1 wt %).
Xylene (final concentration was 0.02 wt %) and Tween 20 (Trade
Name) (final concentration was 0.02 wt %) were added to the
solution. The resulting mixture was diluted with water to give a
test solution which contained a given concentration (ppm) of the
active ingredient. A spreader adjuvant SINDAIN (Trade Name,
Manufactured by Takeda Chemical Industries, Ltd, and comprises 20
wt % of polyoxyethylene nonylphenyl ether and 12 wt % of calcium
ligninsulfonate) was added to this solution in the final
concentration of 0.05 wt % to give a spray agent.
[1306] This spray agent was sprayed in an amount of 10 ml/pot on
young rice plants (cultural variety: Nihonbare or Asahi No. 4)
cultivated for 3 to 4 weeks in a greenhouse. After drying up in a
room, the treated rice plants were inoculated with Cochliobolus
miyabeanus spores by spraying suspension of 3 to 5.times.10.sup.5
spores/ml, and had been kept in a high-humidity room at 28.degree.
C. for 2 days. After cultivation for 5 days further in a
greenhouse, the ratio of the lesion area on the plants treated with
the test compound and that on the plants treated with another test
substance to that on untreated plants was investigated. The results
are shown as protection value above. Table 5 shows the results.
[1307] Compounds No. 289 showed a higher protection effect when
used in combination with ferimzone than the estimated protective
effect which was obtainable when each compound was used
individually, thus Synergy effects were shown by the results.
5TABLE 5 Concentration of the active Lesion ingredient area
Protection E Test substances (ppm) ratio (%) value value Compound
No. 289 100 4.5 74.3 -- 25 5.0 71.4 -- Ferimzone 100 0.4 98.0 -- 25
1.5 91.4 -- Compound No. 289 + 100 + 25 0.2 98.9 97.8 Ferimzone 25
+ 25 0.3 98.6 97.6 Untreated plot -- 25.0 -- --
Test Example 9
[1308] Protective Effect Against Cucumber Gray Mold (Botrytis
cinerea)
[1309] The test compound (denoted by the compound No. in Table 1
above), azoxystrobin, mepanipyrim and iprodione, individually or in
combination, were dissolved in dimethylformamide (final
concentration was 1 wt %). Xylene (final concentration was 0.02 wt
%) and Tween 20 (Trade Name) (final concentration was 0.02 wt %)
were added to the solution. The resulting mixture was diluted with
water to give a test solution which contained a given concentration
(ppm) of the active ingredient. A spreader adjuvant SINDAIN (Trade
Name, Manufactured by Takeda Chemical Industries, Ltd, and
comprises 20 wt % of polyoxyethylene nonylphenyl ether and 12 wt %
of calcium ligninsulfonate) was added to this solution in the final
concentration of 0.05 wt % to give a spray agent.
[1310] The spray agent was sprayed in an amount of 10 ml/pot on
young cucumber (cultural variety: Yotsuba) cultivated for 3 to 4
weeks in a greenhouse. After drying up in a room, the treated
cucumbers were inoculated with pathogenic fangi on the leaves by
placing the mycelial disks which were cut out from a PSA medium
grown with Botrytis cinerea and then kept in a greenhouse at
28.degree. C. for 3 days. Then, the ratio of the lesion area on the
plants treated with the test compound and that on the plants
treated with another substances to that on untreated plants was
investigated. The results are shown as protection value above.
Table 6 shows the results.
[1311] Compounds No. 289 showed a higher protection effect when
used in combination with azoxystrobin, mepanipyrim and iprodione
than the estimated protection effect which was obtainable when each
compound was used individually, thus Synergy effects were shown by
the results.
6TABLE 6 Concentration of the active Lesion Ingredient area
Protection E Test substances (ppm) ratio (%) value value Compound
No. 289 100 13.2 0.0 -- Azoxystrobin 10 3.9 69.8 -- Mepanipyrim 10
6.0 53.8 -- Iprodione 10 3.7 71.3 -- Compound No. 289 + 100 + 10
1.9 85.4 69.3 Azoxystrobin Compound No. 289 + 100 + 10 5.3 59.2
53.0 Mepanipyrim Compound No. 289 + 100 + 10 2.9 77.2 70.8
Iprodione Untreated plot -- 25.0 -- --
[1312] Industrial Applicability
[1313] Compound (I.sup.0) or salts thereof, more specifically
compound (I) to (V) or salts thereof are useful as excellent
agricultural or horticultural microbicides, because they are
sulfonamide derivatives, are safe to use because they have little
influence on human and animals, natural enemies and the
environment, and show an excellent preventive effect even on
drug-resistant microbes. They have especially effective as
protective against blast, Helminthosporium leaf spot and Fusarium
leaf spot of rice plant, leaf spot, yellow mottle leaf and net
blotch of barley, yellow nottle leaf and leaf blotch of wheat,
southern leaf blight of corn, early blight of potato, Alternaria
sooty spot, ring spot and black rot of tomato, black rot of Chinese
cabbage, black rot of pear, and Alternaria leaf blotch of apple,
and so on.
* * * * *