U.S. patent application number 10/517957 was filed with the patent office on 2006-05-18 for spiroindolinepiperidine derivatives.
Invention is credited to Mark Richard Ashton, Jerome Cassayre, Fredrik Cederbaum, Eric Daniel Clarke, Thomas Stephen Coulter, David John Hughes, Peter Maienfisch, Louis-Pierre Molleyres, James Edward Peace, Richard Spurring Roberts, Charles Adam Russell, Paul Anthony Worthington.
Application Number | 20060106045 10/517957 |
Document ID | / |
Family ID | 9938602 |
Filed Date | 2006-05-18 |
United States Patent
Application |
20060106045 |
Kind Code |
A1 |
Hughes; David John ; et
al. |
May 18, 2006 |
Spiroindolinepiperidine derivatives
Abstract
Insecticidal, acaricidal, nematicidal or molluscicidal compounds
of formula (I) wherein Y is a single bond, C.dbd.O, C.dbd.S or
C.dbd.(O).sub.q where q is 0, 1 or 2; and R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.8, R.sup.9 and R.sup.10 are as defined in
the claims or salts or N-oxides thereof, processes for preparing
them and compositions containing them. ##STR1##
Inventors: |
Hughes; David John;
(Bracknell, Berkshire, GB) ; Worthington; Paul
Anthony; (Bracknell, Berkshire, GB) ; Russell;
Charles Adam; (Bracknell, Berkshire, GB) ; Clarke;
Eric Daniel; (Bracknell, Berkshire, GB) ; Peace;
James Edward; (Bracknell, Berkshire, GB) ; Ashton;
Mark Richard; (Abingdon, GB) ; Coulter; Thomas
Stephen; (Milton Park, GB) ; Roberts; Richard
Spurring; (Barcelona, ES) ; Molleyres;
Louis-Pierre; (Basel, CH) ; Cederbaum; Fredrik;
(Basel, CH) ; Cassayre; Jerome; (Basel, CH)
; Maienfisch; Peter; (Basel, CH) |
Correspondence
Address: |
SYNGENTA CROP PROTECTION , INC.;PATENT AND TRADEMARK DEPARTMENT
410 SWING ROAD
GREENSBORO
NC
27409
US
|
Family ID: |
9938602 |
Appl. No.: |
10/517957 |
Filed: |
June 4, 2003 |
PCT Filed: |
June 4, 2003 |
PCT NO: |
PCT/GB03/02424 |
371 Date: |
August 11, 2005 |
Current U.S.
Class: |
514/278 |
Current CPC
Class: |
C07B 2200/11 20130101;
A61P 5/00 20180101; C07D 471/10 20130101; A01N 43/90 20130101; C07D
211/76 20130101; A01N 47/38 20130101; A01N 47/34 20130101; C07D
491/10 20130101; C07D 211/70 20130101 |
Class at
Publication: |
514/278 |
International
Class: |
A01N 43/42 20060101
A01N043/42 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 14, 2002 |
GB |
02137`5.6 |
Claims
1. A method of combating and controlling insects, acarines,
nematodes or molluscs which comprises applying to a pest, to a
locus of a pest, or to a plant susceptible to attack by a pest an
insecticidally, acaricidally, nematicidally or molluscicidally
effective amount of a compound of formula (I): ##STR64## wherein Y
is a single bond, C.dbd.O, C.dbd.S or S(O).sub.q where q is 0, 1 or
2; R.sup.1 is hydrogen, optionally substituted alkyl, optionally
substituted alkoxycarbonyl, optionally substituted alkylcarbonyl,
aminocarbonyl, optionally substituted alkylaminocarbonyl,
optionally substituted dialkylaminocarbonyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
alkoxy, optionally substituted aryloxy, optionally substituted
heteroaryloxy, optionally substituted heterocyclyloxy, cyano,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, formyl, optionally substituted heterocyclyl,
optionally substituted alkylthio, NO or NR.sup.13R.sup.14 where
R.sup.13 and R.sup.14 are independently hydrogen, COR.sup.40,
optionally substituted alkyl, optionally substituted aryl,
optionally substituted heteroaryl, optionally substituted
heterocyclyl or R.sup.13 and R.sup.14 together with the N atom to
which they are attached form a group
--N.dbd.C(R.sup.41)--NR.sup.42R.sup.43; R.sup.2and R.sup.3 are
independently hydrogen, halogen, cyano, optionally substituted
alkyl, optionally substituted alkoxy, optionally substituted aryl
or C(O)NR.sup.15R.sup.16 where R.sup.15 and R.sup.16 are
independently hydrogen, optionally substituted alkyl, optionally
substituted aryl, optionally substituted heteroaryl or optionally
substituted heterocyclyl, or R.sup.2 and R.sup.3 together are
.dbd.O, or R.sup.2 and R.sup.3 together with the atoms to which
they are attached form a 4, 5, 6,or 7 membered carbocyclic or
heterocyclic ring; each R.sup.4 is independently halogen, nitro,
cyano, optionally substituted C.sub.1-8 alkyl, optionally
substituted C.sub.2-6alkenyl, optionally substituted
C.sub.2-6alkynyl, optionally substituted alkoxycarbonyl, optionally
substituted alkylcarbonyl, optionally substituted
alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl,
optionally substituted C.sub.3-7 cycloalkyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
heterocyclyl, optionally substituted alkoxy, optionally substituted
aryloxy, optionally substituted heteroaryloxy, optionally
substituted alkylthio or R.sup.19R.sup.20N where R.sup.19 and
R.sup.20 are, independently, hydrogen, C.sub.1-8 alkyl, C.sub.3-7
cycloalkyl, C.sub.3-6 alkenyl, C.sub.3-6 alkynyl, C.sub.3-7
cycloalkyl(C.sub.1-4)alkyl, C.sub.2-6 haloalkyl, C.sub.1-6
alkoxy(C.sub.1-6)alkyl, C.sub.1-6 alkoxycarbonyl or R.sup.19 and
R.sup.20 together with the N atom to which they are attached form a
five, six or seven-membered heterocyclic ring which may contain one
or two further heteroatoms selected from O, N or S and which may be
optionally substituted by one or two C.sub.1-6 alkyl groups, or 2
adjacent groups R.sup.4 together with the carbon atoms to which
they are attached form a 4, 5, 6,or 7 membered carbocyclic or
heterocyclic ring which may be optionally substituted by halogen; n
is 0, 1, 2, 3 or 4; R.sup.8 is optionally substituted alkyl,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted aryl,
optionally substituted alkoxy, optionally substituted aryloxy,
optionally substituted alkoxycarbonyl, optionally substituted
alkylcarbonyl or optionally substituted alkenylcarbonyl; R.sup.9
and R.sup.10 are independently hydrogen, halogen, optionally
substituted alkyl, optionally substituted aryl or R.sup.9 and
R.sup.10 together form a group --CH.sub.2--, --CH.dbd.CH-- or
--CH.sub.2CH.sub.2--; R.sup.40 is H, optionally substituted alkyl,
optionally substituted alkoxy, optionally substituted aryl,
optionally substituted aryloxy optionally substituted heteroaryl,
optionally substituted heteroaryloxy or NR.sup.44R.sup.45;
R.sup.41, R.sup.42 and R.sup.43 are each independently H or lower
alkyl; R.sup.44 and R.sup.45 are independently optionally
substituted alkyl, optionally substituted aryl or optionally
substituted heteroaryl or salts or N-oxides thereof.
2. A method according to claim 1 wherein Y is a bond or is
C.dbd.O.
3. A method according to claim 1 wherein R.sup.1 is hydrogen,
C.sub.1-6 alkyl, C.sub.1-6 cyanoalkyl, C.sub.1-6 haloalkyl,
C.sub.3-7 cycloalkyl(C.sub.1-4)alkyl, C.sub.1-6
alkoxy(C.sub.1-6)alkyl, heteroaryl(C.sub.1-6)alkyl (wherein the
heteroaryl group may be optionally substituted by halo, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy,
C.sub.1-6 haloalkoxy, C.sub.1-6 alkylsulfonyl, C.sub.1-6
alkylsulfinyl, C.sub.1-6 alkylthio, C.sub.1-6 alkoxycarbonyl,
C.sub.1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent
positions on the heteroaryl system may be cyclised to form a 5, 6
or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), aryl(C.sub.1-6)alkyl (wherein the aryl
group may be optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfinyl,
C.sub.1-6 alkylthio, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the
aryl system may be cyclised to form a 5, 6 or 7 membered
carbocyclic or heterocyclic ring, itself optionally substituted
with halogen), C.sub.1-6 alkylcarbonylamino(C.sub.1-6)alkyl, aryl
(which may be optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfinyl,
C.sub.1-6 alkylthio, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the
aryl system may be cyclised to form a 5, 6 or 7 membered
carbocyclic or heterocyclic ring, itself optionally substituted
with halogen), heteroaryl (which may be optionally substituted by
halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy, C.sub.1-6 haloalkoxy, C.sub.1-6 alkylsulfonyl, C.sub.1-6
alkylsulfinyl, C.sub.1-6 alkylthio, C.sub.1-6 alkoxycarbonyl,
C.sub.1-6 alkylcarbonylamino, arylcarbonyl, or two adjacent
positions on the heteroaryl system may be cyclised to form a 5, 6
or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
phenoxy (wherein the phenyl group is optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), heteroaryloxy (optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), heterocycyloxy (optionally
substituted by halo, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), cyano, C.sub.2-6
alkenyl, C.sub.2-6 alkynyl, C.sub.3-6 cycloalkyl, C.sub.5-7
cycloalkenyl, heterocyclyl (optionally substituted by halo, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), C.sub.1-6 alkylthio, C.sub.1-6 haloalkylthio
or NR.sup.13R.sup.14 where R.sup.13 and R.sup.14 are independently
hydrogen, C.sub.2-6 alkyl, C.sub.2-6 haloalkyl, phenyl (which may
be optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino, dialkylamino or C.sub.1-4 alkoxycarbonyl)
or heteroaryl (which may be optionally substituted by halo, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy, C.sub.1-4 alkoxycarbonyl C.sub.1-6
alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl
group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), amino,
C.sub.1-6 alkylamino or phenylamino (wherein the phenyl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino).
4. A method according to claim 1, wherin R.sup.2 and R.sup.3 are
are independently hydrogen or C.sub.1-4 alkyl.
5. A method according to claim 1, wherein each R.sup.4 is
independently halogen, cyano, C.sub.1-8 alkyl, C.sub.1-8 haloalkyl,
C.sub.1-6 cyanoalkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6 cycloalkenyl(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-4)alkyl
(wherein the heteroaryl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl
(wherein the heterocyclyl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6 alkenyl,
aminocarbonyl(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)-alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkynyl,
trimethylsilyl(C.sub.2-6)alkynyl, aminocarbonyl(C.sub.2-6)alkynyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.2-6)alkynyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkynyl, C.sub.1-6
alkoxycarbonyl, C.sub.3-7 cycloalkyl, C.sub.3-7 halocycloalkyl,
C.sub.3-7 cyanocycloalkyl, C.sub.1-3 alkyl(C.sub.3-7)-cycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)halocycloalkyl,phenyl (optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), heterocyclyl
(wherein the heterocyclyl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), or 2 adjacent groups R.sup.4
together with the carbon atoms to which they are attached form a 4,
5, 6,or 7 membered carbocylic or heterocyclic ring which may be
optionally substituted by halogen, C.sub.1-8 alkoxy, C.sub.1-6
haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), C.sub.1-8 alkylthio or R.sup.19R.sup.20N
where R.sup.19 and R.sup.20 are, independently, hydrogen, C.sub.1-8
alkyl, C.sub.3-7 cycloalkyl, C.sub.3-6 alkenyl, C.sub.3-6 alkynyl,
C.sub.2-6 haloalkyl, alkoxycarbonyl or R.sup.19 and R.sup.20
together with the N atom to which they are attached form a five,
six or seven-membered heterocyclic ring which may contain one or
two further heteroatoms selected from O, N or S and which may be
optionally substituted by one or two C.sub.1-6 alkyl groups; n is
0, 1, 2, 3 or 4.
6. A method according to claim 1, wherin R.sup.8 is C.sub.1-10
alkyl, C.sub.1-10 haloalkyl, aryl(C.sub.1-6)alkyl (wherein the aryl
group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), arylcarbonyl-(C.sub.1-6)alkyl
(wherein the aryl group may be optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino
and the alkyl group may be optionally substituted by aryl),
C.sub.2-8 alkenyl, C.sub.2-8 haloalkenyl, aryl(C.sub.2-6)alkenyl
(wherein the aryl group is optionally substituted halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino,
C.sub.1-6 alkoxycarbonyl, or two adjacent substituents can cyclise
to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring),
C.sub.2-6 alkynyl, phenyl(C.sub.2-6)alkynyl (wherein the phenyl
group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), C.sub.3-7
cycloalkyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl,
C.sub.1-6 haloalkylcarbonyl or aryl(C.sub.2-6)alkenylcarbonyl
(wherein the aryl group may be optionally substituted halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
or --C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each
independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl
and R.sup.55 is optionally substituted aryl or optionally
substituted heteroaryl.
7. A method according to claim 1, wherein R.sup.9 and R.sup.10 are
both hydrogen.
8. A compound of formula IK ##STR65## wherein Y is a single bond,
C.dbd.O or S(O).sub.q where is 0, 1 or 2; R.sup.1 is C.sub.1-8
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy-(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)-alkyl, C.sub.1-6
alkylsulfinyl(C.sub.1-6)alkyl, C.sub.1-6
alkylsulfonyl(C.sub.1-6)alkyl, aminocarbonyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl(C.sub.1-4)alkyl (wherein the heteroaryl group may be
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heterocyclyl(C.sub.1-4)alkyl (wherein the heterocyclyl group may be
substituted by halogen, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), phenyl
(optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.2-6
alkenyl, C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl, C.sub.2-6
alkynyl, C.sub.3-7 cycloalkyl, formyl, heterocyclyl (optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy) or C.sub.1-6
alkylthio; R.sup.2 and R.sup.3 are independently hydrogen or
C.sub.1-4 alkyl; each R.sup.4 is independently halogen, cyano,
C.sub.1-10 alkyl optionally substituted by C.sub.1-6 alkoxy,
halogen, phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy), C.sub.2-6alkenyl optionally
substituted by C.sub.1-6alkoxy, halogen, phenyl (itself optionally
substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy) or
C.sub.2-6 alkynyl optionally substituted by C.sub.1-6 alkoxy,
halogen, phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy); n is 0, 1, 2, 3 or 4; R.sup.8
is C.sub.1-10 alkyl optionally substituted by C.sub.1-6 alkoxy,
halogen or phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy), C.sub.2-6 alkenyl optionally
substituted by C.sub.1-6alkoxy, halogen or phenyl (itself
optionally substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4
alkoxy) or C.sub.2-6 alkynyl optionally substituted by C.sub.1-6
alkoxy, halogen or phenyl (itself optionally substituted by
halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy); R.sup.9 and R.sup.10
are both hydrogen; and salts or N-oxides thereof provided that
R.sup.8 is not methyl and YR.sup.1 is not SO.sub.2CH.sub.3, methyl,
ethyl, phenyl or fluoro-substituted phenyl.
9. A compound of formula (11) ##STR66## where R.sup.8 is
phenyl(C.sub.2-4)alkenyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino, provided the substituent is not
para-fluoro); or a compound of formula (10) ##STR67## where R.sup.8
is phenyl(C.sub.2-4)alkenyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino, provided the substituent is not
a para-fluoro); or a compound of formula (9) ##STR68## where
R.sup.2 is as defined for formula (I) in claim 1 and R.sup.8 is
phenyl(C.sub.2-4)alkenyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino); or a compound of formula (9A)
##STR69## where R.sup.2 and where (R.sup.4)n are as defined for
formula (I) in claim 1 and R.sup.8 is phenyl(C.sub.2-4)alkenyl
(wherein the phenyl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino).
10. An insecticidal acaricidal and nematicidal composition
comprising an insecticidally, acaricidally or nematicidally
effective amount of a compound of formula I as defined in claim 1.
Description
[0001] The present invention relates to spiroindoline derivatives,
to processes for preparing them, to insecticidal, acaricidal,
molluscicidal and nematicidal compositions comprising them and to
methods of using them to combat and control insect, acarine,
mollusc and nematode pests.
[0002] Spiroindoline derivatives with pharmaceutical properties are
disclosed in for example WO9825605, WO9429309, WO9828297 and
WO9964002. Synthetic routes to selected compounds with
pharmaceutical properties are described in Proc. Natl. Acad. Sci.
USA (1995), 92, 7001, Tetrahedron (1997), 53, 10983 and Tetrahedron
Letters (1997), 38, 1497. It has now surprisingly been found that
certain spiroindolines have insecticidal properties.
[0003] The present invention therefore provides a method of
combating and controlling insects, acarines, nematodes or molluscs
which comprises applying to a pest, to a locus of a pest, or to a
plant susceptible to attack by a pest an insecticidally,
acaricidally, nematicidally or molluscicidally effective amount of
a compound of formula (I): ##STR2## wherein Y is a single bond,
C.dbd.O, C.dbd.S or S(O).sub.q where q is 0, 1 or 2; R.sup.1 is
hydrogen, optionally substituted alkyl, optionally substituted
alkoxycarbonyl, optionally substituted alkylcarbonyl,
aminocarbonyl, optionally substituted alkylaminocarbonyl,
optionally substituted dialkylaminocarbonyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
alkoxy, optionally substituted aryloxy, optionally substituted
heteroaryloxy, optionally substituted heterocyclyloxy, cyano,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, formyl, optionally substituted heterocyclyl,
optionally substituted alkylthio, NO or NR.sup.13R.sup.14 where
R.sup.13 and R.sup.14 are independently hydrogen, COR.sup.40,
optionally substituted alkyl, optionally substituted aryl,
optionally substituted heteroaryl, optionally substituted
heterocyclyl or R.sup.13 and R.sup.14 together with the N atom to
which they are attached form a group
--N.dbd.C(R.sup.41)--NR.sup.42R.sup.43; R.sup.2 and R.sup.3 are
independently hydrogen, halogen, cyano, optionally substituted
alkyl, optionally substituted alkoxy, optionally substituted aryl
or C(O)NR.sup.15R.sup.16 where R.sup.15 and R.sup.16 are
independently hydrogen, optionally substituted alkyl, optionally
substituted aryl, optionally substituted heteroaryl or optionally
substituted heterocyclyl, or R.sup.2 and R.sup.3 together are
.dbd.O, or R.sup.2 and R.sup.3 together with the atoms to which
they are attached form a 4, 5, 6, or 7 membered carbocyclic or
heterocyclic ring; each R.sup.4 is independently halogen, nitro,
cyano, optionally substituted C.sub.1-8 alkyl, optionally
substituted C.sub.2-6 alkenyl, optionally substituted C.sub.2-6
alkynyl, optionally substituted alkoxycarbonyl, optionally
substituted alkylcarbonyl, optionally substituted
alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl,
optionally substituted C.sub.3-7 cycloalkyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
heterocyclyl, optionally substituted alkoxy, optionally substituted
aryloxy, optionally substituted heteroaryloxy, optionally
substituted alkylthio or R.sup.19R.sup.20N where R.sup.19 and
R.sup.20 are, independently, hydrogen, C.sub.1-8 alkyl, C.sub.3-7
cycloalkyl, C.sub.3-6 alkenyl, C.sub.3-6 alkynyl, C.sub.3-7
cycloalkyl(C.sub.1-4)alkyl, C.sub.2-6 haloalkyl, C.sub.1-6
alkoxy(C.sub.1-6)alkyl, C.sub.1-6 alkoxycarbonyl or R.sup.19 and
R.sup.20 together with the N atom to which they are attached form a
five, six or seven-membered heterocyclic ring which may contain one
or two further heteroatoms selected from O, N or S and which may be
optionally substituted by one or two C.sub.1-6 alkyl groups, or 2
adjacent groups R.sup.4 together with the carbon atoms to which
they are attached form a 4, 5, 6,or 7 membered carbocyclic or
heterocyclic ring which may be optionally substituted by halogen; n
is 0, 1, 2, 3 or 4; R.sup.8 is optionally substituted alkyl,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted aryl,
optionally substituted alkoxy, optionally substituted aryloxy,
optionally substituted alkoxycarbonyl, optionally substituted
alkylcarbonyl or optionally substituted alkenylcarbonyl; R.sup.9
and R.sup.10 are independently hydrogen, halogen, optionally
substituted alkyl, optionally substituted aryl or R.sup.9 and
R.sup.10 together form a group --CH.sub.2--, CH.dbd.CH-- or
--CH.sub.2CH.sub.2--; R.sup.40 is H, optionally substituted alkyl,
optionally substituted alkoxy, optionally substituted aryl,
optionally substituted aryloxy optionally substituted heteroaryl,
optionally substituted heteroaryloxy or NR.sup.44R.sup.45; R.sup.41
, R.sup.42 and R.sup.43 are each independently H or lower alkyl;
R.sup.44 and R.sup.45 are independently optionally substituted
alkyl, optionally substituted aryl or optionally substituted
heteroaryl or salts or N-oxides thereof
[0004] The compounds of formula (I) may exist in different
geometric or optical isomers or tautomeric forms. This invention
covers all such isomers and tautomers and mixtures thereof in all
proportions as well as isotopic forms such as deuterated
compounds.
[0005] Each alkyl moiety either alone or as part of a larger group
(such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,
dialkylaminocarbonyl) is a straight or branched chain and is, for
example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or
neo-pentyl.
[0006] When present, the optional substituents on an alkyl moiety
(alone or as part of a larger group such as alkoxy, alkoxycarbonyl,
alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) include
one or more of halogen, nitro, cyano, NCS--, C.sub.3-7 cycloalkyl
(itself optionally substituted with C.sub.1-6 alkyl or halogen),
C.sub.5-7 cycloalkenyl (itself optionally substituted with
C.sub.1-6 alkyl or halogen), hydroxy, C.sub.1-10 alkoxy, C.sub.1-10
alkoxy(C.sub.1-10)alkoxy,
tri(C.sub.1-4)alkylsilyl(C.sub.1-6)alkoxy, C.sub.1-6
alkoxycarbonyl(C.sub.1-10)alkoxy, C.sub.1-10 haloalkoxy,
aryl(C.sub.1-4)-alkoxy (where the aryl group is optionally
substituted), C.sub.3-7 cycloalkyloxy (where the cycloalkyl group
is optionally substituted with C.sub.1-6 alkyl or halogen),
C.sub.2-10 alkenyloxy, C.sub.2-10 alkynyloxy, SH, C.sub.1-10
alkylthio, C.sub.1-10 haloalkylthio, aryl(C.sub.1-4)alkylthio
(where the aryl group is optionally substituted), C.sub.3-7
cycloalkylthio (where the cycloalkyl group is optionally
substituted with C.sub.1-6 alkyl or halogen),
tri(C.sub.1-4)alkylsilyl(C.sub.1-6)alkylthio, arylthio (where the
aryl group is optionally substituted), C.sub.1-6 alkylsulfonyl,
C.sub.1-6 haloalkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6
haloalkylsulfinyl, arylsulfonyl (where the aryl group may be
optionally substituted), tri(C.sub.1-4)alkylsilyl,
aryldi(C.sub.1-4)alkylsilyl, (C.sub.1-4)alkyldiarylsilyl,
triarylsilyl, C.sub.1-10 alkylcarbonyl, HO.sub.2C, C.sub.1-10
alkoxycarbonyl, aminocarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6 alkyl)aminocarbonyl, N--(C.sub.1-3
alkyl)-N--(C.sub.1-3 alkoxy)aminocarbonyl, C.sub.1-6
alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is
optionally substituted), di(C.sub.1-6)alkylaminocarbonyloxy, oximes
such as .dbd.NOalkyl, .dbd.NOhaloalkyl and .dbd.NOaryl (itself
optionally substituted), aryl (itself optionally substituted),
heteroaryl (itself optionally substituted), heterocyclyl (itself
optionally substituted with C.sub.1-6 alkyl or halogen), aryloxy
(where the aryl group is optionally substituted), heteroaryloxy,
(where the heteroaryl group is optionally substituted),
heterocyclyloxy (where the heterocyclyl group is optionally
substituted with C.sub.1-6 alkyl or halogen), amino, C.sub.1-6
alkylamino, di(C.sub.1-6)alkylamino, C.sub.1-6 alkylcarbonylamino,
N--(C.sub.1-6)alkylcarbonyl-N--(C.sub.1-6)alkylamino, C.sub.2-6
alkenylcarbonyl, C.sub.2-6 alkynylcarbonyl, C.sub.3-6
alkenyloxycarbonyl, C.sub.3-6 alkynyloxycarbonyl, aryloxycarbonyl
(where the aryl group is optionally substituted) and arylcarbonyl
(where the aryl group is optionally substituted).
[0007] Alkenyl and alkynyl moieties can be in the form of straight
or branched chains, and the alkenyl moieties, where appropriate,
can be of either the (E) or (Z)-configuration. Examples are vinyl,
allyl and propargyl.
[0008] When present, the optional substituents on alkenyl or
alkynyl include those optional substituents given above for an
alkyl moiety.
