U.S. patent application number 10/403014 was filed with the patent office on 2004-01-01 for triketone derivatives and herbicides.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Ogawa, Shinichiro, Saitou, Masatoshi, Sekiguchi, Hiroki.
Application Number | 20040002425 10/403014 |
Document ID | / |
Family ID | 27324443 |
Filed Date | 2004-01-01 |
United States Patent
Application |
20040002425 |
Kind Code |
A1 |
Saitou, Masatoshi ; et
al. |
January 1, 2004 |
Triketone derivatives and herbicides
Abstract
The present invention relates to a novel triketone derivative
having a specific structure and a herbicide containing the
triketone derivative as an active ingredient. The herbicide is
effective for controlling weeds which inhibit growth of crop
plants, inter alia, for paddy weeds such as Sanwa millet and
Scirups juncoides.
Inventors: |
Saitou, Masatoshi; (Chiba,
JP) ; Sekiguchi, Hiroki; (Chiba, JP) ; Ogawa,
Shinichiro; (Chiba, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
1-1, Marunouchi 3-chome, Chiyoda-ku
Tokyo
JP
100-8321
|
Family ID: |
27324443 |
Appl. No.: |
10/403014 |
Filed: |
April 1, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10403014 |
Apr 1, 2003 |
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09806948 |
Apr 23, 2001 |
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09806948 |
Apr 23, 2001 |
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PCT/JP99/05477 |
Oct 5, 1999 |
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Current U.S.
Class: |
504/289 ;
549/53 |
Current CPC
Class: |
A01N 43/18 20130101;
A01N 43/12 20130101; C07D 333/54 20130101 |
Class at
Publication: |
504/289 ;
549/53 |
International
Class: |
A01N 043/10; C07D
333/72 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 6, 1998 |
JP |
284086/1998 |
Jun 23, 1999 |
JP |
177562/1999 |
Jun 23, 1999 |
JP |
177563/1999 |
Claims
1. A triketone derivative represented by formula [I-1]: 133wherein
R represents a methyl group; each of X and Y represents a hydrogen
atom, a halogen atom, a nitro group, an amino group, a cyano group,
a hydroxy group, a mercapto group, --R.sup.1, --OR.sup.1,
--SR.sup.1, --SO.sub.2R.sup.1, --NR.sup.2R.sup.3, or --NHCOR.sup.1,
wherein R.sup.1 represents a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted; each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure; M represents a hydrogen
atom, an alkali metal, an alkaline earth metal, or an organic base;
R.sup.4 represents a hydrogen atom or a C1-C6 alkyl group; and m is
an integer between 0 and 4 inclusive; provided that not all of X,
Y, and R.sup.4 simultaneously represent methyl groups.
2. A triketone derivative represented by formula [I-2]: 134wherein
R, X, Y, M, and m have the same definitions as described in
relation to formula [I-1].
3. A triketone derivative represented by formula [I-3]: 135wherein
R, X, M, R.sup.4, and m have the same definitions as described in
relation to formula [I-1].
4. A triketone derivative represented by formula [I-4]: 136wherein
R represents a methyl group; each of X and Y represents a hydrogen
atom, a halogen atom, a nitro group, a cyano group, --R.sup.1,
--OR.sup.1, --SR.sup.1, or --NR.sup.2R.sup.3, wherein R.sup.1
represents a C1-C6 alkyl group which may have a branched structure,
a cyclic structure, or an unsaturated bond, a C1-C6 haloalkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a phenyl group which may be substituted, or a
benzyl group which may be substituted; each of R.sup.2 and R.sup.3
represents a hydrogen atom, a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted, or R.sup.2
and R.sup.3 may be bonded to each other to form a group having a
cyclic structure; Z represents --OR.sup.1, --SO.sub.pR.sup.1,
--A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
--N(OR.sup.1)R.sup.2, --O(C.dbd.O)R.sup.1, --O(C.dbd.O)OR.sup.1,
--O(C.dbd.O)SR.sup.1, --O(C.dbd.O)NR.sup.2R.sup.3, or
--O(C.dbd.S)NR.sup.2R.sup.3 (wherein R.sup.1, R.sup.2, and R.sup.3
have the same definitions as described in relation to X and Y, each
of A and Q represents an oxygen atom or a sulfur atom, p is 0, 1,
or 2, n is 1 or 2), --OM (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base), or a
halogen atom; and m is an integer between 0 and 4 inclusive.
5. A triketone derivative according to claim 4, wherein Z
represents an --OM group (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base).
6. A triketone derivative according to any one of claims 1, 2, 4,
and 5, wherein Y represents a hydrogen atom, a C1-C6 alkyl group,
or a halogen atom.
7. A triketone derivative according to any one of claims 1, 2, 4,
and 5, wherein Y represents a hydrogen atom or a methyl group.
8. A triketone derivative according to any one of claims 2, 4, and
5, wherein Y represents a hydrogen atom.
9. A triketone derivative according to any one of claims 1 through
8, wherein X represents --R.sup.1, --OR.sup.1, or --SR.sup.1.
10. A triketone derivative according to claim 1 or 9, wherein X
represents a halogen atom or a methyl group.
11. A triketone derivative according to any one of claims 1 through
10, wherein M represents a hydrogen atom.
12. A herbicide containing a triketone derivative as recited in any
one of claims 1 through 11 as an active ingredient.
13. A herbicide for use in cultivation of a paddy rice plant, which
herbicide contains a triketone derivative as recited in any one of
claims 1 through 11 as an active ingredient.
14. A triketone derivative represented by formula [II-1]:
137wherein R represents a methyl group; X represents a hydrogen
atom, a halogen atom, a nitro group, an amino group, a cyano group,
a hydroxy group, a mercapto group, --R.sup.1, --OR.sup.1,
--SR.sup.1, --SO.sub.2R.sup.1, --NR.sup.2R.sup.3, or --NHCOR.sup.1
(wherein R.sup.1 represents a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted; each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure); G contains 3 to 5
ring-constituting atoms which form a 5- to 7-membered saturated or
unsaturated condensed ring including two carbon atoms of the
benzene ring adjacent to G, wherein two or less ring-constituting
atoms are selected from among nitrogen, oxygen, and sulfur, and the
ring-constituting atoms may have one or more substituents selected
from among a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6
alkoxy group, a C1-C6 haloalkoxy group, a hydroxy group, a mercapto
group, an oxo group, a thioxo group, a hydroxyimino group, a C1-C6
alkoxyimino group, a hydrazono group, a C1-C6 monoalkylhydrazono
group, and a C1-C6 dialkylhydrazono group, and a carbon atom or the
adjacent carbon atom of the ring-constituting atom may have a
substituent selected from among an ethylenedioxy group, an
ethylenedithio group, a propylenedioxy group, and a propylenedithio
group, with these substituents optionally being substituted with a
halogen atom or a C1-C6 alkyl group; Z.sup.1 represents a halogen
atom, --OR.sup.1, --SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1,
--NR.sup.2R.sup.3, --N (OR.sup.1) R.sup.2, --O(C.dbd.O)R.sup.1,
--O(C.dbd.O)OR.sup.1, --O(C.dbd.O)SR.sup.1,
--O(C.dbd.O)NR.sup.2R.sup.3, or --O(C.dbd.S)NR.sup.2R.sup.3
(wherein R.sup.1, R.sup.2, and R.sup.3 have the same definitions as
described in relation to X, each of A and Q represents an oxygen
atom or a sulfur atom, p is 0, 1, or 2, n is 1 to 3), or a halogen
atom; m is an integer between 0 and 4 inclusive; and q is 1 or
2.
15. A triketone derivative according to claim 14, which is
represented by formula [II-2] or [II-3]: 138wherein R, X, G,
Z.sup.1, m, and q have the same definitions as described in
relation to formula [II-1].
16. A triketone derivative according to claim 14 or 15, which is
represented by any one of formulas [II-4] to [II-9]: 139wherein R,
X, G, Z.sup.1, m, and q have the same definitions as described in
relation to formula [II-1], each of G.sup.1 to G.sup.4 represents
an optionally substituted atom that constitutes G in formula
[II-1], and i is 0, 1, or 2.
17. A triketone derivative according to any one of claims 14
through 16, wherein X represents a halogen atom, --R.sub.1,
--OR.sup.1, or --SR.sup.1.
18. A triketone derivative according to claim 16 or 17, wherein
each of G.sup.1 to G.sup.4 represents a ring-constituting atom
having one or more substituents selected from the substituent group
consisting of an unsubstituted or C1-C6 alkyl group, a C1-C6 alkoxy
group, an oxo group, and a C1-C6 alkoxyimino group.
19. A triketone derivative according to any one of claims 14 to 18,
wherein Z.sup.1 is selected from among a halogen atom, --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, and
--N(OR.sup.1)R.sup.2.
20. A triketone derivative represented by formula [II-10]:
140wherein R represents a methyl group; each of X and Y represents
a hydrogen atom, a halogen atom, a nitro group, a cyano group,
--R.sup.1, --OR.sup.1, --SR.sup.1, or --NR.sup.2R.sup.3 (wherein
R.sup.1 represents a C1-C6 alkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a C1-C6
haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted, each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure); Z represents --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
--N(OR.sup.1)R.sup.2, O(C.dbd.O)R.sup.1, --O(C.dbd.O)OR.sup.1,
--O(C.dbd.O)SR.sup.1, --O(C.dbd.O)NR.sup.2R.sup.3, or
--O(C.dbd.S)NR.sup.2R.sup.3 (wherein R.sup.1, R.sup.2, and R.sup.3
have the same definitions as described in relation to X and Y, each
of A and Q represents an oxygen atom or a sulfur atom, p is 0, 1,
or 2, n is 1 or 2), --OM (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base), or a
halogen atom; and m is an integer between 0 and 4 inclusive.
21. A triketone derivative according to claim 20, wherein Y
represents a hydrogen atom or a methyl group.
22. A triketone derivative according to claim 20, wherein Y
represents a hydrogen atom.
23. A triketone derivative according to any one of claims 20
through 22, wherein Z represents a halogen atom, --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, or
--N(OR.sup.1)R.sup.2.
24. A triketone derivative according to any one of claims 14
through 23, wherein X represents a halogen atom or a methyl
group.
25. A herbicide containing a triketone derivative as recited in any
one of claims 14 through 24 as an active ingredient.
26. A herbicide for use in cultivation of a paddy rice plant, which
herbicide contains a triketone derivative as recited in any one of
claims 14 through 24 as an active ingredient.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a novel triketone
derivative and a herbicide containing the triketone derivative as
an active ingredient. More particularly, the invention relates to a
triketone derivative useful for a herbicide effective on weeds
which inhibit growth of crop plants, inter alia, for paddy field
weeds such as Echinochloa crus-galli and Scirups juncoides, and to
a herbicide containing the triketone derivative as an active
ingredient.
BACKGROUND ART
[0002] Herbicides are important chemicals for facilitating weed
control and enhancing productivity of field and garden crops.
Therefore, development of herbicides which is safe and has
excellent weed-controlling property even at a low dose have been
actively carried out for many years.
[0003] There is proposed a herbicide containing a triketone
derivative having a bicyclic benzoyl structure as an active
ingredient, for the herbicide has excellent safety to field crops
and excellent weed-controlling activity to field weeds. For
example, there is proposed a herbicide containing a compound
disclosed in Japanese Patent No. 2579663 and International Patent
Publication WO97/08164 as an active ingredient, which herbicide has
an excellent weed-controlling property suitable for growth of field
crops. However, a herbicide containing such a compound as an active
ingredient has poor activity for controlling paddy field weeds, and
disadvantageously has insufficient safety to a paddy rice
plant.
DISCLOSURE OF THE INVENTION
[0004] In view of the foregoing, an object of the present invention
is to provide a herbicide containing a triketone derivative as an
active ingredient, which herbicide can control a wide range of
weeds at a low dose and imparts a low level of chemical injury to
cultivated crops, particularly a paddy rice plant.
[0005] In order to attain the above object, the present inventors
have conducted earnest studies, and have found that a triketone
derivative having a specific chemical structure can control a wide
range of weeds at a low dose and imparts a low level of chemical
injury to cultivated crops. The present invention has accomplished
based on this finding.
[0006] The present invention includes first and second aspects as
described below.
[0007] The first aspect of the present invention encompasses the
following.
[0008] (1) A triketone derivative represented by formula [I-1]:
1
[0009] wherein R represents a methyl group; each of X and Y
represents a hydrogen atom, a halogen atom, a nitro group, an amino
group, a cyano group, a hydroxy group, a mercapto group, --R.sup.1,
--OR.sup.1, --SR.sup.1, --SO.sub.2R.sup.1, --NR.sup.2R.sup.3, or
--NHCOR.sup.1, wherein R.sup.1 represents a C1-C6 alkyl group which
may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted; each of R.sup.2 and R.sup.3 represents a hydrogen
atom, a C1-C6 alkyl group which may have a branched structure, a
cyclic structure, or an unsaturated bond, a C1-C6 haloalkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a phenyl group which may be substituted, or a
benzyl group which may be substituted, or R.sup.2 and R.sup.3 may
be bonded to each other to form a group having a cyclic structure;
M represents a hydrogen atom, an alkali metal, an alkaline earth
metal, or an organic base; R.sup.4 represents a hydrogen atom or a
C1-C6 alkyl group; and m is an integer between 0 and 4 inclusive;
provided that not all of X, Y, and R.sup.4 simultaneously represent
methyl groups.
[0010] (2) A triketone derivative represented by formula [I-2]:
2
[0011] wherein R, X, Y, M, and m have the same definitions as
described in relation to formula [I-1].
[0012] (3) A triketone derivative represented by formula [I-3]:
3
[0013] wherein R, X, M, R.sup.4, and m have the same definitions as
described in relation to formula [I-1].
[0014] (4) A triketone derivative represented by formula [I-4]:
4
[0015] wherein R represents a methyl group; each of X and Y
represents a hydrogen atom, a halogen atom, a nitro group, a cyano
group, --R.sup.1, --OR.sup.1, --SR.sup.1, or --NR.sup.2R.sup.3,
wherein R.sup.1 represents a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted; each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure; Z represents --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
--N(OR.sup.1)R.sup.2, --O(C.dbd.O)R.sup.1, --O(C.dbd.O)OR.sup.1,
--O(C.dbd.O)SR.sup.1, --O(C.dbd.O)NR.sup.2R.sup.3, or
--O(C.dbd.S)NR.sup.2R.sup.3 (wherein R.sup.1, R.sup.2, and R.sup.3
have the same definitions as described in relation to X and Y. each
of A and Q represents an oxygen atom or a sulfur atom, p is 0, 1,
or 2, n is 1 or 2), --OM (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base), or a
halogen atom; and m is an integer between 0 and 4 inclusive.
[0016] (5) A triketone derivative according to (4), wherein Z
represents an --OM group (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base).
[0017] (6) A triketone derivative according to any one of (1), (2),
(4), and (5), wherein Y represents a hydrogen atom, a C1-C6 alkyl
group, or a halogen atom.
[0018] (7) A triketone derivative according to any one of (1), (2),
(4), and (5), wherein Y represents a hydrogen atom or a methyl
group.
[0019] (8) A triketone derivative according to any one of (2), (4),
and (5), wherein Y represents a hydrogen atom.
[0020] (9) A triketone derivative according to any one of (1) to
(8), wherein X represents --R.sup.1, --OR.sup.1, or --SR.sup.1.
[0021] (10) A triketone derivative according to (1) or (9), wherein
X represents a halogen atom or a methyl group.
[0022] (11) A triketone derivative according to any one of (1) to
(10), wherein M represents a hydrogen atom.
[0023] (12) A herbicide containing a triketone derivative as
recited in any one of (1) to (11) as an active ingredient.
[0024] (13) A herbicide for use in cultivation of a paddy rice
plant, which herbicide contains a triketone derivative as recited
in any one of (1) to (11) as an active ingredient.
[0025] The second aspect of the present invention encompasses the
following.
[0026] (1) A triketone derivative represented by formula [II-1]:
5
[0027] wherein R represents a methyl group; X represents a hydrogen
atom, a halogen atom, a nitro group, an amino group, a cyano group,
a hydroxy group, a mercapto group, --R.sup.1, --OR.sup.1,
--SR.sup.1, SO.sub.2R.sup.1, --NR.sup.2R.sup.3, or --NHCOR.sup.1
(wherein R.sup.1 represents a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted; each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure);
[0028] G contains 3 to 5 ring-constituting atoms which form a 5- to
7-membered saturated or unsaturated condensed ring including two
carbon atoms of the benzene ring adjacent to G, wherein two or less
ring-constituting atoms are selected from among nitrogen, oxygen,
and sulfur, and the ring-constituting atoms may have one or more
substituents selected from among a C1-C6 alkyl group, a C1-C6
haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a
hydroxy group, a mercapto group, an oxo group, a thioxo group, a
hydroxyimino group, a C1-C6 alkoxyimino group, a hydrazono group, a
C1-C6 monoalkylhydrazono group, and a C1-C6 dialkylhydrazono group,
and a carbon atom or the adjacent carbon atom of the
ring-constituting atom may have a substituent selected from among
an ethylenedioxy group, an ethylenedithio group, a propylenedioxy
group, and a propylenedithio group, with these substituents
optionally being substituted with a halogen atom or a C1-C6 alkyl
group;
[0029] Z.sup.1 represents a halogen atom, --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
--N(OR.sup.1)R.sup.2, --O(C.dbd.O)R.sup.1, --O(C.dbd.O)OR.sup.1,
--O(C.dbd.O)SR.sup.1, --O(C.dbd.O)NR.sup.2R.sup.3, or
--O(C.dbd.S)NR.sup.2R.sup.3 (wherein R.sup.1, R.sup.2, and R.sup.3
have the same definitions as described in relation to X, each of A
and Q represents an oxygen atom or a sulfur atom, p is 0, 1, or 2,
n is 1 to 3), or a halogen atom; m is an integer between 0 and 4
inclusive; and q is 1 or 2.
[0030] (2) A triketone derivative according to (1), which is
represented by formula [II-2] or [II-3]: 6
[0031] wherein R, X, G, Z.sup.1, m, and q have the same definitions
as described in relation to formula [II-1].
[0032] (3) A triketone derivative according to (1) or (2), which is
represented by any one of formulas [II-4] to [II-9]: 7
[0033] wherein R, X, G, Z.sup.1, m, and q have the same definitions
as described in relation to formula [II-1], each of G.sup.1 to
G.sup.4 represents an optionally substituted atom that constitutes
G in formula [II-1], and i is 0, 1, or 2.
[0034] (4) A triketone derivative according to any one of (1) to
(3), wherein X represents a halogen atom, --R.sup.1, --OR.sup.1, or
--SR.sup.1.
[0035] (5) A triketone derivative according to (3) or (4), wherein
each of G.sup.1 to G.sup.4 represents a ring-constituting atom
having one or more substituents selected from the substituent group
consisting of an unsubstituted or C1-C6 alkyl group, a C1-C6 alkoxy
group, an oxo group, and a C1-C6 alkoxyimino group.
[0036] (6) A triketone derivative according to any one of (1) to
(5), wherein Z.sup.1 is selected from among a halogen atom,
--OR.sup.1, --SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, and
--N(OR.sup.1)R.sup.2.
[0037] (7) A triketone derivative represented by formula [II-10]:
8
[0038] wherein R represents a methyl group; each of X and Y
represents a hydrogen atom, a halogen atom, a nitro group, a cyano
group, --R.sup.1, --OR.sup.1, --SR.sup.1, or --NR.sup.2R.sup.3
(wherein R.sup.1 represents a C1-C6 alkyl group which may have a
branched structure, a cyclic structure, or an unsaturated bond, a
C1-C6 haloalkyl group which may have a branched structure, a cyclic
structure, or an unsaturated bond, a phenyl group which may be
substituted, or a benzyl group which may be substituted, each of
R.sup.2 and R.sup.3 represents a hydrogen atom, a C1-C6 alkyl group
which may have a branched structure, a cyclic structure, or an
unsaturated bond, a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, a phenyl
group which may be substituted, or a benzyl group which may be
substituted, or R.sup.2 and R.sup.3 may be bonded to each other to
form a group having a cyclic structure); Z represents --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
--N(OR.sup.1)R.sup.2, --O(C.dbd.O)R.sup.1, --O(C.dbd.O) OR.sup.1,
--O(C.dbd.O)SR.sup.1, --O(C.dbd.O)NR.sup.2R.sup.3, or
--O(C.dbd.S)NR.sup.2R.sup.3 (wherein R.sup.1, R.sup.2, and R.sup.3
have the same definitions as described in relation to X and Y, each
of A and Q represents an oxygen atom or a sulfur atom, p is 0, 1,
or 2, n is 1 or 2), --OM (wherein M represents a hydrogen atom, an
alkali metal, an alkaline earth metal, or an organic base), or a
halogen atom; and m is an integer between 0 and 4 inclusive.
[0039] (8) A triketone derivative according to (7), wherein Y
represents a hydrogen atom or a methyl group.
[0040] (9) A triketone derivative according to (7), wherein Y
represents a hydrogen atom.
[0041] (10) A triketone derivative according to any one of (7) to
(9), wherein Z represents a halogen atom, --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, or
--N(OR.sup.1)R.sup.2.
[0042] (11) A triketone derivative according to any one of (1) to
(10), wherein X represents a halogen atom or a methyl group.
[0043] (12) A herbicide containing a triketone derivative as
recited in any one of (1) to (11) as an active ingredient.
[0044] (13) A herbicide for use in cultivation of a paddy rice
plant, which herbicide contains a triketone derivative as recited
in any one of (1) to (11) as an active ingredient.
BEST MODE FOR CARRYING OUT THE INVENTION
[0045] Hereafter, various modes for carrying out the present
invention will be described.
[0046] I. The First Aspect of the Invention
[0047] The triketone derivative of the first aspect of the present
invention (may be simply referred to as "the present invention"
throughout section I) is represented by chemical formula [I-1]. Of
these, triketone derivatives represented by formulas [I-2] and
[I-3] are preferred in that they provide a low level of chemical
injury to cultivated plants and have an excellent weed-controlling
effect.
[0048] When each of R.sup.1 to R.sup.3 in formulas [I-1] to [I-4]
represents a C1-C6 alkyl group which may have a branched structure,
a cyclic structure, or an unsaturated bond, examples of the alkyl
group include a methyl group, an ethyl group, an n-propyl group, an
i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl
group, a tert-butyl group, an n-pentyl group, an i-pentyl group, a
sec-pentyl group, an n-hexyl group, and an i-hexyl group. The ethyl
group, propyl groups, and butyl groups may have an unsaturated
bond, and the propyl groups, butyl groups, pentyl groups, and hexyl
groups may be linear, branched, or cyclic. Of these, a methyl group
and an ethyl group are preferred.
[0049] When each of R.sup.1 to R.sup.3 in formulas [I-1] to [I-4]
represents a C1-C6 haloalkyl group which may have a branched
structure, a cyclic structure, or an unsaturated bond, examples of
the haloalkyl group include the above-described alkyl groups in
which some or all of the hydrogen atoms are substituted by a
halogen atom such as a chlorine atom, a fluorine atom, a bromine
atom, or an iodine atom. Specific examples include a chloromethyl
group, a difluoromethyl group, a trichloromethyl group, a
trifluoromethyl group, a 2-chloroethyl group, a 2-fluoroethyl
group, a 3-chloropropyl group, and a 3-fluoropropyl group. Of
these, a trifluoromethyl group and a trichloromethyl group are
preferred.
[0050] When each of R.sup.1 to R.sup.3 in formulas [I-1] to [I-4]
represents a phenyl group which may be substituted, examples of the
phenyl group include a phenyl group, a tolyl group, an
m-chlorophenyl group, a p-methoxyphenyl group, a p-nitrophenyl
group, and p-cyanophenyl group. When each of R.sup.1 to R.sup.3
represents a benzyl group which may be substituted, examples of the
benzyl group include a benzyl group, an .alpha.-methylbenzyl group,
an o-methylbenzyl group, an m-chlorobenzyl group, a p-methoxybenzyl
group, a p-nitrobenzyl group, and a p-cyanobenzyl group.
[0051] When each of X and Y in formulas [I-1] to [I-4] or Z in
formula [I-4] represents an --OR.sup.1, examples of the alkoxy
group include a methoxy group, an ethoxy group, an n-propoxy group,
an i-propoxy group, an n-butoxy group, an i-butoxy group, a
sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an
i-pentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, and
an i-hexyloxy group. The propoxy groups and butoxy groups may have
an unsaturated bond and may be linear, branched, or cyclic. In the
above-described alkoxy groups, some or all of the hydrogen atoms
may be substituted by a halogen atom. Examples of such haloalkoxy
groups include a chloromethyloxy group, a difluoromethyloxy group,
a trichloromethyloxy group, a trifluoromethyloxy group, a
2-chloroethyloxy group, a 2-fluoroethyloxy group, a
3-chloropropyloxy group, and a 3-fluoropropyloxy group. Of these, a
methoxy group, an ethoxy group, a difluoromethyloxy group, and a
trifluoromethyloxy group are preferred.
[0052] When each of X and Y in formulas [I-1] to [I-4] represents
an --SR.sup.1 group, examples of the alkylthio group include a
methylthio group, an ethylthio group, an n-propylthio group, an
i-propylthio group, an n-butylthio group, an i-butylthio group, a
sec-butylthio group, a tert-butylthio group, an n-pentylthio group,
an i-pentylthio group, an n-hexylthio group, and an i-hexylthio
group. The propylthio groups and butylthio groups may have an
unsaturated bond and may be linear, branched, or cyclic. In the
above-described alkylthio groups, some or all of the hydrogen atoms
may be substituted by a halogen atom. Examples of such
haloalkylthio groups include a chloromethylthio group, a
difluoromethylthio group, a trichloromethylthio group, a
trifluoromethylthio group, a 2-chloroethylthio group, a
2-fluoroethylthio group, a 3-chloropropylthio group, and a
3-fluoropropylthio group. Of these, a methylthio group, an
ethylthio group, and a trifluoromethylthio group are preferred.
[0053] Examples of the --SO.sub.2R.sup.1 group include a
methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl
group, an i-propylsulfonyl group, an n-butylsulfonyl group, an
i-butylsulfonyl group, a sec-butylsulfonyl group, and a
tert-butylsulfonyl group. Of these, a methylsulfonyl group and an
ethylsulfonyl group are preferred.
[0054] When each of X, Y, and Z in formulas [I-1] to [I-4]
represents an --NR.sup.2R.sup.3 group, examples thereof include a
methylamino group, a dimethylamino group, an ethylamino group, a
pyrrolidinyl group, and a piperidino group. Examples of the
--N(OR.sup.1) R.sup.2 group include a methoxyamino group, a
methoxymethylamino group, a benzyloxyamino group, and an
allyloxyamino group.
[0055] Example of the --NHCOR.sup.1 include --NHCOCH.sub.3,
--NHCOC.sub.2H.sub.5, --NHCOC.sub.3H.sub.7, and
--NHCOC.sub.4H.sub.10.
[0056] R.sup.4 in formulas [I-1] and [I-3] represents a hydrogen
atom or a C1-C6 alkyl group. Examples of the C1-C6 alkyl group
include a methyl group, an ethyl group, an n-propyl group, an
i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl
group, a tert-butyl group, an n-pentyl group, an i-pentyl group, a
sec-pentyl group, an n-hexyl group, and an i-hexyl group. Of these,
a hydrogen atom and a methyl group are preferred, with a hydrogen
atom being particularly preferred.
[0057] Examples of preferable X in formulas [I-1] to [I-4] include
a halogen atom, --R.sup.1, --OR.sup.1, and --SR.sup.1, with a
halogen atom and a methyl group being particularly preferred.
Examples of preferable Y in formulas [I-1] to [I-4] include a
hydrogen atom, a halogen atom, and --R.sup.1, with a hydrogen atom,
a methyl group, and a fluorine atom being particularly
preferred.
[0058] The number "m" in formulas [I-1] to [I-4] is 0-4, preferably
0-2, particularly preferably 0.
[0059] When Z in formula [I-4] represents an --SOPR.sup.1 group,
examples thereof include alkylsulfonyl groups such as a
methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl
group, a butylsulfonyl group, a pentylsulfonyl group, and a
hexylsulfonyl group; alkylsulfinyl groups such as a methylsulfinyl
group, an ethylsulfinyl group, a propylsulfinyl group, a
butylsulfinyl group, a pentylsulfinyl group, and a hexylsulfinyl
group; and alkylthio groups such as a methylthio group, an
ethylthio group, a propylthio group, a butylthio group, a
pentylthio group, and a hexylthio group.
[0060] Examples of M contained in the --OM group in formulas [I-1]
to [I-3] and in formula [I-4] when Z represents an --OM group
include a hydrogen atom; alkali metal atoms such as lithium,
sodium, and potassium; alkaline earth metal atoms such as
magnesium, calcium, and barium; organic bases such as
trimethylamine, triethylamine, and aniline. Of these, a hydrogen
atom is particularly preferred as M.
[0061] When Z in a triketone derivative represented by formula
[I-4] is a hydroxy group, the derivative may be tautomers having
the following structures: 9
[0062] wherein R, R.sup.4, X, Y, and m have the same definitions as
described in relation to formula [I-4]. The triketone derivative of
the present invention encompasses all these tautomeric compounds
and mixtures thereof.
[0063] A process for producing the triketone derivative of the
present invention will next be described. First of all, an
intermediate for producing the triketone derivative of the present
invention; i.e., benzothiophene-2-carboxylic acid, is produced. For
example, the intermediate can be effectively produced through the
following steps.
[0064] (1) First Step: 10
[0065] In the first step, Compounds (a) and (b) are used in an
amount of 1 mol each to carry out the above reaction in the
presence of 1 mol or more of a base to thereby obtain Compound (c).
Either of Compound (a) or Compound (b) may be used in an amount in
excess of equimol with respect to the other.
[0066] Examples of the base which can be used in the reaction
include an alkali metal carbonate, an alkaline earth metal
carbonate, and an alkali metal hydroxide. Examples of a solvent
which is inert to the reaction and used in the reaction include
alcohols such as methanol and ethanol; halohydrocarbons such as
chloroform and dichloromethane; hydrocarbons such as hexane and
toluene; N,N dimethylformamide; and water. The reaction is carried
out in the temperature range of 0.degree. C. to the boiling point
of the employed solvent, with stirring until completion of the
reaction.
[0067] Alternatively, the reaction may be carried out in a
two-phase system in the presence of a quaternary ammonium salt.
Furthermore, Compound (a) may be reacted with sodium
hydrogensulfide or potassium hydrogensulfide, and chloroacetic acid
or bromoacetic acid, to thereby obtain Compound (c).
[0068] When the substituent X or Y in Compound (c) is a leaving
group, the product may be obtained as a mixture. In this case, the
product is purified through a process such as distillation,
recrystallization, or chromatographic purification, to thereby
yield the target compound.
[0069] (2) Second Step: 11
[0070] In the second step, Compound (c) is cyclized to form
Compound (d) as shown in the above reaction. The cyclization is
carried out in the presence of an acidic reagent in a catalyst
amount or in an amount of equimol or more. Examples of preferred
acidic reagents include hydrochloric acid, sulfuric acid,
phosphorus trichloride, phosphorus pentachloride, phosphorus
oxychloride, polyphosphoric acid, acetic acid, acetic anhydride,
trifluoromethanesulfonic acid/ trifluoromethanesulfonic anhydride,
and sulfuryl chloride. The reaction may be carried out in the
absence of a solvent. When a solvent is employed, examples of
preferred solvents include hexane, dichloromethane,
1,2-dichloroethane, chloroform, and N,N-dimethylformamide. The
reaction is carried out in the temperature range of -20.degree. C.
to the boiling point of the employed solvent, with stirring until
completion of the reaction.
[0071] Alternatively, Compound (c) is transformed into its acid
halide, and the acid halide is reacted in the presence of a Lewis
acid. In this case, the transformation is carried out by use of a
halogenating agent such as oxalyl chloride or thionyl chloride in
an amount of equimol or more in the absence of a solvent or in the
presence of a solvent such as methylene chloride,
1,2-dichloroethane, or chloroform. The reaction is carried out in
the temperature range of room temperature to the boiling point of
the employed solvent, with stirring until completion of the
reaction. The subsequent reaction is carried out by use of a Lewis
acid such as aluminum chloride, titanium tetrachloride, or tin
tetrachloride. The reaction is carried out in the temperature range
of -20.degree. C. to the boiling point of the employed solvent,
with stirring until completion of the reaction. When Y of Compound
(d) is a hydrogen atom, the other isomer may be intermingled with
the product as an impurity. In such a case, the product is purified
through a method as described above.
[0072] (3) Third Step: 12
[0073] In the third step, Compound (d) is reduced to form Compound
(e) as shown in the above reaction. Examples of preferred reducing
agents used in the reduction include sodium borohydride and
aluminum triisopropoxide. Examples of preferred solvents include
methanol, ethanol, water, dichloromethane, and toluene. The
reduction is carried out in the temperature range of -20.degree. C.
to the boiling point of an employed solvent, with stirring until
completion of the reaction.
[0074] (4) Fourth Step: 13
[0075] In the fourth step, Compound (e) is dehydrated to form
Compound (f) as shown in the above reaction. The dehydration may be
carried out in the presence of a catalyst amount of an acidic
substance such as hydrochloric acid, sulfuric acid,
p-toluenesulfonic acid, or Amberlist. In this case, a solvent such
as benzene or toluene is preferred as a reaction solvent, in that
water formed during dehydration can be removed through azeotropic
distillation. The formed water is adsorbed in an adsorbent such as
a molecular sieve, or is removed through azeotropic distillation
with the solvent, to thereby accelerate dehydration. When such an
adsorbent is used, the dehydration is carried out in the
temperature range of room temperature to 50.degree. C. with
stirring until completion of the reaction. Azeotropic distillation
is carried out through refluxing with heat at the boiling point of
the employed solvent until the theoretical amount of water is
removed.
[0076] (5) Fifth Step: 14
[0077] In the fifth step, Compound (f) is oxidized to form Compound
(g) as shown in the above reaction. The oxidation is carried out in
the presence of an organic peroxide such as hydrogen peroxide or
m-chloroperbenzoic acid in an amount of 2 mol or more. In this
case, a solvent such as acetic acid or methylene chloride is
preferred as a reaction solvent. The oxidation is carried out in
the temperature range of -20.degree. C. to 100.degree. C., with
stirring until completion of the reaction.
[0078] (6) Sixth Step: 15
[0079] In the sixth step, Compound (g) is hydrogenated to form
Compound (h) as shown in the above reaction. The hydrogenation is
carried out under similar conditions as employed for customary
catalytic hydrogenation. Examples of preferred catalysts include
palladium-on-active carbon, Raney nickel, and platinum oxide. In
this case, a solvent such as tetrahydrofuran, methanol, ethanol,
ethyl acetate, or water is preferred as a reaction solvent. The
hydrogenation is carried out in a hydrogen gas atmosphere, with or
without pressure, and in the temperature range of room temperature
to the boiling point of the employed solvent, with stirring until
completion of the reaction.
[0080] (7) Seventh Step: 16
[0081] In the seventh step, Compound (h) is hydrolyzed to form
Compound (i) as shown in the above reaction. The hydrogenation is
carried out in the presence of an alkali metal hydroxide in an
amount of equimol or more in a mixture of water and alcohol such as
ethanol as a solvent. The hydrolysis is carried out in the
temperature range of room temperature to the boiling point of the
employed solvent, with stirring until completion of the
reaction.
[0082] The thus-obtained intermediate, benzothiophene-2-carboxylic
acid, is used in the following reaction: 17
[0083] wherein R, R.sup.4, X, Y, and m have the same definitions as
described in relation to formula [I-1] to [I-4], to thereby produce
triketone derivatives as represented by formula [I-1] to [I-3] and
a triketone derivative as represented by formula [I-4] wherein Z
represents a hydroxy group.
[0084] The intermediate, benzothiophene-2-carboxylic acid, is
transformed into an acid halide thereof as described in relation to
the above-described cyclization. The thus-formed acid halide is
reacted with a diketone in the presence of an organic base such as
triethylamine at 0-20.degree. C. in an inert organic reaction
solvent such as acetonitrile, and the reaction mixture is allowed
to react with stirring at room temperature in the presence of a
catalyst amount of a cyanide-donor such as acetone cyanohydrin.
[0085] Furthermore, the thus-obtained triketone derivatives
represented by formula [I-1] to [I-3] and triketone derivative
represented by formula [I-4] wherein Z represents a hydroxy group
are reacted with a compound which can substitute some or all of the
hydroxy groups in accordance with reaction, e.g., reaction as
described in Japanese Patent Application Laid-Open (kokai) Nos.
62-298563, 62-242755, or 63-2947, to thereby produce substituted
triketone derivatives represented by formula [I-1] to [I-3] and
triketone derivative represented by formula [I-4] wherein Z
represents a variety of substituents.
[0086] II. The Second Aspect of the Invention
[0087] The triketone derivative of the second aspect of the present
invention (may be simply referred to as "the present invention"
throughout section II) is represented by chemical formula [II-1].
Of these, triketone derivatives represented by formulas [II-2] and
[II-3] are preferred. Furthermore, among the triketone derivatives
represented by formulas [II-2] and [II-3], triketone derivatives
represented by formulas [II-4] to [II-9] are more preferred in that
they provide a low level of chemical injury to cultivated plants
and have an excellent weed-controlling effect.
[0088] In the triketone derivatives represented by formulas [II-1]
to [II-9], the substituent represented by X is preferably a halogen
atom, an alkyl group represented by --R.sup.1, an alkoxy group
represented by --OR.sup.1, or an alkylthio group represented by
--SR.sup.1. In the triketone derivative represented by formula
[II-10], the substituent Y represents a hydrogen atom or a variety
of groups. Of these, a hydrogen atom and a methyl group are
preferred. In the triketone derivative represented by formula
[II-10], the substituent X represents a variety of groups. Of
these, a halogen atom and a methyl group are preferred.