[0009] In the context of this specification acyl is optionally
substituted C.sub.1-6 alkylcarbonyl (for example acetyl),
optionally substituted C.sub.2-6 alkenylcarbonyl, optionally
substituted C.sub.2-6 alkynylcarbonyl, optionally substituted
arylcarbonyl (for example benzoyl) or optionally substituted
heteroarylcarbonyl.
[0010] Halogen is fluorine, chlorine, bromine or iodine.
[0011] Haloalkyl groups are alkyl groups which are substituted with
one or more of the same or different halogen atoms and are, for
example, CF.sub.3, CF.sub.2Cl, CF.sub.3CH.sub.2 or
CHF.sub.2CH.sub.2.
[0012] In the context of the present specification the terms "aryl"
and "aromatic ring system" refer to ring systems which may be
mono-, bi- or tricyclic. Examples of such rings include phenyl,
naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred
aryl group is phenyl. In addition, the terms "heteroaryl",
"heteroaromatic ring" or "heteroaromatic ring system" refer to an
aromatic ring system containing at least one heteroatom and
consisting either of a single ring or of two or more fused rings.
Preferably, single rings will contain up to three and bicyclic
systems up to four heteroatoms which will preferably be chosen from
nitrogen, oxygen and sulphur. Examples of such groups include
furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl,
1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,
1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl,
1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl,
1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl,
pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,
1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl,
benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl,
benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl,
quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl,
quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl
and indolizinyl. Preferred examples of heteroaromatic radicals
include pyridyl, pyrimidyl, triazinyl, thienyl, furyl, oxazolyl,
isoxazolyl, and thiazolyl.
[0013] The terms heterocycle and heterocyclyl refer to a
non-aromatic ring containing up to 10 atoms including one or more
(preferably one or two) heteroatoms selected from O, S and N.
Examples of such rings include 1,3-dioxolane, tetrahydrofuran and
morpholine.
[0014] When present, the optional substituents on heterocyclyl
include C.sub.1-6 alkyl and C.sub.1-6 haloalkyl as well as those
optional substituents given above for an alkyl moiety.
[0015] Cycloalkyl includes cyclopropyl, cyclopentyl and
cyclohexyl.
[0016] Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
[0017] When present, the optional substituents on cycloalkyl or
cycloalkenyl include C.sub.1-3 alkyl as well as those optional
substituents given above for an alkyl moiety.
[0018] Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl
groups.
[0019] When present, the optional substituents on aryl or
heteroaryl are selected independently, from halogen, nitro, cyano,
NCS--, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy-(C.sub.1-6)alkyl, C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl,
C.sub.2-6 alkynyl, C.sub.3-7 cycloalkyl (itself optionally
substituted with C.sub.1-6 alkyl or halogen), C.sub.5-7
cycloalkenyl (itself optionally substituted with C.sub.1-6 alkyl or
halogen), hydroxy, C.sub.1-10 alkoxy, C.sub.1-10
alkoxy(C.sub.1-10)alkoxy,
tri(C.sub.1-4)alkyl-silyl(C.sub.1-6)alkoxy, C.sub.1-6
alkoxycarbonyl(C.sub.1-10)alkoxy, C.sub.1-10 haloalkoxy,
aryl(C.sub.1-4)alkoxy (where the aryl group is optionally
substituted with halogen or C.sub.1-6 alkyl), C.sub.3-7
cycloalkyloxy (where the cycloalkyl group is optionally substituted
with C.sub.1-6 alkyl or halogen), C.sub.2-10 alkenyloxy, C.sub.2-10
alkynyloxy, SH, C.sub.1-10 alkylthio, C.sub.1-10 haloalkylthio,
aryl(C.sub.1-4)alkylthio C.sub.3-7 cycloalkylthio (where the
cycloalkyl group is optionally substituted with C.sub.1-6 alkyl or
halogen), tri(C.sub.1-4)-alkylsilyl(C.sub.1-6)alkylthio, arylthio,
C.sub.1-6 alkylsulfonyl, C.sub.1-6 haloalkylsulfonyl, C.sub.1-6
alkylsulfinyl, C.sub.1-6 haloalkylsulfinyl, arylsulfonyl,
tri(C.sub.1-4)alkylsilyl, aryldi(C.sub.1-4)-alkylsilyl,
(C.sub.1-4)alkyldiarylsilyl, triarylsilyl, C.sub.1-10
alkylcarbonyl, HO.sub.2C, C.sub.1-10 alkoxycarbonyl, aminocarbonyl,
C.sub.1-6 alkylaminocarbonyl, di(C.sub.1-6 alkyl)-aminocarbonyl,
N--(C.sub.1-3 alkyl)-N--(C.sub.1-3 alkoxy)aminocarbonyl, C.sub.1-6
alkylcarbonyloxy, arylcarbonyloxy,
di(C.sub.1-6)alkylamino-carbonyloxy, aryl (itself optionally
substituted with C.sub.1-6 alkyl or halogen), heteroaryl (itself
optionally substituted with C.sub.1-6 alkyl or halogen),
heterocyclyl (itself optionally substituted with C.sub.1-6 alkyl or
halogen), aryloxy (where the aryl group is optionally substituted
with C.sub.1-6 alkyl or halogen), heteroaryloxy (where the
heteroaryl group is optionally substituted with C.sub.1-6 alkyl or
halogen), heterocyclyloxy (where the heterocyclyl group is
optionally substituted with C.sub.1-6 alkyl or halogen), amino,
C.sub.1-6 alkylamino, di(C.sub.1-6)alkylamino, C.sub.1-6
alkylcarbonylamino,
N--(C.sub.1-6)alkylcarbonyl-N--(C.sub.1-6)alkylamino, arylcarbonyl,
(where the aryl group is itself optionally substituted with halogen
or C.sub.1-6 alkyl) or two adjacent positions on an aryl or
heteroaryl system may be cyclised to form a 5, 6 or 7 membered
carbocyclic or heterocyclic ring, itself optionally substituted
with halogen or C.sub.1-6 alkyl. Further substituents for aryl or
heteroaryl include aryl carbonyl amino (where the aryl group is
substituted by C.sub.1-6 alkyl or halogen),
(C.sub.1-6)alkyloxycarbonylamino
(C.sub.1-6)alkyloxycarbonyl-N--(C.sub.1-6)alkylamino,
aryloxycarbonylamino (where the aryl group is substituted by
C.sub.1-6 alkyl or halogen),
aryloxycarbonyl-N--(C.sub.1-6)alkylamino, (where the aryl group is
substituted by C.sub.1-6 alkyl or halogen), arylsulphonylamino
(where the aryl group is substituted by C.sub.1-6 alkyl or
halogen), arylsulphonyl-N--(C.sub.1-6)alkylamino (where the aryl
group is substituted by C.sub.1-6 alkyl or halogen),
aryl-N--(C.sub.1-6)alkylamino (where the aryl group is substituted
by C.sub.1-6 alkyl or halogen), arylamino (where the aryl group is
substituted by C.sub.1-6 alkyl or halogen), heteroaryl amino (where
the heteroaryl group is substituted by C.sub.1-6 alkyl or halogen),
heterocyclylamino (where the heterocyclyl group is substituted by
C.sub.1-6 alkyl or halogen), aminocarbonylamino, C.sub.1-6
alkylaminocarbonyl amino, di(C.sub.1-6)alkylaminocarbonyl amino,
arylaminocarbonyl amino where the aryl group is substituted by
C.sub.1-6 alkyl or halogen),
aryl-N--(C.sub.1-6)alkylaminocarbonylamino where the aryl group is
substituted by C.sub.1-6 alkyl or halogen), C.sub.1-6
alkylaminocarbonyl-N--(C.sub.1-6)alkyl amino,
di(C.sub.1-6)alkylaminocarbonyl-N--(C.sub.1-6)alkyl amino,
arylaminocarbonyl-N--(C.sub.1-6)alkyl amino (where the aryl group
is substituted by C.sub.1-6 alkyl or halogen) and
aryl-N--(C.sub.1-6)alkylaminocarbonyl-N--(C.sub.1-6)alkyl amino
(where the aryl group is substituted by C.sub.1-6 alkyl or
halogen).
[0020] For substituted phenyl moieties, heterocyclyl and heteroaryl
groups it is preferred that one or more substituents are
independently selected from halogen, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.1-6 alkoxy,
C.sub.1-6 haloalkoxy, C.sub.1-6 alkylthio, C.sub.1-6 haloalkylthio,
C.sub.1-6 alkylsulfinyl, C.sub.1-6 haloalkylsulfinyl, C.sub.1-6
alkylsulfonyl, C.sub.1-6 haloalkylsulfonyl, C.sub.2-6 alkenyl,
C.sub.2-6 haloalkenyl, C.sub.2-6 alkynyl, C.sub.3-7 cycloalkyl,
nitro, cyano, CO.sub.2H, C.sub.1-6 alkylcarbonyl, C.sub.1-6
alkoxycarbonyl, R.sup.31R.sup.32N or R.sup.33R.sup.34NC(O); wherein
R.sup.31, R.sup.32, R.sup.33 and R.sup.34 are, independently,
hydrogen or C.sub.1-6 alkyl. Further preferred substituents are
amino, dialkylamino, aryl and heteroaryl groups.
[0021] Haloalkenyl groups are alkenyl groups which are substituted
with one or more of the same or different halogen atoms
[0022] It is to be understood that dialkylamino substituents
include those where the dialkyl groups together with the N atom to
which they are attached form a five, six or seven-membered
heterocyclic ring which may contain one or two further heteroatoms
selected from O, N or S and which is optionally substituted by one
or two independently selected (C.sub.1-6)alkyl groups. When
heterocyclic rings are formed by joining two groups on an N atom,
the resulting rings are suitably pyrrolidine, piperidine,
thiomorpholine and morpholine each of which may be substituted by
one or two independently selected (C.sub.1-6) alkyl groups.
[0023] Preferably the optional substituents on an alkyl moiety
include one or more of halogen, nitro, cyano, HO.sub.2C, C.sub.1-10
alkoxy (itself optionally substituted by C.sub.1-10 alkoxy),
aryl(C.sub.1-4)alkoxy, C.sub.1-10 alkylthio, C.sub.1-10
alkylcarbonyl, C.sub.1-10 alkoxycarbonyl, C.sub.1-6
alkylaminocarbonyl, di(C.sub.1-6 alkyl)aminocarbonyl,
(C.sub.1-6)alkylcarbonyloxy, optionally substituted phenyl,
heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl,
heterocyclyloxy, C.sub.3-7 cycloalkyl (itself optionally
substituted with (C.sub.1-6)alkyl or halogen), C.sub.3-7
cycloalkyloxy, C.sub.5-7 cycloalkenyl, C.sub.1-6 alkylsulfonyl,
C.sub.1-6 alkylsulfinyl, tri(C.sub.1-4)alkylsilyl,
tri(C.sub.1-4)alkylsilyl(C.sub.1-6)alkoxy,
aryldi(C.sub.1-4)alkylsilyl, (C.sub.1-4)alkyldiarylsilyl and
triarylsilyl.
[0024] Preferably the optional substituents on alkenyl or alkynyl
include one or more of halogen, C.sub.3-7 cycloalkyl and aryl; the
aryl group may be optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino.
[0025] A preferred optional substituent for heterocyclyl is
C.sub.1-6 alkyl.
[0026] Preferably the optional substituents for cycloalkyl include
halogen, cyano and C.sub.1-3 alkyl.
[0027] Preferably the optional substituents for cycloalkenyl
include C.sub.1-3 alkyl, halogen and cyano.
[0028] One group of preferred compounds are those of formula (IA)
which are compounds of formula (I) wherein Y is a single bond,
C.dbd.O, C.dbd.S or S(O).sub.q where q is 0, 1 or 2; R.sup.1 is
hydrogen, optionally substituted alkyl, optionally substituted
alkoxycarbonyl, optionally substituted alkylcarbonyl,
aminocarbonyl, optionally substituted alkylaminocarbonyl,
optionally substituted dialkylaminocarbonyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
alkoxy, optionally substituted aryloxy, optionally substituted
heteroaryloxy, optionally substituted heterocyclyloxy, cyano,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, formyl, optionally substituted heterocyclyl,
optionally substituted alkylthio or NR.sup.13R.sup.14 where
R.sup.13 and R.sup.14 are independently hydrogen, optionally
substituted alkyl, optionally substituted aryl, optionally
substituted heteroaryl or optionally substituted heterocyclyl;
R.sup.2 and R.sup.3 are independently hydrogen, halogen, cyano,
optionally substituted alkyl, optionally substituted alkoxy,
optionally substituted aryl or C(O)NR.sup.15R.sup.16 where R.sup.15
and R.sup.16 are independently hydrogen, optionally substituted
alkyl, optionally substituted aryl, optionally substituted
heteroaryl or optionally substituted heterocyclyl, or R.sup.2 and
R.sup.3 together are .dbd.O, or R.sup.2 and R.sup.3 together with
the atoms to which they are attached form a 4, 5, 6,or 7 membered
carbocylic or heterocyclic ring; each R.sup.4 is independently
halogen, nitro, cyano, optionally substituted C.sub.1-8 alkyl,
optionally substituted C.sub.2-6 alkenyl, optionally substituted
C.sub.2-6 alkynyl, optionally substituted alkoxycarbonyl,
optionally substituted alkylcarbonyl, optionally substituted
alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl,
optionally substituted C.sub.3-7 cycloalkyl, optionally substituted
aryl, optionally substituted heteroaryl, optionally substituted
heterocyclyl, optionally substituted alkoxy, optionally substituted
aryloxy, optionally substituted heteroaryloxy, optionally
substituted alkylthio or R.sup.19R.sup.20N where R.sup.19 and
R.sup.20 are, independently, hydrogen, C.sub.1-8 alkyl, C.sub.3-7
cycloalkyl, C.sub.3-6 alkenyl, C.sub.3-6 alkynyl, C.sub.3-7
cycloalkyl(C.sub.1-4)alkyl, C.sub.2-6 haloalkyl, C.sub.1-6
alkoxy(C.sub.1-6)alkyl, C.sub.1-6 alkoxycarbonyl or R.sup.19 and
R.sup.20 together with the N atom to which they are attached form a
five, six or seven-membered heterocyclic ring which may contain one
or two further heteroatoms selected from O, N or S and which may be
optionally substituted by one or two C.sub.1-6 alkyl groups, or 2
adjacent groups R.sup.4 together with the carbon atoms to which
they are attached form a 4, 5, 6,or 7 membered carbocylic or
heterocyclic ring which may be optionally substituted by halogen; n
is 0, 1, 2, 3 or 4; R.sup.8 is optionally substituted alkyl,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted cycloalkyl, optionally substituted aryl,
optionally substituted alkoxy, optionally substituted aryloxy,
optionally substituted alkoxycarbonyl, optionally substituted
alkylcarbonyl or optionally substituted alkenylcarbonyl; R.sup.9
and R.sup.10 are independently hydrogen, halogen, optionally
substituted alkyl, optionally substituted aryl or R.sup.9 and
R.sup.10 together form a group --CH.sub.2--, --CH.dbd.CH-- or
--CH.sub.2CH.sub.2--; or salts or N-oxides thereof.
[0029] Another group of preferred compounds are those of formula
(IB) which are compounds of formula (I) wherein Y is a single bond,
C.dbd.O or S(O).sub.q where q is 0, 1 or 2; R.sup.1 is hydrogen,
C.sub.1-8 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl,
C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6
cycloalkenyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl-(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)-alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)-alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group may be optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-4)alkyl
(wherein the heteroaryl group may be substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl (wherein the
heterocyclyl group may be substituted by halogen, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl,
aminocarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)alkyl-aminocarbonyl, phenyl (optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), heteroaryl (optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, aryloxy (wherein the aryl group may be optionally
substituted with halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryloxy (wherein the
heteroaryl group may be optionally substituted with halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), cyano, C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 cyanoalkenyl,
aminocarbonyl-(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group may be
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), C.sub.2-6 alkynyl,
aminocarbonyl(C.sub.2-6)-alkynyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)-alkynyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkynyl, C.sub.3-7
cycloalkyl, C.sub.3-7 halocycloalkyl, C.sub.3-7, cyanocycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)cycloalkyl, C.sub.1-3
alkyl-(C.sub.3-7)halocycloalkyl, C.sub.5-6 cycloalkenyl, formyl,
heterocyclyl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-8 alkylthio, or R.sup.13R.sup.14N where
R.sup.13 and R.sup.14 are independently hydrogen, COR.sup.40,
C.sub.1-6 alkyl, aryl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl amino or dialkylamino), heteroaryl
(optionally substituted by halogen or C.sub.1-3 alkyl) or R.sup.13
and R.sup.14 together with the N atom to which they are attached
form a group --N.dbd.C(R.sup.41)--NR.sup.42R.sup.43 where R.sup.41,
R.sup.42 and R.sup.43 are independently H or C.sub.1-4 lower alkyl;
R.sup.2 and R.sup.3 are independently hydrogen, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or cyano; each R.sup.4 is
independently halogen, nitro, cyano, C.sub.1-8 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.1-6 alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-6)alkyl (wherein the phenyl group may be optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-6)alkyl
(wherein the heteroaryl group is optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 alkynyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)alkylaminocarbonyl, C.sub.3-7 cycloalkyl, phenyl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-8
alkoxy, C.sub.1-8 haloalkoxy, aryloxy (where the aryl group is
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (where
the heteroaryl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino);
n is 0, 1, 2, 3 or 4; R.sup.8 is C.sub.1-10 alkyl optionally
substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself optionally
substituted by optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
(itself optionally substituted by halogen, C.sub.1-4 alkyl or
C.sub.1-4 alkoxy), C.sub.2-6 alkenyl optionally substituted by
C.sub.1-6 alkoxy, halogen or phenyl (itself optionally substituted
by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), C.sub.2-6
alkynyl optionally substituted by C.sub.1-6 alkoxy, halogen or
phenyl (itself optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino) or
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54].sub.z--R.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each
independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl
and R.sup.55 is aryl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino) or
heteroaryl (optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamin); R.sup.9 and
R.sup.10 are independently hydrogen, C.sub.1-2 alkyl or halogen;
R.sup.40 is H, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy, C.sub.1-6 haloalkoxy, phenoxy (wherein the phenyl group may
be optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.11-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), phenyl (optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy),
heteroaryloxy (wherein the heteroaryl group may be optionally
substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy) or
NR.sup.44R.sup.45 where R.sup.44 and R.sup.45 are independently
C.sub.1-6 alkyl (optionally substituted with halogen, nitro, cyano,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
phenyl (optionally substituted with halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino) or heteroaryl
(optionally substituted with halogen, nitro, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy) and salts or N-oxides thereof.
[0030] A further group of preferred compounds are those of formula
(IC) which are compounds of formula (I) wherein Y is a single bond,
C.dbd.O or S(O).sub.q where q is 0, 1 or 2; R.sup.1 is hydrogen,
C.sub.1-8 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl,
C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6
cycloalkenyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl-(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)-alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)-alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl(C.sub.1-4)alkyl (wherein the heteroaryl group may be
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heterocyclyl(C.sub.1-4)alkyl (wherein the heterocyclyl group may be
substituted by halogen, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6
alkoxycarbonyl, C.sub.1-6 alkylcarbonyl, aminocarbonyl, C.sub.1-6
alkylaminocarbonyl, di(C.sub.1-6)alkylaminocarbonyl, phenyl
(optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, aryloxy
(wherein the aryl group may be optionally substituted with halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy),heteroaryloxy (wherein the
heteroaryl group may be optionally substituted with halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy),cyano, C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 cyanoalkenyl,
aminocarbonyl-(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group is optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6
alkynyl, aminocarbonyl(C.sub.2-6)-alkynyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkynyl, C.sub.3-7
cycloalkyl, C.sub.3-7 halocycloalkyl, C.sub.3-7 cyanocycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)cycloalkyl, C.sub.1-3
alkyl-(C.sub.3-7)halocycloalkyl, C.sub.5-6 cycloalkenyl, formyl,
heterocyclyl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-8 alkylthio, or R.sup.13R.sup.14N where
R.sup.13 and R.sup.14 are independently hydrogen, C.sub.1-6 alkyl,
aryl (optionally substituted by halogen, C.sub.1,3 alkyl, nitro,
cyano, C.sub.1-3 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy) or heteroaryl (optionally substituted by halogen or
C.sub.1-3 alkyl); R.sup.2 and R.sup.3 are independently hydrogen,
C.sub.1-6 alkyl, C.sub.1-6haloalkyl, C.sub.1-6alkoxy or cyano; each
R.sup.4is independently halogen, nitro, cyano, C.sub.1-8 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.1-6 alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl-(C.sub.1-6)alkyl,
phenyl(C.sub.1-6)alkyl (wherein the phenyl group is optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.2-6 alkynyl,
C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl, C.sub.1-6
alkylaminocarbonyl, di(C.sub.1-6)alkylaminocarbonyl, C.sub.3-7
cycloalkyl, phenyl (optionally substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heteroaryl (optionally substituted by
halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-8 alkoxy,
C.sub.1-8 haloalkoxy, aryloxy (where the aryl group is optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy) or
heteroaryloxy (where the heteroaryl group is optionally substituted
by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy); n is 0, 1, 2, 3 or 4;
R.sup.8 is C.sub.1-10 alkyl optionally substituted by C.sub.1-6
alkoxy, halogen or phenyl (itself optionally substituted by
halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy), C.sub.2-6 alkenyl
optionally substituted by C.sub.1-6 alkoxy, halogen or phenyl
(itself optionally substituted by halogen, C.sub.1-4 alkyl or
C.sub.1-4 alkoxy) or C.sub.2-6 alkynyl optionally substituted by
C.sub.1-6 alkoxy, halogen or phenyl (itself optionally substituted
by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy); R.sup.9 and
R.sup.10 are independently hydrogen, C.sub.1-2 alkyl or halogen;
and salts or N-oxides thereof.
[0031] Another group of preferred compounds are those of formula
(ID) which are compounds of formula (I) wherein Y is a single bond
or C.dbd.O; R.sup.1 is hydrogen, C.sub.1-8 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6 cycloalkenyl(C.sub.1-6)alkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6 alkynyloxy(C.sub.1-6)alkyl,
aryloxy(C.sub.1-6)alkyl, C.sub.1-6 carboxyalkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl-(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)-alkyl, C.sub.1-6 alkylthio(C.sub.1-
6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl, C.sub.1-6
alkylsulfonyl(C.sub.1-6)alkyl, aminocarbonyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)-alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl (C.sub.1-4)alkyl
(wherein the heteroaryl group may be substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl (wherein the
heterocyclyl group maybe substituted by halogen, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl,
aminocarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)alkylaminocarbonyl, phenyl (optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), heteroaryl (optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, aryloxy (wherein the aryl group may be optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino),heteroaryloxy (wherein the
heteroaryl group may be optionally substituted with halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy),cyano, C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 cyanoalkenyl,
aminocarbonyl-(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkynyl,
aminocarbonyl(C.sub.2-6)-alkynyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkynyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkynyl, C.sub.3-7
cycloalkyl, C.sub.3-7 halocycloalkyl, C.sub.3-7 cyanocycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)cycloalkyl, C.sub.1-3
alkyl-(C.sub.3-7)halocycloalkyl, C.sub.5-6 cycloalkenyl, formyl,
heterocyclyl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-8 alkylthio, or R.sup.13R.sup.14N where
R.sup.13 and R.sup.14 are independently hydrogen, COR.sup.40,
C.sub.1-6 alkyl, aryl (optionally substituted by halogen, C.sub.1-3
alkyl, nitro, cyano, C.sub.1-3 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heteroaryl (optionally substituted by
halogen or C.sub.1-3 alkyl); R.sup.2 and R.sup.3 are independently
hydrogen or methyl, preferably both ydrogen; each R.sup.4 is
independently halogen, nitro, cyano, C.sub.1-8 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.1-6 alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-6)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl-(C.sub.1-6)alkyl
(wherein the heteroaryl group is optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 akynyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)alkylaminocarbonyl, C.sub.3-7 cycloalkyl, phenyl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-8
alkoxy, Cis haloalkoxy, aryloxy (where the aryl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino) or heteroaryloxy (where the
heteroaryl group is optionally substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy); n is 0, 1, 2, 3 or 4; R.sup.8 is C.sub.1-10
alkyl optionally substituted by C.sub.1-6 alkoxy, halogen, phenyl
(itself optionally substituted by halogen, C.sub.1-4 alkyl or
C.sub.1-4 alkoxy), heteroaryl (itself optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino); or
--C(R.sup.51)(R.sup.52)--[CR.sup.53=CR.sup.54].sub.z--R.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each
independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl
and R.sup.55 is aryl (optionally substituted by halogen,
C.sub.1-4alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino)
or heteroaryl (optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino); R.sup.9 and
R.sup.10 are both hydrogen; R.sup.40 is H, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
phenoxy (wherein the phenyl group may be optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), phenyl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) and salts or N-oxides
thereof.