[0089] In the triketone derivative represented by formulas [II-1]
to [II-10], each of the substituents Z and Z.sup.1 represents a
variety of groups. Of these, a halogen atom, and --OR.sup.1,
--SO.sub.pR.sup.1, --A(CH.sub.2).sub.nQR.sup.1, --NR.sup.2R.sup.3,
and --N(OR.sup.1)R.sup.2 described below are preferred.
[0090] When each of R.sup.1 to R.sup.3 in formulas [II-1] to [II-9]
represents a C1-C6 alkyl group which may have a branched structure,
a cyclic structure, or an unsaturated bond, examples of the alkyl
group include a methyl group, an ethyl group, an n-propyl group, an
i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl
group, a tert-butyl group, an n-pentyl group, an i-pentyl group, a
sec-pentyl group, an n-hexyl group, and an i-hexyl group. The ethyl
group, propyl groups, and butyl groups may have an unsaturated
bond, and the propyl groups, butyl groups, pentyl groups, and hexyl
groups may be linear, branched, or cyclic. Of these, a methyl group
and an ethyl group are preferred.
[0091] When each of R.sup.1 to R.sup.3 represents a C1-C6 haloalkyl
group which may have a branched structure, a cyclic structure, or
an unsaturated bond, examples of the haloalkyl group include the
above-described alkyl groups in which some or all of the hydrogen
atoms are substituted by a halogen atom such as a chlorine atom, a
fluorine atom, a bromine atom, or an iodine atom. Specific examples
include a chloromethyl group, a difluoromethyl group, a
trichloromethyl group, a trifluoromethyl group, a 2-chloroethyl
group, a 2-fluoroethyl group, a 3-chloropropyl group, and a
3-fluoropropyl group. Of these, a trifluoromethyl group is
preferred.
[0092] When each of R.sup.1 to R.sup.3 represents a phenyl group
which may be substituted, examples of the phenyl group include a
phenyl group, a tolyl group, an m-chlorophenyl group, a
p-methoxyphenyl group, a p-nitrophenyl group, and p-cyanophenyl
group. When each of R.sup.1 to R.sup.3 represents a benzyl group
which may be substituted, examples of the benzyl group include a
benzyl group, an a-methylbenzyl group, an o-methylbenzyl group, an
m-chlorobenzyl group, a p-methoxybenzyl group, a p-nitrobenzyl
group, and a p-cyanobenzyl group. Of these, a phenyl group and a
benzyl group are preferred. When each of X, Y, and Z.sup.1 in
formulas [II-1] to [II-9] represents an --OR.sup.1 group, examples
of the alkoxy group include a methoxy group, an ethoxy group,
propoxy groups, butoxy groups, pentyloxy groups, and hexyloxy
groups. The propoxy groups and butoxy groups may have an
unsaturated bond and may be linear, branched, or cyclic. In the
above-described alkoxy groups, some or all of the hydrogen atoms
may be substituted by a halogen atom. Examples of such haloalkoxy
groups include a chloromethyloxy group, a difluoromethyloxy group,
a trichloromethyloxy group, a trifluoromethyloxy group, a
2-chloroethyloxy group, a 2-fluoroethyloxy group, a
3-chloropropyloxy group, and a 3-fluoropropyloxy group. Of these, a
methoxy group, an ethoxy group, and an isopropoxy group are
preferred.
[0093] When each of X, Y, and Z.sup.1 in formulas [II-1] to [II-9]
represents an --SR.sup.1 group, examples of the alkylthio group
include a methylthio group, an ethylthio group, propylthio groups,
butylthio groups, pentylthio groups, and hexylthio groups. The
propylthio groups and butylthio groups may have an unsaturated bond
and may be linear, branched, or cyclic. In the above-described
alkylthio groups, some or all of the hydrogen atoms may be
substituted by a halogen atom. Examples of such haloalkylthio
groups include a chloromethylthio group, a difluoromethylthio
group, a trichloromethylthio group, a trifluoromethylthio group, a
2-chloroethylthio group, a 2-fluoroethylthio group, a
3-chloropropylthio group, and a 3-fluoropropylthio group. Of these,
a methylthio group, an ethylthio group, an i-propylthio group, and
a t-butylthio group are preferred.
[0094] When each of X, Y, and Z.sup.1 in formulas [II-1] to [II-9]
represents an --SO.sub.pR.sup.1 group, examples of the
--SO.sub.pR.sup.1 group include alkylsulfonyl groups such as a
methylsulfonyl group, an ethylsulfonyl group, propylsulfonyl
groups, butylsulfonyl groups, pentylsulfonyl groups, and
hexylsulfonyl groups; alkylsulfinyl groups such as a methylsulfinyl
group, an ethylsulfinyl group, propylsulfinyl groups, butylsulfinyl
groups, pentylsulfinyl groups, and hexylsulfinyl groups; and
alkylthio groups such as a methylthio group, an ethylthio group,
propylthio groups, butylthio groups, pentylthio groups, and
hexylthio groups. Of these, a methylsulfonyl group and an
ethylsulfonyl group are preferred. In addition, when each of X, Y,
and Z.sup.1 in the formulas represents an --NR.sup.2R.sup.3 group,
examples thereof include a methylamino group, a dimethylamino
group, an ethylamino group, a pyrrolidinyl group, and a piperidino
group. When each of X, Y, and Z.sup.1 in the formulas represents an
--N(OR.sup.1)R.sup.2 group, examples of the --N(OR.sup.1)R.sup.2
group include a methoxyamino group, a methoxymethylamino group, a
benzyloxyamino group, and an allyloxyamino group. Of these, a
methoxymethylamino group is preferred.
[0095] The number "q," the number of the substituent X, is 1 or 2,
with 1 being preferred.
[0096] When Z in formula [II-10] represents an --O(C.dbd.O)R.sup.1
group, examples include an acetoxy group and a propionyloxy
group.
[0097] When each of Z and Z.sup.1 in formulas [II-1] to [II-10]
represents an --O(C.dbd.O)OR.sup.1 group, examples of the
--O(C.dbd.O)OR.sup.1 group include a methoxycarbonyloxy group, an
ethoxycarbonyloxy group, and a propoxycarbonyloxy group. When each
of Z and Z.sup.1 in formulas [II-1] to [II-10] represents an
--O(C.dbd.O)SR.sup.1 group, examples of the --O(C.dbd.O)SR.sup.1
group include a methylthiocarbonyloxy group, an
ethylthiocarbonyloxy group, and a propylthiocarbonyloxy group. When
each of Z and Z.sup.1 in formulas [II-1] to [II-10] represents an
--O(C.dbd.O)NR.sup.1R.sup.2 group, examples of the
--O(C.dbd.O)NR.sup.1R.sup.2 group include an N-methylcarbamoyl
group, an N-ethylcarbamoyl group, and an N-dimethylcarbamoyl group.
When each of Z and Z.sup.1 in formulas [II-1] to [II-10] represents
an --O(C.dbd.S)NR.sup.1R.sup.2 group, examples of the
--O(C.dbd.S)NR.sup.1R.sup.2 group include an N-methylthiocarbamoyl
group, an N-ethylthiocarbamoyl group, and an
N-dimethylthiocarbamoyl group.
[0098] In these formulas, m is preferably 0-2, with 0 being
particularly preferred.
[0099] The triketone derivative represented by formula [II-1] may
be tautomers having the following structures: 18
[0100] wherein R, X, G, Z.sup.1, m and q have the same definitions
as described in relation to formula [II-1]. The triketone
derivative of the present invention encompasses all these
tautomeric compounds and mixtures thereof.
[0101] Furthermore, examples of the optionally substituted
ring-constituting atoms represented by G.sup.1 to G.sup.4 in
formulas [II-4] to [II-9], which are described as preferable
examples of G, include an unsubstituted ring-constituting atom and
a ring-constituting atom which has one or two substituents selected
from the group consisting of a methyl group, an oxo group, a
methoxy group, an isopropyloxy group, and a methoxyimino group. In
the above formulas, i is preferably 2.
[0102] The process for producing the triketone derivative of the
present invention will next be described. First of all, when G in
formula [II-1] forms a 5-membered ring including two carbon atoms
of the benzene ring adjacent to G, an intermediate for producing
the triketone derivative of the present invention, i.e.,
benzothiophene-2-carboxylic acid, is produced. For example, the
intermediate can be effectively produced through the following
steps.
[0103] (1) First Step: 19
[0104] In the first step, Compounds (a) and (b) are used in an
amount of 1 mol each to carry out the above reaction in the
presence of 1 mol or more of a base to thereby obtain Compound (c).
Either of Compound (a) or Compound (b) may be used in an amount in
excess of equimol with respect to the other.
[0105] Examples of the base which can be used in the reaction
include an alkali metal carbonate, an alkaline earth metal
carbonate, and an alkali metal hydroxide. Examples of a solvent
which is inert to the reaction and used in the reaction include
alcohols such as methanol and ethanol; halohydrocarbons such as
chloroform and dichloromethane; hydrocarbons such as hexane and
toluene; and water. The reaction is carried out in the temperature
range of 0.degree. C. to the boiling point of the employed solvent,
with stirring until completion of reaction.
[0106] Alternatively, the reaction may be carried out in a
two-phase system in the presence of a quaternary ammonium salt.
Furthermore, Compound (a) may be reacted with sodium
hydrogensulfide or potassium hydrogensulfide and chloroacetic acid
or bromoacetic acid, to thereby obtain Compound (c).
[0107] When the substituent X or Y in Compound (c) is a leaving
group, the product may be obtained as a mixture. In this case, the
product is purified through a process such as distillation,
recrystallization, or chromatographic purification, to thereby
yield the target compound.
[0108] (2) Second Step: 20
[0109] In the second step, Compound (c) is cyclized to form
Compound (d) as shown in the above reaction. The cyclization is
carried out in the presence of an acidic reagent in a catalyst
amount or in an amount of equimol or more. Examples of preferred
acidic reagents include hydrochloric acid, sulfuric acid,
phosphorus trichloride, phosphorus pentachloride, phosphorus
oxychloride, polyphosphoric acid, acetic acid, acetic anhydride,
trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride,
and sulfuryl chloride. The reaction may be carried out in the
absence of a solvent. When a solvent is used, examples of preferred
solvents include hexane, dichloromethane, 1,2-dichloroethane
chloroform, and N,N-dimethylformamide. The reaction is carried out
in the temperature range of -20.degree. C. to the boiling point of
the employed solvent, with stirring until completion of the
reaction.
[0110] Alternatively, Compound (c) is transformed into its acid
chloride, and the acid chloride is reacted in the presence of a
Lewis acid. In this case, the transformation is carried out by use
of a halogenating agent such as oxalyl chloride or thionyl chloride
in an amount of equimol or more in the absence of a solvent or in
the presence of a solvent such as methylene chloride,
1,2-dichloroethane, or chloroform. The reaction is carried out in
the temperature range of room temperature to the boiling point of
the employed solvent, with stirring until completion of the
reaction. The subsequent reaction is carried out by use of a Lewis
acid such as aluminum chloride, titanium tetrachloride, or tin
tetrachloride. The reaction is carried out in the temperature range
of -20.degree. C. to the boiling point of the employed solvent,
with stirring until completion of the reaction. When Y of Compound
(d) is a hydrogen atom, the other isomer may be intermingled with
the product as an impurity. In such a case, the product is purified
through a method as described above.
[0111] (3) Third Step: 21
[0112] In the third step, Compound (d) is reduced to form Compound
(e) as shown in the above reaction. Examples of preferred reducing
agents used in the reduction include sodium borohydride and
aluminum triisopropoxide. Examples of preferred solvents include
methanol, ethanol, water, dichloromethane, and toluene. The
reduction is carried out in the temperature range of -20.degree. C.
to the boiling point of the employed solvent with stirring until
completion of the reaction.
[0113] (4) Fourth Step: 22
[0114] In the fourth step, Compound (e) is dehydrated to form
Compound (f) as shown in the above reaction. The dehydration may be
carried out in the presence of a catalyst amount of an acidic
substance such as hydrochloric acid, sulfuric acid, or
p-toluenesulfonic acid. In this case, a solvent such as benzene or
toluene is preferred as a reaction solvent, in that water formed
during dehydration can be removed through azeotropic distillation.
The formed water is adsorbed in an adsorbent such as a molecular
sieve, or is removed through azeotropic distillation with the
solvent, to thereby accelerate dehydration. When such an adsorbent
is used, the dehydration is carried out in the temperature range of
room temperature to 50.degree. C., with stirring until completion
of the reaction. Azeotropic distillation is carried out through
refluxing with heat at the boiling point of the employed solvent by
the time a theoretical amount of water is removed.
[0115] (5) Fifth Step: 23
[0116] In the fifth step, Compound (f) is oxidized to form Compound
(g) as shown in the above reaction. The oxidation is carried out in
the presence of an organic peroxide such as hydrogen peroxide or
m-chloroperbenzoic acid in an amount of 2 mol or more. In this
case, a solvent such as acetic acid or methylene chloride is
preferred as a reaction solvent. The oxidation is carried out in
the temperature range of -20.degree. C. to 100.degree. C., with
stirring until completion of the reaction.
[0117] (6) Sixth Step: 24
[0118] In the sixth step, Compound (g) is hydrogenated to form
Compound (h) as shown in the above reaction. The hydrogenation is
carried out under similar conditions as employed for customary
catalytic hydrogenation. Examples of preferred catalysts include
palladium-on-active carbon, Raney nickel, and platinum oxide. In
this case, a solvent such as tetrahydrofuran, methanol, ethanol,
ethyl acetate, or water is preferred as a reaction solvent. The
hydrogenation is carried out in a hydrogen gas atmosphere, with or
without pressure, and in the temperature range of room temperature
to the boiling point of the employed solvent, with stirring until
completion of the reaction.
[0119] (7) Seventh Step: 25
[0120] In the seventh step, Compound (h) is hydrolyzed to form
Compound (i) as shown in the above reaction. The hydrogenation is
carried out in the presence of an alkali metal hydroxide in an
amount of equimol or more in a mixture of water and alcohol such as
ethanol as a solvent. The hydrolysis is carried out in the
temperature range of room temperature to the boiling point of the
employed solvent, with stirring until completion of the
reaction.
[0121] The thus-obtained intermediate is used in the following
reaction: 26
[0122] wherein R, X, Y, and m have the same definitions as
described in relation to the above-described formulas, to thereby
produce triketone derivatives as represented by the above-described
formulas wherein Z represents a hydroxy group.
[0123] The intermediate carboxylic acid is transformed into an acid
halide thereof as described in relation to the above-described
cyclization. The thus-formed acid halide is reacted with a diketone
in the presence of an organic base such as triethylamine at
0-20.degree. C. in an inert organic reaction solvent such as
acetonitrile, and the reaction mixture is allowed to react with
stirring at room temperature in the presence of a catalyst amount
of a cyanide-donor such as acetone cyanohydrin.
[0124] When G in the above formulas forms a 6- or 7-membered ring
including two carbon atoms of the benzene ring adjacent to G, an
intermediate for producing the triketone derivative can be produced
through a method described in WO94/04524, WO94/08988, or
WO97/03064.
[0125] Furthermore, either one of the thus-obtained triketone
derivatives represented by the above formulas wherein Z represents
a hydroxy group is reacted with a compound which can substitute
some or all of the hydroxy groups in accordance with a reaction
described, for example, in Japanese Patent Application Laid-Open
(kokai) Nos. 62-298563, 62-242755, or 63-2947, to thereby produce
substituted triketone derivatives represented by the above formulas
wherein Z represents a variety of substituents.
[0126] III. Herbicides
[0127] The herbicides of the first and second aspects of the
present invention (may be simply referred to as "the present
invention" throughout section III) contain, as an active
ingredient, triketone derivatives represented by formulas [I-1] to
[I-4] in the first aspect or represented by formulas as described
above in the second aspect. The herbicides are produced through
mixing the triketone derivative with a liquid carrier such as a
solvent or a solid carrier such as a mineral powder, and are
prepared into a variety of forms such as water-dispersible powder,
emulsion, powder, and granules for use. During preparation of the
herbicide, a surfactant is preferably added to the herbicide so as
to impart properties such as an emulsifying property,
dispersibility, and extendability to the herbicide.
[0128] When the herbicide of the present invention is used in the
form of water-dispersible powder, the triketone derivative, a solid
carrier, and a surfactant are typically mixed, in amounts of 5-55
wt. %, 40-93 wt. %, and 2-5 wt. %, respectively, to thereby prepare
a composition, which serves as a herbicide.
[0129] When the herbicide of the present invention is used in the
form of emulsion, the triketone derivative, a solvent, and a
surfactant are typically mixed in amounts of 10-50 wt. %, 35-85 wt.
%, and 5-15 wt. %, respectively, to thereby prepare a composition,
which serves as a herbicide.
[0130] When the herbicide of the present invention is used in the
form of powder, the triketone derivative, a solid carrier, and a
surfactant are typically mixed in amounts of 1-15 wt. %, 80-97 wt.
%, and 2-5 wt. %, respectively, to thereby prepare a composition,
which serves as a herbicide.
[0131] When the herbicide of the present invention is used in the
form of granules, the triketone derivative, a solid carrier, and a
surfactant are typically admixed in amounts of 1-15 wt. %, 80-97
wt. %, and 2-5 wt. %, respectively, to thereby prepare a
composition, which serves as a herbicide.
[0132] Examples of preferred solid carriers include oxides such as
diatomaceous earth and slaked lime; phosphates such as apatite;
sulfates such as gypsum; and mineral micropowders such as talc,
pyrophyllite, clay, kaolin, bentonite, acidic terra alba, white
carbon, quartz powder, and silica stone powder.
[0133] Examples of preferred organic solvents include aromatic
hydrocarbons such as benzene, toluene, and xylene;
chlorohydrocarbons such as o-chlorotoluene, trichloroethane, and
trichloroethylnene; alcohols such as cyclohexanol, amyl alcohol,
and ethylene glycol; ketones such as isophorone, cyclohexanone, and
cyclohexenyl-cyclohexanone; ethers such as butyl cellosolve,
diethyl ether, and methyl ethyl ether; esters such as isopropyl
acetate, benzyl acetate, and methyl phthalate; amides such as
dimethylformamide; and mixtures thereof.
[0134] Examples of the surfactant which can be used in the
invention include anionic, nonionic, cationic, and ampholytic
surfactants such as amino acid-type and betaine-type
surfactants.
[0135] To the herbicide of the present invention, an ingredient
having a weed-controlling activity may optionally be added other
than the triketone derivative represented by formulas [I-1] to
[II-10]. Examples of the compound contained in such an ingredient
include diphenyl ether, triazine, urea, carbamate, thiocarbamate,
acid anilide, pyrazole, phosphoric acid, sulfonylurea, and
oxadiazone. These ingredients may appropriately be used in
combination.