[0032] Yet another group of preferred compounds are those of
formula (IE), which are compounds of formula (I) wherein Y,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.8 and n are as defined
for compounds of formula IC; R.sup.9 and R.sup.10 are independently
hydrogen, C.sub.1-2 alkyl or halogen, and preferably all are
hydrogen; and salts or N-oxides thereof.
[0033] A further group of preferred compounds are those of formula
(IF), which are compounds of formula (I) wherein Y, R.sup.1,
R.sup.4, R.sup.8, R.sup.9, R.sup.10 and n are as defined for
compounds of formula (IE) and R.sup.2 and R.sup.3 are independently
hydrogen, halogen, C.sub.1-2 alkyl, C.sub.1-2 haloalkyl, C.sub.1-2
alkoxy, cyano, or R.sup.2 and R.sup.3 together are .dbd.O, or
R.sup.2 and R.sup.3 together with the atoms to which they are
attached form a 4, 5, 6, or 7 membered carbocylic or heterocyclic
ring; and salts or N-oxides thereof.
[0034] Yet another group of preferred compounds are those of
formula (IG), which are compounds of formula () wherein Y, R.sup.1,
R.sup.2, R.sup.3, R.sup.8, R.sup.9, R.sup.10 and n are as defined
for compounds of formula (IF) and each R.sup.4 is independently
halogen, nitro, cyano, C.sub.1-8 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 cyanoalkyl, C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-6)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy,
C.sub.1-6 haloalkyl, C.sub.1-4 haloalkoxy, CN, or NO.sub.2),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.2-6 alkynyl,
C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl, C.sub.1-6
alkylaminocarbonyl, di(C.sub.1-6)alkyl-aminocarbonyl, C.sub.3-7
cycloalkyl, phenyl (optionally substituted by halogen, C.sub.1-6
alkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkyl, C.sub.1-4 haloalkoxy,
CN, or NO.sub.2), heteroaryl (optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-8 alkoxy, C.sub.1-8
haloalkoxy, aryloxy (where the aryl group is optionally substituted
by halogen, C.sub.1-6 alkyl, C,6 alkoxy, C, haloalkyl, C.sub.1-4
haloalkoxy, CN, or NO.sub.2) or heteroaryloxy (where the heteroaryl
group is optionally substituted by halogen, nitro, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy); and salts or N-oxides thereof.
[0035] A further group of preferred compounds are those of formula
(IG'), which are compounds of formula (I) wherein Y, R.sup.1,
R.sup.2, R.sup.3, R.sup.8, R.sup.9, R.sup.10 and n are as defined
for compounds of formula (IB) and each R.sup.4 is independently
halogen, nitro, cyano, C.sub.1-8 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 cyanoalkyl, C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-6)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-6)alkyl
(wherein the heteroaryl group is optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6 alkenyl, C.sub.2-6
haloalkenyl, C.sub.2-6 alkynyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)alkyl-aminocarbonyl, C.sub.3-7 cycloalkyl, phenyl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-8
alkoxy, C.sub.1-8 haloalkoxy, phenoxy (where the phenyl group is
optionally substituted by halogen, C.sub.1-6 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy (where
the heteroaryl group is optionally substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy); and salts or N-oxides thereof.
[0036] Another group of preferred compounds are those of formula
(IH), which are compounds of formula (I) wherein R.sup.2, R.sup.3,
R.sup.4, R.sup.8, R.sup.9, R.sup.10 and n are as defined for
compounds of formula (IG) and Y is a single bond or C.dbd.O;
R.sup.1 is C.sub.1-8 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
cyanoalkyl, C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6
cycloalkenyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)-alkyl,
C.sub.3-6 alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6
alkynyl-oxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy,
C.sub.1-6 haloalkyl, C.sub.1-4 haloalkoxy, CN, or NO.sub.2),
heteroaryl(C.sub.1-4)alkyl (wherein the heteroaryl group may be
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heterocyclyl(C.sub.1-4)alkyl (wherein the heterocyclyl group may be
substituted by halogen, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6
alkoxycarbonyl, C.sub.1-6 alkylcarbonyl, aminocarbonyl, C.sub.1-6
alkylaminocarbonyl, di(C.sub.1-6)-alkylaminocarbonyl, phenyl
(optionally substituted by halogen, C.sub.1-6 alkyl, C.sub.1-6
alkoxy, C.sub.1-6 haloalkyl, C.sub.1-4 haloalkoxy, CN, or
NO.sub.2), heteroaryl (optionally substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
aryloxy (where the arylyl group may be optionally substituted
halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkyl,
C.sub.1-4 haloalkoxy, CN, or NO.sub.2), cyano, C.sub.2-6 alkenyl,
C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl,
aminocarbonyl(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)-alkenyl,
di(C.sub.1-6)alkyl-aminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group is optionally
substituted halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, C.sub.1-6
haloalkyl, C.sub.1-4 haloalkoxy, CN, or NO.sub.2), C.sub.2-6
alkynyl, aminocarbonyl(C.sub.2-6)alkynyl,
alkylaminocarbonyl(C.sub.2-6)alkynyl,
di(C.sub.1-6)alkylamino-carbonyl(C.sub.2-6)alkynyl, C.sub.3-7
cycloalkyl, C.sub.3-7 halocycloalkyl, C.sub.3-7 cyanocycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)cycloalkyl, C.sub.1-3
alkyl(C.sub.3-7)halocycloalkyl, C.sub.5-6 cycloalkenyl, formyl,
heterocyclyl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-8 alkylthio or R.sup.13R.sup.14N where
R.sup.13 and R.sup.14 are independently hydrogen, C.sub.1-6 alkyl,
aryl (optionally substituted by halogen, C.sub.1-6 alkyl, C.sub.1-6
alkoxy, C.sub.1-6 haloalkyl, C.sub.1-4 haloalkoxy, CN, or NO.sub.2)
or heteroaryl (optionally substituted by halogen or C.sub.1-3
alkyl); and salts or N-oxides thereof.
[0037] Another group of preferred compounds are those of formula
(IH'), which are compounds of formula (I) wherein R.sup.2, R.sup.3,
R.sup.4, R.sup.8, R.sup.9, R.sup.10 and n are as defined for
compounds of formula (IG') and R.sup.1 is C.sub.1-8 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6 cycloalkenyl(C.sub.1-6)alkyl,
C.sub.1-6 alkoxy(C.sub.1-6)-alkyl, C.sub.3-6
alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6 alkynyloxy(C.sub.1-6)alkyl,
aryloxy(C.sub.1-6)alkyl, C.sub.1-6 carboxyalkyl, C.sub.1-6
alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6
alkynyl-oxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl-(C.sub.1-4)alkyl
(wherein the heteroaryl group may be substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl (wherein the
heterocyclyl group may be substituted by halogen, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl,
aminocarbonyl, C.sub.1-6 alkylaminocarbonyl,
di(C.sub.1-6)-alkylaminocarbonyl, phenyl (optionally substituted
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), heteroaryl (optionally substituted by halogen,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, aryloxy (where the aryl group may be optionally
substituted with halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), cyano,
C.sub.2-6 alkenyl, C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl,
aminocarbonyl(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)-alkenyl,
di(C.sub.1-6)alkyl-aminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)alkenyl, (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkynyl,
aminocarbonyl(C.sub.2-6)alkynyl,
alkylaminocarbonyl(C.sub.2-6)alkynyl,
di(C.sub.1-6)alkylamino-carbonyl(C.sub.2-6)alkynyl, C.sub.3-7
cycloalkyl, C.sub.3-7 halocycloalkyl, C.sub.3-7 cyanocycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)cycloalkyl, C.sub.1-3
alkyl(C.sub.3-7)halocycloalkyl, C.sub.5-6 cycloalkenyl, formyl,
heterocyclyl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-8 alkylthio or R.sup.13R.sup.14N where
R.sup.13 and R.sup.14 are independently hydrogen, C.sub.1-6 alkyl,
COR.sup.40, where C.sub.1-6 alkylcarbonylamino,
phenyloxycarbonylamino (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), amino, C.sub.1-6 alkylamino,
phenylamino (wherein the phenyl group is optionally substituted
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino)and salts or N-oxides thereof.
[0038] A further group of preferred compounds are those of formula
(IJ), which are compounds of formula (I) wherein Y, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.9, R.sup.10 and n are as defined
for compounds of formula (IH) and R.sup.8 is C.sub.1-10 alkyl
optionally substituted by C.sub.1-6 alkoxy, halogen or phenyl
(itself optionally substituted by halogen, C.sub.1-4 alkyl or
C.sub.1-4 alkoxy), C.sub.2-6 alkenyl optionally substituted by
C.sub.1-6 alkoxy, halogen or phenyl (itself optionally substituted
by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy) or C.sub.2-6 alkyl
optionally substituted by C.sub.1-6 alkoxy, halogen or phenyl
(itself optionally substituted by halogen, C.sub.1-4 alkyl or
C.sub.1-4 alkoxy); and salts or N-oxides thereof.
[0039] A further group of preferred compounds are those of formula
(IJ'), which are compounds of formula (I) wherein Y, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.9, R.sup.10 and n are as defined
for compounds of formula (IH') and R.sup.8 is C.sub.1-6 alkyl
optionally substituted by phenyl or heteroaryl (the phenyl and
heteroaryl groups being optionally substituted halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino); or
--C(R.sup.51)(.sup.52)--[CR.sup.53.dbd.CR.sup.54].sub.zR.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each
independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl
and R.sup.55 is aryl substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino, or heteroaryl
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino.
[0040] Yet another preferred group of compounds are those of
formula (IK), which are compounds of formula (I) wherein Y is a
single bond, C.dbd.O or S(O).sub.q where q is 0, 1 or 2; R.sup.1 is
C.sub.1-8 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 cyanoalkyl,
C.sub.3-7 cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxy(C.sub.1-6)alkyl, C.sub.3-6 alkenyloxy-(C.sub.1-6)alkyl,
C.sub.3-6 alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl,
C.sub.1-6 carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl,
C.sub.2-6 alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)-alkyl, C.sub.1-6
alkylsulfinyl(C.sub.1-6)alkyl, C.sub.1-6
alkylsulfonyl(C.sub.1-6)alkyl, aminocarbonyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl(C.sub.1-4)alkyl (wherein the heteroaryl group may be
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heterocyclyl(C.sub.1-4)alkyl (wherein the heterocyclyl group may be
substituted by halogen, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), phenyl
(optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heteroaryl (optionally substituted by halogen, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.2-6
alkenyl, C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl, C.sub.2-6
alkynyl, C.sub.3-7 cycloalkyl, formyl, heterocyclyl (optionally
substituted by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy) or C.sub.1-6
alkylthio; R.sup.2 and R.sup.3 are independently hydrogen or
C.sub.1-4 alkyl; each R.sup.4 is independently halogen, cyano,
C.sub.1-10 alkyl optionally substituted by C.sub.1-6 alkoxy,
halogen, phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy), C.sub.2-6 alkenyl optionally
substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself optionally
substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy) or
C.sub.2-6 alkynyl optionally substituted by C.sub.1-6 alkoxy,
halogen, phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy); n is 0, 1, 2, 3 or 4; R.sup.8
is C.sub.1-10 alkyl optionally substituted by C.sub.1-6 alkoxy,
halogen or phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl or C.sub.1-4 alkoxy), C.sub.2-6 alkenyl optionally
substituted by C.sub.1-6 alkoxy, halogen or phenyl (itself
optionally substituted by halogen, C.sub.1-4 alkyl or C.sub.1-4
alkoxy) or C.sub.2-6 alkyl optionally substituted by C.sub.1-6
alkoxy, halogen or phenyl (itself optionally substituted by
halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy); R.sup.9 and R.sup.10
are both hydrogen; and salts or N-oxides thereof.
[0041] Yet another preferred group of compounds are those of
formula (IL), which are compounds of formula (I) wherein Y is a
single bond or C.dbd.O; R.sup.1 is C.sub.1-8 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy-(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)-alkyl, C.sub.1-6
alkylsulfinyl(C.sub.1-6)alkyl, C.sub.1-6
alkylsulfonyl(C.sub.1-6)alkyl, aminocarbonyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl-(C.sub.1-4)alkyl
(wherein the heteroaryl group may be substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl (wherein the
heterocyclyl group may be substituted by halogen, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), phenyl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
(optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.2-6 alkenyl,
C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl, C.sub.2-6 alkynyl,
C.sub.3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted
by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy) or C.sub.1-6 alkylthio,
C.sub.1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the
phenyl group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), amino,
C.sub.1-6 alkylamino, phenylamino (wherein the phenyl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino); R.sup.2 and R.sup.3 are
independently hydrogen or C.sub.1-4 alkyl; each R.sup.4 is
independently halogen, cyano, C.sub.1-10 alkyl optionally
substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkenyl optionally
substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino) or C.sub.2-6 alkynyl optionally
substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino); n is 0, 1, 2, 3 or 4; R.sup.8
is C.sub.1-10 alkyl optionally substituted by C.sub.1-6 alkoxy,
halogen or phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
C.sub.2-6 alkenyl optionally substituted by C.sub.1-6 alkoxy,
halogen or phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino)
or C.sub.2-6 alkynyl optionally substituted by C.sub.1-6 alkoxy,
halogen or phenyl (itself optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
or --C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54)z-R.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each
independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl
and R.sup.55 is phenyl substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino or heteraryl
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl amino or dialkylamino; R.sup.40 is H, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
phenoxy (wherein the phenyl group may be optionally substituted
with halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4
haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl,
amino or dialkylamino), phenyl (optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
heteroaryl (optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino); R.sup.9 and R.sup.10 are
both hydrogen or methyl; and salts or N-oxides thereof.
[0042] An even more preferred group of compounds are those of
formula (IM), which are compounds of formula (I) wherein Y is a
single bond or C.dbd.O; R.sup.1 is C.sub.1-8 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 cyanoalkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy-(C.sub.1-6)-alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl-(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)-alkyl, C.sub.3-6 alkynyloxycarbonyl
(C.sub.1-6)alkyl, aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)-alkyl, C.sub.1-6
alkylsulfinyl(C.sub.1-6)-alkyl, C.sub.1-6
alkylsulfonyl(C.sub.1-6)alkyl, aminocarbonyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.1-6)-alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-4)alkyl
(wherein the heteroaryl group may be substituted by halogen, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl (wherein the
heterocyclyl group may be substituted by halogen, cyano, C.sub.1-6
alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), phenyl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
(optionally substituted by halogen, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.2-6 alkenyl,
C.sub.2-6 haloalkenyl, C.sub.2-6 cyanoalkenyl, C.sub.2-6 alkynyl,
C.sub.3-7 cycloalkyl, formyl, heterocyclyl (optionally substituted
by halogen, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy) or C.sub.1-6 alkylthio,
C.sub.1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the
phenyl group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), amino,
C.sub.1-6 alkylamino, phenylamino (wherein the phenyl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino); R.sup.2 and R.sup.3 are
independently hydrogen or methyl, preferably both hydrogen; each
R.sup.4 is independently halogen, cyano, C.sub.1-10 alkyl
optionally substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), C.sub.2-6 alkenyl
optionally substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) or C.sub.2-6 alkynyl
optionally substituted by C.sub.1-6 alkoxy, halogen, phenyl (itself
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino); n is 0, 1, 2, 3 or 4;
R.sup.8 is phenyl(C.sub.1-4)alkyl (wherein the phenyl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-4)alkyl
(wherein the heteroaryl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
--C(R.sup.51)(R.sup.52)--[CR.sup.53=]z-R.sup.55 where z is 1 or 2
and more preferably z is 1, R.sup.51 and R.sup.52 are each
independently H, halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are
each independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4
haloalkyl and R.sup.55 is phenyl substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino or heteraryl
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino; R.sup.40 is H, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
phenoxy (wherein the phenyl group may be optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino), phenyl (optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) or heteroaryloxy
(optionally substituted by halogen, C.sub.1-14 allyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino) and salts or N-oxides
thereof.
[0043] It is preferred that Y is a single bond, C.dbd.O, C.dbd.S or
S(O).sub.q where q is 0, 1 or 2.
[0044] More preferably Y is a single bond, C.dbd.O or SO.sub.2.
[0045] Most preferably Y is a single bond or C.dbd.O, especially
C.dbd.O.
[0046] R.sup.1 is preferably hydrogen, C.sub.1-6 alkyl, C.sub.1-6
cyanoalkyl, C.sub.1-6 haloalkyl, C.sub.3-7
cycloalkyl(C.sub.1-4)alkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group may be
optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6
alkylthio, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino,
arylcarbonyl, or two adjacent positions on the heteroaryl system
may be cyclised to form a 5, 6 or 7 membered carbocyclic or
heterocyclic ring, itself optionally substituted with halogen),
aryl(C.sub.1-6)alkyl (wherein the aryl group may be optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.1-6
alkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6 alkylthio,
C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino,
arylcarbonyl, or two adjacent positions on the aryl system may be
cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic
ring, itself optionally substituted with halogen), C.sub.1-6
alkylcarbonylamino(C.sub.1-6)alkyl, aryl (which may be optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.1-6
alkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6 alkylthio,
C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino,
arylcarbonyl, or two adjacent positions on the aryl system may be
cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic
ring, itself optionally substituted with halogen), heteroaryl
(which may be optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6
haloalkoxy, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfinyl,
C.sub.1-6 alkylthio, C.sub.1-6 alkoxycarbonyl, C.sub.1-6
alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the
heteroaryl system may be cyclised to form a 5, 6 or 7 membered
carbocyclic or heterocyclic ring, itself optionally substituted
with halogen), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, phenoxy
(wherein the phenyl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
heteroaryloxy (optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), heterocycyloxy (optionally substituted by halo,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), cyano, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, C.sub.3-6
cycloalkyl, C.sub.5-7 cycloalkenyl, heterocyclyl (optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), C.sub.1-6
alkylthio, C.sub.1-6 haloalkylthio or NR.sup.13R.sup.14 where
R.sup.13 and R.sup.14 are independently hydrogen, C.sub.2-6 alkyl,
C.sub.2-6 haloalkyl, phenyl (which may be optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino,
dialkylamino or C.sub.1-4 alkoxycarbonyl) or heteroaryl (which may
be optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy,
C.sub.1-4 alkoxycarbonyl C.sub.1-6 alkylcarbonylamino,
phenyloxycarbonylamino (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), amino, C.sub.1-6 alkylamino or
phenylamino (wherein the phenyl group is optionally substituted
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino).
[0047] More preferably R.sup.1 is hydrogen, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group may be
optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6
alkylthio, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino,
arylcarbonyl, or two adjacent positions on the heteroaryl system
may be cyclised to form a 5, 6 or 7 membered carbocyclic or
heterocyclic ring, itself optionally substituted with halogen),
phenyl(C.sub.1-6)alkyl (wherein the phenyl group may be optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino, C.sub.1-6 alkylsulfonyl,
C.sub.1-6 alkylsulfinyl, C.sub.1-6 alkylthio, C.sub.1-6
alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino, arylcarbonyl, or two
adjacent positions on the phenyl ring may be cyclised to form a 5,
6 or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), C.sub.1-6
alkylcarbonylamino(C.sub.1-6)alkyl, phenyl (which may be optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino, C.sub.1-6 alkylsulfonyl,
C.sub.1-6 alkylsulfinyl, C.sub.1-6 alkylthio, C.sub.1-6
alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino, arylcarbonyl, or two
adjacent positions on the phenyl ring may be cyclised to form a 5,
6 or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), heteroaryl (which may be optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.1-6
alkylsulfonyl, C.sub.1-6 alkylsulfinyl, C.sub.1-6 alkylthio,
C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonylamino,
arylcarbonyl, or two adjacent positions on the heteroaryl system
may be cyclised to form a 5, 6 or 7 membered carbocyclic or
heterocyclic ring, itself optionally substituted with halogen),
C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, phenoxy (wherein the phenyl
group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryloxy
(optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
heterocycyloxy (optionally substituted by halo, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
cyano, C.sub.2-6 alkenyl, C.sub.3-6 cycloalkyl, C.sub.5-7
cycloalkenyl, heterocyclyl (optionally substituted by halo, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), C.sub.1-6 alkylthio, C.sub.1-6 haloalkylthio,
NR.sup.13R.sup.14 where R.sup.13 and R.sup.14 are independently
hydrogen, COR.sup.40, C.sub.2-6 alkyl, C.sub.2-6 haloalkyl, phenyl
(which may be optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino, dialkylamino, C.sub.1-4
alkoxycarbonyl) or heteroaryl (which may be optionally substituted
by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy, C.sub.1-4 alkoxycarbonyl);
C.sub.1-6 alkylcarbonylamino, phenyloxycarbonylamino (wherein the
phenyl group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), amino,
C.sub.1-6 alkylamino, phenylamino (wherein the phenyl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino).
[0048] Even more preferably R.sup.1 is C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy(C.sub.1-6)alkyl,
heteroaryl(C.sub.1-3)alkyl (wherein the heteroaryl group may be
optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkoxycarbonyl, or two adjacent
positions on the heteroaryl system may be cyclised to form a 5, 6
or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), phenyl(C.sub.1-3)alkyl (wherein the
phenyl group may be optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino, dialkylamino, C.sub.1-6
alkylsulfonyl, C.sub.1-6 alkoxycarbonyl, or two adjacent positions
on the phenyl ring may be cyclised to form a 5, 6 or 7 membered
carbocyclic or heterocyclic ring, itself optionally substituted
with halogen), phenyl (which may be optionally substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino,
dialkylamino, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkoxycarbonyl, or
two adjacent positions on the phenyl ring may be cyclised to form a
5, 6 or 7 membered carbocyclic or heterocyclic ring, itself
optionally substituted with halogen), heteroaryl (which may be
optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkoxycarbonyl, or two adjacent
positions on the heteroaryl system may be cyclised to form a 5, 6
or 7 membered carbocyclic or heterocyclic ring, itself optionally
substituted with halogen), C.sub.1-6 alkoxy, C.sub.1-6 haloalkoxy,
C.sub.2-6 alkenyl, heterocyclyl (optionally substituted by halo,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), C.sub.1-6 alkylthio, C.sub.1-6 haloalkylthio
or NR.sup.13R.sup.14 where R.sup.13 and R.sup.14 independently
hydrogen, C.sub.2-6 alkyl or C.sub.2-6 haloalkyl, C.sub.2-6
alkylcarbonyl or phenylcarbonyl, (where the phenyl is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino).
[0049] Yet more preferably R.sup.1 is C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, heteroaryl(C.sub.1-3)alkyl (wherein the heteroaryl group
maybe optionally substituted by halo, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl) where the heteroaryl group is a pyridine,
pyrimidine, pyrazine or pyridazine ring, heteroaryl (optionally
substituted by halo, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl)
where the heteroaryl group is a pyridine, pyrimidine, pyrazine or
pyridazine ring, C.sub.1-6 alkoxy or heterocyclyl (optionally
substituted by halo, cyano, C.sub.1-3 alkyl, C.sub.1-3 haloalkyl,
or C.sub.1-3 alkoxy).
[0050] Most preferably R.sup.1 is pyridyl (optionally substituted
by halo, C.sub.1-3 alkyl or C.sub.1-3 haloalkyl) or C.sub.1-6
alkoxy, especially halo-substituted pyridyl.
[0051] It is preferred that R.sup.2 and R.sup.3 are independently
hydrogen or C.sub.1-4 alkyl.
[0052] More preferably R.sup.2 and R.sup.3 are independently
hydrogen or methyl.
[0053] Even more preferably R.sup.2 is hydrogen and R.sup.3 is
hydrogen or methyl;
[0054] Most preferably R.sup.2 and R.sup.3 are both hydrogen.
[0055] Preferably each R.sup.4 is independently halogen, cyano,
C.sub.1-8 alkyl, C.sub.1-8 haloalkyl, C.sub.1-6 cyanoalkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.3-7
cycloalkyl(C.sub.1-6)alkyl, C.sub.5-6 cycloalkenyl(C.sub.1-6)alkyl,
C.sub.3-6 alkenyloxy(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxy(C.sub.1-6)alkyl, aryloxy(C.sub.1-6)alkyl, C.sub.1-6
carboxyalkyl, C.sub.1-6 alkylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkenylcarbonyl(C.sub.1-6)alkyl, C.sub.2-6
alkynylcarbonyl(C.sub.1-6)-alkyl, C.sub.1-6
alkoxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkenyloxycarbonyl(C.sub.1-6)alkyl, C.sub.3-6
alkynyloxycarbonyl(C.sub.1-6)alkyl,
aryloxycarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylthio(C.sub.1-6)alkyl, C.sub.1-6 alkylsulfinyl(C.sub.1-6)alkyl,
C.sub.1-6 alkylsulfonyl(C.sub.1-6)alkyl,
aminocarbonyl(C.sub.1-6)alkyl, C.sub.1-6
alkylaminocarbonyl(C.sub.1-6)alkyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.1-6)alkyl,
phenyl(C.sub.1-4)alkyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl(C.sub.1-4)alkyl
(wherein the heteroaryl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), heterocyclyl(C.sub.1-4)alkyl
(wherein the heterocyclyl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), C.sub.2-6 alkenyl,
aminocarbonyl(C.sub.2-6)alkenyl, C.sub.1-6
alkylaminocarbonyl(C.sub.2-6)alkenyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkenyl,
phenyl(C.sub.2-4)-alkenyl, (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkynyl,
trimethylsilyl(C.sub.2-6)alkynyl, aminocarbonyl(C.sub.2-6)alkynyl,
C.sub.1-6 alkylaminocarbonyl(C.sub.2-6)alkynyl,
di(C.sub.1-6)alkylaminocarbonyl(C.sub.2-6)alkynyl, C.sub.1-6
alkoxycarbonyl, C.sub.3-7 cycloalkyl, C.sub.3-7 halocycloalkyl,
C.sub.3-7 cyanocycloalkyl, C.sub.1-3 alkyl(C.sub.3-7)-cycloalkyl,
C.sub.1-3 alkyl(C.sub.3-7)halocycloalkyl,phenyl (optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl (optionally
substituted by halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy), heterocyclyl
(wherein the heterocyclyl group is optionally substituted by halo,
nitro, cyano, C.sub.1-6 allyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), or 2 adjacent groups R.sup.4
together with the carbon atoms to which they are attached form a 4,
5, 6,or 7 membered carbocylic or heterocyclic ring which may be
optionally substituted by halogen, C.sub.1-8 alkoxy, C.sub.1-6
haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano,
C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6
haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro,
cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or
C.sub.1-6 haloalkoxy), C.sub.1-8 alkylthio or R.sup.19R.sup.20N
where R.sup.19 and R.sup.20 are, independently, hydrogen, C.sub.1-8
alkyl, C.sub.3-7 cycloalkyl, C.sub.3-6 alkenyl, C.sub.3-6 alkynyl,
C.sub.2-6 haloalkyl, C.sub.1-6 alkoxycarbonyl or R.sup.19 and
R.sup.20 together with the N atom to which they are attached form a
five, six or seven-membered heterocyclic ring which may contain one
or two further heteroatoms selected from O, N or S and which may be
optionally substituted by one or two C.sub.1-6 alkyl groups; n is
0, 1, 2, 3 or 4.
[0056] More preferably each R.sup.4 is independently halogen,
cyano, C.sub.1-8 alkyl, C.sub.1-8 haloalkyl, C.sub.1-8 cyanoalkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.2-6 alkynyl,
trimethylsilyl(C.sub.2-6)alkynyl, C.sub.1-6 alkoxycarbonyl,
C.sub.3-7 cycloalkyl, C.sub.1-3 alkyl (C.sub.3-7) cycloalkyl,
phenyl (optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heterocyclyl
(optionally substituted by halo, nitro, cyano, C.sub.1-6 alkyl,
C.sub.1-6 haloalkyl, C.sub.1-6 alkoxy or C.sub.1-6 haloalkoxy),
C.sub.1-8 alkoxy, C.sub.1-6 haloalkoxy, phenoxy (optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryloxy (optionally
substituted by halo, nitro, cyano, C.sub.1-3 alkyl, C.sub.1-3
haloalkyl, C.sub.1-3 alkoxy or C.sub.1-3 haloalkoxy),
di(C.sub.1-8)alkylamino, or 2 adjacent groups R.sup.4 together with
the carbon atoms to which they are attached form a 4, 5, 6,or 7
membered carbocylic or heterocyclic ring which may be optionally
substituted by halogen; n is 0, 1, 2, 3 or 4.
[0057] Even more preferably each R.sup.4 is independently halogen,
cyano, C.sub.1-8 alkyl, C.sub.1-8 haloalkyl, C.sub.1-8 cyanoalkyl,
C.sub.1-6 alkoxy(C.sub.1-6)alkyl, C.sub.2-6 alkynyl, heterocyclyl
(optionally substituted by C.sub.1-6 alkyl), C.sub.1-8 alkoxy,
C.sub.1-6 haloalkoxy, phenoxy (optionally substituted by halo,
cyano, C.sub.1-3 alkyl or C.sub.1-3 haloalkyl), heteroaryloxy
(optionally substituted by halo, cyano, C.sub.1-3 alkyl or
C.sub.1-3 haloalkyl), di(C.sub.1-8)alkylamino or 2 adjacent groups
R.sup.4 together with the carbon atoms to which they are attached
form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which
may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4;
[0058] Yet more preferably each R.sup.4 is independently fluoro,
chloro, bromo, cyano, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl,
C.sub.1-4 cyanoalkyl or C.sub.1-3 alkoxy(C.sub.1-3)alkyl; n is 0, 1
or 2;
[0059] Most preferably each R.sup.4 is independently fluoro,
chloro, bromo, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl; n is 1 or
2.
[0060] Preferably R.sup.8 is C.sub.1-10 alkyl, C.sub.1-10
haloalkyl, aryl(C.sub.1-6)alkyl (wherein the aryl group is
optionally substituted by halogen, C.sub.1-4alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), arylcarbonyl-(C.sub.1-6)alkyl
(wherein the aryl group may be optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino
and the alkyl group may be optionally substituted by aryl),
C.sub.2-8 alkenyl, C.sub.2-8 haloalkenyl, aryl(C.sub.2-6)-alkenyl
(wherein the aryl group is optionally substituted halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino,
C.sub.1-6 alkoxycarbonyl, or two adjacent substituents can cyclise
to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring),
C.sub.2-6 alkynyl, phenyl(C.sub.2-6)alkynyl (wherein the phenyl
group is optionally substituted by halogen, C.sub.1-4 alkyl,
C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN,
NO.sub.2, aryl, heteroaryl, amino or dialkylamino), C.sub.3-7
cycloalkyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylcarbonyl,
C.sub.1-6 haloalkylcarbonyl or aryl(C.sub.2-6)alkenylcarbonyl
(wherein the aryl group may be optionally substituted halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
or --C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55
where z is 1 or 2, R.sup.51 and R.sup.52 are each independently H,
halo or C.sub.1-2 alkyl, R.sup.53 R.sup.54 are each independently
H, halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl and R.sup.55 is
optionally substituted aryl or optionally substituted
heteroaryl.
[0061] R.sup.8 is more preferably C.sub.1-6 alkyl, C.sub.1-6
haloalkyl, aryl(C.sub.1-4)alkyl (wherein the aryl group is
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), C.sub.2-6 alkenyl,
aryl(C.sub.2-6)alkenyl (wherein the aryl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), C.sub.2-6 alkyl,
phenyl(C.sub.2-6)alkynyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino); or
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55 where
z is 1 or 2, R.sup.51 and R.sup.52 are each independently H, halo
or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each independently H,
halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl and R.sup.55 is
optionally substituted aryl or optionally substituted heteraryl
[0062] Even more preferably R.sup.8 is phenyl(C.sub.1-4)alkyl
(wherein the phenyl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino),
heteroaryl(C.sub.1-6)alkyl (wherein the heteroaryl group is
optionally substituted halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), phenyl(C.sub.2-6)alkenyl
(wherein the phenyl group is optionally substituted by halogen,
C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4
haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino)
or phenyl(C.sub.2-6)alkynyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino, or
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55 where
z is 1 or 2, R.sup.51 and R.sup.52 are each independently H, halo
or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each independently H,
halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl and R.sup.55 is
optionally substituted aryl or optionally substituted heteraryl
[0063] Even more preferably R.sup.8 is phenylCH.sub.2-- (wherein
the phenyl group is optionally substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino), heteroaryl
CH.sub.2-- (wherein the heteroaryl group is a bicyclic group
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino), or
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.]z-R.sup.55 where z is 1 or
2, R.sup.51 and R.sup.52 are each independently H, halo or
C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each independently H,
halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl and R.sup.55 is
optionally substituted aryl or optionally substituted heteroaryl
Yet more preferably R.sup.8 is phenyl(C.sub.2-4)alkenyl (wherein
the phenyl group is optionally substituted by halo, nitro, cyano,
C.sub.1-3 alkyl, C.sub.1-3 haloalkyl, C.sub.1-3 alkoxy, C.sub.1-3
alkoxycarbonyl or C.sub.1-3 haloalkoxy) or phenyl(C.sub.2-4)alkynyl
(wherein the phenyl group is optionally substituted by halo, nitro,
cyano, C.sub.1-3 alkyl, C.sub.1-3 haloalkyl, C.sub.1-3 alkoxy,
C.sub.1-3 alkoxycarbonyl or C.sub.1-3 haloalkoxy).; or R.sup.8 is
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55 where
z is 1 or 2, R.sup.51 and R.sup.52 are each independently H, halo
or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each independently H,
halogen, C.sub.1-4 alkyl or C.sub.1-4haloalkyl and R.sup.55 is
phenyl substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino or heteroaryl substituted by
halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl,
C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl, heteroaryl, amino or
dialkylamino.
[0064] Most preferably R.sup.8 is
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55 where
z is 1 or 2, preferably 1, R.sup.51 and R.sup.52 are each
independently H, halo or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are
each independently H, halogen, C.sub.1-4 alkyl or C.sub.1-4
haloalkyl and R.sup.55 is phenyl substituted by halogen, C.sub.1-4
alkyl, C.sub.1-4 alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy,
CN, NO.sub.2, aryl, heteroaryl, amino or dialkylamino or heteroaryl
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino
[0065] It is preferred that R.sup.9 and R.sup.10 are both
hydrogen.
[0066] R.sup.51 and R.sup.52 are preferably hydrogen.
[0067] R.sup.53 and R.sup.54 are preferably hydrogen or halogen,
especially hydrogen.
[0068] R.sup.55 is preferably phenyl substituted with one to three
substituents selected from halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino
[0069] Certain compounds of formula (I) are novel and as such form
a further aspect of the invention. For example there are provided
novel compounds of formula (IK) as defined above and salts or
N-oxides thereof provided that R.sup.8 is not methyl and YR.sup.1
is not SO.sub.2CH.sub.3, methyl, ethyl, phenyl or
fluoro-substituted phenyl.
[0070] Further novel compounds are those of formula IN which are
compounds of formual I wherein Y is a single bond or C.dbd.O;
R.sup.1 is C.sub.1-6 alkyl, C.sub.1-6 haloalkyl,
heteroaryl(C.sub.1-3)alkyl (wherein the heteroaryl group may be
optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino and the heteroaryl group is
a pyridine, pyrimidine, pyrazine or pyridazine ring), heteroaryl
(optionally substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4
alkoxy, C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2,
aryl, heteroaryl, amino or dialkylamino and where the heteroaryl
group is a pyridine, pyrimidine, pyrazine or pyridazine ring),
C.sub.1-6 alkoxy or heterocyclyl (optionally substituted by halo,
cyano, C.sub.1-3 alkyl, C.sub.1-3 haloalkyl, or C.sub.1-3 alkoxy);
R.sup.4 is independently fluoro, chloro, bromo, cyano, C.sub.1-4
alkyl, C.sub.1-4 haloalkyl, C.sub.1-4 cyanoalkyl or C.sub.1-3
alkoxy(C.sub.1-3)alkyl; n is 0, 1 or 2; R.sup.8 is
phenyl(C.sub.2-4)alkenyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino, dialkylamino or C.sub.1-3 alkoxycarbonyl) or
phenyl(C.sub.2-4)alkynyl (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino, dialkylamino or C.sub.1-3 alkoxycarbonyl) and
R.sup.2 R.sup.3 R.sup.9 and R.sup.10 are all hydrogen.
[0071] Further novel compounds are those of formula IP which are
compounds of formual I wherein Y is C(O); R.sup.1 is pyridyl
(optionally substituted by halo, C.sub.1-3 alkyl or C.sub.1-3
haloalkyl) or C.sub.1-6 alkoxy, R.sup.2, R.sup.3, R.sup.9 and
R.sup.10 are all hydrogen; R.sup.4 is fluoro, chloro, bromo,
C.sub.1-4 alkyl or C.sub.1-4 haloalkyl; n is 1 or 2 and R.sup.8 is
phenylCH.sub.2-- (wherein the phenyl group is optionally
substituted by halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy,
C.sub.1-4 haloalkyl, C.sub.1-4 haloalkoxy, CN, NO.sub.2, aryl,
heteroaryl, amino or dialkylamino), heteroaryl CH.sub.2-- (wherein
the heteroaryl group is a bicyclic group optionally substituted by
halo, nitro, cyano, C.sub.1-6 alkyl, C.sub.1-6 haloalkyl, C.sub.1-6
alkoxy or C.sub.1-6 haloalkoxy), or
--C(R.sup.51)(R.sup.52)--[CR.sup.53.dbd.CR.sup.54]z-R.sup.55 where
z is 1 or 2, R.sup.51 and R.sup.52 are each independently H, halo
or C.sub.1-2 alkyl, R.sup.53 and R.sup.54 are each independently H,
halogen, C.sub.1-4 alkyl or C.sub.1-4 haloalkyl and R.sup.55 is
optionally substituted aryl or optionally substituted heteroaryl
provided that a) when R.sup.4n is 5-fluoro and R.sup.1 is
2,6-dichloropyrid-4-yl then R.sup.8 is not 4-methylbenzyl,
3-methylbenzyl, 4-trifluormethoxybenzyl, 4-trifluormethybenzyl,
4-cyanobenzyl, 4-methylcarbonylbenzyl or cinnamyl and b) when
R.sup.4n is 5-fluoro and R.sup.1 is 2-chloropyrid-4-yl then R.sup.8
is not 3-chlorobenzyl, 3,5-difluorobenzyl, 4-trifluormethoxybenzyl,
4-trifluormethybenzyl, 4-cyanobenzyl or 4-methylcarbonylbenzyl.
[0072] The compounds in Tables I to XXXII below illustrate the
compounds of the invention.
[0073] Table I provides 301 compounds of formula Ia ##STR3##
[0074] wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c
and R.sup.4d are given in Table 1 TABLE-US-00001 TABLE 1 Com- pound
R.sup.8 R.sup.4a R.sup.4b R.sup.4c R.sup.4d I-1 Cinnamyl H H H H
I-2 4-chlorocinnamyl H H H H I-3 4-fluorocinnamyl H H H H I-4
4-nitrocinnamyl H H H H I-5 4-methoxycinnamyl H H H H I-6
4-methylcinnamyl H H H H I-7 4-trifluoromethylcinnamyl H H H H I-8
4-cyanocinnamyl H H H H I-9 2,4-dichlorocinnamyl H H H H I-10
2,4-difluorocinnamyl H H H H I-11 cinnamyl Cl H H H I-12
4-chlorocinnamyl Cl H H H I-13 4-fluorocinnamyl Cl H H H I-14
4-nitrocinnamyl Cl H H H I-15 4-methoxycinnamyl Cl H H H I-16
4-methylcinnamyl Cl H H H I-17 4-trifluoromethylcinnamyl Cl H H H
I-18 4-cyanocinnamyl Cl H H H I-19 2,4-dichlorocinnamyl Cl H H H
I-20 2,4-difluorocinnamyl Cl H H H I-21 cinnamyl H Cl H H I-22
4-chlorocinnamyl H Cl H H I-23 4-fluorocinnamyl H Cl H H I-24
4-nitrocinnamyl H Cl H H I-25 4-methoxycinnamyl H Cl H H I-26
4-methylcinnamyl H Cl H H I-27 4-tifluoromethylcinnamyl H Cl H H
I-28 4-cyanocinnamyl H Cl H H I-29 2,4-dichlorocinnamyl H Cl H H
I-30 2,4-difluorocinnamyl H Cl H H I-31 cinnamyl H H Cl H I-32
4-chlorocinnamyl H H Cl H I-33 4-fluorocinnamyl H H Cl H I-34
4-nitrocinnamyl H H Cl H I-35 4-methoxycinnamyl H H Cl H I-36
4-methylcinnamyl H H Cl H I-37 4-trifluoromethylcinnamyl H H Cl H
I-38 4-cyanocinnamyl H H Cl H I-39 2,4-dichlorocinnamyl H H Cl H
I-40 2,4-difluorocinnamyl H H Cl H I-41 cinnamyl H H H Cl I-42
4-chlorocinnamyl H H H Cl I-43 4-fluorocinnamyl H H H Cl I-44
4-nitrocinnamyl H H H Cl I-45 4-methoxycinnamyl H H H Cl I-46
4-methylcinnamyl H H H Cl I-47 4-trifluoromethylcinnamyl H H H Cl
I-48 4-cyanocinnamyl H H H Cl I-49 2,4-dichlorocinnamyl H H H Cl
I-50 2,4-difluorocinnamyl H H H Cl I-51 cinnamyl F H H H I-52
4-chlorocinnamyl F H H H I-53 4-fluorocinnamyl F H H H I-54
4-nitrocinnamyl F H H H I-55 4-methoxycinnamyl F H H H I-56
4-methylcinnamyl F H H H I-57 4-trifluoromethylcinnamyl F H H H
I-58 4-cyanocinnamyl F H H H I-59 2,4-dichlorocinnamyl F H H H I-60
2,4-difluorocinnamyl F H H H I-61 cinnamyl H F H H I-62
4-chlorocinnamyl H F H H I-63 4-fluorocinnamyl H F H H I-64
4-nitrocinnamyl H F H H I-65 4-methoxycinnamyl H F H H I-66
4-methylcinnamyl H F H H I-67 4-trifluoromethylcinnamyl H F H H
I-68 4-cyanocinnamyl H F H H I-69 2,4-dichlorocinnamyl H F H H I-70
2,4-difluorocinnamyl H F H H I-71 cinnamyl H H F H I-72
4-chlorocinnamyl H H F H I-73 4-fluorocinnamyl H H F H I-74
4-nitrocinnamyl H H F H I-75 4-methoxycinnamyl H H F H I-76
4-methylcinnamyl H H F H I-77 4-trifluoromethylcinnamyl H H F H
I-78 4-cyanocinnamyl H H F H I-79 2,4-dichlorocinnamyl H H F H I-80
2,4-difluorocinnamyl H H F H I-81 cinnamyl H H H F I-82
4-chlorocinnamyl H H H F I-83 4-fluorocinnamyl H H H F I-84
4-nitrocinnamyl H H H F I-85 4-methoxycinnamyl H H H F I-86
4-methylcinnamyl H H H F I-87 4-trifluoromethylcinnamyl H H H F
I-88 4-cyanocinnamyl H H H F I-89 2,4-dichlorocinnamyl H H H F I-90