[0136] Furthermore, additives such as a pesticide, a bactericide, a
plant-growth-regulator, and a fertilizer may optionally be
incorporated into the herbicide of the present invention.
[0137] The herbicide of the present invention is applied directly
to a weed or to a field where the weed grows, before or after
germination of the weed. The manner of application depends on the
type of a cultivated plant or the environment of use, and a form of
application such as spraying, sprinkling, water sprinkling, or
injecting may be employed.
[0138] Examples of the cultivated plant to which the herbicide is
applied include graminaceous plants such as rice, wheat, barley,
corn, oat, and sorghum; broad-leaved crops such as soybean, cotton,
beet, sunflower, and rape; fruit trees; vegetables such as fruit,
root, and leaf vegetables; and turf grass.
[0139] Examples of paddy weeds to which the herbicide of the
present invention applies include Alismataceae such as Alisma
canaliculatum, Sagittaria trifolia, and Sagittaria pygmaea;
Cyperaceae such as Cyperus difformis, Cyperus serotinus, Scirpus
juncoides, and Eleocharis kuroguwai; Scrothulariaceae such as
Lindernia pyxidaria; Pontenderiaceae such as Monochoria vaginalis;
Potamogetonaceae such as Potamogeton distinctus; Lythraceae such as
Rotala indica; and Gramineae such as Echinochloa crus-galli.
[0140] Examples of field weeds include broad-leaved weeds,
graminaceous weeds, and cyperaceous weeds. Specific examples of
broad-leaved weeds include Solanaceae such as Solanum nigrum and
Datura stramonium; Malvaceae such as Abutilon theophrasti and Sida
spinosa; Convolvulaceae such as Ipomoea purpurea; Amaranthaceae
such as Amaranthus lividus; Compositae such as Xanthium strumarium,
Ambrosia artemisifolia, Galinsoga ciliata, Cirsium arvense, Senecio
Vulgaris, and Erigeron annus; Brassicaceae such as Rorippa indica,
Sinapis arvensis, and Capsella bursa-pastoris; Polygonaceae such as
Polygonum bulumei and Polygonum convolvulus; Portulacaceae such as
Portulaca oleracea; Chenopodiaceae such as Chenopodium alubum,
Chenopodium ficiolium, and Kochia scoparia; Caryophyllaceae such as
Stellaria media; Scrophulariaceae such as Veronica persica;
Commelinaceae such as Commelina communis; Euphorbiaceae such as
Lamium amplexicaule, Euphorbia supina, and Euphorbia maculata;
Rubiaceae such as Galium spurium, Galium aparine, and Rubia akane;
Vilaceae such as Viola arvensis; and Leguminosae such as Sesbania
exaltata and Cassia obtusifolia. Specific examples of Graminaceous
weeds include Sorghum bicolor, Panicum dichotomiflorum, Sorghum
haepense, Echinochloa crus-galli, Digitaria adscendes, Avena fatua,
Eleusine indica, Setaria viridis, and Alopecurus aequalis. Specific
examples of Cyperaceous weeds include Cyperus rotundus and Cyperus
esculentus.
[0141] The present invention will next be described in more detail
with reference to working examples and comparative examples.
EXAMPLES RELATED TO THE FIRST ASPECT OF THE INVENTION
Example I-1
[1] Synthesis of
4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-diox- ide
[0142] (1) Synthesis of Ethyl
4-carboxymethylsulfenyl-2-chlorobenzoate
[0143] A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g),
potassium carbonate (9.44 g), dimethylformamide (50 ml), and
mercaptoacetic acid (3.8 ml) was allowed to react with heat at
80.degree. C. for 4 hours.
[0144] Next, the resultant reaction mixture was poured into ice
water and was subjected to extraction with ethyl acetate. The
extract was dried over sodium sulfate and filtered, then
concentrated to thereby obtain a crude reaction product (12.3
g).
[0145] (2) Synthesis of
4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzoth- iophene
[0146] A mixture of ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate
(12.3 g) obtained in (1), 1,2-dichloroethane (36 ml), and thionyl
chloride (3.9 ml) was refluxed with heat over 1 hour.
[0147] Acid chloride obtained by concentration of the reaction
mixture was dissolved in dichloromethane (36 ml). Under cooling on
ice, the solution was added dropwise over 1 hour to a solution of
aluminum chloride (14.3 g, 107 mmol) and dichloromethane (150 ml)
prepared in advance, after which reaction was continued for a
further 2 hours at room temperature.
[0148] The thus-obtained reaction mixture was poured into ice water
and subjected to extraction with dichloromethane. The extract was
dried over sodium sulfate, filtered, and concentrated to thereby
obtain a crude reaction product in the form of liver brown oil
(12.3 g). Further, the crude reaction product was purified by
column chromatography to thereby obtain the compound of interest as
brown oil (5.3 g, yield: 23%).
[0149] (3) Synthesis of
4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydroben- zothiophene
[0150] A solution comprising
4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobe- nzothiophene (5.3 g)
obtained in (2), dichloromethane (25 ml), and ethanol (25 ml) was
cooled in an ice-bath and sodium boron hydride (0.26 g) was added
thereto, after which the solution was allowed to stand
overnight.
[0151] Subsequently, the obtained reaction mixture was poured into
ice water and subjected to extraction with dichloromethane. The
extract was dried over sodium sulfate and filtered to thereby
obtain the compound of interest (5.3 g, yield: 98%).
[0152] (4) Synthesis of 4-chloro-5-ethoxycarbonylbenzothiophene
[0153] A mixture of
4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzoth- iophene
(5.3 g) obtained in (3), toluene (50 ml), and p-toluene sulfate
(0.2 g) was subjected to azeotropic dehydration over 1 hour.
[0154] The resultant reaction mixture was diluted with toluene,
washed with a saturated solution of sodium hydrogencarbonate, and
dried over sodium sulfate, followed by filtration and concentration
to thereby obtain the compound of interest as brown oil (4.6 g,
yield: 95%).
[0155] (5) Synthesis of
4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxid- e
[0156] A mixture containing 4-chloro-5-ethoxycarbonylbenzothiophene
(4.6 g) obtained in (4), acetic acid (30 ml), and a 30 wt. %
aqueous solution of hydrogen peroxide (5.4 ml) was allowed to react
at 80.degree. C. for 2 hours with stirring.
[0157] After the reaction product was allowed to cool to room
temperature, it was diluted with water and filtered to thereby
obtain a solid. The solid was dried and purified by column
chromatography to thereby obtain the compound of interest as
colorless crystals (3.7 g, yield: 95%).
[0158] (6) Synthesis of
4-chloro-5-ethoxycabonyl-2,3-dihydrobenzothiophene-
-1,1-dioxide
[0159] A mixture of
4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide (3.7 g)
obtained in (5), tetrahydrofuran (40 ml), and 5% palladium/carbon
was allowed to react in an atmosphere of hydrogen gas at ordinary
temperature and pressure for 8 hours.
[0160] Subsequently, the resultant mixture was filtered and
concentrated to thereby obtain the compound of interest as pale
yellow oil (3.44 g, yield: 91%).
[0161] (7) Synthesis of
4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1,- 1-dioxide
[0162]
4-Chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
(3.44 g) obtained in (6) was dissolved in ethanol (35 ml). To the
solution, a 20 wt. % aqueous solution of sodium hydroxide (5 ml)
was added and the mixture was allowed to stand overnight.
[0163] Subsequently, the reaction mixture was concentrated and
acidified by adding a 5 wt. % aqueous solution of hydrochloric
acid, followed by filtration and drying of the produced precipitate
to thereby yield the compound of interest as colorless crystals
(2.6 g, yield: 84%).
[0164] A .sup.1H-NMR analysis (acetone-d.sup.6; TMS standard) of
the thus-obtained colorless crystals showed peaks of 3.4-3.8 (m,
4H), 7.85 (1H, d), and 8.06 (1H, d). Also, under infrared spectrum
analysis, there were observed peaks at 3080 cm.sup.-1, 3010
cm.sup.-1, 1690 cm.sup.-1, 1410 cm.sup.-1, 1400 cm.sup.-1, 1310
cm.sup.-1, 1290 cm.sup.-1, 1250 cm.sup.-1, 1190 cm.sup.-1, and 1130
cm.sup.-1. From these results, the compound was identified as
4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophen- e-1,1-dioxide, and
its measured melting point was 232-233.degree. C.
[2] Synthesis of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide [Compound No. A-1]
[0165] As raw materials,
4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1- ,1-dioxide (1.0
g) obtained in (1) and a suspension (4 ml) of thionyl chloride
(0.54 g) in 1,2-dichloroethane were reacted over 1 hour under
reflux with heat.
[0166] From the obtained product, solvent was removed through
distillation under reduced pressure, and the obtained acid chloride
and 1,3-cyclohexanedione (0.47 g) were dissolved in acetonitrile
(10 ml) serving as a solvent. Thereafter, at room temperature, a
solution of triethylamine (0.82 g) in acetonitrile (5 ml) was added
dropwise thereto.
[0167] After the mixture was stirred for 2 hours at room
temperature, acetone cyanhydrin (0.01 g) was added thereto,
followed by stirring for 20 hours at room temperature.
[0168] To the resultant mixture, ethyl acetate was added and
subjected to extraction with saturated sodium carbonate. To an
aqueous phase, 10% hydrochloric acid was added so as to adjust the
pH of the phase to 1, and extraction with ethyl acetate was carried
out. The thus-obtained organic phase was washed with water and
aqueous saturated brine and then dried over anhydrous sodium
sulfate. The solvent was removed from the product through
distillation under reduced pressure to thereby obtain the compound
of interest, 4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-d-
ihydrobenzothiophene-1,1-dioxide (1.24 g, yield: 90%).
[0169] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-2
Synthesis of
4-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene -1,1-dioxide [Compound No. A-2]
[0170] The target compound was obtained in the same manner as
described in Example I-1, except that
4-methyl-5-oxycabonyl-2,3-dihydrobenzothiophene-- 1,1-dioxide was
used instead of 4-chloro-5-oxycabonyl-2,3-dihydrobenzothio-
phene-1,1-dioxide.
[0171] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-3
Synthesis of 4-chloro-7-methyl-5-(1,3-dioxocyclohexan-2-yl)
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
A-3]
[0172] The target compound was obtained in the same manner as
described in Example I-1, except that
4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzo-
thiophene-1,1-dioxide was used instead of
4-chloro-5-oxycarbonyl-2,3-dihyd- robenzothiophene-1,1-dioxide.
[0173] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-4
Synthesis of
4,7-dimethyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide [Compound No. A-4]
[0174] The target compound was obtained in the same manner as
described in Example I-1, except that
4,7-dimethyl-5-oxycarbonyl-2,3-dihydrobenzothiop- hene-1,1-dioxide
was used instead of 4-chloro-5-oxycarbonyl-2,3-dihydroben-
zothiophene-1,1-dioxide.
[0175] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-5
Synthesis of
4-methoxy-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydroben-
zothiophene-1,1-dioxide [Compound No. A-5]
[0176] The target compound was obtained in the same manner as
described in Example I-1, except that
4-methoxy-5-oxycarbonyl-2,3-dihydrobenzothiophen- e-1,1-dioxide was
used instead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzot-
hiophene-1,1-dioxide.
[0177] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-6
Synthesis of
4-methylthio-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide [Compound No. A-6]
[0178] The target compound was obtained in the same manner as
described in Example I-1, except that
4-methylthio-5-oxycarbonyl-2,3-dihydrobenzothiop- hene-1,1-dioxide
was used instead of 4-chloro-5-oxycarbonyl-2,3-dihydroben-
zothiophene-1,1-dioxide.
[0179] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-7
Synthesis of
4-chloro-5-(4-methyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. A-7]
[0180] The target compound was obtained in the same manner as
described in Example I-1, except that 4-methyl-1,3-cyclohexanedione
was used instead of 1,3-cyclohexanedione.
[0181] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-8
Synthesis of
4-chloro-5-(4,4-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-8]
[0182] The target compound was obtained in the same manner as
described in Example I-1, except that
4,4-dimethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0183] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-9
Synthesis of
4-chloro-5-(5,5-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-9]
[0184] The target compound was obtained in the same manner as
described in Example I-1, except that
5,5-dimethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0185] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-10
Synthesis of
4-chloro-7-methyl-5-(5,5-dimethyl-1,3-dioxocyclohexan-2-yl)ca-
rbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
A-10]
[0186] The target compound was obtained in the same manner as
described in Example I-1, except that
5,5-dimethyl-1,3-cyclohexanedione and
4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
were used instead of 1,3-cyclohexanedione and
4-chloro-5-oxycarbonyl-2,3-- dihydrobenzothiophene-1,1-dioxide,
respectively.
[0187] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-11
Synthesis of
4-chloro-7-methyl-5-(4,4-dimethyl-1,3-dioxocyclohexan-2-yl)ca-
rbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
A-11]
[0188] The target compound was obtained in the same manner as
described in Example I-1, except that
4,4-dimethyl-1,3-cyclohexanedione and
4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
were used instead of 1,3-cyclohexanedione and
4-chloro-5-oxycarbonyl-2,3-- dihydrobenzothiophene-1,1-dioxide,
respectively.
[0189] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-12
Synthesis of
4-chloro-5-(5-methyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. A-12]
[0190] The target compound was obtained in the same manner as
described in Example I-1, except that 5-methyl-1,3-cyclohexanedione
was used instead of 1,3-cyclohexanedione.
[0191] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-13
Synthesis of
4-chloro-5-(4,4,6-trimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-
-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-13]
[0192] The target compound was obtained in the same manner as
described in Example I-1, except that
4,4,6-trimethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0193] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-14
Synthesis of
4-chloro-5-(4,6-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-14]
[0194] The target compound was obtained in the same manner as
described in Example I-1, except that
4,6-dimethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0195] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-15
Synthesis of
4-chloro-5-(4,4,6,6-tetramethyl-1,3-dioxocyclohexan-2-yl)carb-
onyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-15]
[0196] The target compound was obtained in the same manner as
described in Example I-1, except that
4,4,6,6-tetramethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0197] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-16
Synthesis of
4-chloro-5-(4,5-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-16]
[0198] The target compound was obtained in the same manner as
described in Example I-1, except that
4,5-dimethyl-1,3-cyclohexanedione was used instead of
1,3-cyclohexanedione.
[0199] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-17
Synthesis of
4-chloro-2-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. A-17]
[0200] The target compound was obtained in the same manner as
described in Example I-1, except that
4-chlodro-2-methyl-5-oxycarbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide was used instead of
4-chloro-B-oxycarbonyl-2,3-dihy- drobenzothiophene-1,1-dioxide.
[0201] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-18
Synthesis of
4-methoxy-2-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-d-
ihydrobenzothiophene-1,1-dioxide [Compound No. A-18]
[0202] The target compound was obtained in the same manner as
described in Example I-1, except that
4-methoxy-2-methyl-5-oxycarbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide was used instead of
4-chloro-5-oxycarbonyl-2,3-dihy- drobenzothiophene-1,1-dioxide.
[0203] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-19
Synthesis of a Sodium Salt of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbony-
l-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-19]
[0204]
4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiop-
hene-1,1-dioxide (0.1 g) obtained in the same manner as described
in Example I-1 was dissolved in tetrahydrofuran (8 ml) and the
solution was added dropwise to a suspension of sodium hydroxide
(0.006 g) in tetrahydrofuran (2 ml).
[0205] After the mixture was stirred at room temperature for 25
hours, the solvent was removed through distillation under reduced
pressure, and extraction with ethyl acetate was carried out. The
extract was dried and crystallized to thereby yield the compound of
interest (0.08 g, yield: 75%).
[0206] The chemical structure and the measured melting point of the
obtained target compound are shown in Table I-1.
Example I-20
Synthesis of
4-bromo-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzo-
thiophene-1,1-dioxide [Compound No. A-20]
[0207] The target compound was obtained in the same manner as
described in Example I-1, except that
4-bromo-5-oxycarbonyl-2,3-dihydrobenzothiophene-- 1,1-dioxide was
used instead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothi-
ophene-1,1-dioxide.
[0208] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
Example I-21
Synthesis of
4-cyano-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzo-
thiophene-1,1-dioxide [Compound No. A-21]
[0209] The target compound was obtained in the same manner as
described in Example I-1, except that
4-cyano-5-oxycarbonyl-2,3-dihydrobenzothiophene-- 1,1-dioxide was
used instead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothi-
ophene-1,1-dioxide.
[0210] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table I-1.
[0211] In the Table I-1, "(1)" to "(6)" indicates respectively as
follows.
[0212] (1) Example No.
[0213] (2) Compound No.
[0214] (3) Chemical structure
[0215] (4) NMR/ppm (CDCl.sub.3, TMS standard)
[0216] (5) Infra Red Absorption (cm.sup.-1)
[0217] (6) Property (mp: .degree. C.)
1TABLE I-1 (1) (2) (3) (4) (5) (6) I-1 A-1 27 1.9-2.3 (2H, m)
2.3-2.7 (2H, m) 2.6-3.0 (2H, m) 3.1-3.8 (4H, m) 7.32 (1H, d) 7.69
(1H, d) 1675 1575 1550 1400 1295 1125 156.0-159.7 I-2 A-2 28
1.9-2.2 (2H, m) 2.20 (3H, s) 2.3-2.6 (2H, m) 2.7-3.0 (2H, m)
3.2-3.7 (4H, m) 7.17 (1H, d) 7.60 (1H, d) 1670 1590 1300 1190 1120
203.8-204.3 I-3 A-3 29 1.9-2.3 (2H, m) 2.4-2.6 (2H, m) 2.60 (3H, s)
2.7-2.9 (2H, m) 3.2-3.7 (4H, m) 7.03 (1H, s) 1670 1560 1420 1300
1200 1135 213.0-214.7 I-4 A-4 30 1.9-2.2 (2H, m) 2.13 (3H, s)
2.3-2.6 (2H, m) 2.58 (3H, s) 2.7-3.0 (2H, m) 3.1-3.7 (4H, m) 6.90
(1H, s) 1675 1580 1425 1410 1295 1125 218.5-220.7 I-5 A-5 31
1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.7-2.9 (2H, m) 3.3-3.6 (4H, m)
3.83 (3H, s) 7.23 (1H, d) 7.50 (1H, d) 1660 1590 1400 1300 1175
1115 syrup I-6 A-6 32 1.9-2.2 (2H, m) 2.25 (3H, s) 2.3-2.6 (2H, m)
2.7-3.0 (2H, m) 3.54 (4H, s) 7.21 (1H, d) 7.74 (1H, d) 1675 1570
1405 1300 1175 1125 195.2-196.1 I-7 A-7 33 1.09 (3H, d) 1.5-3.0
(5H, m) 3.2-3.7 (4H, m) 7.26 (1H, d) 7.66 (1H, d) 1680 1580 1565
1315 1195 1140 syrup I-8 A-8 34 1.0-1.5 (6H, m) 1.7-3.0 (4H, m)
3.2-3.7 (4H, m) 7.29 (1H, d) 7.70 (1H, d) 1600 1390 1305 1185 1170
1120 161.1-161.6 I-9 A-9 35 1.14 (6H, s) 2.3-2.7 (4H, m) 3.2-3.7
(4H, m) 7.30 (1H, d) 7.69 (1H, d) 1670 1585 1555 1305 1195 1135
142.9-146.7 I-10 A-10 36 1.09 (6H, s) 2.32 (2H, s) 2.62 (3H, s)
2.68 (2H, s) 3.4-3.7 (4H, m) 7.05 (1H, s) 2970 1660 1580 1290 1220
1190 syrup I-11 A-11 37 1.34 (6H, s) 1.8-2.0 (2H, m) 2.3-2.9 (2H,
m) 2.63 (3H, s) 3.3-3.7 (4H, m) 7.03 (1H, s) 2970 1670 1580 1420
1380 1300 syrup I-12 A-12 38 1.13 (3H, d) 2.0-3.0 (5H, m) 3.3-3.7
(4H, m) 7.30 (1H, d) 7.70 2970 1670 1590 1400 1300 1180 syrup I-13
A-13 39 1.0-1.4 (9H., m) 1.6-2.0 (2H, m) 2.5-3.0 (1H, m) 3.3-3.7
(4H, m) 7.30 (1H, d) 7.70 (1H, d) 2980 1730 1670 1580 1410 1310
syrup I-14 A-14 40 1.07 (3H, d) 1.09 (3H, d) 1.8-2.6 (3H, m)
2.8-3.2 (1H, m) 3.3-3.7 (4H, m) 7.30 (1H, d) 7.70 (1H, d) syrup
I-15 A-15 41 1.19 (12H, d) 1.8-1.9 (2H, m) 3.3-3.6 (4H, m) 7.30
(1H, d) 7.70 (1H, d) syrup I-16 A-16 42 1.0-1.6 (6H, m) 2.0-2.8
(4H, m) 3.3-3.7 (4H, m) 7.30 (1H, d) 7.70 (1H, d) syrup I-17 A-17
43 1.56 (3H, d) 1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.7-3.1 (3H, m)
3.4-3.8 (2H, m) 7.28 (1H, d) 7.71 (1H, d) 1670 1575 1555 1450 1305
1140 152.5-154.6 I-18 A-18 44 1.45 (3H, d) 2.0-3.1 (8H, m) 3.5-3.7
(1H, m) 3.79 (3H, s) 7.30 (1H, d) 7.44 (1H, d) 1680 1580 1410 1300
1130 1010 syrup I-19 A-19 45 -- -- -- I-20 A-20 46 1.9-2.3 (2H, m)
2.3-2.6 (2H, m) 2.7-3.0 (2H, m) 3.2-3.7 (4H, m) 7.24 (1H, d) 7.74
(1H, d) 1670 1560 1395 1300 1195 1125 I-21 A-21 47 1.9-2.3 (2H, m)
2.3-3.0 (4H, m) 3.58 (4H, s) 7.51 (1H, d) 7.97 (1H, d) 1660 1600
1580 1555 1300 1125 208.8-242.3
Example I-22
[0218] (1) Preparation of Herbicide
[0219] Talc (57 parts by weight) and bentonite (40 parts by
weight), both serving as carriers, and sodium alkylbenzenesulfate
(3 parts by weight) serving as a surfactant were homogeneously
ground and mixed to thereby obtain a carrier for water-dispersible
powder.
[0220] Subsequently, to the water-dispersible powder (90 parts by
weight), the triketone derivative (compound No. A-1) produced in
Example I-1 (10 parts by weight) was added, and the resultant
mixture was homogeneously ground and mixed to thereby obtain a
herbicide.
[0221] (2) Biological Tests of Herbicide
[0222] (i) Biological Test 1 (Soaking in Water/Treatment on the 3rd
Day After Transplantation)
[0223] A Wagner pot (1/2000 are) was filled with paddy soil, and
seeds of barnyard grass were planted on the surface layer of the
soil, and further, rice seedlings grown to the 2.5-leaf stage were
transplanted.
[0224] Subsequently, water was poured in the pot to a height of 3
cm above the soil surface, and placed in a greenhouse where the
temperature was maintained at 20-25.degree. C., to thereby grow the
plant under suitable conditions.
[0225] On the 3rd day after transplantation, the herbicide prepared
in (1) above was applied to the plant in a predetermined amount. On
the 30th day after treatment with the herbicide, weed-killing
ratio, herbicidal effect, and extent of chemical injury to paddy
rice were examined.
[0226] (ii) Biological Test 2 (Soaking in Water/Treatment on the
10th Day After Transplantation)
[0227] A Wagner pot (1/2000 are) was filled with paddy soil, and
seeds of barnyard grass were planted on the surface layer of the
soil, and further, a rice seedling grown to the 2.5-leaf stage was
transplanted.
[0228] Next, water was poured to the pot to a height of 3 cm above
the soil surface, and placed in a greenhouse where the temperature
was maintained at 20-25.degree. C., to thereby grow the plant under
suitable conditions.
[0229] On the 10th day after transplantation, the herbicide
prepared in (1) above was applied to the plant in a predetermined
amount. On the 30th day after treatment with the herbicide,
weed-killing ratio, herbicidal effect, and extent of chemical
injury to paddy rice were examined.
[0230] In Biological tests 1 and 2, herbicidal effect and extent of
chemical injury were evaluated according to the below-described
standards.
[0231] 1) Weed-Killing Ratio
[0232] Weight of plants growing in the soil which had been treated
with the herbicide and weight of plants growing in the soil which
had not been treated with the herbicide were measured, and
weed-killing ratio (%) was calculated according to the following
formula:
Weed-killing ratio (%)=[1-(Weight of plants growing in the soil
which had been treated with the herbicide)/(weight of plants
growing in the soil which had not been treated with the
herbicide)].times.100
[0233] 2) Herbicidal Effect
[0234] Herbicidal effect was evaluated according to the following
criteria.
2 [Rating of [Herbicidal effect herbicidal effect] (weed-killing
ratio)] 0 less than 5% (almost no effect) 1 5% or more and less
than 20% 2 20% or more and less than 40% 3 40% or more and less
than 70% 4 70% or more and less than 90% 5 90% or more (almost
completely withered)
[0235] 3) Chemical Injury to Paddy Rice
[0236] Chemical injury to paddy rice was evaluated according to the
following criteria.
3 [Rating of chemical injury to paddy rice] [Chemical injury to
paddy rice] 0 No chemical injury to paddy rice was found. 1
Chemical injury to paddy rice was hardly found. 2 slight chemical
injury to paddy rice was found. 3 Chemical injury to paddy rice was
found. 4 Chemical injury to paddy rice was predominantly found. 5
Paddy rice was almost completely withered.
[0237] The biological test results are shown in Table I-2.
Examples I-23 to I-40
[0238] (1) Preparation of Herbicides
[0239] Various herbicides were prepared in the same manner as
described in Example I-22 (1), except that the respective triketone
derivatives obtained in Examples I-2 to I-21 were used instead of
the triketone derivative used in Example I-22 (1).
[0240] (2) Biological Tests of Herbicide
[0241] Biological tests of herbicide were carried out in the same
manner as described in Example I-22 (2), except that the respective
herbicides prepared in (1) were used instead of the herbicide
prepared in Example I-22 (1).
[0242] The biological test results are shown in Table I-2.
Comparative Example I-1
[0243] (1) Preparation of Herbicide
[0244] A herbicide was prepared in the same manner as described in
Example I-22 (1), except that a publicly known compound represented
by the following formula was used instead of the triketone
derivative. 48
[0245] (2) Biological Tests of Herbicide
[0246] Biological tests of herbicide were carried out in the same
manner as described in Example I-22 (2), except that a herbicide
prepared in (1) was used instead of the herbicide prepared in
Example I-22 (1).
[0247] The biological test results are shown in Table I-2.
Comparative Example I-2
[0248] (1) Preparation of Herbicide
[0249] A herbicide was prepared in the same manner as described in
Example I-22 (1), except that a publicly known compound represented
by the following formula was used instead of the triketone
derivative. 49
[0250] (2) Biological Tests of Herbicide
[0251] Biological tests of herbicide were carried out in the same
manner as described in Example I-22 (2), except that a herbicide
prepared in (1) was used instead of the herbicide prepared in
Example 1-22 (1).
[0252] The biological test results are shown in Table I-2.
Comparative Example I-3
[0253] (1) Preparation of Herbicide
[0254] A herbicide was prepared in the same manner as described in
Example I-22 (1), except that a publicly known compound represented
by the following formula was used instead of the triketone
derivative. 50
[0255] (2) Biological Tests of Herbicide
[0256] Biological tests of herbicide were carried out in the same
manner as described in Example I-22 (2), except that a herbicide
prepared in (1) was used instead of the herbicide prepared in
Example I-22 (1).
[0257] The biological test results are shown in Table I-2.
Comparative Example I-4
[0258] (1) Preparation of Herbicide
[0259] A herbicide was prepared in the same manner as described in
Example I-22(1), except that a publicly known compound represented
by the following formula was used instead of the triketone
derivative. 51
[0260] (2) Biological Tests of Herbicide
[0261] Biological tests of herbicide were carried out in the same
manner as described in Example I-22 (2), except that a herbicide
prepared in (1) was used instead of the herbicide prepared in
Example I-22 (1).
[0262] The biological test results are shown in Table I-2(1) and
(2).
[0263] In the Table I-2 (1) and (2), "(1)" to "(11)" indicates
respectively as follows.
[0264] (1) Example No.
[0265] (2) Compound No.
[0266] (3) Dose (g/ha)
[0267] (4) Treatment performed 3 days after transplantation
[0268] (5) Treatment performed 10 days after transplantation
[0269] (6) Weed-killing effect
[0270] (7) Chemical injury
[0271] (8) Echinochloa crug-galli
[0272] (9) Scirups juncoides
[0273] (10) Transplanted paddy rice plant
[0274] (11) Comparative Example
4 TABLE I-2 (1) (4) (5) (6) (7) (6) (1) (2) (3) (8) (9) (10) (8)
(9) I- A-1 100 5 5 0 5 5 22 200 5 5 0 5 5 I- A-2 100 4 5 0 3 5 23
200 5 5 0 4 5 I- A-3 100 5 5 1 5 5 24 200 5 5 3 5 5 I- A-4 100 4 5
0 4 5 25 200 5 5 1 4 5 I- A-5 100 3 4 0 3 4 26 200 5 5 0 4 4 I- A-6
100 5 5 1 4 4 27 200 5 5 3 5 5 I- A-7 100 5 5 1 4 5 28 200 5 5 2 5
5 I- A-8 100 5 5 1 5 5 29 200 5 5 3 5 5 I- A-9 100 5 5 1 5 5 30 200
5 5 3 5 5 I- A-10 100 5 5 1 5 5 31 200 5 5 3 5 5 I- A-11 100 5 5 1
5 5 32 200 5 5 3 5 5 I- A-12 100 5 5 1 5 5 33 200 5 5 2 5 5 I- A-13
100 5 5 1 5 5 34 200 5 5 3 5 5 I- A-14 100 5 5 1 5 5 35 200 5 5 2 5
5 I- A-15 100 5 5 1 5 5 36 200 5 5 3 5 5 I- A-16 100 5 5 1 5 5 37
200 5 5 3 5 5 I- A-17 100 3 4 0 3 4 38 200 4 5 1 4 4 I- A-18 100 3
4 0 2 4 39 200 4 4 1 3 4 I- A-19 100 5 5 0 5 5 40 200 5 5 1 5 5
I-41 A-20 100 5 5 0 5 5 200 5 5 0 5 5 I-42 A-21 100 5 5 0 5 5 200 5
5 0 5 5
[0275]
5 TABLE I-2 (2) (4) (5) (6) (7) (6) (11) (3) (8) (9) (10) (8) (9)
I-1 100 5 4 3 0 1 200 5 5 4 3 2 I-2 100 0 0 0 0 0 200 1 1 0 0 0 I-3
100 4 3 3 3 2 200 5 4 4 5 3 I-4 100 3 3 2 1 1 200 5 3 4 2 2
THE SECOND ASPECT OF THE INVENTION
Example II-1
[1] Synthesis of
4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-diox- ide
[0276] (1) Synthesis of Ethyl
4-carboxymethylsulfenyl-2-chlorobenzoate
[0277] A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g),
potassium carbonate (9.44 g), dimethylformamide (50 ml), and
mercaptoacetic acid (3.8 ml) was allowed to react with heat at
80.degree. C. for 4 hours.
[0278] Next, the resultant reaction mixture was poured into ice
water and was subjected to extraction with ethyl acetate. The
extract was dried over sodium sulfate and filtered, then
concentrated to thereby obtain a crude reaction product (12.3
g).
[0279] (2) Synthesis of
4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzoth- iophene
[0280] A mixture of ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate
(12.3 g) obtained in (1), 1,2-dichloroethane (36 ml), and thionyl
chloride (3.9 ml) was refluxed with heat over 1 hour.
[0281] Acid chloride obtained by concentration of the reaction
mixture was dissolved in dichloromethane (36 ml). The solution was
added dropwise under cooling on ice over 1 hour to a solution of
aluminum chloride (14.3 g, 107 mmol) and dichloromethane (150 ml)
prepared in advance, after which the reaction was continued for a
further 2 hours at room temperature.
[0282] The thus-obtained reaction mixture was poured into ice water
and subjected to extraction with dichloromethane. The extract was
dried over sodium sulfate, filtered, and concentrated to thereby
obtain a crude reaction product in the form of liver brown oil
(12.3 g). Further, the crude reaction product was purified by
column chromatography to thereby obtain the compound of interest as
brown oil (5.3 g, yield: 23%).
[0283] (3) Synthesis of
4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydroben- zothiophene
[0284] A solution comprising
4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobe- nzothiophene (5.3 g)
obtained in (2), dichloromethane (25 ml), and ethanol (25 ml) was
cooled in an ice-bath and sodium boron hydride (0.26 g) was added
thereto, after which the solution was allowed to stand
overnight.
[0285] Subsequently, the obtained reaction mixture was poured into
ice water and subjected to extraction with dichloromethane. The
extract was dried over sodium sulfate and filtered to thereby
obtain the compound of interest (5.3 g, yield: 98%).
[0286] (4) Synthesis of 4-chloro-5-ethoxycarbonylbenzothiophene
[0287] A mixture of
4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzoth- iophene
(5.3 g) obtained in (3), toluene (50 ml), and p-toluene sulfate
(0.2 g) was subjected to azeotropic dehydration over 1 hour.
[0288] The resultant reaction mixture was diluted with toluene,
washed with a saturated solution of sodium hydrogencarbonate, and
dried over sodium sulfate, followed by filtration and concentration
to thereby obtain the compound of interest as brown oil (4.6 g,
yield: 95%).
[0289] (5) Synthesis of
4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxid- e
[0290] A mixture containing 4-chloro-5-ethoxycarbonylbenzothiophene
(4.6 g) obtained in (4), acetic acid (30 ml), and a 30 wt. %
aqueous solution of hydrogen peroxide (5.4 ml) was allowed to react
at 80.degree. C. for 2 hours with stirring.
[0291] After the reaction product was allowed to cool to room
temperature, it was diluted with water and filtered to thereby
obtain a solid. The solid was dried and purified by column
chromatography to thereby obtain the compound of interest as
colorless crystals (3.7 g, yield: 95%).
[0292] (6) Synthesis of
4-chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophen-
e-1,1-dioxide
[0293] A mixture of
4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide (3.7 g)
obtained in (5), tetrahydrofuran (40 ml), and 5% palladium/carbon
was allowed to react in an atmosphere of hydrogen gas at ordinary
temperature and pressure for 8 hours.
[0294] Subsequently, the resultant mixture was filtered and
concentrated to thereby obtain the compound of interest as pale
yellow oil (3.44 g, yield: 91%).
[0295] (7) Synthesis of
4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1- ,1-dioxide
[0296]
4-Chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
(3.44 g) obtained in (6) was dissolved in ethanol (35 ml). To the
solution, a 20 wt. % aqueous solution of sodium hydroxide (5 ml)
was added and the mixture was allowed to stand overnight.
[0297] Subsequently, the reaction mixture was concentrated and
acidified by adding a 5 wt. % aqueous solution of hydrochloric
acid, followed by filtration and drying of the produced precipitate
to thereby yield the compound of interest as colorless crystals
(2.6 g, yield: 84%).
[0298] A .sup.1H-NMR analysis (acetone-d.sup.6; TMS standard) of
the thus-obtained colorless crystals showed peaks of 3.4-3.8 (m,
4H), 7.85 (1H, d), and 8.06 (1H, d). Also, under infrared spectrum
analysis, there were observed peaks at 3080 cm.sup.-1, 3010
cm.sup.-1, 1690 cm.sup.-1, 1410 cm.sup.-11400 cm.sup.-1, 1310
cm.sup.-1, 1290 cm.sup.-1, 1250 cm.sup.-1, 1190 cm.sup.-1, and 1130
cm.sup.-1. From these results, the compound was identified as
4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophe- ne-1,1-dioxide, and
its measured melting point was 232-233.degree. C.
[2] Synthesis of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide
[0299] As raw materials,
4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-- 1,1-dioxide (1.0
g) obtained in (7) and a suspension (4 ml) of thionyl chloride
(0.54 g) in 1,2-dichloroethane were reacted over 1 hour under
reflux with heat.
[0300] The solvent was removed from the obtained product through
distillation under reduced pressure, and the obtained acid chloride
and 1,3-cyclohexanedione (0.47 g) were dissolved in acetonitrile
(10 ml) serving as a solvent. Thereafter, at room temperature, a
solution of triethylamine (0.82 g) in acetonitrile (5 ml) was added
dropwise thereto.
[0301] After the mixture was stirred for 2 hours at room
temperature, acetone cyanhydrin (0.01 g) was added thereto,
followed by stirring for 20 hours at room temperature.
[0302] To the resultant mixture, ethyl acetate was added and
subjected to extraction with saturated sodium carbonate. To an
aqueous phase, 10% hydrochloric acid was added so as to adjust the
pH of the phase to 1 and extraction with ethyl acetate was carried
out. The thus-obtained organic phase was washed with water and
aqueous saturated brine, and then dried over anhydrous sodium
sulfate. The solvent was removed from the product through
distillation under reduced pressure to thereby obtain the compound
of interest, 4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-d-
ihydrobenzothiophene-1,1-dioxide (1.24 g, yield: 90%).
[3] Synthesis of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. B-1]
[0303]
4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiop-
hene-1,1-dioxide (1.00 g) obtained in [2] was dissolved in
1,2-dichloroethane (5 ml) and to the resultant solution, at room
temperature, oxalyl chloride (0.56 g) and dimethylformamide (0.01
g) were added, followed by reaction over 1 hour under reflux with
heat.
[0304] Subsequently, from the resultant mixture, solvent was
removed through distillation under reduced pressure, and the
obtained crude product was purified by column chromatography to
thereby yield
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothioph-
ene-1,1-dioxide (0.99 g, yield: 94%).