2,4-difluorocinnamyl H H H F I-91 cinnamyl Br H H H I-92
4-chlorocinnamyl Br H H H I-93 4-fluorocinnamyl Br H H H I-94
4-nitrocinnamyl Br H H H I-95 4-methoxycinnamyl Br H H H I-96
4-methylcinnamyl Br H H H I-97 4-trifluoromethylcinnamyl Br H H H
I-98 4-cyanocinnamyl Br H H H I-99 2,4-dichlorocinnamyl Br H H H
I-100 2,4-difluorocinnamyl Br H H H I-101 cinnamyl H Br H H I-102
4-chlorocinnamyl H Br H H I-103 4-fluorocinnamyl H Br H H I-104
4-nitrocinnamyl H Br H H I-105 4-methoxycinnamyl H Br H H I-106
4-methylcinnamyl H Br H H I-107 4-trifluoromethylcinnamyl H Br H H
I-108 4-cyanocinnamyl H Br H H I-109 2,4-dichlorocinnamyl H Br H H
I-110 2,4-difluorocinnamyl H Br H H I-111 cinnamyl H H Br H I-112
4-chlorocinnamyl H H Br H I-113 4-fluorocinnamyl H H Br H I-114
4-nitrocinnamyl H H Br H I-115 4-methoxycinnamyl H H Br H I-116
4-methylcinnamyl H H Br H I-117 4-trifluoromethylcinnamyl H H Br H
I-118 4-cyanocinnamyl H H Br H I-119 2,4-dichlorocinnamyl H H Br H
I-120 2,4-difluorocinnamyl H H Br H I-121 cinnamyl H H H Br I-122
4-chlorocinnamyl H H H Br I-123 4-fluorocinnamyl H H H Br I-124
4-nitrocinnamyl H H H Br I-125 4-methoxycinnamyl H H H Br I-126
4-methylcinnamyl H H H Br I-127 4-trifluoromethylcinnamyl H H H Br
I-128 4-cyanocinnamyl H H H Br I-129 2,4-dichlorocinnamyl H H H Br
I-130 2,4-difluorocinnamyl H H H Br I-131 cinnamyl H Cl H Cl I-132
4-chlorocinnamyl H Cl H Cl I-133 4-fluorocinnamyl H Cl H Cl I-134
4-nitrocinnamyl H Cl H Cl I-135 4-methoxycinnamyl H Cl H Cl I-136
4-methylcinnamyl H Cl H Cl I-137 4-trifluoromethylcinnamyl H Cl H
Cl I-138 4-cyanocinnamyl H Cl H Cl I-139 2,4-dichlorocinnamyl H Cl
H Cl I-140 2,4-difluorocinnamyl H Cl H Cl I-141 cinnamyl H F H F
I-142 4-chlorocinnamyl H F H F I-143 4-fluorocinnamyl H F H F I-144
4-nitrocinnamyl H F H F I-145 4-methoxycinnamyl H F H F I-146
4-methylcinnamyl H F H F I-147 4-trifluoromethylcinnamyl H F H F
I-148 4-cyanocinnamyl H F H F I-149 2,4-dichlorocinnamyl H F H F
I-150 2,4-difluorocinnamyl H F H F I-151 cinnamyl Cl F H H I-152
4-chlorocinnamyl Cl F H H I-153 4-fluorocinnamyl Cl F H H I-154
4-nitrocinnamyl Cl F H H I-155 4-methoxycinnamyl Cl F H H I-156
4-methylcinnamyl Cl F H H I-157 4-trifluoromethylcinnamyl Cl F H H
I-158 4-cyanocinnamyl Cl F H H I-159 2,4-dichlorocinnamyl Cl F H H
I-160 2,4-difluorocinnamyl Cl F H H I-161 cinnamyl H F Cl H I-162
4-chlorocinnamyl H F Cl H I-163 4-fluorocinnamyl H F Cl H I-164
4-nitrocinnamyl H F Cl H I-165 4-methoxycinnamyl H F Cl H I-166
4-methylcinnamyl H F Cl H I-167 4-trifluoromethylcinnamyl H F Cl H
I-168 4-cyanocinnamyl H F Cl H I-169 2,4-dichlorocinnamyl H F Cl H
I-170 2,4-difluorocinnamyl H F Cl H I-171 cinnamyl H Cl Cl H I-172
4-chlorocinnamyl H Cl Cl H I-173 4-fluorocinnamyl H Cl Cl H I-174
4-nitrocinnamyl H Cl Cl H I-175 4-methoxycinnamyl H Cl Cl H I-176
4-methylcinnamyl H Cl Cl H I-177 4-trifluoromethylcinnamyl H Cl Cl
H I-178 4-cyanocinnamyl H Cl Cl H I-179 2,4-dichlorocinnamyl H Cl
Cl H I-180 2,4-difluorocinnamyl H Cl Cl H I-181 cinnamyl H I H H
I-182 4-chlorocinnamyl H I H H I-183 4-fluorocinnamyl H I H H I-184
4-nitrocinnamyl H I H H I-185 4-methoxycinnamyl H I H H I-186
4-methylcinnamyl H I H H I-187 4-trifluoromethylcinnamyl H I H H
I-188 4-cyanocinnamyl H I H H I-189 2,4-dichlorocinnamyl H I H H
I-190 2,4-difluorocinnamyl H I H H I-191 cinnamyl H OMe H H I-192
4-chlorocinnamyl H OMe H H I-193 4-fluorocinnamyl H OMe H H I-194
4-nitrocinnamyl H OMe H H I-195 4-methoxycinnamyl H OMe H H I-196
4-methylcinnamyl H OMe H H I-197 4-trifluoromethylcinnamyl H OMe H
H I-198 4-cyanocinnamyl H OMe H H I-199 2,4-dichlorocinnamyl H OMe
H H I-200 2,4-difluorocinnamyl H OMe H H I-201 cinnamyl H Me H H
I-202 4-chlorocinnamyl H Me H H I-203 4-fluorocinnamyl H Me H H
I-204 4-nitrocinnamyl H Me H H I-205 4-methoxycinnamyl H Me H H
I-206 4-methylcinnamyl H Me H H I-207 4-trifluoromethylcinnamyl H
Me H H I-208 4-cyanocinnamyl H Me H H I-209 2,4-dichlorocinnamyl H
Me H H I-210 2,4-difluorocinnamyl H Me H H I-211 cinnamyl H CN H H
I-212 4-chlorocinnamyl H CN H H I-213 4-fluorocinnamyl H CN H H
I-214 4-nitrocinnamyl H CN H H I-215 4-methoxycinnamyl H CN H H
I-216 4-methylcinnamyl H CN H H I-217 4-trifluoromethylcinnamyl H
CN H H I-218 4-cyanocinnamyl H CN H H I-219 2,4-dichlorocinnamyl H
CN H H I-220 2,4-difluorocinnamyl H CN H H I-221 cinnamyl H CCH H H
I-222 4-chlorocinnamyl H CCH H H I-223 4-fluorocinnamyl H CCH H H
I-224 4-nitrocinnamyl H CCH H H I-225 4-methoxycinnamyl H CCH H H
I-226 4-methylcinnamyl H CCH H H I-227 4-trifluoromethylcinnamyl H
CCH H H I-228 4-cyanocinnamyl H CCH H H I-229 2,4-dichlorocinnamyl
H CCH H H I-230 2,4-difluorocinnamyl H CCH H H I-231 cinnamyl H
COOMe H H I-232 4-chlorocinnamyl H COOMe H H I-233 4-fluorocinnamyl
H COOMe H H I-234 4-nitrocinnamyl H COOMe H H I-235
4-methoxycinnamyl H COOMe H H I-236 4-methylcinnamyl H COOMe H H
I-237 4-trifluoromethylcinnamyl H COOMe H H I-238 4-cyanocinnamyl H
COOMe H H I-239 2,4-dichlorocinnamyl H COOMe H H I-240
2,4-difluorocinnamyl H COOMe H H I-241 cinnamyl H Me Cl H I-242
4-chlorocinnamyl H Me Cl H I-243 4-fluorocinnamyl H Me Cl H
I-244 4-nitrocinnamyl H Me Cl H I-245 4-methoxycinnamyl H Me Cl H
I-246 4-methylcinnamyl H Me Cl H I-247 4-trifluoromethylcinnamyl H
Me Cl H I-248 4-cyanocinnamyl H Me Cl H I-249 2,4-dichlorocinnamyl
H Me Cl H I250 2,4difluorocinnamyl H Me Cl H I-251 cinnamyl Cl Me H
H I-252 4-chlorocinnamyl Cl Me H H I-253 4-fluorocinnamyl Cl Me H H
I-254 4-nitrocinnamyl Cl Me H H I-255 4-methoxycinnamyl Cl Me H H
I-256 4-methylcinnamyl Cl Me H H I-257 4-trifluoromethylcinnamyl Cl
Me H H I-258 4-cyanocinnamyl Cl Me H H I-259 2,4-dichlorocinnamyl
Cl Me H H I-260 2,4-difluorocinnamyl Cl Me H H I-261 cinnamyl H Cl
H Me I-262 4-chlorocinnamyl H Cl H Me I-263 4-fluorocinnamyl H Cl H
Me I-264 4-nitrocinnamyl H Cl H Me I-265 4-methoxycinnamyl H Cl H
Me I-266 4-methylcinnamyl H Cl H Me I-267 4-trifluoromethylcinnamyl
H Cl H Me I-268 4-cyanocinnamyl H Cl H Me I-269
2,4-dichlorocinnamyl H Cl H Me I-270 2,4-difluorocinnamyl H Cl H Me
I-271 cinnamyl H H 4-Cl-PhO H I-272 4-chlorocinnamyl H H 4-Cl-PhO H
I-273 4-fluorocinnamyl H H 4-Cl-PhO H I-274 4-nitrocinnamyl H H
4-Cl-PhO H I-275 4-methoxycinnamyl H H 4-Cl-PhO H I-276
4-methylcinnamyl H H 4-Cl-PhO H I-277 4-trifluoromethylcinnamyl H H
4-Cl-PhO H I-278 4-cyanocinnamyl H H 4-Cl-PhO H I-279
2,4-dichlorocinnamyl H H 4-Cl-PhO H I-280 2,4-difluorocinnamyl H H
4-Cl-PhO H I-281 cinnamyl H 4-F-Ph H H I-282 4-chlorocinnamyl H
4-F-Ph H H I-283 4-fluorocinnamyl H 4-F-Ph H H I-284
4-nitrocinnamyl H 4-F-Ph H H I-285 4-methoxycinnamyl H 4-F-Ph H H
I-286 4-methylcinnamyl H 4-F-Ph H H I-287 4-trifluoromethylcinnamyl
H 4-F-Ph H H I-288 4-cyanocinnamyl H 4-F-Ph H H I-289
2,4-dichlorocinnamyl H 4-F-Ph H H I-290 2,4-difluorocinnamyl H
4-F-Ph H H I-291 cinnamyl H CF.sub.3O H H I-292 4-chlorocinnamyl H
CF.sub.3O H H I-293 4-fluorocinnamyl H CF.sub.3O H H I-294
4-nitrocinnamyl H CF.sub.3O H H I-295 4-methoxycinnamyl H CF.sub.3O
H H I-296 4-methylcinnamyl H CF.sub.3O H H I-297
4-trifluoromethylcinnamyl H CF.sub.3O H H I-298 4-cyanocinnamyl H
CF.sub.3O H H I-299 2,4-dichlorocinnamyl H CF.sub.3O H H I-300
2,4-difluorocinnamyl H CF.sub.3O H H I-301 C(O)CH.dbd.CH-4- H
4-CF.sub.3-Ph H H chlorophenyl
[0075] Table II provides 301 compounds of formula Ib ##STR4##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0076] Table III provides 301 compounds of formula Ic ##STR5##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0077] Table IV provides 301 compounds of formula Id ##STR6##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0078] Table V provides 301 compounds of formula Ie ##STR7##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0079] Table VI provides 301 compounds of formula If ##STR8##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0080] Table VII provides 301 compounds of formula Ig ##STR9##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0081] Table VIII provides 301 compounds of formula Ih ##STR10##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0082] Table IX provides 301 compounds of formula Ii ##STR11##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0083] Table X provides 301 compounds of formula Ij ##STR12##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0084] Table XI provides 301 compounds of formula Ik ##STR13##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0085] Table XII provides 301 compounds of formula Il ##STR14##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0086] Table XIII provides 301 compounds of formula Im ##STR15##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0087] Table XIV provides 301 compounds of formula In ##STR16##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0088] Table XV provides 301 compounds of formula Io ##STR17##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are give in Table 1
[0089] Table XVI provides 301 compounds of formula Ip ##STR18##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0090] Table XVII provides 301 compounds of formula Iq ##STR19##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0091] Table XVIII provides 301 compounds of formula Ir ##STR20##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R4 and R.sup.4d
are given in Table 1
[0092] Table XIX provides 301 compounds of formula Is ##STR21##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0093] Table XX provides 301 compounds of formula It ##STR22##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0094] Table XXI provides 301 compounds of formula Iu ##STR23##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0095] Table XXII provides 301 compounds of formula Iv ##STR24##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0096] Table XXIII provides 301 compounds of formula Iw ##STR25##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0097] Table XXIV provides 301 compounds of formula Ix ##STR26##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0098] Table XXV provides 301 compounds of formula Iy ##STR27##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0099] Table XXVI provides 301 compounds of formula Iz ##STR28##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0100] Table XXVII provides 301 compounds of formula Iaa ##STR29##
wherein the values of R.sup.8, R.sup.4a, R.sup.4b, R.sup.4c and
R.sup.4d are given in Table 1
[0101] Table XXVIIl provides 270 compounds of formula Iab
##STR30##
[0102] wherein the values of R.sup.8, R.sup.4a, R.sup.4b,
R.sup.4c,R.sup.4d and (R.sup.a).sub.n are given in Table 2
TABLE-US-00002 TABLE 2 Compound R.sup.8 R.sup.4a R.sup.4b R.sup.4c
R.sup.4d (R.sup.a).sub.n XXVIII-1 cinnamyl H H H H 4-SMe XXVIII-2
4-chlorocinnamyl H H H H 4-SMe XXVIII-3 4-fluorocinnamyl H H H H
4-SMe XXVIII-4 4-trifluoromethylcinnamyl H H H H 4-SMe XXVIII-5
4-cyanocinnamyl H H H H 4-SMe XXVIII-6 cinnamyl H Cl H H 4-SMe
XXVIII-7 4-chlorocinnamyl H Cl H H 4-SMe XXVIII-8 4-fluorocinnamyl
H Cl H H 4-SMe XXVIII-9 4-trifluoromethylcinnamyl H Cl H H 4-SMe
XXVIII-10 4-cyanocinnamyl H Cl H H 4-SMe XXVIII-11 cinnamyl H F H H
4-SMe XXVIII-12 4-chlorocinnamyl H F H H 4-SMe XXVIII-13
4-fluorocinnamyl H F H H 4-SMe XXVIII-14 4-trifluoromethylcinnamyl
H F H H 4-SMe XXVIII-15 4-cyanocinnamyl H F H H 4-SMe XXVIII-16
cinnamyl H H F H 4-SMe XXVIII-17 4-chlorocinnamyl H H F H 4-SMe
XXVIII-18 4-fluorocinnamyl H H F H 4-SMe XXVIII-19
4-trifluoromethylcinnamyl H H F H 4-SMe XXVIII-20 4-cyanocinnamyl H
H F H 4-SMe XXVIII-21 cinnamyl H F H F 4-SMe XXVIII-22
4-chlorocinnamyl H F H F 4-SMe XXVIII-23 4-fluorocinnamyl H F H F
4-SMe XXVIII-24 4-trifluoromethylcinnamyl H F H F 4-SMe XXVIII-25
4-cyanocinnamyl H F H F 4-SMe XXVIII-26 cinnamyl H OMe H H 4-SMe
XXVIII-27 4-chlorocinnamyl H OMe H H 4-SMe XXVIII-28
4-fluorocinnamyl H OMe H H 4-SMe XXVIII-29
4-trifluoromethylcinnamyl H OMe H H 4-SMe XXVIII-30 4-cyanocinnamyl
H OMe H H 4-SMe XXVIII-31 cinnamyl H H H H 4-C(O)Ph XXVIII-32
4-chlorocinnamyl H H H H 4-C(O)Ph XXVIII-33 4-fluorocinnamyl H H H
H 4-C(O)Ph XXVIII-34 4-trifluoromethylcinnamyl H H H H 4-C(O)Ph
XXVIII-35 4-cyanocinnamyl H H H H 4-C(O)Ph XXVIII-36 cinnamyl H Cl
H H 4-C(O)Ph XXVIII-37 4-chlorocinnamyl H Cl H H 4-C(O)Ph XXVIII-38
4-fluorocinnamyl H Cl H H 4-C(O)Ph XXVIII-39
4-trifluoromethylcinnamyl H Cl H H 4-C(O)Ph XXVIII-40
4-cyanocinnamyl H Cl H H 4-C(O)Ph XXVIII-41 cinnamyl H F H H
4-C(O)Ph XXVIII-42 4-chlorocinnamyl H F H H 4-C(O)Ph XXVIII-43
4-fluorocinnamyl H F H H 4-C(O)Ph XXVIII-44
4-trifluoromethylcinnamyl H F H H 4-C(O)Ph XXVIII-45
4-cyanocinnamyl H F H H 4-C(O)Ph XXVIII-46 cinnamyl H H F H
4-C(O)Ph XXVIII-47 4-chlorocinnamyl H H F H 4-C(O)Ph XXVIII-48
4-fluorocinnamyl H H F H 4-C(O)Ph XXVIII-49
4-trifluoromethylcinnamyl H H F H 4-C(O)Ph XXVIII-50
4-cyanocinnamyl H H F H 4-C(O)Ph XXVIII-51 cinnamyl H F H F
4-C(O)Ph XXVIII-52 4-chlorocinnamyl H F H F 4-C(O)Ph XXVIII-53
4-fluorocinnamyl H F H F 4-C(O)Ph XXVIII-54
4-trifluoromethylcinnamyl H F H F 4-C(O)Ph XXVIII-55
4-cyanocinnamyl H F H F 4-C(O)Ph XXVIII-56 cinnamyl H OMe H H
4-C(O)Ph XXVIII-57 4-chlorocinnamyl H OMe H H 4-C(O)Ph XXVIII-58
4-fluorocinnamyl H OMe H H 4-C(O)Ph XXVIII-59
4-trifluoromethylcinnamyl H OMe H H 4-C(O)Ph XXVIII-60
4-cyanocinnamyl H OMe H H 4-C(O)Ph XXVIII-61 cinnamyl H H H H 4-F
XXVIII-62 4-chlorocinnamyl H H H H 4-F XXVIII-63 4-fluorocinnamyl H
H H H 4-F XXVIII-64 4-trifluoromethylcinnamyl H H H H 4-F XXVIII-65
4-cyanocinnamyl H H H H 4-F XXVIII-66 cinnamyl H Cl H H 4-F
XXVIII-67 4-chlorocinnamyl H Cl H H 4-F XXVIII-68 4-fluorocinnamyl
H Cl H H 4-F XXVIII-69 4-trifluoromethylcinnamyl H Cl H H 4-F
XXVIII-70 4-cyanocinnamyl H Cl H H 4-F XXVIII-71 cinnamyl H F H H
4-F XXVIII-72 4-chlorocinnamyl H F H H 4-F XXVIII-73
4-fluorocinnamyl H F H H 4-F XXVIII-74 4-trifluoromethylcinnamyl H
F H H 4-F XXVIII-75 4-cyanocinnamyl H F H H 4-F XXVIII-76 cinnamyl
H H F H 4-F XXVIII-77 4-chlorocinnamyl H H F H 4-F XXVIII-78
4-fluorocinnamyl H H F H 4-F XXVIII-79 4-trifluoromethylcinnamyl H
H F H 4-F XXVIII-80 4-cyanocinnamyl H H F H 4-F XXVIII-81 cinnamyl
H F H F 4-F XXVIII-82 4-chlorocinnamyl H F H F 4-F XXVIII-83
4-luorocinnamyl H F H F 4-F XXVIII-84 4-trifluoromethylcinnamyl H F
H F 4-F XXVIII-85 4-cyanocinnamyl H F H F 4-F XXVIII-86 cinnamyl H
OMe H H 4-F XXVIII-87 4-chlorocinnamyl H OMe H H 4-F XXVIII-88
4-fluorocinnamyl H OMe H H 4-F XXVIII-89 4-trifluoromethylcinnamyl
H OMe H H 4-F XXVIII-90 4-cyanocinnamyl H OMe H H 4-F XXVIII-91
cinnamyl H H H H 3-CN XXVIII-92 4-chlorocinnamyl H H H H 3-CN
XXVIII-93 4-fluorocinnamyl H H H H 3-CN XXVIII-94
4-trifluoromethylcinnamyl H H H H 3-CN XXVIII-95 4-cyanocinnamyl H
H H H 3-CN XXVIII-96 cinnamyl H Cl H H 3-CN XXVIII-97
4-chlorocinnamyl H Cl H H 3-CN XXVIII-98 4-fluorocinnamyl H Cl H H
3-CN XXVIII-99 4-trifluoromethylcinnamyl H Cl H H 3-CN XXVIII-100
4-cyanocinnamyl H Cl H H 3-CN XXVIII-101 cinnamyl H F H H 3-CN
XXVIII-102 4-chlorocinnamyl H F H H 3-CN XXVIII-103
4-fluorocinnamyl H F H H 3-CN XXVIII-104 4-trifluoromethylcinnamyl
H F H H 3-CN XXVIII-105 4-cyanocinnamyl H F H H 3-CN XXVIII-106
cinnamyl H H F H 3-CN XXVIII-107 4-chlorocinnamyl H H F H 3-CN
XXVIII-108 4-fluorocinnamyl H H F H 3-CN XXVIII-109
4-trifluoromethylcinnamyl H H F H 3-CN XXVIII-110 4-cyanocinnamyl H
H F H 3-CN XXVIII-111 cinnamyl H F H F 3-CN XXVIII-112
4-chlorocinnamyl H F H F 3-CN XXVIII-113 4-fluorocinnamyl H F H F
3-CN XXVIII-114 4-trifluoromethylcinnamyl H F H F 3-CN XXVIII-115
4-cyanocinnamyl H F H F 3-CN XXVIII-116 cinnamyl H OMe H H 3-CN
XXVIII-117 4-chlorocinnamyl H OMe H H 3-CN XXVIII-118
4-fluorocinnamyl H OMe H H 3-CN XXVIII-119
4-trifluoromethylcinnamyl H OMe H H 3-CN XXVIII-120 4-cyanocinnamyl
H OMe H H 3-CN XXVIII-121 cinnamyl H H H H 4-n-Pr XXVIII-122
4-chlorocinnamyl H H H H 4-n-Pr XXVIII-123 4-fluorocinnamyl H H H H
4-n-Pr XXVIII-124 4-trifluoromethylcinnamyl H H H H 4-n-Pr
XXVIII-125 4-cyanocinnamyl H H H H 4-n-Pr XXVIII-126 cinnamyl H Cl
H H 4-n-Pr XXVIII-127 4-chlorocinnamyl H Cl H H 4-n-Pr XXVIII-128
4-fluorocinnamyl H Cl H H 4-n-Pr XXVIII-129
4-trifluoromethylcinnamyl H Cl H H 4-n-Pr XXVIII-130
4-cyanocinnamyl H Cl H H 4-n-Pr XXVIII-131 cinnamyl H F H H 4-n-Pr
XXVIII-132 4-chlorocinnamyl H F H H 4-n-Pr XXVIII-133
4-fluorocinnamyl H F H H 4-n-Pr XXVIII-134
4-trifluoromethylcinnamyl H F H H 4-n-Pr XXVIII-135 4-cyanocinnamyl
H F H H 4-n-Pr XXVIII-136 cinnamyl H H F H 4-n-Pr XXVIII-137
4-chlorocinnamyl H H F H 4-n-Pr XXVIII-138 4-fluorocinnamyl H H F H
4-n-Pr XXVIII-139 4-trifluoromethylcinnamyl H H F H 4-n-Pr
XXVIII-140 4-cyanocinnamyl H H F H 4-n-Pr XXVIII-141 cinnamyl H F H
F 4-n-Pr XXVIII-142 4-chlorocinnamyl H F H F 4-n-Pr XXVIII-143
4-fluorocinnamyl H F H F 4-n-Pr XXVIII-144
4-trifluoromethylcinnamyl H F H F 4-n-Pr XXVIII-145 4-cyanocinnamyl
H F H F 4-n-Pr XXVIII-146 cinnamyl H OMe H H 4-n-Pr XXVIII-147
4-chlorocinnamyl H OMe H H 4-n-Pr XXVIII-148 4-fluorocinnamyl H OMe
H H 4-n-Pr XXVIII-149 4-trifluoromethylcinnamyl H OMe H H 4-n-Pr
XXVIII-150 4-cyanocinnamyl H OMe H H 4-n-Pr XXVIII-151 cinnamyl H H
H H 2-OMe-4-SMe XXVIII-152 4-chlorocinnamyl H H H H 2-OMe-4-SMe
XXVIII-153 4-fluorocinnamyl H H H H 2-OMe-4-SMe XXVIII-154
4-trifluoromethylcinnamyl H H H H 2-OMe-4-SMe XXVIII-155
4-cyanocinnamyl H H H H 2-OMe-4-SMe XXVIII-156 cinnamyl H Cl H H
2-OMe-4-SMe XXVIII-157 4-chlorocinnamyl H Cl H H 2-OMe-4-SMe
XXVIII-158 4-fluorocinnamyl H Cl H H 2-OMe-4-SMe XXVIII-159
4-trifluoromethylcinnamyl H Cl H H 2-OMe-4-SMe XXVIII-160