[0305] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-2
Synthesis of
4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide [Compound No. B-2]
[0306]
4-Chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzo-
thiophene-1,1-dioxide (0.50 g) and ethanethiol (0.15 g) were
dissolved in 1,2-dichloroethane (5 ml) and to the resultant
solution, at room temperature, triethylamine (0.15 g) was added,
followed by reaction for 5 hours with stirring.
[0307] After the resultant mixture was combined with water and
subjected to extraction with ethyl acetate, the organic phase was
washed with aqueous saturated brine, and dried over anhydrous
sodium sulfate. Further, the solvent was removed through
distillation under reduced pressure, and the obtained crude product
was purified by column chromatography to thereby yield
4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-
-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide (0.50 g, yield:
83%).
[0308] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-3
Synthesis of
4-chloro-5-(3-phenylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. B-3]
[0309] The target compound was prepared in the same manner as
described in Example II-2, except that benzenethiol was used
instead of ethanethiol.
[0310] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-4
Synthesis of
4-chloro-7-methyl-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2-
,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-4]
[0311] The target compound was prepared in the same manner as
described in Example II-1, except that
4-chloro-7-methyl-5-(1,3-dioxocyclohexan-2-yl)c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0312] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-5
Synthesis of
4-chloro-7-methyl-5-(3-phenylthio-1-oxocyclohexan-2-yl)carbon-
yl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-5]
[0313] The target compound was prepared in the same manner as
described in Example II-2, except that
4-chloro-7-methyl-5-(3-chloro-1-oxocyclohexan-2-
-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide and benzenethiol
were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide and ethanethiol, respectively.
[0314] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-6
Synthesis of
4-chloro-5-(3-bromo-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide [Compound No. B-6]
[0315] The target compound was prepared in the same manner as
described in Example II-1, except that oxalyl bromide was used
instead of oxalyl chloride.
[0316] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-7
Synthesis of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. B-7]
[0317] The target compound was prepared in the same manner as
described in Example II-2, except that methanethiol was used
instead of ethanethiol.
[0318] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-8
Synthesis of
4-chloro-5-[3-(3-propyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-8]
[0319] The target compound was prepared in the same manner as
described in Example II-2, except that 1-propanethiol was used
instead of ethanethiol.
[0320] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-9
Synthesis of
4-chloro-5-(3-isopropylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-
-dihydrobenzothiophene-1,1-dioxide [Compound No. B-9]
[0321] The target compound was prepared in the same manner as
described in Example II-2, except that 2-propanethiol was used
instead of ethanethiol.
[0322] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-10
Synthesis of
4-chloro-5-[3-(4-butyl)thio-1-oxocyclohexan-2-yl)carbonyl-2,3-
-dihydrobenzothiophene-1,1-dioxide [Compound No. B-10]
[0323] The target compound was prepared in the same manner as
described in Example II-2, except that 1-butanethiol was used
instead of ethanethiol.
[0324] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-11
Synthesis of
4-chloro-5-(3-benzylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide [Compound No. B-11]
[0325] The target compound was prepared in the same manner as
described in Example II-2, except that benzylthiol was used instead
of ethanethiol.
[0326] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-12
Synthesis of
4-chloro-5-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]car-
bonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-12]
[0327] As raw materials,
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbony-
l-2,3-dihydrobenzothiophene-1,1-dioxide (0.50 g) and
N,O-dimethylhydroxylamine hydrochloride (0.14 g) were dissolved in
1,2-dichloroethane (5 ml) and to the resultant solution,
triethylamine (0.15 g) was added, followed by stirring for 5 hours
to thereby react the solution.
[0328] After the resultant mixture was combined with water, and
then subjected to extraction with ethyl acetate, the extract was
washed with aqueous saturated brine and dried over anhydrous sodium
sulfate. Further, the solvent was evaporated under reduced
pressure, and the obtained crude product was purified by column
chromatography to thereby yield
4-chloro-5-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide (0.43 g, yield: 80%).
[0329] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-13
Synthesis of
4-chloro-5-(3-dimethylamino-1-oxocyclohexan-2-yl)carbonyl-2,3-
-dihydrobenzothiophene-1,1-dioxide [Compound No. B-13]
[0330] The target compound was prepared in the same manner as
described in Example II-12, except that dimethylamine hydrochloride
was used instead of N,O-dimethylhydroxylamine hydrochloride.
[0331] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-14
Synthesis of
4-chloro-5-[3-(4-methylphenyl)thio-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-14]
[0332] The target compound was prepared in the same manner as
described in Example II-2, except that 4-methylbenzenethiol was
used instead of ethanethiol.
[0333] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-15
Synthesis of
4-chloro-5-[3-(3-methylphenyl)thio-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-15]
[0334] The target compound was prepared in the same manner as
described in Example II-2, except that 3-methylbenzenethiol was
used instead of ethanethiol.
[0335] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-16
Synthesis of
4-chloro-5-[3-(2-methylphenyl)thio-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-16]
[0336] The target compound was prepared in the same manner as
described in Example II-2, except that 2-methylbenzenethiol was
used instead of ethanethiol.
[0337] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-17
Synthesis of
4-chloro-5-[3-(2-chlorophenyl)thio-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-17]
[0338] The target compound was prepared in the same manner as
described in Example II-2, except that 2-chlorobenzenethiol was
used instead of ethanethiol.
[0339] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-18
Synthesis of
4-chloro-5-[3-(2-isopropylphenyl)thio-1-oxocyclohexan-2-yl]ca-
rbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-18]
[0340] The target compound was prepared in the same manner as
described in Example II-2, except that 2-(2-propyl)benzenethiol was
used instead of ethanethiol.
[0341] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-19
Synthesis of
4-chloro-5-[3-(2-methoxycarbonylphenyl)thio-1-oxocyclohexan-2-
-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-19]
[0342] The target compound was prepared in the same manner as
described in Example II-2, except that
2-methoxycarbonylbenzenethiol was used instead of ethanethiol.
[0343] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-20
Synthesis of
4-chloro-5-[3-(4-methoxyphenyl)thio-1-oxocyclohexan-2-yl]carb-
onyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-20]
[0344] The target compound was prepared in the same manner as
described in Example II-2, except that 4-methoxybenzenethiol was
used instead of ethanethiol.
[0345] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-21
Synthesis of
4-chloro-5-[3-(4-bromophenyl)thio-1-oxocyclohexan-2-yl]carbon-
yl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-21]
[0346] The target compound was prepared in the same manner as
described in Example II-2, except that 4-bromobenzenethiol was used
instead of ethanethiol.
[0347] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-22
Synthesis of
4-chloro-5-[3-(3-propenyl)thio-1-oxocyclohexan-2-yl]carbonyl--
2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-22]
[0348] The target compound was prepared in the same manner as
described in Example II-2, except that 3-propenylthiol was used
instead of ethanethiol.
[0349] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-23
Synthesis of
4-chloro-5-[3-(2-methyl-2-propyl)thio-1-oxocyclohexan-2-yl]ca-
rbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-23]
[0350] The target compound was prepared in the same manner as
described in Example II-2, except that 2-(2-methylpropane)thiol was
used instead of ethanethiol.
[0351] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-24
Synthesis of
4-chloro-5-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzdthiophene-1,1-dioxide [Compound No. B-24]
[0352]
4-Chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrob-
enzothiophene-1,1-dioxide (0.80 g) was dissolved in dichloromethane
(8 ml) and to the resultant solution, m-chlorobenzoic acid (1.0 g)
was added at room temperature, followed by allowing to stand
overnight.
[0353] The resultant mixture was diluted with methylene chloride
and filtered. The filtrate was washed with a 5% aqueous solution of
sodium sulfite, a 5% aqueous solution of potassium carbonate, and
aqueous saturated brine, and dried over anhydrous sodium sulfate.
After the filtration of the drying agent, the filtered was
concentrated to thereby obtain
4-chloro-5-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide (0.76 g, yield: 87%).
[0354] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-25
Synthesis of
4-chloro-5-(3-chloro-5-methyl-1-oxocyclohexan-2-yl)carbonyl-2-
,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-25]
[0355] The target compound was prepared in the same manner as
described in Example II-1, except that
4-chloro-5-(5-methyl-1,3-dioxocyclohexan-2-yl)c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0356] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-26
Synthesis of
4-chloro-5-(3-phenylthio-5-methyl-1-oxocyclohexan-2-yl)carbon-
yl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-26]
[0357] The target compound was prepared in the same manner as
described in Example II-2, except that
4-chloro-5-(3-chloro-5-methyl-1-oxocyclohexan-2-
-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide and benzenethiol
were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-di-
hydrobenzothiophene-1,1-dioxide and ethanethiol, respectively.
[0358] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-27
Synthesis of
4-chloro-5-(3-ethylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-
-dihydrobenzothiophene-1,1-dioxide [Compound No. B-27]
[0359] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-yl)c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0360] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-28
Synthesis of
4-chloro-5-[3-(3-propyl)sulfonyl-1-oxocyclohexan-2-yl]carbony-
l-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-28]
[0361] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(3-propyl)thio-1-oxocyclohexan-2-
-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead
of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0362] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-29
Synthesis of
4-chloro-5-(3-isopropylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-
-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-29]
[0363] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-(3-isopropylthio-1-oxocyclohexan-2--
yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead
of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0364] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-30
Synthesis of
4-chloro-5-[3-(4-butyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-
-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-30]
[0365] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-butyl)thio-1-oxocyclohexan-2--
yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead
of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0366] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-31
Synthesis of
4-chloro-5-(3-phenylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-31]
[0367] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-(3-phenylthio-1-oxocyclohexan-2-yl)-
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0368] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-32
Synthesis of
4-chloro-5-[3-(2-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-32]
[0369] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-methylphenyl)thio-1-oxocycloh-
exan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0370] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-33
Synthesis of
4-chloro-5-[3-(3-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-33]
[0371] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(3-methylphenyl)thio-1-oxocycloh-
exan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0372] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-34
Synthesis of
4-chloro-5-[3-(4-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-34]
[0373] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-methylphenyl)thio-1-oxocycloh-
exan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0374] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-35
Synthesis of
4-chloro-5-[3-(2-chlorophenyl)sulfonyl-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-35]
[0375] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-chlorophenyl)thio-1-oxocycloh-
exan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0376] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-36
Synthesis of
4-chloro-5-[3-(2-isopropylphenyl)sulfonyl-1-oxocyclohexan-2-y-
l]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-36]
[0377] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-isopropylphenyl)thio-1-oxocyc-
lohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was
used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide.
[0378] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-37
Synthesis of
4-chloro-5-[3-(4-methoxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]-
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-37]
[0379] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-methoxyphenyl)thio-1-oxocyclo-
hexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0380] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-38
Synthesis of
4-chloro-5-[3-(3-propenyl)sulfonyl-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-38]
[0381] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(3-propenyl)thio-1-oxocyclohexan-
-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0382] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-39
Synthesis of
4-chloro-5-[3-(2-methyl-2-propyl)sulfonyl-1-oxocyclohexan-2-y-
l]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-39]
[0383] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-methyl-2-propyl)thio-1-oxocyc-
lohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was
used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide.
[0384] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-40
Synthesis of
4-chloro-5-(3-benzylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,-
3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-40]
[0385] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-(3-benzylthio-1-oxocyclohexan-2-yl)-
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0386] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-41
Synthesis of
4-chloro-5-[3-(4-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carb-
onyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-41]
[0387] The target compound was prepared in the same manner as
described in Example II-2, except that 4-hydroxybenzenethiol was
used instead of ethanethiol.
[0388] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-42
Synthesis of
4-chloro-5-[3-(4-bromophenyl)sulfonyl-1-oxocyclohexan-2-yl]ca-
rbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-42]
[0389] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-bromophenyl)thio-1-oxocyclohe-
xan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0390] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-43
Synthesis of
4-chloro-5-[3-(4-hydroxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]-
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-43]
[0391] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-hydroxyphenyl)thio-1-oxocyclo-
hexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0392] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-44
Synthesis of
4-chloro-5-[3-(2-methoxycarbonylphenyl)sulfonyl-1-oxocyclohex-
an-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound
No. B-44]
[0393] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-methoxycarbonylphenyl)thio-1--
oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide.
[0394] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-45
Synthesis of
4-chloro-5-[3-(4-acetylphenyl)thio-1-oxocyclohexan-2-yl]carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-45]
[0395] The target compound was prepared in the same manner as
described in Example II-2, except that 4-acetylbenzenethiol was
used instead of ethanethiol.
[0396] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-46
Synthesis of
4-chloro-5-[3-(4-acetylphenyl)sulfonyl-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-46]
[0397] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(4-acetylphenyl)thio-1-oxocycloh-
exan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0398] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table 11-1.
Example II-47
Synthesis of
4-methyl-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydr-
obenzothiophene-1,1-dioxide [Compound No. B-47]
[0399] The target compound was prepared in the same manner as
described in Example II-1, except that
.sup.4-methyl-5-(1,3-dioxocyclohexan-2-yl)carbo-
nyl-2,3-dihydrobenzothiophene-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0400] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-48
Synthesis of
4-chloro-5-[3-(2-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carb-
onyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-48]
[0401] The target compound was prepared in the same manner as
described in Example II-2, except that 2-hydroxybenzenethiol was
used instead of ethanethiol.
[0402] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-49
Synthesis of
4-chloro-5-[3-(2-hydroxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]-
carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-49]
[0403] The target compound was prepared in the same manner as
described in Example II-24, except that
4-chloro-5-[3-(2-hydroxyphenyl)thio-1-oxocyclo-
hexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenz-
othiophene-1,1-dioxide.
[0404] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-50
Synthesis of
4-methyl-5-(3-ethoxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydr-
obenzothiophene-1,1-dioxide [Compound No. B-50]
[0405]
4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiop-
hene-1,1-dioxide (1.7 g) was dissolved in methylene chloride (17
ml). Diethylaminosulfate trifluoride (1.03 ml) was added to the
resultant solution under cooling with ice, followed by reaction
with stirring for 1 hour at room temperature. To the resultant
reaction mixture, ethanol (2 ml) was added, and reaction was
allowed to proceed for one hour with stirring.
[0406] The resultant mixture was diluted with methylene chloride,
washed with aqueous saturated sodium bicarbonate solution, and
dried over anhydrous sodium sulfate. After the desiccant was
removed through filtration and the solvent was evaporated, the
crude product was recrystallized from methanol to thereby obtain
4-methyl-5-(3-ethoxy-1-oxo-
cyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide
(0.15 g, yield: 59%).
[0407] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-51
Synthesis of
4-methyl-5-(3-isopropyloxy-1-oxocyclohexan-2-yl)carbonyl-2,3--
dihydrobenzothiophene-1,1-dioxide [Compound No. B-51]
[0408] The target compound was prepared in the same manner as
described in Example II-50, except that isopropanol was used
instead of ethanol.
[0409] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-52
Synthesis of
4-methyl-5-(3-methoxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihyd-
robenzothiophene-1,1-dioxide [Compound No. B-52]
[0410] The target compound was prepared in the same manner as
described in Example II-50, except that methanol was used instead
of ethanol.
[0411] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-53
Synthesis of
4-chloro-5-[3-(2-methoxyethoxy)-1-oxocyclohexan-2-yl]carbonyl-
-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. B-53]
[0412] The target compound was prepared in the same manner as
described in Example II-50, except that 2-methoxyethanol was used
instead of ethanol.
[0413] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-54
Synthesis of
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)-
carbonylthiochroman-1,1-1,1-dioxide [Compound No. B-54]
[0414] The target compound was prepared in the same manner as
described in Example II-1, except that
4-methoxyimino-5,8-dimethyl-6-(1,3-dioxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0415] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-55
Synthesis of
4-methoxyimino-5,8-dimethyl-6-(3-dimethylamino-1-oxocyclohexa-
n-2-yl)carbonylthiochroman-1,1-1,1-dioxide [Compound No. B-55]
[0416] The target compound was prepared in the same manner as
described in Example II-12, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxoc-
yclohexan-2-yl)carbonylthiochroman-1,1-dioxide and dimethylamine
hydrochloride were used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide and
N,O-dimethylhydroxylamin- e hydrochloride, respectively.
[0417] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-56
Synthesis of
4-methoxyimino-5,8-dimethyl-6-(3-methylthio-1-oxocyclohexan-2-
-yl)carbonylthiochroman-1,1-1,1-dioxide [Compound No. B-56]
[0418] The target compound was prepared in the same manner as
described in Example II-2, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and methanethiol were
used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0419] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-57
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(N-methoxymethyl)amino-1-oxo-
cyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide [Compound No.
B-57]
[0420] The target compound was prepared in the same manner as
described in Example II-12, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxoc-
yclohexan-2-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothioph-
ene-1,1-dioxide.
[0421] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-58
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)amino-1-oxoc-
yclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide [Compound No.
B-58]
[0422] The target compound was prepared in the same manner as
described in Example II-12, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxoc-
yclohexan-2-yl)carbonylthiochroman-1,1-dioxide and
4-methylphenylamine were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2-
,3-dihydrobenzothiophene-1,1-dioxide and N,O-dimethylhydroxylamine,
respectively.
[0423] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and-measured melting point
of the compound are shown in Table II-1.
Example II-59
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)thio-1-oxocy-
clohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide [Compound No.
B-59]
[0424] The target compound was prepared in the same manner as
described in Example II-2, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and
4-methylbenzenethiol were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2-
,3-dihydrobenzothiophene-1,1-dioxide and ethanethiol,
respectively.
[0425] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-60
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)sulfonyl-1-o-
xocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide [Compound No.
B-60]
[0426] The target compound was prepared in the same manner as
described in Example II-24, except that
4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphen-
yl)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-dioxide was
used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide.
[0427] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-61
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)thio-1-oxocyclohex-
an-2-yl)carbonylthiochroman-1,1-1,1-dioxide [Compound No. B-61]
[0428] The target compound was prepared in the same manner as
described in Example II-2, except that
4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and 3-propanethiol
were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0429] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-62
Synthesis of
4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)sulfonyl-1-oxocycl-
ohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide [Compound No.
B-62]
[0430] The target compound was prepared in the same manner as
described in Example II-24, except that
4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)thi-
o-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-dioxide was used
instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0431] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-63
Synthesis of
3,3,5-trimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthio-
chroman-4-one-1,1-dioxide [Compound No. B-63]
[0432] The target compound was prepared in the same manner as
described in Example II-1 except that
3,3,5-trimethyl-6-(1,3-dioxocyclohexan-2-yl)carb-
onylthiochroman-4-one-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0433] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-64
Synthesis of
3,3,5-trimethyl-6-[3-(4-chloro)thio-1-oxocyclohexan-2-yl]carb-
onylthiochroman-4-one-1,1-dioxide [Compound No. B-64]
[0434] The target compound was prepared in the same manner as
described in Example II-2 except that
3,3,5-trimethyl-6-(3-chloro-1-oxocyclohexan-2-yl-
)carbonylthiochroman-4-one-1,1-dioxide and 4-chlorobenzenethiol
were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0435] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting
Example II-65
Synthesis of
4-methoxyimino-5,6-dimethyl-6-(3-(4-chlorophenyl)sulfonyl-1-o-
xocyclohexan-2-yl]carbonylthiochroman-4-one-1,1-dioxide [Compound
No. B-65]
[0436] The target compound was prepared in the same manner as
described in Example II-24 except that
4-methoxyimino-5,8-dimethyl-6-[3-(4-chloropheny-
l)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-4-one-1,1-dioxide
was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dih-
ydrobenzothiophene-1,1-dioxide.