4-cyanocinnamyl H Cl H H 2-OMe-4-SMe XXVIII-161 cinnamyl H F H H
2-OMe-4-SMe XXVIII-162 4-chlorocinnamyl H F H H 2-OMe-4-SMe
XXVIII-163 4-fluorocinamyl H F H H 2-OMe-4-SMe XXVIII-164
4-trifluoromethylcinnamyl H F H H 2-OMe-4-SMe XXVIII-165
4-cyanocinnamyl H F H H 2-OMe-4-SMe XXVIII-166 cinnamyl H H F H
2-OMe-4-SMe XXVIII-167 4-chlorocinnamyl H H F H 2-OMe-4-SMe
XXVIII-168 4-fluorocinnamyl H H F H 2-OMe-4-SMe XXVIII-169
4-trifluoromethylcinnamyl H H F H 2-OMe-4-SMe XXVIII-170
4-cyanocinnamyl H H F H 2-OMe-4-SMe XXVIII-171 cinnamyl H F H F
2-OMe-4-SMe XXVIII-172 4-chlorocinnamyl H F H F 2-OMe-4-SMe
XXVIII-173 4-fluorocinnamyl H F H F 2-OMe-4-SMe XXVIII-174
4-trifluoromethylcinnamyl H F H F 2-OMe-4-SMe XXVIII-175
4-cyanocinnamyl H F H F 2-OMe-4-SMe XXVIII-176 cinnamyl H OMe H H
2-OMe-4-SMe XXVIII-177 4-chlorocinnamyl H OMe H H 2-OMe-4-SMe
XXVIII-178 4-fluorocinnamyl H OMe H H 2-OMe-4-SMe XXVIII-179
4-trifluoromethylcinnamyl H OMe H H 2-OMe-4-SMe XXVIII-180
4-cyanocinnamyl H OMe H H 2-OMe-4-SMe XXVIII-181 cinnamyl H H H H
2-Cl-4-SO.sub.2Me XXVIII-182 4-chlorocinnamyl H H H H
2-Cl-4-SO.sub.2Me XXVIII-183 4-fluorocinnamyl H H H H
2-Cl-4-SO.sub.2Me XXVIII-184 4-trifluoromethylcinnamyl H H H H
2-Cl-4-SO.sub.2Me XXVIII-185 4-cyanocinnamyl H H H H
2-Cl-4-SO.sub.2Me XXVIII-186 cinnamyl H Cl H H 2-Cl-4-SO.sub.2Me
XXVIII-187 4-chlorocinnamyl H Cl H H 2-Cl-4-SO.sub.2Me XXVIII-188
4-fluorocinnamyl H Cl H H 2-Cl-4-SO.sub.2Me XXVIII-189
4-trifluoromethylcinnamyl H Cl H H 2-Cl-4-SO.sub.2Me XXVIII-190
4-cyanocinnamyl H Cl H H 2-Cl-4-SO.sub.2Me XXVIII-191 cinnamyl H F
H H 2-Cl-4-SO.sub.2Me XXVIII-192 4-chlorocinnamyl H F H H
2-Cl-4-SO.sub.2Me XXVIII-193 4-fluorocinnamyl H F H H
2-Cl-4-SO.sub.2Me XXVIII-194 4-trifluoromethylcinnamyl H F H H
2-Cl-4-SO.sub.2Me XXVIII-195 4-cyanocinnamyl H F H H
2-Cl-4-SO.sub.2Me XXVIII-196 cinnamyl H H F H 2-Cl-4-SO.sub.2Me
XXVIII-197 4-chlorocinnamyl H H F H 2-Cl-4-SO.sub.2Me XXVIII-198
4-fluorocinnamyl H H F H 2-Cl-4-SO.sub.2Me XXVIII-199
4-trifluoromethylcinnamyl H H F H 2-Cl-4-SO.sub.2Me XXVIII-200
4-cyanocinnamyl H H F H 2-Cl-4-SO.sub.2Me XXVIII-201 cinnamyl H F H
F 2-Cl-4-SO.sub.2Me XXVIII-202 4-chlorocinnamyl H F H F
2-Cl-4-SO.sub.2Me XXVIII-203 4-fluorocinnamyl H F H F
2-Cl-4-SO.sub.2Me XXVIII-204 4-trifluoromethylcinnamyl H F H F
2-Cl-4-SO.sub.2Me XXVIII-205 4-cyanocinnamyl H F H F
2-Cl-4-SO.sub.2Me XXVIII-206 cinnamyl H OMe H H 2-Cl-4-SO.sub.2Me
XXVIII-207 4-chlorocinnamyl H OMe H H 2-Cl-4-SO.sub.2Me XXVIII-208
4-fluorocinnamyl H OMe H H 2-Cl-4-SO.sub.2Me XXVIII-209
4-trifluoromethylcinnamyl H OMe H H 2-Cl-4-SO.sub.2Me XXVIII-210
4-cyanocinnamyl H OMe H H 2-Cl-4-SO.sub.2Me XXVIII-211 cinnamyl H H
H H 4-n-PrO XXVIII-212 4-chlorocinnamyl H H H H 4-n-PrO XXVIII-213
4-fluorocinnamyl H H H H 4-n-PrO XXVIII-214
4-trifluoromethylcinnamyl H H H H 4-n-PrO XXVIII-215
4-cyanocinnamyl H H H H 4-n-PrO XXVIII-216 cinnamyl H Cl H H
4-n-PrO XXVIII-217 4-chlorocinnamyl H Cl H H 4-n-PrO XXVIII-218
4-fluorocinnamyl H Cl H H 4-n-PrO XXVIII-219
4-trifluoromethylcinnamyl H Cl H H 4-n-PrO XXVIII-220
4-cyanocinnamyl H Cl H H 4-n-PrO XXVIII-221 cinnamyl H F H H
4-n-PrO XXVIII-222 4-chlorocinnamyl H F H H 4-n-PrO XXVIII-223
4-fluorocinnamyl H F H H 4-n-PrO XXVIII-224
4-trifluoromethylcinnamyl H F H H 4-n-PrO XXVIII-225
4-cyanocinnamyl H F H H 4-n-PrO XXVIII-226 cinnamyl H H F H 4-n-PrO
XXVIII-227 4-chlorocinnamyl H H F H 4-n-PrO XXVIII-228
4-fluorocinnamyl H H F H 4-n-PrO XXVIII-229
4-trifluoromethylcinnamyl H H F H 4-n-PrO XXVIII-230
4-cyanocinnamyl H H F H 4-n-PrO XXVIII-231 cinnamyl H F H F 4-n-PrO
XXVIII-232 4-chlorocinnamyl H F H F 4-n-PrO XXVIII-233
4-fuorocinnamyl H F H F 4-n-PrO XXVIII-234
4-trifluoromethylcinnamyl H F H F 4-n-PrO XXVIII-235
4-cyanocinnamyl H F H F 4-n-PrO XXVIII-236 cinnamyl H OMe H H
4-n-PrO XXVIII-237 4-chlorocinnamyl H OMe H H 4-n-PrO XXVIII-238
4-fluorocinnamyl H OMe H H 4-n-PrO XXVIII-239
4-trifluoromethylcinnamyl H OMe H H 4-n-PrO XXVIII-240
4-cyanocinnamyl H OMe H H 4-n-PrO XXVIII-241 cinnamyl H H H H 2-Me
XXVIII-242 4-chlorocinnamyl H H H H 2-Me XXVIII-243
4-fluorocinnamyl H H H H 2-Me
XXVIII-244 4-trifluoromethylcinnamyl H H H H 2-Me XXVIII-245
4-cyanocinnamyl H H H H 2-Me XXVIII-246 cinnamyl H Cl H H 2-Me
XXVIII-247 4-chlorocinnamyl H Cl H H 2-Me XXVIII-248
4-fluorocinnamyl H Cl H H 2-Me XXVIII-249 4-trifluoromethylcinnamyl
H Cl H H 2-Me XXVIII-250 4-cyanocinnamyl H Cl H H 2-Me XXVIII-251
cinnamyl H F H H 2-Me XXVIII-252 4-chlorocinnamyl H F H H 2-Me
XXVIII-253 4-fluorocinnamyl H F H H 2-Me XXVIII-254
4-trifluoromethylcinnamyl H F H H 2-Me XXVIII-255 4-cyanocinnamyl H
F H H 2-Me XXVIII-256 cinnamyl H H F H 2-Me XXVIII-257
4-chlorocinnamyl H H F H 2-Me XXVIII-258 4-fluorocinnamyl H H F H
2-Me XXVIII-259 4-trifluoromethylcinnamyl H H F H 2-Me XXVIII-260
4-cyanocinnamyl H H F H 2-Me XXVIII-261 cinnamyl H F H F 2-Me
XXVIII-262 4-chlorocinnamyl H F H F 2-Me XXVIII-263
4-fluorocinnamyl H F H F 2-Me XXVIII-264 4-trifluoromethylcinnamyl
H F H F 2-Me XXVIII-265 4-cyanocinnamyl H F H F 2-Me XXVIII-266
cinnamyl H OMe H H 2-Me XXVIII-267 4-chlorocinnamyl H OMe H H 2-Me
XXVIII-268 4-fluorocinnamyl H OMe H H 2-Me XXVIII-269
4-trifluoromethylcinnamyl H OMe H H 2-Me XXVIII-270 4-cyanocinnamyl
H OMe H H 2-Me
[0103] Table XXIX provides 214 compounds of formula Iac
##STR31##
[0104] wherein the values of R.sup.8, R.sup.4a, R.sup.4b, Y and
R.sup.1 are given in Table 3 TABLE-US-00003 TABLE 3 R8 R4a R4b Y R1
XXIX-1 2- H Cl C(O) 2-chloropyrid-4-yl (benzoxazolyl)methyl XXIX-2
2- H F C(O) 2-chloropyrid-4-yl (benzoxazolyl)methyl XXIX-3 2- H Cl
bond carbomethoxy (benzoxazolyl)methyl XXIX-4 2- H F bond
carbomethoxy (benzoxazolyl)methyl XXIX-5 2- H Cl bond acetyl
(benzoxazolyl)methyl XXIX-6 2- H F bond acetyl (benzoxazolyl)methyl
XXIX-7 2-methyl-3-(3',4'- H Cl C(O) 2-chloropyrid-4-yl
methylenedioxyphenyl) prop-2-enyl XXIX-8 2-methyl-3-(3',4'- H F
C(O) 2-chloropyrid-4-yl methylenedioxyphenyl) prop-2-enyl XXIX-9
2-methyl-3-(3',4'- H Cl bond Carbomethoxy methylenedioxyphenyl)
prop-2-enyl XXIX-10 2-methyl-3-(3',4'- H F bond carbomethoxy
methylenedioxyphenyl) prop-2-enyl XXIX-11 2-methyl-3-(3',4'- H Cl
bond acetyl methylenedioxyphenyl) prop-2-enyl XXIX-12
2-methyl-3-(3',4'- H F bond acetyl methylenedioxyphenyl)
prop-2-enyl XXIX-13 3-phenylprop-2-ynyl H Cl C(O)
2-chloropyrid-4-yl XXIX-14 3-phenylprop-2-ynyl H F C(O)
2-chloropyrid-4-yl XXIX-15 3-phenylprop-2-ynyl H Cl bond
carbomethoxy XXIX-16 3-phenylprop-2-ynyl H F bond carbomethoxy
XXIX-17 3-phenylprop-2-ynyl H Cl bond acetyl XXIX-18
3-phenylprop-2-ynyl H F bond acetyl XXIX-19 trifluoroacetamido H Cl
C(O) 2-chloropyrid-4-yl XXIX-20 trifluoroacetamido H F C(O)
2-chloropyrid-4-yl XXIX-21 trifluoroacetamido H Cl bond
carbomethoxy XXIX-22 trifluoroacetamido H F bond carbomethoxy
XXIX-23 trifluoroacetamido H Cl bond acetyl XXIX-24
trifluoroacetamido H F bond acetyl XXIX-25 4-chlorocinnamate H Cl
C(O) 2-chloropyrid-4-yl XXIX-26 4-chlorocinnamate H F C(O)
2-chloropyrid-4-yl XXIX-27 4-chlorocinnamate H Cl bond carbomethoxy
XXIX-28 4-chlorocinnamate H F bond carbomethoxy XXIX-29
4-chlorocinnamate H Cl bond acetyl XXIX-30 4-chlorocinnamate H F
bond acetyl XXIX-31 2-oxo-2-(2'-chloro- H Cl C(O)
2-chloropyrid-4-yl 4'- methylphenyl)ethyl XXIX-32
2-oxo-2-2'-chloro- H F C(O) 2-chloropyrid-4-yl 4'-
methylphenyl)ethyl XXIX-33 2-oxo-2-(2'-chloro- H Cl bond
carbomethoxy 4'- methylphenyl)ethyl XXIX-34 2-oxo-2-(2'-chloro- H F
bond carbomethoxy 4'- methylphenyl)ethyl XXIX-35
2-oxo-2-(2'-chloro- H Cl bond acetyl 4'- methylphenyl)ethyl XXIX-36
2-oxo-2-(2'-chloro- H F bond acetyl 4'- methylphenyl)ethyl XXIX-37
2-oxo-1,2- H Cl C(O) 2-chloropyrid-4-yl diphenylethyl XXIX-38
2-oxo-1,2- H F C(O) 2-chloropyrid-4-yl diphenylethyl XXIX-39
2-oxo-1,2- H Cl bond carbomethoxy diphenylethyl XXIX-40 2-oxo-1,2-
H F bond carbomethoxy diphenylethyl XXIX-41 2-oxo-1,2- H Cl bond
acetyl diphenylethyl XXIX-42 2-oxo-1,2- H F bond acetyl
diphenylethyl XXIX-43 3,3-dichloroallyl H Cl C(O)
2-chloropyrid-4-yl XXIX-44 3,3-dichloroallyl H F C(O)
2-chloropyrid-4-yl XXIX-45 3,3-dichloroallyl H Cl bond carbomethoxy
XXIX-46 3,3-dichloroallyl H F bond carbomethoxy XXIX-47
3,3-dichloroallyl H Cl bond acetyl XXIX-48 3,3-dichloroallyl H F
bond acetyl XXIX-49 t-butyloxycarbonyl H F bond H XXIX-50
t-butyloxycarbonyl H Cl bond H XXIX-51 t-butyloxycarbonyl H Cl C(O)
2-chloropyrid-4-yl XXIX-52 t-butyloxycarbonyl H F C(O)
2-chloropyrid-4-yl XXIX-53 t-butyloxycarbonyl H Cl bond
carbomethoxy XXIX-54 t-butyloxycarbonyl H F bond carbomethoxy
XXIX-55 t-butyloxycarbonyl H Cl bond acetyl XXIX-56
t-butyloxycarbonyl H F bond acetyl XXIX-57 4-chlorocinnamyl H Cl
bond 5-trifluoromethylpyrid-2- yl XXIX-58 4-chlorocinnamyl H F bond
5-trifluoromethylpyrid-2- yl XXIX-59 4-chlorocinnamyl Br H bond
5-trifluoromethylpyrid-2- yl XXIX-60 4-fluorocinnamyl H Cl bond
5-trifluoromethylpyrid-2- yl XXIX-61 4-fluorocinnamyl H F bond
5-trifluoromethylpyrid-2- yl XXIX-62 4-fluorocinnamyl Br H bond
5-trifluoromethylpyrid-2- yl XXIX-63 4-chlorocinnamyl H Cl bond
pyrimidin-2-yl XXIX-64 4-chlorocinnamyl H F bond pyrimidin-2-yl
XXIX-65 4-chlorocinnamyl Br H bond pyrimidin-2-yl XXIX-66
4-fluorocinnamyl H Cl bond pyrimidin-2-yl XXIX-67 4-fluorocinnamyl
H F bond pyrimidin-2-yl XXIX-68 4-fluorocinnamyl Br H bond
pyrimidin-2-yl XXIX-69 4-chlorocinnamyl H Cl C(O) pyrazinyl XXIX-70
4-chlorocinnamyl H F C(O) pyrazinyl XXIX-71 4-chlorocinnamyl Br H
C(O) pyrazinyl XXIX-72 4-fluorocinnamyl H Cl C(O) pyrazinyl XXIX-73
4-fluorocinnamyl H F C(O) pyrazinyl XXIX-74 4-fluorocinnamyl Br H
C(O) pyrazinyl XXIX-75 4-chlorocinnamyl H Cl C(O)
2-chloropyrid-5-yl XXIX-76 4-chlorocinnamyl H F C(O)
2-chloropyrid-5-yl XXIX-77 4-chlorocinnamyl Br H C(O)
2-chloropyrid-5-yl XXIX-78 4-fluorocinnamyl H Cl C(O)
2-chloropyrid-5-yl XXIX-79 4-fluorocinnamyl H F C(O)
2-chloropyrid-5-yl XXIX-80 4-fluorocinnamyl Br H C(O)
2-chloropyrid-5-yl XXIX-81 4-chlorocinnamyl H Cl C(O)
1,2,3-thiadiazol-4-yl XXIX-82 4-chlorocinnamyl H F C(O)
1,2,3-thiadiazol-4-yl XXIX-83 4-chlorocinnamyl Br H C(O)
1,2,3-thiadiazol-4-yl XXIX-84 4-fluorocinnamyl H Cl C(O)
1,2,3-thiadiazol-4-yl XXIX-85 4-fluorocinnamyl H F C(O)
1,2,3-thiadiazol-4-yl XXIX-86 4-fluorocinnamyl Br H C(O)
1,2,3-thiadiazol-4-yl XXIX-87 4-chlorocinnamyl H Cl C(O)
1-methyl-5-nitro-[1H]- pyrazol-4-yl XXIX-88 4-chlorocinnamyl H F
C(O) 1-methyl-5-nitro-[1H]- pyrazol-4-yl XXIX-89 4-chlorocinnamyl
Br H C(O) 1-methyl-5-nitro-[1H]- pyrazol-4-yl XXIX-90
4-fluorocinnamyl H Cl C(O) 1-methyl-5-nitro-[1H]- pyrazol-4-yl
XXIX-91 4-fluorocinnamyl H F C(O) 1-methyl-5-nitro-[1H]-
pyrazol-4-yl XXIX-92 4-fluorocinnamyl Br H C(O)
1-methyl-5-nitro-[1H]- pyrazol-4-yl XXIX-93 4-chlorocinnamyl H Cl
C(O) 5-carbomethoxypyrid-2- yl XXIX-94 4-chlorocinnamyl H F C(O)
5-carbomethoxypyrid-2- yl XXIX-95 4-chlorocinnamyl Br H C(O)
5-carbomethoxypyrid-2- yl XXIX-96 4-fluorocinnamyl H Cl C(O)
5-carbomethoxypyrid-2- yl XXIX-97 4-fluorocinnamyl H F C(O)
5-carbomethoxypyrid-2- yl XXIX-98 4-fluorocinnamyl Br H C(O)
5-carbomethoxypyrid-2- yl XXIX-99 4-chlorocinnamyl H Cl C(O)
4-chloropyrid-2-yl XXIX-100 4-chlorocinnamyl H F C(O)
4-chloropyrid-2-yl XXIX-101 4-chlorocinnamyl Br H C(O)
4-chloropyrid-2-yl XXIX-102 4-fluorocinnamyl H Cl C(O)
4-chloropyrid-2-yl XXIX-103 4-fluorocinnamyl H F C(O)
4-chloropyrid-2-yl XXIX-104 4-fluorocinnamyl Br H C(O)
4-chloropyrid-2-yl XXIX-105 4-chlorocinnamyl H Cl C(O) 2-methyl-6-
trifluoromethylpyrid-3-yl XXIX-106 4-chlorocinnamyl H F C(O)
2-methyl-6- trifluoromethylpyrid-3-yl XXIX-107 4-chlorocinnamyl Br
H C(O) 2-methyl-6- trifluoromethylpyrid-3-yl XXIX-108
4-fluorocinnamyl H Cl C(O) 2-methyl-6- trifluoromethylpyrid-3-yl
XXIX-109 4-fluorocinnamyl H F C(O) 2-methyl-6-
trifluoromethylpyrid-3-yl XXIX-110 4-fluorocinnamyl Br H C(O)
2-methyl-6- trifluoromethylpyrid-3-yl XXIX-111 4-chlorocinnamyl H
Cl C(O) 5-methylisoxazol-3-yl XXIX-112 4-chlorocinnamyl H F C(O)
5-methylisoxazol-3-yl XXIX-113 4-chlorocinnamyl Br H C(O)
5-methylisoxazol-3-yl XXIX-114 4-fluorocinnamyl H Cl C(O)
5-methylisoxazol-3-yl XXIX-115 4-fluorocinnamyl H F C(O)
5-methylisoxazol-3-yl XXIX-116 4-fluorocinnamyl Br H C(O)
5-methylisoxazol-3-yl XXIX-117 4-chlorocinnamyl H Cl C(O)
(pyrid-4-yl)methyl XXIX-118 4-chlorocinnamyl H F C(O)
(pyrid-4-yl)methyl XXIX-119 4-chlorocinnamyl Br H C(O)
(pyrid-4-yl)methyl XXIX-120 4-fluorocinnamyl H Cl C(O)
(pyrid-4-yl)methyl XXIX-121 4-fluorocinnamyl H F C(O)
(pyrid-4-yl)methyl XXIX-122 4-fluorocinnamyl Br H C(O)
(pyrid-4-yl)methyl XXIX-123 4-chlorocinnamyl H Cl C(O)
(thiophen-2-yl)methyl XXIX-124 4-chlorocinnamyl H F C(O)
(thiophen-2-yl)methyl XXIX-125 4-chlorocinnamyl Br H C(O)
(thiophen-2-yl)methyl XXIX-126 4-fluorocinnamyl H Cl C(O)
(thiophen-2-yl)methyl XXIX-127 4-fluorocinnamyl H F C(O)
(thiophen-2-yl)methyl XXIX-128 4-fluorocinnamyl Br H C(O)
(thiophen-2-yl)methyl XXIX-129 4-chlorocinnamyl H Cl C(O)
cyclopentyl XXIX-130 4-chlorocinnamyl H F C(O) cyclopentyl XXIX-131
4-chlorocinnamyl Br H C(O) cyclopentyl XXIX-132 4-fluorocinnamyl H
Cl C(O) cyclopentyl XXIX-133 4-fluorocinnamyl H F C(O) cyclopentyl
XXIX-134 4-fluorocinnamyl Br H C(O) cyclopentyl XXIX-135
4-chlorocinnamyl H Cl C(O) acetylaminomethyl XXIX-136
4-chlorocinnamyl H F C(O) acetylaminomethyl XXIX-137
4-chlorocinnamyl Br H C(O) acetylaminomethyl XXIX-138
4-fluorocinnamyl H Cl C(O) acetylaminomethyl XXIX-139
4-fluorocinnamyl H F C(O) acetylaminomethyl XXIX-140
4-fluorocinnamyl Br H C(O) acetylaminomethyl XXIX-141
4-chlorocinnamyl H Cl SO.sub.2 4-acetylaminophenyl XXIX-142
4-chlorocinnamyl H F SO.sub.2 4-acetylaminophenyl XXIX-143
4-chlorocinnamyl Br H SO.sub.2 4-acetylaminophenyl XXIX-144
4-fluorocinnamyl H Cl SO.sub.2 4-acetylaminophenyl XXIX-145
4-fluorocinnamyl H F SO.sub.2 4-acetylaminophenyl XXIX-146
4-fluorocinnamyl Br H SO.sub.2 4-acetylaminophenyl XXIX-147
4-chlorocinnamyl H Cl SO2 3,5-dimethylisoxazol-4- yl XXIX-148
4-chlorocinnamyl H F SO.sub.2 3,5-dimethylisoxazol-4- yl XXIX-149
4-chlorocinnamyl Br H SO.sub.2 3,5-dimethylisoxazol-4- yl XXIX-150
4-fluorocinnamyl H Cl SO.sub.2 3,5-dimethylisoxazol-4- yl XXIX-151
4-fluorocinnamyl H F SO.sub.2 3,5-dimethylisoxazol-4- yl XXIX-152
4-fluorocinnamyl Br H SO.sub.2 3,5-dimethylisoxazol-4- yl XXIX-153
4-chlorocinnamyl H Cl C(O) (2-methoxyphenyl)amino XXIX-154
4-chlorocinnamyl H F C(O) (2-methoxyphenyl)amino XXIX-155
4-chlorocinnamyl Br H C(O) (2-methoxyphenyl)amino XXIX-156
4-fluorocinnamyl H Cl C(O) (2-methoxyphenyl)amino XXIX-157
4-fluorocinnamyl H F C(O) (2-methoxyphenyl)amino XXIX-158
4-fluorocinnamyl Br H C(O) (2-methoxyphenyl)amino XXIX-159
4-chlorocinnamyl H F C(O) cyclohexen-1-yl XXIX-160 4-chlorocinnamyl
H Cl C(O) cyclohexen-1-yl XXIX-161 4-chlorocinnamyl Br H C(O)
cyclohexen-1-yl XXIX-162 4-fluorocinnamyl H Cl C(O) cyclohexen-1-yl
XXIX-163 4-fluorocinnamyl H F C(O) cyclohexen-1-yl XXIX-164
4-fluorocinnamyl Br H C(O) cyclohexen-1-yl XXIX-165
4-chlorocinnamyl H F C(O) quinolin-3-yl XXIX-166 4-chlorocinnamyl H
Cl C(O) quinolin-3-yl XXIX-167 4-chlorocinnamyl Br H C(O)
quinolin-3-yl XXIX-168 4-fluorocinnamyl H Cl C(O) quinolin-3-yl
XXIX-169 4-fluorocinnamyl H F C(O) quinolin-3-yl XXIX-170
4-fluorocinnamyl Br H C(O) quinolin-3-yl XXIX-171 4-chlorocinnamyl
H F C(O) benzothiophen-2-yl XXIX-172 4-chlorocinnamyl H Cl C(O)
benzothiophen-2-yl XXIX-173 4-chlorocinnamyl Br H C(O)
benzothiophen-2-yl XXIX-174 4-fluorocinnamyl H Cl C(O)
benzothiophen-2-yl XXIX-175 4-fluorocinnamyl H F C(O)
benzothiophen-2-yl XXIX-176 4-fluorocinnamyl Br H C(O)
benzothiophen-2-yl XXIX-177 4-chlorocinnamyl H F C(O)
5-nitro-[1H]-pyrazol-3-yl
XXIX-178 4-chlorocinnamyl H Cl C(O) 5-nitro-[1H]-pyrazol-3-yl
XXIX-179 4-chlorocinnamyl Br H C(O) 5-nitro-[1H]-pyrazol-3-yl
XXIX-180 4-fluorocinnamyl H Cl C(O) 5-nitro-[1H]-pyrazol-3-yl
XXIX-181 4-fluorocinnamyl H F C(O) 5-nitro-[1H]-pyrazol-3-yl
XXIX-182 4-fluorocinnamyl Br H C(O) 5-nitro-[1H]-pyrazol-3-yl
XXIX-183 4-chlorocinnamyl H F C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-184 4-chlorocinnamyl H Cl C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-185 4-chlorocinnamyl Br H C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-186 4-fluorocinnamyl H Cl C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-187 4-fluorocinnamyl H F C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-188 4-fluorocinnamyl Br H C(O) ([1H]-tetrazol-1- yl)methyl
XXIX-189 4-chlorocinnamyl H Cl bond benzyl XXIX-190
4-chlorocinnamyl H F bond benzyl XXIX-191 4-chlorocinnamyl Br H
bond benzyl XXIX-192 4-fluorocinnamyl H Cl bond benzyl XXIX-193
4-fluorocinnamyl H F bond benzyl XXIX-194 4-fluorocinnamyl Br H
bond benzyl XXIX-195 4-chlorocinnamyl H F C(O) (4-cyanophenyl)amino
XXIX-196 4-chlorocinnamyl H Cl C(O) (4-cyanophenyl)amino XXIX-197
4-chlorocinnamyl Br H C(O) (4-cyanophenyl)amino XXIX-198
4-fluorocinnamyl H Cl C(O) (4-cyanophenyl)amino XXIX-199
4-fluorocinnamyl H F C(O) (4-cyanophenyl)amino XXIX-200
4-fluorocinnamyl Br H C(O) (4-cyanophenyl)amino XXIX-201
4-chlorocinnamyl H Me.sub.3Si C(O) 2-chloropyrid-4-yl CC XXIX-202
4-fluorocinnamyl H Me.sub.3Si C(O) 2-chloropyrid-4-yl CC XXIX-203
4-chlorocinnamyl H Me.sub.3Si bond carbomethoxy CC XXIX-204
4-fluorocinnamyl H Me.sub.3Si bond carbomethoxy CC XXIX-205
4-chlorocinnamyl H Me.sub.3Si bond acetyl CC XXIX-206
4-fluorocinnamyl H Me.sub.3Si bond acetyl CC XXIX-207
4-chlorocinnamyl H OMe SO.sub.2 n-butyl XXIX-208 4-chlorocinnamyl H
F SO.sub.2 n-butyl XXIX-209 4-chlorocinnamyl H Cl SO.sub.2 n-butyl
XXIX-210 4-chlorocinnamyl Br H SO.sub.2 n-butyl XXIX-211
4-fluorocinnamyl H OMe SO.sub.2 n-butyl XXIX-212 4-fluorocinnamyl H
Cl SO.sub.2 n-butyl XXIX-213 4-fluorocinnamyl H F SO.sub.2 n-butyl
XXIX-214 4-fluorocinnamyl Br H SO.sub.2 n-butyl
[0105] Table XXX provides 121 compounds of formula Iad
TABLE-US-00004 (Iad) ##STR32## R.sup.4n R53 R54 R.sup.Sn Y R1 XXX-1
6-OCF.sub.3 H H 4-Cl C(O) Me XXX-2 6-OCF.sub.3 H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-3 4-OCF.sub.3 H H 4-Cl C(O) Me XXX-4
6-OCF.sub.2CHF.sub.2 H H 4-Cl C(O) Me XXX-5 4-OCF.sub.2CHF.sub.2 H
H 4-Cl C(O) Me XXX-6 4-OCF.sub.3 H H 4-Cl C(O) 2-chloropyrid-4-yl
XXX-7 6-OCF.sub.2CHF.sub.2 H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-8
4-OCF.sub.2CHF.sub.2 H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-9 7-O--Ph
H H 4-Cl C(O) Me XXX-10 7-O--Ph H H 4-Cl C(O) 2-chloropyrid-4-yl
XXX-11 5-OCH.sub.2CH.sub.3 H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-12
6-OCF.sub.3 H H 4-Cl C(O) 2,6-dibromopyrid- 4-yl XXX-13 6-OCF.sub.3
H H 4-Cl C(O) 2,6-dichloropyrid- 4-yl XXX-14 6-OCF.sub.3 H H 4-Cl
C(O) pyrid-3-yl XXX-15 4-OCF.sub.2CHF.sub.2 H H 4-Cl C(O)
2,6-dibromopyrid- 4-yl XXX-16 4-OCF.sub.2CHF.sub.2 H H 4-Cl C(O)
2,6-dichloropyrid- 4-yl XXX-17 4-OCF.sub.2CHF.sub.2 H H 4-Cl C(O)
pyrid-3-yl XXX-18 4-OCF.sub.3 H H 4-Cl C(O) 2,6-dibromopyrid- 4-yl
XXX-19 4-OCF.sub.3 H H 4-Cl C(O) 2,6-dichloropyrid- 4-yl XXX-20
4-OCF.sub.3 H H 4-Cl C(O) pyrid-3-yl XXX-21 6-OCF.sub.2CHF.sub.2 H
H 4-Cl C(O) 2,6-dibromopyrid- 4-yl XXX-22 6-OCF.sub.2CHF.sub.2 H H
4-Cl C(O) 3,5-dichloropyrid- 4-yl XXX-23 4-OCF.sub.3 H H 4-Cl C(O)
4,6-dimethoxy- pyrimidin-2-yl XXX-24 4-OCF.sub.2CHF.sub.2 H H 4-Cl
C(O) 4,6-dimethoxy- pyrimidin-2-yl XXX-25 6-OCF.sub.3 H H 4-Cl C(O)
2-chloropyrid-3-yl XXX-26 7-OCF.sub.3 H H 4-Cl C(O)
2-chloropyrid-3-yl XXX-27 6-OCF.sub.2CHF.sub.2 H H 4-Cl C(O)
2-chloropyrid-3-yl XXX-28 4-OCF.sub.2CHF.sub.2 H H 4-Cl C(O)
2-chloropyrid-3-yl XXX-29 5-O-(4- H H 4-Cl C(O) 2-chloropyrid-4-yl
trifluoromethyl- phenyl) XXX-30 5-OCF.sub.3 H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-31 5-F H H 4-F C(O) 2-chloropyrid-4-yl
XXX-32 5-Cl H H 2,4-Cl.sub.2 C(O) 2-chloropyrid-4-yl XXX-33
5,7-Cl.sub.2 H H 4-Cl C(O) Me XXX-34 7-Cl H H 4-Cl C(O) Me XXX-35
7-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-36 5,7-dimethyl H H 4-Cl
C(O) 2-chloropyrid-4-yl XXX-37 4,7-dimethyl H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-38 6-CF.sub.3 H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-39 4,6-Cl.sub.2 H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-40 4,6-Cl.sub.2 H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-41 5-isopropyl H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-42 5-Br H H 4-Cl C(O) 2-chloropyrid-4-yl
XXX-43 6,7-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-44
5,6-Cl.sub.2 H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-45 4-CF.sub.3 H H
4-Cl C(O) 2-chloropyrid-4-yl XXX-46 7-CH.sub.2Cl H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-47 7-Br H H 4-Cl C(O) 2-chloropyrid-4-yl
XXX-48 5-tert-butyl H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-49
4,6-dimethyl H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-50
4-CF.sub.3-7-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl XXX-51 5-Cl H H
4-CF.sub.3 C(O) 2-chloropyrid-4-yl XXX-52 5-Cl H H 4- C(O)
2-chloropyrid-4-yl CH.dbd.CH.sub.2 XXX-53 5-Cl H H 4-CF.sub.3 C(O)
2-chloropyrid-4-yl XXX-54 5-Cl H H 4-Cl C(O) 2-chloropyrid-4-yl
XXX-55 5-Cl H H 4-NO.sub.2 C(O) 2-chloropyrid-4-yl XXX-56 5-Cl H H
3,5-(CF.sub.3).sub.2 C(O) 2-chloropyrid-4-yl XXX-57 5-Cl H H 3-Br
C(O) 2-chloropyrid-4-yl XXX-58 5-Cl H H 3-ethoxy C(O)
2-chloropyrid-4-yl XXX-59 5-Cl H H 2-Me C(O) 2-chloropyrid-4-yl
XXX-60 5-Cl H H 4-Me C(O) 2-chloropyrid-4-yl XXX-61 5-Cl H H
3-Cl,4-F C(O) 2-chloropyrid-4-yl XXX-62 5-Cl H H 3,5-Cl.sub.2 C(O)
2-chloropyrid-4-yl XXX-63 5-Cl H H 4-N.sub.3 C(O)
2-chloropyrid-4-yl XXX-64 5-Cl H H 2-Br C(O) 2-chloropyrid-4-yl
XXX-65 5-Cl H H 2,6- C(O) 2-chloropyrid-4-yl dimethoxy XXX-66 5-Cl
H H 4-ethoxy C(O) 2-chloropyrid-4-yl XXX-67 5-Cl H H 3-Cl C(O)
2-chloropyrid-4-yl XXX-68 5-Cl H H 3-Me,4- C(O) 2-chloropyrid-4-yl
OMe,5-Cl XXX-69 5-Cl H H 4-OPh C(O) 2-chloropyrid-4-yl XXX-70 5-Cl
H H 4-CN C(O) 2-chloropyrid-4-yl XXX-71 5-Cl H H 3-F,4-Ph C(O)
2-chloropyrid-4-yl XXX-72 5-Cl H H 4-SMe C(O) 2-chloropyrid-4-yl
XXX-73 5-Cl H H 3-Br C(O) 2-chloropyrid-4-yl XXX-74 5-Cl H H 4-F
C(O) 2-chloropyrid-4-yl XXX-75 5-Cl H H 4-Br C(O)
2-chloropyrid-4-yl XXX-76 5-Cl H H 2,4-Cl.sub.2 C(O)
2-chloropyrid-4-yl XXX-77 5-Cl H H 2,4-F.sub.2 C(O)
2-chloropyrid-4-yl XXX-78 5-Cl H H 3-CF.sub.3 C(O)
2-chloropyrid-4-yl XXX-79 5-Cl H H 3,4- C(O) 2-chloropyrid-4-yl
diethoxy XXX-80 5-Cl H H 3-Me,4-F C(O) 2-chloropyrid-4-yl XXX-81
5-Cl H H 4-Ph C(O) 2-chloropyrid-4-yl XXX-82 5-Cl H Me 4-Cl C(O)
2-chloropyrid-4-yl XXX-83 5-Cl H Me 4-Cl C(O) Me XXX-84 5-Cl H Me
4-F C(O) 2-chloropyrid-4-yl XXX-85 5-Cl H Me 4-F C(O) Me XXX-86
5-Cl H H 4-OCF.sub.3 C(O) 2-chloropyrid-4-yl XXX-87 5-Cl H H
4-OCF.sub.3 C(O) Me XXX-88 5-Cl H F H C(O) 2-chloropyrid-4-yl
XXX-89 5-Cl H F 4-Cl C(O) 2-chloropyrid-4-yl XXX-90 5-Cl H F 4-Cl
C(O) Me XXX-91 5-Cl H CF.sub.3 4-Cl C(O) 2-chloropyrid-4-yl XXX-92
5-Cl H CF.sub.3 4-Cl C(O) Me XXX-93 5-F H H 4-Cl C(O) imidazol-1-yl
XXX-94 5-F H H 4-Cl Bond NH.sub.2 XXX-95 5-F H H 4-Cl Bond --NHCO-
2-chloropyrid-4-yl XXX-96 5-Cl H H 4-NO.sub.2 C(O) Me XXX-97 5-Cl H
H 4-Cl Bond NHCO-4- trifluoromethoxy- phenyl XXX-98 5-Cl H H 4-Cl
Bond --NHCO- pyrid-4-yl XXX-99 5-Cl H H 4-Cl Bond --NHCO-
3-chloropyrid-4-yl XXX-100 5-F H H 4-Cl Bond --NHCONH-4-
trifluoromethoxy- phenyl XXX-101 5-F H H 4-Cl Bond --NHCONH-3-
chlorophenyl XXX-102 5-Cl H H 4-Cl Bond --N.dbd.C(Me)NMe.sub.2
XXX-103 5-Cl H H 4-Cl Bond --NHCONH-4- trifluoromethyl- phenyl
XXX-104 5-F H H 4-Cl C(O) --NH-isopropyl XXX-105 5-F H H 4-Cl C(O)
--NH(CH.sub.2).sub.2OMe XXX-106 5-F H H 4-Cl C(O)
--NHCH.sub.2-pyrid-3-yl XXX-107 5-F H H 4-Cl C(O)
--NH(CH.sub.2).sub.2OH XXX-108 5-F H H 4-Cl C(O)
--NH(CH.sub.2).sub.2- morpholinyl XXX-109 5-F H H 4-Cl C(O)
--NHCH.sub.2-pyrid-4-yl XXX-110 5-F H H 4-Cl C(O) --NH-ethyl
XXX-111 5-F H H 4-Cl C(O) --NH-methyl XXX-112 5-F H H 4-Cl C(O)
--NH-benzyl XXX-113 5-Cl F H 4-Cl C(O) 2-chloropyrid-4-yl XXX-114
5-Cl F H 4-CF.sub.3 C(O) 2-chloropyrid-4-yl XXX-115 5-Cl H Cl 4-Cl
C(O) 2-chloropyrid-4-yl XXX-116 5 + 6 -O--CF.sub.2--O-- H H 4-Cl
C(O) Me XXX-117 5 + 6 -O--CF.sub.2--O-- H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-118 5 + 6 -O--CH.sub.2--O-- H H 4-Cl C(O)
2-chloropyrid-4-yl XXX-119 5-F H H 4-Cl Bond --NHCONH-4-
chlorophenyl XXX-120 5-F H H 4-Cl Bond Ethyl XXX-121 5-Cl H H 4-Cl
Bond NO
[0106] Table XXXI provides 8 compounds of formula Iae
TABLE-US-00005 (Iae) ##STR33## R.sup.4n R53 R54 Rt Y R1 XXXI-1 5-Cl
H H 5-trifluoromethyl- C(O) 2-chloropyrid- pyrid-2-yl 4-yl XXXI-2
5-F H H 5-chloro- C(O) 2-chloropyrid- thiophen-2-yl 4-yl XXXI-3
5-Cl H H thiophen-2-yl C(O) 2-chloropyrid- 4-yl XXXI-4 5-Cl H H
naphtha-2-yl C(O) 2-chloropyrid- 4-yl XXXI-5 5-Cl H H --CH.dbd.CH-
C(O) 2-chloropyrid- phenyl 4-yl XXXI-6 5-Cl H H benzothiophen-2-
C(O) 2-chloropyrid- yl 4-yl XXXI-7 5-Cl H H --CH.dbd.CH- C(O)
2-chloropyrid- 4-chlorophenyl 4-yl XXXI-8 5-Cl H H Br C(O)
2-chloropyrid- 4-yl
[0107] Table XXXII provides 10 compounds of formula Iaf
TABLE-US-00006 (Iaf) ##STR34## R.sup.4n Ru Y R1 XXXII-1 5-Cl 4-F-Ph
C(O) 2-chloropyrid-4-yl XXXII-2 5-Cl 4-OCF.sub.3-Ph C(O)
2-chloropyrid-4-yl XXXII-3 5-Cl 4-Cl-Ph C(O) 2-chloropyrid-4-yl
XXXII-4 5-F 6-F-naphth-2-yl C(O) 2-chloropyrid-4-yl XXXII-5 5-Cl
--CH(OH)CH.sub.2O-4-Cl- C(O) 2-chloropyrid-4-yl Ph XXXII-6 5-Cl
--C(Me).dbd.NO-Ph C(O) 2-chloropyrid-4-yl XXXII-7 5-Cl
5-Cl-benzoxazol-2-yl C(O) 2-chloropyrid-4-yl XXXII-8 5-Cl
4-NHCOOCH(Me).sub.2-Ph C(O) 2-chloropyrid-4-yl XXXII-9 5-Cl
4-NHCOOCH(Me).sub.2-Ph C(O) 2-chloropyrid-4-yl XXXII-10 5-Cl
(2-ethyl-terazol-5-yl)- C(O) 2-chloropyrid-4-yl 4--Ph
[0108] Mass spectra data were obtained for selected compounds of
Tables I to XXIX on Micromass Platform 2 machines. The data are
shown in Table 3. TABLE-US-00007 TABLE 3 Compound No MS data I-1
444 (95%), 446 (100%) I-2 478 (100%), 480 (70%), 482 (15%) I-3 462
(100%), 464 (95%) I-4 489 (100%), 491 (70%) I-5 147 (100%), 474
(30%), 476 (80%) I-12 512 (95%), 514 (100%), 516 (35%), 518 (5%)
I-21 478 (100%), 480 (70%), 482 (15%) I-22 512 (100%), 514 (98%),
516 (35%), 518 (5%) I-23 496 (100%), 498 (75%), 500 (15%) I-32 512
(90%), 514 (100%), 516 (35%), 518 (5%) I-52 496 (100%), 498 (70%),
500 (15%) I-61 462 (100%), 464 (30%) I-62 496 (100%), 498 (80%),
500 (20%) I-72 496 (100%), 498 (70%), 500 (15%) I-82 496 (100%),
498 (75%), 500 (15%) I-92 556 (55%), 558 (100%), 560 (40%), 562
(8%) I-112 556 (55%), 558 (100%), 560 (40%), 562 (8%) I-132 546
(75%), 548 (100%), 550 (40%), 552 (10%) I-142 514 (100%), 516
(70%), 518 (15%) I-152 530 (97%), 532 (100%), 534 (40%), 536 (5%)
I-162 530 (100%), 532 (97%), 534 (40%), 536 (5%) I-171 512 (98%),
514 (100%), 516 (35%), 518 (5%) I-182 604 (100%), 606 (70%), 608
(15%) I-192 508 (100%), 510 (80%), 512 (20%) I-202 492 (100%), 494
(70%), 496 (15%) I-212 503 (100%), 505 (70%), 507 (15%) I-222 502
(100%), 504 (70%), 506 (15%) I-232 536 (100%), 538 (70%), 540 (15%)
I-242 526 (100%), 528 (99%), 530 (35%), 532 (5%) I-252 526 (100%),
528 (90%), 530 (35%), 532 (5%) I-262 526 (95%), 528 (100%), 530
(35%), 532 (5%) I-282 572 (100%), 574 (80%), 576 (20%) I-292 562
(100%), 564 (70%), 566 (15%) II-22 431 (100%), 433 (60%), 435 (15%)
II-62 415 (100%), 417 (35%) V-21 381 (100%), 383 (35%) V-22 415
(100%), 417 (70%), 419 (15%) V-62 399 (100%), 401 (40%) V-192 411
(100%), 413 (60%) V-202 395 (100%), 397 (80%) VI-1 410 (100%) VI-22
478 (100%), 480 (70%), 482 (15%) VI-62 462 (100%), 464 (30%) VI-101
488 (100%), 490 (100%) VI-202 458 (100%), 460 (30%) IX-62 435
(100%), 437 (40%) X-22 459 (100%), 461 (75%), 463 (15%) X-62 443
(100%), 445 (40%) XI-62 467 (100%), 469 (40%) XII-22 478 (100%),
480 (75%), 482 (35%), 484 (5%) XIII-22 471 (100%), 473 (70%), 475
(15%) XIII-62 455 (100%), 457 (35%) XIV-22 451 (100%), 453 (70%),
455 (15%) XV-22 528 (100%), 530 (70%), 532 (10%) XVII-62 533
(100%), 535 (40%) XVIII-22 555 (100%), 557 (80%), 559 (20%)
XVIII-202 535 (100%), 537 (40%) XIX-22 502 (100%), 504 (70%), 506
(10%) XIX-202 482 (100%), 484 (40%) XX-22 521 (100%), 523 (75%),
525 (15%) XX-62 505 (100%), 507 (40%) XXI-22 557 (100%), 559 (70%),
561 (15%) XXI-62 541 (100%), 543 (40%) XXII-22 526 (100%), 528
(97%), 530 (30%), 532 (5%) XXV-62 357 (100%), 359 (55%) XXV-222 363
(100%), 365 (30%) XXVI-1 460 (100%), 462 (100%) XXVI-2 494 (100%),
496 (100%), 498 (20%) XXVI-22 528 (100%), 530 (97%), 532 (30%), 534
(5%) XXVIII-7 523 (100%), 525 (80%), 527 (20%) XXVIII-27 519
(100%), 521 (40%) XXVIII-42 565 (100%), 567 (40%) XXVIII-67 495
(100%), 497 (70%), 499 (10%) XXVIII-97 502 (100%), 504 (70%), 506
(10%) XXVIII-132 503 (100%), 505 (40%) XXVIII-162 537 (100%), 539
(40%) XXVIII-187 589 (95%), 591 (100%), 593 (40%), 595 (5%)
XXVIII-217 535 (100%), 537 (70%), 539 (10%) XXVIII-252 475 (100%),
477 (40%) XXIX-1 492 (100%), 494 (70%), 496 (15%) XXIX-7 536
(100%), 538 (70%), 540 (15%) XXIX-13 476 (100%), 478 (80%), 480
(20%) XXIX-19 458 (100%), 460 (85%), 462 (15%) XXIX-31 528 (100%),
530 (97%), 532 (30%), 534 (5%) XXIX-37 556 (100%), 558 (70%), 560
(15%) XXIX-43 470 (100%), 472 (100%),
474 (100%), 476 (30%) XXIX-49 251 (100%), 307 (70%) XXIX-69 479
(100%), 481 (70%), 483 (15%) XXIX-75 512 (95%), 514 (100%), 516
(40%), 518 (5%) XXIX-81 485 (100%), 487 (75%), 489 (20%) XXIX-87
526 (100%), 528 (70%), 530 (10%) XXIX-93 536 (100%), 538 (70%), 540
(15%) XXIX-99 512 (95%), 514 (100%), 516 (30%), 518 (5%) XXIX-105
560 (100%), 562 (70%), 564 (15%) XXIX-111 482 (100%), 484 (70%),
486 (15%) XXIX-117 373 (100%), 375 (70%), 377 (15%) 492 (20%), 494
(15%) XXIX-123 497 (100%), 499 (75%), 501 (15%) XXIX-129 469
(100%), 471 (75%), 473 (15%) XXIX-135 472 (100%), 474 (70%), 476
(15%) XXIX-141 570 (100%), 572 (75%), 574 (15%) XXIX-147 532
(100%), 534 (80%), 536 (20%) XXIX-153 522 (100%), 524 (75%), 526
(15%) XXIX-159 465 (100%), 467 (40%) XXIX-165 512 (100%), 514 (40%)
XXIX-171 517 (100%), 519 (40%) XXIX-177 427 (100%), 496 (80%), 498
(30%) XXIX-183 467 (100%), 469 (35%) XXIX-189 463 (100%), 465
(55%), 467 (15%) XXIX-195 501 (100%), 503 (40%) XXIX-196 517
(100%), 519 (70%), 521 (15%) XXIX-201 574 (100%), 576 (80%), 578
(20%) XXIX-207 489 (100%), 491 (40%)
[0109] Mass spectra data were obtained for selected compounds of
Tables XXX to XXXII using LCMS: LC5: 254 nm--gradient 10% A to 100%
B A=H2O+0.01% HCOOH B=CH3CN/CH3OH+0.010% HCOOH positive
electrospray 150-1000 m/z
[0110] The data are shown in Table 4. TABLE-US-00008 TABLE 4 LCMS
(Ret. Time, LCMS Compound mp (.degree. C.) min) (M + H) XXX-1 2'27
465 XXX-2 2'55 562 XXX-3 2'26 465 XXX-4 2'30 497 XXX-5 2'30 497
XXX-6 2'48 562 XXX-7 2'48 594 XXX-8 2'51 594 XXX-9 2'28 473 XXX-10
2'43 570 XXX-11 2'26 522 XXX-12 2'57 686 XXX-13 2'56 596 XXX-14
2'09 528 XXX-15 2'60 718 XXX-16 2'71 630 XXX-17 2'22 560 XXX-18
2'66 686 XXX-19 2'64 596 XXX-20 2'29 528 XXX-21 2'68 718 XXX-22
2'68 630 XXX-23 2'43 589 XXX-24 2'53 621 XXX-25 2'30 562 XXX-26
2'33 562 XXX-27 2'35 594 XXX-28 2'42 594 XXX-29 2'60 638 XXX-30 562
XXX-31 480 XXX-32 546 XXX-33 171-172 2'27 449 XXX-34 59-61 2'01 415
XXX-35 182-184 2'33 512 XXX-36 158-160 2'43 506 XXX-37 199-201 2'42
506 XXX-38 2'48 546 XXX-39 157-159 2'52 546 XXX-40 2'46 546 XXX-41
2'47 520 XXX-42 140-142 2'37 556 XXX-43 106-110 2'39 506 XXX-44
2'53 546 XXX-45 170-172 2'39 546 XXX-46 146-148 2'36 506 XXX-47
196-198 2'31 556 XXX-48 149-151 2'49 534 XXX-49 194-196 2'33 506
XXX-50 165-167 2'48 580 XXX-51 546 XXX-52 504 XXX-53 546 XXX-54 513
XXX-55 523 XXX-56 614 XXX-57 557 XXX-58 522 XXX-59 492 XXX-60 492
XXX-61 531 XXX-62 547 XXX-63 533 XXX-64 557 XXX-65 538 XXX-66 522
XXX-67 513 XXX-68 557 XXX-69 571 XXX-70 503 XXX-71 573 XXX-72 525
XXX-73 557 XXX-74 496 XXX-75 557 XXX-76 547 XXX-77 514 XXX-78 546
XXX-79 538 XXX-80 510 XXX-81 555 XXX-82 2'45 528 XXX-83 2'22 429
XXX-84 2'30 510 XXX-85 2'05 413 XXX-86 70 2'40 562 XXX-87 2'27 465
XXX-88 2'22 497 XXX-89 2'44 530 XXX-90 2'15 433 XXX-91 XXX-92 2'53
483 XXX-93 1'93 451 XXX-94 1'74 372 XXX-95 2'08 511 XXX-96 1'93 426
XXX-97 2'57 576 XXX-98 1'99 493 XXX-99 2'20 527 XXX-100 2'55 575
XXX-101 2'46 525 XXX-102 1'45 457 XXX-103 2'60 575 XXX-104 2'13 442
XXX-105 1'96 458 XXX-106 1'67 491 XXX-107 1'86 444 XXX-108 1'41 513
XXX-109 1'55 491 XXX-110 2'00 428 XXX-111 1'90 414 XXX-112 2'31 490
XXX-113 2'74 530 XXX-114 2'44 520 XXX-115 2'53 548 XXX-116 2'20 461
XXX-117 2'47 558 XXX-118 2'17 522 XXX-120 399 XXX-121 2'05 427
XXX1-1 547 XXXI-2 147-148 XXXI-3 484 XXX1-4 528 XXXI-5 504 XXXI-6
535 XXXI-7 539 XXXI-8 1'86 482 XXXII-1 470 XXXII-2 536 XXXII-3 486
XXXII-4 504 XXXII-5 546 XXXII-6 509 XXXII-7 527 XXXII-8 2'27
XXXII-9 1'96 XXXII-10 2'21
[0111] The compounds of the invention may be made in a variety of
ways. For example they may be made by the reactions summarised in
Scheme I. ##STR35## ##STR36##
[0112] Thus a compound of formula 1 may be synthesised from
compounds of formula 2a or 2b by reaction with an alkylating agent
of the formula R8-L, where L is chloride, bromide, iodide or a
sulfonate (e.g. mesylate or tosylate) or similar leaving group at a
temperature of between ambient temperature and 100.degree. C.,
typically 65.degree. C., in an organic solvent such as
dichloromethane, chloroform or 1,2-dichloroethane in the presence
of a tertiary amine base such as triethylamine or
diisopropylethylamine and optionally catalysed by halide salts such
as sodium iodide, potassium iodide or tetrabutylammonium
iodide.
[0113] Alternatively, a compound of formula 2a or 2b may be reacted
with an aldehyde of the formula RCHO at a temperature between
ambient temperature and 100.degree. C. in an organic solvent such
as tetrahydrofuran or ethanol or mixtures of solvents in the
presence of a reducing agent such as borane-pyridine complex,
sodium borohydride, sodium (triacetoxy)borohydride, sodium
cyanoborohydride or such like, to produce a compound of formula 1
where R8 is CH.sub.2--R.
[0114] Alternatively, a compound of formula 2a or 2b may be reacted
with paraformaldehyde and a boronic acid of the formula
R--B(OH).sub.2 at a temperature between ambient temperature and 1
00.degree. C. in an organic solvent such as ethanol, 1,4dioxane or
water to produce a compound of formula 1 where R8 is
CH.sub.2--R.
[0115] A compound of formula 2a may be obtained from a compound of
formula 3 by reaction with an acid such as trifluoroacetic acid at
ambient temperature in an organic solvent such as dichloromethane,
chloroform or 1,2-dichloroethane followed by neutralisation of the
reaction mixture with an aqueous solution of an inorganic base such
as sodium carbonate, sodium bicarbonate or similar compound.
[0116] Similarly a compound of formula 2b may be formed by reaction
of a compound of formula 3 with an acid such as trifluoroacetic
acid at ambient temperature in an organic solvent such as
dichloromethane, chloroform or 1,2-dichloroethane followed by
evaporation of the solvents and trituration with organic solvents
such as ether or hexane.
[0117] Compounds of formula 3 may be obtained from compounds of
formula 4 by reaction with a suitable electrophilic species.