[0437] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-66
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl-
)carbonylthiochroman-1,1-dioxide [Compound No. B-66]
[0438] The target compound was prepared in the same manner as
described in Example II-1 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(1,3-dioxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0439] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-67
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylthio-1-oxocyclohexan--
2-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-67]
[0440] The target compound was prepared in the same manner as
described in Example II-2 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and methanethiol were
used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0441] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-68
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-phenylthio-1-oxocyclohexan--
2-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-68]
[0442] The target compound was prepared in the same manner as
described in Example II-2 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and benzenethiol were
used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0443] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-69
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylsulfonyl-1-oxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-69]
[0444] The target compound was prepared in the same manner as
described in Example II-24 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylthio-1--
oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide was used instead
of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0445] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-70
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylthio-1-oxocyclohexan--
2-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-70]
[0446] The target compound was prepared in the same manner as
described in Example II-2 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide and benzylthiol were
used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0447] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-71
Synthesis of
4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylsulfonyl-1-oxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-71]
[0448] The target compound was prepared in the same manner as
described in Example II-24 except that
4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylthio-1--
oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide was used instead
of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0449] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-72
Synthesis of
4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohexan-2-yl)carb-
onylthiochroman-1,1-dioxide [Compound No. B-72]
[0450] The target compound was prepared in the same manner as
described in Example II-1 except that
4-methoxyimino-5-methyl-6-(1,3-dioxocyclohexan-2-
-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1-
,1-dioxide.
[0451] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-73
Synthesis of
4-methoxyimino-5-methyl-6-(3-methylthio-1-oxocyclohexan-2-yl)-
carbonylthiochroman-1,1-dioxide [Compound No. B-73]
[0452] The target compound was prepared in the same manner as
described in Example II-2 except that
4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide and methanethiol were used
instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0453] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-74
Synthesis of
4-methoxyimino-5-methyl-6-(3-phenylthio-1-oxocyclohexan-2-yl)-
carbonylthiochroman-1,1-dioxide [Compound No. B-74]
[0454] The target compound was prepared in the same manner as
described in Example II-2 except that
4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohe-
xan-2-yl)carbonylthiochroman-1,1-dioxide and benzenethiol were used
instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydro-
benzothiophene-1,1-dioxide and ethanethiol, respectively.
[0455] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-75
Synthesis of
4-methoxyimino-5-methyl-6-(3-phenylsulfonyl-1-oxocyclohexan-2-
-yl)carbonylthiochroman-1,1-dioxide [Compound No. B-75]
[0456] The target compound was prepared in the same manner as
described in Example II-24 except that
4-methoxyimino-5-methyl-6-(3-phenylthio-1-oxocy-
clohexan-2-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzoth-
iophene-1,1-dioxide.
[0457] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-76
Synthesis of
4-methoxyimino-5-methyl-6-[3-(N-methoxymethyl)amino-1-oxocycl-
ohexan-2-yl]carbonylthiochroman-1,1-dioxide [Compound No. B-76]
[0458] The target compound was prepared in the same manner as
described in Example II-12 except that
4-methoxyimino-5-methyl-6-(3-chloro-1-oxocycloh-
exan-2-yl)carbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothioph-
ene-1,1-dioxide.
[0459] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-77
Synthesis of
5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-
-1,1-dioxide [Compound No. B-77]
[0460] The target compound was prepared in the same manner as
described in Example II-1 except that
5-chloro-6-(1,3-dioxocyclohexan-2-yl)carbonylthi-
ochroman-1,1-dioxide was used instead of
4-chloro-5-(1,3-dioxocyclohexan-2-
-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.
[0461] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-78
Synthesis of
5-chloro-6-(3-phenylthio-1-oxocyclohexan-2-yl)carbonylthiochr-
oman-1,1-dioxide [Compound No. B-78]
[0462] The target compound was prepared in the same manner as
described in Example II-2 except that
5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbon-
ylthiochroman-1,1-dioxide and benzenethiol were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothioph-
ene-1,1-dioxide and ethanethiol.
[0463] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-79
Synthesis of
5-chloro-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochr-
oman-1,1-dioxide [Compound No. B-79]
[0464] The target compound was prepared in the same manner as
described in Example II-2 except that
5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbon-
ylthiochroman-1,1-dioxide and methanethiol were used instead of
4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothioph-
ene-1,1-dioxide and ethanethiol.
[0465] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-80
Synthesis of
5-chloro-6-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonylthi-
ochroman-1,1-dioxide [Compound No. B-80]
[0466] The target compound was prepared in the same manner as
described in Example II-24 except that
5-chloro-6-(3-methylthio-1-oxocyclohexan-2-yl)c-
arbonylthiochroman-1,1-dioxide was used instead of
4-chloro-5-(3-methylthi-
o-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.
[0467] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
Example II-81
Synthesis of
4-chloro-5-[3-(3-methylthio)propylthio-1-oxocyclohexan-2-yl]c-
arbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No.
B-81]
[0468] The target compound was prepared in the same manner as
described in Example II-2 except that 3-methylthiopropanethiol was
used instead of ethanethiol.
[0469] The obtained target compound was subjected to .sup.1H-NMR
(CDCl.sub.3; TMS standard) and infrared spectrometry. The results
of analysis, and the chemical structure and measured melting point
of the compound are shown in Table II-1.
[0470] In the Table II-1, "(1)" to "(6)" indicates respectively as
follows.
[0471] (1) Example No.
[0472] (2) Compound No.
[0473] (3) Chemical structure
[0474] (4) NMR/ppm (CDCl.sub.3, TMS standard)
[0475] (5) Infra Red Absorption (cm.sup.-1)
[0476] (6) Property (mp: .degree. C.)
6TABLE II-1 (1) (2) (3) (4) (5) (6) II-1 B-1 52 2.0-2.4 (2H, m)
2.4-2.7 (2H, m) 2.8-3.0 (2H, m) 3.3-3.7 (4H, m) 7.70 (1H, d) 7.82
(1H, d) 1685 1605 1390 1300 1175 1125 83.8-85.4 II-2 B-2 53 1.37
(3H, t) 2.0-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (4H, m) 3.2-3.7
(4H, m) 7.49 (1H, d) 7.67 (1H, d) 1645 1395 1345 1305 1190 1120
129.5-131.3 II-3 B-3 54 1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 3.2-3.7
(4H, m) 7.3-7.8 (7H, m) 1650 1490 1415 1400 1310 1185 203.8-205.0
II-4 B-4 55 2.0-2.4 (2H, m) 2.4-2.7 (2H, m) 2.62 (3H, s) 2.8-3.0
(2H, m) 3.2-3.7 (4H, m) 7.54 (1H, s) 1660 1610 1300 1280 1135 1120
169.9-170.4 II-5 B-5 56 1.9-2.1 (2H, m) 2.3-2.6 (4H, m) 2.63 (3H,
s) 3.2-3.7 (4H, m) 7.31 (1H, s) 7.4-7.7 (5H, m) 1660 1640 1345 1290
1195 1125 261.9-263.7 II-6 B-6 57 2.0-2.4 (2H, m) 2.4-2.7 (2H, m)
2.9-3.2 (2H, m) 3.3-3.8 (4H, m) 7.69 (1H, d) 7.85 (1H, d) 1670 1615
1415 1400 1315 1290 1190 1135 68.4-69.7 II-7 B-7 58 2.0-2.3 (2H, m)
2.3-2.6 (2H, m) 2.47 (3H, s) 2.8-3.0 (2H, m) 3.2-3.7 (4H, m) 7.46
(1H, d) 7.67 (1H, d) 1655 1615 1440 1400 1345 1295 1175 181.8-182.5
II-8 B-8 59 1.06 (3H, t) 1.5-1.9 (2H, m) 2.0-2.5 (2H, m) 2.5-2.6
(2H, m) 2.8-3.1 (4H, m) 3.2-3.7 (4H, m) 7.49 (1H, d) 7.67 (1H, d)
1645 1395 1345 1300 1240 1180 57-69 II-9 B-9 60 1.39 (6H, d)
2.0-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.8 (5H, m)
7.54 (1H, d) 7.68 (1H, d) 1645 1395 1345 1300 1240 1180 61-72 II-10
B-10 61 0.95 (3H, t) 1.2-1.9 (4H, m) 1.9-2.5 (2H, m) 2.5-2.6 (2H,
m) 2.8-3.1 (4H, m) 3.2-3.7 (4H, m) 7.49 (1H, d) 7.67 (1H, d) 1635
1450 1390 1300 1175 1120 Syrup II-11 B-11 62 1.9-2.3 (2H, m)
2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.7 (4H, m) 4.18 (2H, s) 7.34
(5H, s) 7.45 (1H, d) 7.65 (1H, d) 1625 1395 1335 1290 1165 1110
191.5-192.1 II-12 B-12 63 1.8-2.2 (2H, m) 2.2-2.4 (2H, m) 2.6-2.9
(2H, m) 3.31 (3H, s) 3.3-3.7 (4H, m) 3.68 (3H, s) 7.60 (1H, d) 7.61
(1H, d) 1585 1385 1300 1175 1120 74.3-82.5 II-13 B-13 64 1.8-2.1
(2H, m) 2.1-2.4 (2H, m) 2.7-2.9 (2H, m) 3.26 (6H, s) 3.2-3.7 (4H,
m) 7.33 (1H, d) 7.63 (1H, d) 1585 1390 1295 1170 1115 175.1-175.3
II-14 B-14 65 1.8-2.1 (2H, m) 2.3-2.6 (4H, m) 2.42 (3H, s) 3.2-3.7
(4H, m) 7.25 (2H, d) 7.44 (2H, d) 7.53 (1H, d) 7.70 (1H, d) 1660
1630 1470 1400 1340 1310 1280 1250 183.3-199.5 II-15 B-15 66
1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 2.41 (3H, s) 3.2-3.7 (4H, m) 7.34
(4H, s) 7.54 (1H, d) 7.71 (1H, d) 1640 1340 1295 1275 1245 1175
1120 190.2-196.6 II-16 B-16 67 1.8--2.1 (2H, m) 2.2-2.6 (4H, m)
2.44 (3H, m) 3.2-3.7 (4H, m) 7.1-7.5 (4H, m) 7.56 (1H, d) 7.72 (1H,
d) 1640 1405 1350 1340 1305 1280 1195 1125 198.8-199.5 II-17 B-17
68 1.8-2.2 (2H, m) 2.3`2.6 (4H, m) 3.2-3.7 (4H, m) 7.3-7.8 (6H, m)
1640 1495 1400 1295 1170 1110 190-192 II-18 B-18 69 1.24 (6H, d)
1.8-2.1 (2H, m) 2.2-2.6 (4H, m) 3.2-3.7 (5H, m) 7.1-7.6 (4H, m)
7.59 (1H, d) 7.73 (1H, d) 1645 1470 1410 1395 1305 1175 1120
63-decop. II-19 B-19 70 1.8-2.2 (2H, m) 2.3-2.7 (4H, m) 3.2-3.7
(4H, m) 3.90 (3H, s) 7.5-7.8 (5H, m) 7.8-8.0 (1H, m) 1725 1665 1415
1290 1255 1180 1120 186 II-20 B-20 71 1.8-2.1 (2H, m) 2.3-2.6 (4H,
m) 3.3-3.7 (4H, m) 3.86 (3H, s) 6.96 (2H, d) 7.46 (2H, d) 7.34 (1H,
d) 7.70 (1H, d) 1585 1480 1400 1340 1280 1240 1170 117-decomp.
II-21 B-21 72 1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 3.2-3.7 (4H, m)
7.3-7.8 (6H, m) 1490 1420 1355 1320 1260 1180 1135 196 II-22 B-22
73 1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.7 (6H, m)
5.2-5.5 (2H, m) 5.6-6.2 (1H, m) 7.50 (1H, d) 7.67 (1H, d) 1630 1405
1345 1295 1175 1120 II-23 B-23 74 1.44 (9H, s) 2.0-2.3 (2H, m)
2.4-2.6 (2H, m) 2.8-3.1 (2H, m) 3.3-3.7 (4H, m) 7.69 (2H, s) 2960
1660 1390 1310 1290 1175 1130 151-153 II-24 B-24 75 2.1-2.4 (2H, m)
2.5-2.7 (2H, m) 2.8-3.0 (2H, m) 2.09 (3H, s) 3.3-3.7 (4H, m) 7.72
(1H, d) 8.09 (1H, d) 1665 1580 1390 1295 1175 1120 102-103 II-25
B-25 76 1.15 (3H, d) 2.2-3.1 (5H, m) 3.3-3.8 (4H, m) 7.70 (1H, d)
7.79 (1H, d) 1690 1660 1420 1310 1290 1130 Syrup II-26 B-26 77 0.96
(3H, d) 2.0-2.7 (5H, m) 3.3-3.7 (4H, m) 7.5-7.6 (5H, m) 7.54 (1H,
d) 7.70 (1H, d) 1650 1530 1310 1280 1260 1240 1180 1120 Syrup II-27
B-27 78 1.34 (3H, t) 2.2-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-3.0 (2H,
m) 3.18 (2H, q) .3-3.7 (4H, m) 7.71 (1H, d) 8.09 (1H, d) 2970 1730
1680 1450 1310 1280 1180 1130 Syrup II-28 B-28 79 1.33 (3H, t)
2.1-2.4 (4H, m) 2.5-2.7 (2H, m) 2.8-3.0 (2H, m) 3.3-3.7 (6H, m)
7.72 (1H, d) 8.09 (1H, d) 2980 1720 1700 1400 1310 1290 1180 Syrup
II-29 B-29 80 1.18 (6H, m) 1.8-2.1 (2H, m) 2.4-2.8 (3H, m) 3.0-3.2
(2H, m) 3.4-3.7 (4H, m) 7.74 (1H, d) 8.09 (1H, d) 2970 1700 1680
1400 1320 1310 1180 Syrup II-30 B-30 81 1.03 (3Ht) 1.2-3.8 (16H, m)
7.74 (1H, d) 8.09 (1H, d) 2970 1730 1700 1400 1310 Syrup II-31 B-31
82 1.8-2.0 (2H, m) 2.1-2.8 (4H, m) 3.4-3.7 (4H, m) 7.5-8.2 (7H, m)
2990 1730 1700 1400 1310 1280 1150 Syrup II-32 B-32 83 2.1-2.4 (2H,
m) 2.4-2.8 (4H, m) 2.48 (3H, s) 3.3-3.7 (4H, m) 7.5-7.8 (5H, m)
8.1-8.2 (1H, m) 3000 1730 1700 1390 1310 1280 1150 Syrup II-33 B-33
84 2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.48 (3H, s) 3.3-3.7 (4H, m)
7.5-7.8 (5H, m) 8.1-8.2 (1H, m) 3000 1730 1700 1390 1310 1280 1150
Syrup II-34 B-34 85 2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.47 (3H, s)
3.3-3.7 (4H, m) 7.40 (2H, d) 7.7-7.9 (3H, m) 8.16 (1H, d) 1690 1600
1400 1310 1280 1180 1150 Syrup II-35 B-35 86 2.1-2.3 (2H, m)
2.5-2.8 (4H, m) 3.3-3.7 (4H, m) 7.4-7.8 (4H, m) 8.0-8.1 (2H, m)
2970 1730 1700 1570 1400 1310 1280 Syrup II-36 B-36 87 1.23 (6H, d)
2.0-2.3 (3H, m) 2.4-2.7 (4H, m) 3.3-3.7 (4H, m) 7.3-8.2 (6H, m)
2990 2900 1680 1390 1310 1280 1120 Syrup II-37 B-37 88 2.0-2.2 (2H,
m) 2.4-2.8 (4H, m) 3.4-3.7 (4H, m) 3.90 (3H, s) 7.0-7.1 (2H, m)
7.7-7.9 (3H, m) 8.16 (1H, d) 1730 1700 1390 1310 1280 1180 1150
Syrup II-38 B-38 89 2.1-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-2.9 (2H, m)
3.4-3.7 (4H, m) 3.94 (2H, d) 5.4-6.2 (3H, m) 7.72 (1H, d) 8.06 (1H,
d) 1690 1660 1590 1500 1320 1300 1150 Syrup II-39 B-39 90 1.42 (9H,
s) 2.1-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-2.9 (2H, m) 3.4-3.7 (4H, m)
7.72 (1H, d) 8.13 (1H, d) 2960 1690 1300 1280 1180 1130 1100 810
Syrup II-40 B-40 91 1.7-2.3 (4H, m) 2.3-2.6 (2H, m) 3.4-3.7 (4H, m)
4.48 (2H, s) 7.4-7.6 (5H, m) 7.72 (1H, d) 8.05 (1H, d) 2990 2900
1680 1390 1310 1280 1120 Syrup II-41 B-41 92 1.9-2.2 (2H, m)
2.3-2.6 (4H, m) 3.4-3.8 (4H, m) 6.95 (2H, d) 7.45 (2H, d) 7.65 (1H,
d) 7.71 (1H, d) II-42 B-42 93 2.0-2.3 (2H, m) 2.5-2.8 (4H, m)
3.3-3.7 (4H, m) 7.74 (1H, d) 7.78 (4H, s) 8.16 (1H, d) 1690 1570
1390 1310 1280 1180 1150 Syrup II-43 B-43 94 2.0-2.2 (2H, m)
2.4-2.8 (4H, m) 3.3-3.7 (4H, m) 6.96 (2H, d) 7.73 (2H, d) 7.74 (1H,
d) 8.15 (1H, d) 3300 1690 1600 1580 1310 1280 1150 syrup II-44 B-44
95 2.1-2.4 (2H, m) 2.5-2.8 (4H, m) 3.4-3.7 (4H, m) 3.92 (3H, s)
7.6-7.8 (4H, m) 8.0-8.2 (2H, m) 1720 1700 1670 1310 1280 1150 1140
1100 Syrup II-45 B-45 96 1.9-2.2 (2H, m) 2.3-2.5 (4H, m) 2.65 (3H,
s) 3.4-3.7 (4H, m) 7.57 (2H, d) 7.66 (1H, d) 7.72 (1H, d) 8.03 (2H,
d) 1690 1680 1650 1540 1400 1300 1290 1280 Syrup II-46 B-46 97
2.0-2.3 (2H, m) 2.5-2.8 (4H, m) 2.68 (3H, s) 3.4-3.7 (4H, m) 7.77
(1H, d) 8.0-8.3 (5H, m) 2980 2900 1690 1400 1310 1280 1150 Syrup
II-47 B-47 98 2.1-2.4 (2H, m) 2.4-2.7 (2H, m) 2.54 (3H, s) 2.8-3.0
(2H, m) 3.2-3.7 (4H, m) 7.58 (2H, s) 1695 1675 1295 1195 1120 890
174-176 II-48 B-48 99 1.8-2.1 (2H, m) 2.2-2.8 (4H, m) 3.2-3.6 (4H,
m) 6.23 (1H, s) 6.7-7.8 (6H, m) 3400 1650 1570 1460 1450 1450 1340
1310 syrup II-49 B-49 100 1.9-2.2 (2H, m) 2.3-2.5 (2H, m) 2.8-3.0
(2H, m) 3.3-3.7 (4H, m) 7.2-8.6 (6H, m) 2960 1680 1570 1410 1300
1260 1130 137-139 II-50 B-50 101 1.24 (3H, t) 2.0-2.3 (2H, m)
2.4-2.6 (2H, m) 2.6-2.8 (2H, m) 3.3-3.7 (4H, m) 4.08 (2H, q) 7.65
(2H, s) 1690 1580 1380 1360 1310 1130 1040 180-decomp. II-51 B-51
102 1.14 (6H, d) 2.0-2.3 (2H, m) 2.4-2.6 (2H, m) 2.7-2.8 (2H, m)
3.3-3.7 (4H, m) 4.62 (1H, m) 7.64 (2H, s) 1680 1640 1560 1400 1380
1300 1240 170-174 II-52 B-52 103 2.0-2.3 (2H, m) 2.4-2.5 (2H, m)
2.7-2.9 (2H, m) 3.3-3.7 (4H, m) 3.87 (3H, s) 7.66 (2H, s) 1680 1640
1580 1380 1300 1120 powder II-53 B-53 104 1.9-2.2 (2H, m) 2.3-2.6
(2H, m) 2.7-2.9 (2H, m) 3.29 (3H, s) 3.3-3.7 (6H, m) 4.1-4.2 (2H,
m) 7.66 (2H, s) 1680 1640 1570 1410 1280 1180 Powder II-54 B-54 105
2.0-2.3 (2H, m) 2.4-2.8 (2H, m) 2.8-3.0 (2H, m) 2.72 (3H, s) 2.78
(3H, s) 3.37 (4H, s) 4.07 (3H, s) 7.24 (1H, s) II-55 B-55 106
1.8-2.1 (2H, m) 2.2-2.4 (2H, m) 2.44 (3H, s) 2.63 (3H, s) 2.6-2.8
(2H, m) 3.19 (6H, s) 3.29 (4H, s) 3.99 (3H, s) 6.98 (1H, s) II-56
B-56 107 2.0-2.3 (2H, m) 2.3-2.5 (2H, m) 2.8-3.0 (2H, m) 2.40 (3H,
s) 2.46 (3H, s) 2.77 (3H, s) 3.37 (4H, s) 4.05 (3H, s) 7.02 (1H, s)
II-57 B-57 108 1.9-2.2 (2H, m) 2.3-2.6 (2H, m) 2.6-2.8 (2H, m) 2.62
(3H, s) 2.68 (3H, s) 3.32 (4H, s) 3.36 (3H, s) 3.63 (3H, s) 4.02
(3H, s) 7.24 (1H, s) II-58 B-58 109 1.8-2.1 (2H, m) 2.3-2.9 (4H, m)
2.40 (3H, s) 2.69 (3H, s) 3.37 (4H, s) 4.00 (3H, s) 6.90 (1H, s)
7.19 (2H, d) 7.32 (2H, d) II-59 B-59 110 1.8-2.1 (2H, m) 2.3-2.8
(4H, m) 2.45 (3H, s) 2.60 (1.5H, s) 2.70 (1.5H, s) 3.35 (4H, s)
4.09 (3H, s) 7.12 (1H, s) 7.28 (2H, d) 7.46 (2H, d) II-60 B-60 111
2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.49 (3H, s) 2.68 (1.5H, s) 2.72
(1.5H, s) 2.73 (3H, s) 3.3-3.4 (4H, m) 4.04 (3H, s) 7.20 (1H, s)
7.38 (2H, d) 7.77 (2H, d) II-61 B-61 112 1.05 (3H, t) 1.5-1.9 (2H,
m) 2.0-2.7 (6H, m) 2.51 (3H, s) 2.64 (3H, s) 2.8-3.0 (2H, m) 3.36
(4H, s) 4.03 (3H, s) 7.04 (1H, s) II-62 B-62 113 1.10 (3H, t)
1.7-2.0 (2H, m) 2.2-2.4 (2H, m) 2.6-2.8 (2H, m) 2.64 (3H, s) 2.66
(3H, s) 2.8-3.0 (2H, m) 3.0-3.4 (6H, m) 4.08 (3H, s) 7.32 (1H, s)
II-63 B-63 114 1.48 (6H, s) 2.0-2.4 (2H, m) 2.4-2.6 (2H, m) 2.61
(3H, s) 2.8-3.0 (2H, m) 3.46 (2H, s) 7.69 (1H, d) 7.85 (1H, d) 2980
1720 1680 1620 1320 1290 1190 1030 178-180 II-64 B-64 115 1.48 (6H,
s) 1.5-2.2 (4H, m) 2.3-2.6 (2H, m) 2.51 (3H, s) 3.46 (2H, s) 7.46
(4H, s) 7.51 (1H, d) 7.82 (1H, d) 3000 2980 1700 1640 1590 1560
1310 1290 209-211 II-65 B-65 116 1.48 (6H, s) 1.9-2.2 (2H, m)
2.3-2.6 (2H, m) 2.35 (3H, s) 2.7-2.9 (2H, m) 3.48 (2H, s) 7.4-7.9
(6H, m) 3000 2980 1730 1690 1560 1320 1200 II-66 B-66 117 1.2-1.4
(6H, m) 2.0-3.0 (8H, m) 2.57 (3H, s) 2.73 (3H, s) 3.0-3.4 (1H, m)
3.7-4.2 (2H, m) 4.8-5.0 (1H, m) 7.25 (1H, s) 2980 2940 1690 1660
1610 1300 1280 1110 198-199 II-67 B-67 118 1.2-1.4 (6H, m) 2.0-2.2
(2H, m) 2.4-3.0 (6H, m) 2.42 (3H, s) 2.46 (3H, s) 2.70 (3H, s)
3.0-3.3 (1H, m) 3.7-4.2 (2H, m) 4.8-4.9 (1H, m) 7.08 (1H, s) 2980
2940 1640 1350 1280 1190 1120 1050 960 910 Syrup II-68 B-68 119
1.2-1.4 (6H, m) 1.8-2.1 (2H, m) 2.3-2.8 (6H, m) 2.41 (3H, s) 2.74
(3H, s) 3.1-3.3 (1H, m) 3.7-4.1 (2H, m) 4.8-5.0 (1H, m) 7.17 (1H,
s) 7.4-7.6 (5H, m) 2980 2940 1730 1660 1440 1280 1260 1190 1120
1050 Syrup II-69 B-69 120 1.2-1.4 (6H, m) 1.9-2.2 (2H, m) 2.3-2.9
(6H, m) 2.55 (3H, s) 2.73 (3H, s) 3.01 (3H, s) 3.1-3.4 (1H, m)
3.7-4.2 (2H, m) 4.9-5.0 (1H, m) 7.49 (1H, s) 2980 2940 1720 1700
1440 1380 1320 1300 1140 1120 Syrup II-70 B-70 121 1.2-1.4 (6H, m)
2.0-2.2 (2H, m) 2.4-3.0 (6H, m) 2.47 (3H, s) 2.60 (3H, s) 3.0-3.3
(1H, m) 3.7-4.0 (2H, m) 4.12 (2H, s) 4.8-4.9 (1H, m) 7.01 (1H, s)
7.2-7.3 (5H, m) 2980 2940 1660 1450 1340 1300 1280 1190 1120 1050
910 syrup II-71 B-71 122 1.2-1.4 (6H, m) 1.8-2.0 (2H, m) 2.0-2.8
(6H, m) 2.65 (3H, s) 2.70 (3H, s) 3.1-3.4 (1H, m) 3.7-4.2 (2H, m)
4.48 (2H, s) 4.9-5.0 (1H, m) 7.32 (1H, s) 7.3-7.6 (5H, m) 2980 2930
1660 1450 1290 1270 1160 1120 1050 910 750 Syrup II-72 B-72 123
2.1-2.4 (2H, m) 2.4-2.6 (2H, m) 2.72 (3H, s) 2.8-3.0 (2H, m) 3.33
(4H, s) 4.07 (3H, s) 7.55 (1H, d) 7.87 (1H, d) 2940 1700 1670 1620
1420 1310 1280 1180 Syrup II-73 B-73 124 2.0-2.3 (2H, m) 2.4-2.6
(2H, m) 2.45 (3H, s) 2.58 (3H, s) 2.8-3.0 (2H, m) 3.32 (4H, m) 4.05
(3H, s) 7.30 (1H, d) 7.83 (1H, d) 2940 1660 1530 1350 1280 1220
1180 1150 1040 Syrup II-74 B-74 125 1.8-2.1 (2H, m) 2.3-2.5 (4H, m)
2.64 (3H, s) 3.33 (4H, s) 4.06 (3H, s) 7.39 (1H, d) 7.4-7.6 (5H, m)
7.85 (1H, d) 2940 1740 1660 1520 1410 1340 1310 1240 Syrup II-75
B-75 126 2.0-2.2 (2H, m) 2.4-2.9 (4H, m) 2.43 (1.5H, s) 2.87 (1.5H,
s) 3.33 (4H, s) 4.04 (1.5H, s) 4.08 (1.5H, s) 7.2-8.0 (7H, m) 2940
1680 1560 1450 1420 1310 1280 1150 1120 Syrup II-76 B-76 127
1.9-2.2 (2H, m) 2.2-2.5 (2H, m) 2.6-2.8 (2H, m) 2.70 (3H, s) 3.26
(3H, s) 3.31 (4H, s) 3.56 (3H, s) 4.05 (3H, s) 7.59 (1H, d) 7.78
(1H, d) 2980 1670 1590 1410 1310 1280 1190 1120 970 890 powder
II-77 B-77 128 2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.8-3.2 (4H, m)
3.3-3.5 (2H, m) 7.67 (1H, d) 7.94 (1H, d) 1690 1670 1610 1310 1290
1140 185-190 II-78 B-78 129 1.9-2.1 (2H, m) 2.3-2.7 (6H, m) 2.9-3.2
(2H, m) 3.2-3.5 (2H, m) 7.48 (1H, d) 7.5-7.6 (5H, m) 7.94 (1H, d)
1680 1660 1470 1340 1310 1290 1280 II-79 B-79 130 2.0-2.3 (2H, m)
2.4-2.7 (4H, m) 2.50 (3H, s) 2.9-3.2 (4H, m) 3.3-3.5 (2H, m) 7.35
(1H, d) 7.90 (1H, d) powder II-80 B-80 131 2.1-2.3 (2H, m) 2.4-2.7
(4H, m) 2.8-3.2 (4H, m) 3.09 (3H, s) 3.3-3.5 (2H, m) 7.98 (2H, s)
1680 1380 1310 1140 930 820 syrup II-81 B-81 132 1.9-2.3 (4H, m)
2.11 (3H, s) 2.4-2.8 (4H, m) 2.9-3.2 (4H, m) 3.2-3.7 (4H, m) 7.50
(1H, d) 7.69 (1H, d) 1655 1345 1305 1280 1180 1135
Example II-82.about.161
[0477] Biological tests of Herbicide were carried out in the same
manner as described in Example I-22, except that the respective
triketone derivatives prepared in Examples II-1 to II-81 were used
instead of the herbicide prepared in Example I-22.
[0478] The results of the biological tests are shown in Table
II-2.
[0479] In the Table II-2, "(1)" to "(11)" indicates respectively as
follows.
[0480] (1) Example No.
[0481] (2) Compound No.
[0482] (3) Dose (g/ha)
[0483] (4) Treatment performed 3 days after transplantation
[0484] (5) Treatment performed 10 days after transplantation
[0485] (6) Weed-killing effect
[0486] (7) Chemical injury
[0487] (8) Echinochloa crug-galli
[0488] (9) Scirups juncoides
[0489] (10) Transplanted paddy rice plant
7 TABLE II-2 (4) (5) (6) (7) (6) (1) (2) (3) (8) (9) (10) (8) (9)
II- B-1 100 5 5 0 4 5 82 200 5 5 0 5 5 II- B-2 100 4 5 0 3 4 83 200
5 5 0 4 5 II- B-3 100 3 4 0 3 4 84 200 4 5 0 4 5 II- B-4 100 5 5 1
4 5 85 200 5 5 2 5 5 II- B-5 100 4 4 0 3 4 86 200 4 4 0 4 4 II- B-6
100 5 5 0 4 5 87 200 5 5 0 5 5 II- B-7 100 4 5 0 4 4 88 200 5 5 0 4
5 II- B-8 100 4 5 0 4 5 89 200 5 5 0 4 5 II- B-9 100 4 5 0 4 4 90
200 5 5 0 4 5 II- B-10 100 3 4 0 3 4 91 200 5 5 0 4 5 II- B-11 100
3 4 0 3 4 92 200 4 5 0 3 5 II- B-12 100 5 5 0 5 5 93 200 5 5 1 5 5
II- B-13 100 3 4 0 3 4 94 200 4 4 0 3 4 II- B-14 100 3 4 0 3 4 95
200 4 5 0 4 5 II- B-15 100 3 4 0 3 4 96 200 4 5 0 4 5 II- B-16 100
3 4 0 3 4 97 200 4 5 0 4 5 II- B-17 100 3 4 0 3 4 98 200 4 5 0 4 5
II- B-18 100 3 4 0 3 4 99 200 4 4 0 4 4 II- B-19 100 3 4 0 3 4 100
200 4 4 0 4 4 II- B-20 100 3 4 0 3 4 101 200 4 5 0 4 5 II- B-21 100
3 4 0 3 4 102 200 4 5 0 4 5 II- B-22 100 4 5 0 4 5 103 200 5 5 0 5
5 II- B-23 100 4 5 0 4 5 104 200 5 5 0 5 5 II- B-24 100 5 5 0 4 5
105 200 5 5 0 5 5 II- B-25 100 5 5 0 4 5 106 200 5 5 1 5 5 II- B-26
100 4 4 0 4 4 107 200 5 5 0 4 5 II- B-27 100 5 5 0 4 5 108 200 5 5
0 5 5 II- B-28 100 4 4 0 4 4 109 200 5 5 0 4 5 II- B-29 100 4 4 0 4
4 110 200 5 5 0 4 5 II- B-30 100 4 4 0 3 4 111 200 4 5 0 4 5 II-
B-31 100 4 4 0 3 4 112 200 4 5 0 4 5 II- B-32 100 3 4 0 3 4 113 200
4 5 0 4 5 II- B-33 100 4 4 0 3 4 114 200 4 5 0 4 5 II- B-34 100 4 4
0 3 4 115 200 4 5 0 4 5 II- B-35 100 3 4 0 3 4 116 200 4 5 0 4 5
II- B-36 100 3 4 0 3 4 117 200 4 5 0 4 4 II- B-37 100 4 4 0 3 4 118
200 4 5 0 4 5 II- B-38 100 5 5 0 4 5 119 200 5 5 0 5 5 II- B-39 100
5 5 0 4 5 120 200 5 5 0 5 5 II- B-40 100 4 4 0 3 4 121 200 5 5 0 5
5 II- B-41 100 3 4 0 3 4 122 200 4 5 0 4 5 II- B-42 100 4 4 0 3 4
123 200 4 5 0 4 5 II- B-43 100 4 4 0 3 4 124 200 4 5 0 4 5 II- B-44
100 3 4 0 3 4 125 200 4 5 0 4 4 II- B-45 100 3 4 0 3 4 126 200 4 5
0 4 5 II- B-46 100 4 4 0 3 4 127 200 4 5 0 4 5 II- B-47 100 4 5 0 3
5 128 200 5 5 0 4 5 II- B-48 100 4 4 0 3 4 129 200 4 5 0 4 5 II-
B-49 100 4 4 0 3 4 130 200 4 5 0 4 5 II- B-50 100 5 5 0 4 5 131 200
5 5 0 5 5 II- B-51 100 5 5 0 4 5 132 200 5 5 0 5 5 II- B-52 100 5 5
0 4 5 133 200 5 5 0 5 5 II- B-53 100 5 5 0 4 5 134 200 5 5 0 5 5
II- B-54 100 5 3 1 4 2 135 200 5 5 4 5 5 II- B-55 100 0 0 0 0 0 136
200 1 2 0 1 2 II- B-56 100 5 3 0 4 2 137 200 5 4 0 5 3 II- B-57 100
5 3 0 4 2 138 200 5 4 3 5 3 II- B-58 100 0 0 0 0 0 139 200 1 1 0 1
1 II- B-59 100 5 5 0 4 3 140 200 5 5 0 5 5 II- B-60 100 3 2 0 3 2
141 200 4 4 0 4 4 II- B-61 100 1 1 0 1 1 142 200 5 4 0 5 3 II- B-62
100 2 1 0 2 1 143 200 5 5 0 5 4 II- B-63 100 2 5 3 2 4 144 200 5 5
5 5 5 II- B-64 100 5 3 2 3 3 145 200 5 5 5 5 5 II- B-65 100 5 5 3 3
4 146 200 5 5 4 5 5 II- B-66 100 5 5 0 5 3 147 200 5 5 4 5 5 II-
B-67 100 4 3 0 4 2 148 200 5 5 1 5 5 II- B-68 100 3 3 0 3 2 149 200
5 4 0 5 4 II- B-69 100 4 4 0 4 3 150 200 5 5 1 5 5 II- B-70 100 3 3
0 2 2 151 200 5 4 0 5 4 II- B-71 100 4 4 0 4 3 152 200 5 5 1 5 5
II- B-72 100 4 1 0 3 1 153 200 5 5 0 5 4 II- B-73 100 5 1 0 4 1 154
200 5 5 0 5 4 II- B-74 100 5 2 0 4 1 155 200 5 4 0 5 4 II- B-75 100
5 4 0 4 3 156 200 5 5 1 5 5 II- B-76 100 5 3 0 4 3 157 200 5 5 1 5
5 II- B-77 100 4 5 0 4 5 158 200 5 5 0 5 5 II- B-78 100 3 5 0 3 5
159 200 5 5 0 5 5 II- B-79 100 3 5 0 3 5 160 200 5 5 0 5 5 II- B-80
100 4 5 0 4 5 161 200 5 5 0 5 5 II- B-81 100 5 5 0 4 5 162 200 5 5
0 5 5
[0490] Industrial Applicability
[0491] As described hereinabove, the present invention provides a
herbicide containing a triketone derivative as an active
ingredient, which herbicide can control a wide range of weeds at a
low dose and imparts a low level of chemical injury to cultivated
crops, particularly a paddy rice plant.
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