Compounds of formula 3 where Y is a carbonyl group may be formed by
the reaction of compounds of formula 4 with a carboxylic acid
derivative of formula R1-C(O)-Z where Z is chloride, hydroxy,
alkoxy or acyloxy at a temperature between 0.degree. C. and
150.degree. C. optionally in an organic solvent such as
dichloromethane, chloroform or 1,2-dichloroethane, optionally in
the presence of a tertiary amine base such as triethylamine or
diisopropylethylamine and optionally in the presence of a coupling
agent such as dicyclohexylcarbodiimide. Compounds of formula 3
where Y is a carbonyl group and R1 is an amino substituent of
formula R'--NH-- may be formed by the reaction of compounds of
formula 4 with an isocyanate of formula R'--N.dbd.C.dbd.O under
similar conditions. Compounds of formula 3 where Y is a group of
formula S(O).sub.q may be formed from compounds of formula 4 by
treatment with compounds of formula of R1-S(O).sub.q--Cl under
similar conditions. Compounds of formula 3 where Y is a
thiocarbonyl group and R1 is an amino substituent of formula
R'--NH-- may be formed by the reaction of compounds of formula 3
with an isothiocyanate of formula R'--N.dbd.C.dbd.S under similar
conditions. Alternatively compounds of formula 3 where Y is a
thiocarbonyl group and R1 is a carbon substituent may be formed by
treatment of compounds of formula 3 where Y is a carbonyl group and
R1 is a carbon substituent with a suitable thionating agent such as
Lawesson's reagent.
[0118] In the above procedures, acid derivatives of the formula
R1-C(O)-Z, isocyanates of formula R'--N.dbd.C.dbd.O,
isothiocyanates of formula R'--N.dbd.C.dbd.S and sulfur
electrophiles of formula R1-S(O).sub.q--Cl are either known
compounds or may be formed from known compounds by known methods by
a person skilled in the art.
[0119] Compounds of formula 4 may be obtained by reacting compounds
of formula 5 with compounds of formula 6 at a temperature of
between 0.degree. C. and 100.degree. C. in an organic solvent such
as dichloromethane, chloroform or 1,2-dichloroethane in the
presence of an acid such as hydrochloric acid or trifluoroacetic
acid and a co-solvent such as water, methanol or ethanol, or in the
presence of a Lewis acidic metal salt such as a zinc(II) dihalide.
The intermediates formed (compounds of formula 4a) are subsequently
treated with a nucleophile R3-M (where M is a metallic species.
R3-M is for example a Grignard reagent) or, when R3 is hydrogen, a
reducing agent such as sodium borohydride, sodium
(triacetoxy)borohydride, sodium cyanoborohydride or similar at
ambient temperature in organic solvent such as ethanol or
chloroform. The basic procedure is described in Tetrahedron (1997),
53, 10983-10992.
[0120] Compounds of formula 6 may be obtained from compounds of
formula 7 by reaction with a 1-alkoxy substituted phosphonium salt
such as methoxymethyl(triphenyl)phosphonium chloride and a base
such as potassium tert-butoxide at a temperature of 0.degree. C. to
room temperature in tetrahydrofuran.
[0121] Compounds of formula 5 and 7 are either known compounds or
may be obtained from known compounds by known techniques.
[0122] Certain compounds of formula 2, 3, 4, 4a and 6 are novel and
as such form a further aspect of the invention.
[0123] Further procedures for making compounds of formula 1'
(compounds of formula I where R.sup.2, R.sup.3, R.sup.9 and
R.sup.10 are all hydrogen) are illustrated in scheme II below
##STR37##
[0124] Thus a compound of formula 1' may be obtained from a
compound of formula 8 by reaction with an acid chloride or
chloroformate of the formula R1COCl at a temperature between 0
.degree. C. and ambient in organic solvent such as dichloromethane,
chloroform or 1,2-dichloroethane in the presence of a tertiary
amine base such as triethylamine or diisopropylethylamine.
[0125] Alternatively, a compound of formula 1' may be obtained from
a compound of formula 8 by reaction with a carboxylic acid of the
formula R1COOH and a standard coupling agent such as
2-chloro-1,3-dimethyl-2-imidazolium hexafluorophosphate, or
carbodiimide reagents such as dicyclohexylcarbodiimide or
1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at a
temperature between 0.degree. C. and ambient in organic solvent
such as dichloromethane or tetrahydrofuran in the presence of a
tertiary amine base such as triethylamine or
diisopropylethylamine.
[0126] A compound of formula 1' may alternatively be obtained from
a compound of formula 8 by reaction with a isocyanate or
isothiocyanate of the formula RNCO or RNCS respectively at a
temperature between 0.degree. C. and ambient in organic solvent
such as dichloromethane or tetrahydrofuran, optionally in the
presence of a tertiary amine base such as triethylamine or
diisopropylethylamine.
[0127] A compound of formula 1' may also be obtained from a
compound of formula 8 by reaction with a sulfonyl chloride of the
formula R1SO.sub.2Cl at a temperature between 0.degree. C. and
ambient in organic solvent such as dichloromethane or
tetrahydrofuran, in the presence of a tertiary amine base such as
triethylamine or diisopropylethylamine.
[0128] Alternatively, a compound of formula 1' may be obtained from
a compound of formula 8 by reaction with an aryl or heteroaryl
compound of formula Ar-L where L is a leaving group such as halide
(especially fluoride), such as a 2-halopyridine, a
2-halopyrimidine, a 4-halopyridine, a 2-halopyrazine or such like
at a temperature between 50.degree. C. and 150.degree. C. in a
solvent such as dimethylsulfoxide in the presence of a strong base
such as sodium hydride.
[0129] Compounds of formula 8 may be obtained by reacting compounds
of formula 9 with compounds of formula 5 (in scheme I) at a
temperature of between ambient and 100.degree. C. in organic
solvent such as dichloromethane, chloroform or 1,2-dichloroethane
in the presence of an acid such as trifluoroacetic acid for
typically 4 to 12 hours, followed by addition of a reducing agent
such as triethylsilane and reaction at a temperature of ambient to
100.degree. C. until the reaction is complete.
[0130] Alternatively, Compounds of formula 8 may be obtained by
reacting compounds of formula 9 with compounds of formula 5 at a
temperature of between 0.degree. C. and 100.degree. C. in organic
solvent such as dichloromethane, chloroform or 1,2-dichloroethane
in the presence of an acid such as hydrochloric acid, or
trifluoroacetic acid and a co-solvent of either water or methanol
or ethanol, or in the presence of a Lewis acidic metal salt such as
zinc(II) dihalide. The intermediates formed (compounds of formula
(9a)) are subsequently treated with a reducing agent such as sodium
borohydride, sodium (triacetoxy)borohydride, sodium
cyanoborohydride or such like at ambient temperature in organic
solvent such as ethanol or chloroform.
[0131] Compounds of formula 8 may also be obtained by the
hydrolysis of compounds of formula 1a (which are also a sub-set of
compounds of formula 1) preferably with an aqueous acid, typically
6 N hydrochloric acid at reflux temperature.
[0132] Compounds of formula 9 may be obtained from compounds of
formula 10 by reaction with methoxymethyl(triphenyl)phosphonium
chloride or the corresponding bromide salt and a base such as
potassium tert-butoxide at a temperature of 0.degree. C. to ambient
in tetrahydrofuran.
[0133] Compounds of formula 10 may be obtained by reacting
compounds of formula 11 with an aqueous solution of acid, typically
6 N hydrochloric acid at reflux temperature.
[0134] Compounds of formula 11 may be obtained from compounds of
formula 12 by reaction with an electrophile of the formula R8-L,
where L is chloride, bromide, iodide or a sulfonate (e.g. mesylate
or tosylate) or similar leaving group at between ambient
temperature and 100.degree. C., typically around 60.degree. C. in
an organic solvent such as dichloromethane, chloroform or
1,2-dichloroethane in the presence of an excess of a tertiary amine
base such as triethylamine or diisopropylethylamine and optionally
catalysed by halide salts such as sodium iodide, potassium iodide
or tetrabutylammonium iodide.
[0135] Compounds of formula 12 are known compounds or may be
obtained from known compounds by known techniques.
[0136] Certain compounds of formula 8, 9, 9a, 10 and 11 are novel
and as such form a further aspect of the invention.
[0137] The skilled person will readily recognise that it is
possible to interconvert one compound of formula I to other
compounds of formula I and examples of such procedures are given in
schemes III, IV, V, Va and VI below. ##STR38## ##STR39## ##STR40##
##STR41##
[0138] Compounds of formula I where R.sup.8 is optionally
substituted cinnamyl may be prepared by the reactions in scheme VII
below where R.sup.4, R.sup.53, R.sup.54 and R.sup.S are as defined
above. The scheme is illustrated in Examples 8-12. ##STR42##
[0139] Compounds of formula (I) in which R.sup.2 and R.sup.3
together are an oxo group and R.sup.1, R.sup.4 and R.sup.8 are as
defined above may be made by the methods of WO 0145707 as set out
in scheme VIII below. ##STR43##
[0140] Compounds of formula (I) in which R.sup.2 and R.sup.3
together are an oxo group and and R.sup.8 are as defined above may
be made from compounds of formula 4a by the methods of scheme IX
below. ##STR44##
[0141] The compounds of formula (I) can be used to combat and
control infestations of insect pests such as Lepidoptera, Diptera,
Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera,
Siphonaptera, Hymenoptera and Isoptera and also other invertebrate
pests, for example, acarine, nematode and mollusc pests. Insects,
acarines, nematodes and molluscs are hereinafter collectively
referred to as pests. The pests which may be combated and
controlled by the use of the invention compounds include those
pests associated with agriculture (which term includes the growing
of crops for food and fibre products), horticulture and animal
husbandry, companion animals, forestry and the storage of products
of vegetable origin (such as fruit, grain and timber); those pests
associated with the damage of man-made structures and the
transmission of diseases of man and animals; and also nuisance
pests (such as flies).
[0142] Examples of pest species which may be controlled by the
compounds of formula (I) include: Myzus persicae (aphid), Aphis
gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids),
Dysdercus spp. (capsids), Nilaparvata lugens (planthopper),
Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs),
Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs),
Frankliniella occidentalis (thrip), Thrips spp. (thrips),
Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus
grandis (boll weevil), Aonidiella spp. (scale insects),
Trialeurodes spp. (white flies), Bemisia tabaci (white fly),
Ostrinia nubilalis (European corn borer), Spodoptera littoralis
(cotton leafworm), Heliothis virescens (tobacco budworm),
Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton
bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae
(white butterfly), Plutella xylostella (diamond back moth), Agrotis
spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta
migratoria (locust), Chortiocetes terminifera (locust), Diabrotica
spp. (rootworms), Panonychus ulmi (European red mite), Panonychus
citri (citrus red mite), Tetranychus urticae (two-spotted spider
mite), Tetranychus cinnabarinus (carmine spider mite),
Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus
latus (broad mite), Brevipalpus spp. (flat mites), Boophilus
microplus (cattle tick), Dermacentor variabilis (American dog
tick), Ctenocephalides felis (cat flea), Liriomyza spp.
(leafrniner), Musca domestica (housefly), Aedes aegypti (mosquito),
Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp.
(blowflies), Blattella germanica (cockroach), Periplaneta americana
(cockroach), Blatta orientalis (cockroach), termites of the
Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae
(for example Neotermes spp.), the Rhinotermitidae (for example
Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R.
virginicus, R. hesperus, and R. santonensis) and the Termitidae
(for example Globitermes sulphureus), Solenopsis geminata (fire
ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and
Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root
knot nematodes), Globodera spp. and Heterodera spp. (cyst
nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp.
(banana burrowing nematodes), Tylenchulus spp.(citrus nematodes),
Haemonchus contortus (barber pole worm), Caenorhabditis elegans
(vinegar eelworm), Trichostrongylus spp. (gastro intestinal
nematodes) and Deroceras reticulatum (slug).
[0143] The invention therefore provides a method of combating and
controlling insects, acarines, nematodes or molluscs which
comprises applying an insecticidally, acaricidally, nematicidally
or molluscicidally effective amount of a compound of formula (I),
or a composition containing a compound of formula (I), to a pest, a
locus of pest, or to a plant susceptible to attack by a pest, The
compounds of formula (I) are preferably used against insects,
acarines or nematodes.
[0144] The term "plant" as used herein includes seedlings, bushes
and trees.
[0145] In order to apply a compound of formula (I) as an
insecticide, acaricide, nematicide or molluscicide to a pest, a
locus of pest, or to a plant susceptible to attack by a pest, a
compound of formula (I) is usually formulated into a composition
which includes, in addition to the compound of formula (I), a
suitable inert diluent or carrier and, optionally, a surface active
agent (SFA). SFAs are chemicals which are able to modify the
properties of an interface (for example, liquid/solid, liquid/air
or liquid/liquid interfaces) by lowering the interfacial tension
and thereby leading to changes in other properties (for example
dispersion, emulsification and wetting). It is preferred that all
compositions (both solid and liquid formulations) comprise, by
weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to
60%, of a compound of formula (I). The composition is generally
used for the control of pests such that a compound of formula (I)
is applied at a rate of from 0.1 g to 1 kg per hectare, preferably
from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per
hectare.
[0146] When used in a seed dressing, a compound of formula (I) is
used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g),
preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per
kilogram of seed.
[0147] In another aspect the present invention provides an
insecticidal, acaricidal, nematicidal or molluscicidal composition
comprising an insecticidally, acaricidally, nematicidally or
molluscicidally effective amount of a compound of formula (I) and a
suitable carrier or diluent therefor. The composition is preferably
an insecticidal, acaricidal, nematicidal or molluscicidal
composition.
[0148] In a still further aspect the invention provides a method of
combating and controlling pests at a locus which comprises treating
the pests or the locus of the pests with an insecticidally,
acaricidally, nematicidally or molluscicidally effective amount of
a composition comprising a compound of formula (I). The compounds
of formula (I) are preferably used against insects, acarines or
nematodes.
[0149] The compositions can be chosen from a number of formulation
types, including dustable powders (DP), soluble powders (SP), water
soluble granules (SG), water dispersible granules (WG), wettable
powders (WP), granules (GR) (slow or fast release), soluble
concentrates (SL), oil miscible liquids (OL), ultra low volume
liquids (UL), emulsifiable concentrates (EC), dispersible
concentrates (DC), emulsions (both oil in water (EW) and water in
oil (EO)), micro-emulsions (ME), suspension concentrates (SC),
aerosols, fogging/smoke formulations, capsule suspensions (CS) and
seed treatment formulations. The l0 formulation type chosen in any
instance will depend upon the particular purpose envisaged and the
physical, chemical and biological properties of the compound of
formula (I).
[0150] Dustable powders (DP) may be prepared by mixing a compound
of formula (I) with one or more solid diluents (for example natural
clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite,
kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium
and magnesium carbonates, sulphur, lime, flours, talc and other
organic and inorganic solid carriers) and mechanically grinding the
mixture to a fine powder.
[0151] Soluble powders (SP) may be prepared by mixing a compound of
formula (I) with one or more water-soluble inorganic salts (such as
sodium bicarbonate, sodium carbonate or magnesium sulphate) or one
or more water-soluble organic solids (such as a polysaccharide)
and, optionally, one or more wetting agents, one or more dispersing
agents or a mixture of said agents to improve water
dispersibility/solubility. The mixture is then ground to a fine
powder. Similar compositions may also be granulated to form water
soluble granules (SG).
[0152] Wettable powders (WP) may be prepared by mixing a compound
of formula (I) with one or more solid diluents or carriers, one or
more wetting agents and, preferably, one or more dispersing agents
and, optionally, one or more suspending agents to facilitate the
dispersion in liquids. The mixture is then ground to a fine powder.
Similar compositions may also be granulated to form water
dispersible granules (WG).
[0153] Granules (GR) may be formed either by granulating a mixture
of a compound of formula (I) and one or more powdered solid
diluents or carriers, or from pre-formed blank granules by
absorbing a compound of formula (I) (or a solution thereof, in a
suitable agent) in a porous granular material (such as pumice,
attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths
or ground corn cobs) or by adsorbing a compound of formula (I) (or
a solution thereof, in a suitable agent) on to a hard core material
(such as sands, silicates, mineral carbonates, sulphates or
phosphates) and drying if necessary. Agents which are commonly used
to aid absorption or adsorption include solvents (such as aliphatic
and aromatic petroleum solvents, alcohols, ethers, ketones and
esters) and sticking agents (such as polyvinyl acetates, polyvinyl
alcohols, dextrins, sugars and vegetable oils). One or more other
additives may also be included in granules (for example an
emulsifying agent, wetting agent or dispersing agent).
[0154] Dispersible Concentrates (DC) may be prepared by dissolving
a compound of formula (I) in water or an organic solvent, such as a
ketone, alcohol or glycol ether. These solutions may contain a
surface active agent (for example to improve water dilution or
prevent crystallisation in a spray tank).
[0155] Emulsifiable concentrates (EC) or oil-in-water emulsions
(EW) may be prepared by dissolving a compound of formula (I) in an
organic solvent (optionally containing one or more wetting agents,
one or more emulsifying agents or a mixture of said agents).
Suitable organic solvents for use in ECs include aromatic
hydrocarbons (such as alkylbenzenes or alkylnaphthalenes,
exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200;
SOLVESSO is a Registered Trade Mark), ketones (such as
cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl
alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as
N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of
fatty acids (such as C.sub.8-C.sub.10 fatty acid dimethylamide) and
chlorinated hydrocarbons. An EC product may spontaneously emulsify
on addition to water, to produce an emulsion with sufficient
stability to allow spray application through appropriate equipment.
Preparation of an EW involves obtaining a compound of formula (I)
either as a liquid (if it is not a liquid at room temperature, it
may be melted at a reasonable temperature, typically below
70.degree. C.) or in solution (by dissolving it in an appropriate
solvent) and then emulsifiying the resultant liquid or solution
into water containing one or more SFAs, under high shear, to
produce an emulsion. Suitable solvents for use in EWs include
vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes),
aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and
other appropriate organic solvents which have a low solubility in
water.
[0156] Microemulsions (ME) may be prepared by mixing water with a
blend of one or more solvents with one or more SFAs, to produce
spontaneously a thermodynamically stable isotropic liquid
formulation. A compound of formula (I) is present initially in
either the water or the solvent/SFA blend. Suitable solvents for
use in MEs include those hereinbefore described for use in in ECs
or in EWs. An ME may be either an oil-in-water or a water-in-oil
system (which system is present may be determined by conductivity
measurements) and may be suitable for mixing water-soluble and
oil-soluble pesticides in the same formulation. An ME is suitable
for dilution into water, either remaining as a microemulsion or
forming a conventional oil-in-water emulsion.
[0157] Suspension concentrates (SC) may comprise aqueous or
non-aqueous suspensions of finely divided insoluble solid particles
of a compound of formula (I). SCs may be prepared by ball or bead
milling the solid compound of formula (I) in a suitable medium,
optionally with one or more dispersing agents, to produce a fine
particle suspension of the compound. One or more wetting agents may
be included in the composition and a suspending agent may be
included to reduce the rate at which the particles settle.
Alternatively, a compound of formula (I) may be dry milled and
added to water, containing agents hereinbefore described, to
produce the desired end product.
[0158] Aerosol formulations comprise a compound of formula (I) and
a suitable propellant (for example n-butane). A compound of formula
(I) may also be dissolved or dispersed in a suitable medium (for
example water or a water miscible liquid, such as n-propanol) to
provide compositions for use in non-pressurised, hand-actuated
spray pumps.
[0159] A compound of formula (I) may be mixed in the dry state with
a pyrotechnic mixture to form a composition suitable for
generating, in an enclosed space, a smoke containing the
compound.
[0160] Capsule suspensions (CS) may be prepared in a manner similar
to the preparation of EW formulations but with an additional
polymerisation stage such that an aqueous dispersion of oil
droplets is obtained, in which each oil droplet is encapsulated by
a polymeric shell and contains a compound of formula (I) and,
optionally, a carrier or diluent therefor. The polymeric shell may
be produced by either an interfacial polycondensation reaction or
by a coacervation procedure. The compositions may provide for
controlled release of the compound of formula (I) and they may be
used for seed treatment. A compound of formula (I) may also be
formulated in a biodegradable polymeric matrix to provide a slow,
controlled release of the compound.
[0161] A composition may include one or more additives to improve
the biological performance of the composition (for example by
improving wetting, retention or distribution on surfaces;
resistance to rain on treated surfaces; or uptake or mobility of a
compound of formula (I)). Such additives include surface active
agents, spray additives based on oils, for example certain mineral
oils or natural plant oils (such as soy bean and rape seed oil),
and blends of these with other bio-enhancing adjuvants (ingredients
which may aid or modify the action of a compound of formula
(I)).
[0162] A compound of formula (I) may also be formulated for use as
a seed treatment, for example as a powder composition, including a
powder for dry seed treatment (DS), a water soluble powder (SS) or
a water dispersible powder for slurry treatment (WS), or as a
liquid composition, including a flowable concentrate (FS), a
solution (LS) or a capsule suspension (CS). The preparations of DS,
SS, WS, FS and LS compositions are very similar to those of,
respectively, DP, SP, WP, SC and DC compositions described above.
Compositions for treating seed may include an agent for assisting
the adhesion of the composition to the seed (for example a mineral
oil or a film-forming barrier).
[0163] Wetting agents, dispersing agents and emulsifying agents may
be surface SFAs of the cationic, anionic, amphoteric or non-ionic
type.
[0164] Suitable SFAs of the cationic type include quaternary
ammonium compounds (for example cetyltrimethyl ammonium bromide),
imidazolines and amine salts.
[0165] Suitable anionic SFAs include alkali metals salts of fatty
acids, salts of aliphatic monoesters of sulphuric acid (for example
sodium lauryl sulphate), salts of sulphonated aromatic compounds
(for example sodium dodecylbenzenesulphonate, calcium
dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures
of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates),
ether sulphates, alcohol ether sulphates (for example sodium
laureth-3-sulphate), ether carboxylates (for example sodium
laureth-3-carboxylate), phosphate esters (products from the
reaction between one or more fatty alcohols and phosphoric acid
(predominately mono-esters) or phosphorus pentoxide (predominately
di-esters), for example the reaction between lauryl alcohol and
tetraphosphoric acid; additionally these products may be
ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates,
taurates and lignosulphonates.
[0166] Suitable SFAs of the amphoteric type include betaines,
propionates and glycinates.
[0167] Suitable SFAs of the non-ionic type include condensation
products of alkylene oxides, such as ethylene oxide, propylene
oxide, butylene oxide or mixtures thereof, with fatty alcohols
(such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such
as octylphenol, nonylphenol or octylcresol); partial esters derived
from long chain fatty acids or hexitol anhydrides; condensation
products of said partial esters with ethylene oxide; block polymers
(comprising ethylene oxide and propylene oxide); alkanolamides;
simple esters (for example fatty acid polyethylene glycol esters);
amine oxides (for example lauryl dimethyl amine oxide); and
lecithins.
[0168] Suitable suspending agents include hydrophilic colloids
(such as polysaccharides, polyvinylpyrrolidone or sodium
carboxymethylcellulose) and swelling clays (such as bentonite or
attapulgite).
[0169] A compound of formula (I) may be applied by any of the known
means of applying pesticidal compounds. For example, it may be
applied, formulated or unformulated, to the pests or to a locus of
the pests (such as a habitat of the pests, or a growing plant
liable to infestation by the pests) or to any part of the plant,
including the foliage, stems, branches or roots, to the seed before
it is planted or to other media in which plants are growing or are
to be planted (such as soil surrounding the roots, the soil
generally, paddy water or hydroponic culture systems), directly or
it may be sprayed on, dusted on, applied by dipping, applied as a
cream or paste formulation, applied as a vapour or applied through
distribution or incorporation of a composition (such as a granular
composition or a composition packed in a water-soluble bag) in soil
or an aqueous environment.
[0170] A compound of formula (I) may also be injected into plants
or sprayed onto vegetation using electrodynamic spraying techniques
or other low volume methods, or applied by land or aerial
irrigation systems.
[0171] Compositions for use as aqueous preparations (aqueous
solutions or dispersions) are generally supplied in the form of a
concentrate containing a high proportion of the active ingredient,
the concentrate being added to water before use. These
concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs,
WPs, WGs and CSs, are often required to withstand storage for
prolonged periods and, after such storage, to be capable of
addition to water to form aqueous preparations which remain
homogeneous for a sufficient time to enable them to be applied by
conventional spray equipment. Such aqueous preparations may contain
varying amounts of a compound of formula (I) (for example 0.0001 to
10%, by weight) depending upon the purpose for which they are to be
used.
[0172] A compound of formula (I) may be used in mixtures with
fertilisers (for example nitrogen-, potassium- or
phosphorus-containing fertilisers). Suitable formulation types
include granules of fertiliser. The mixtures suitably contain up to
25% by weight of the compound of formula (I).
[0173] The invention therefore also provides a fertiliser
composition comprising a fertiliser and a compound of formula
(I).
[0174] The compositions of this invention may contain other
compounds having biological activity, for example micronutrients or
compounds having fungicidal activity or which possess plant growth
regulating, herbicidal, insecticidal, nematicidal or acaricidal
activity.
[0175] The compound of formula (I) may be the sole active
ingredient of the composition or it may be admixed with one or more
additional active ingredients such as a pesticide, fungicide,
synergist, herbicide or plant growth regulator where appropriate.
An additional active ingredient may: provide a composition having a
broader spectrum of activity or increased persistence at a locus;
synergise the activity or complement the activity (for example by
increasing the speed of effect or overcoming repellency) of the
compound of formula (I); or help to overcome or prevent the
development of resistance to individual components. The particular
additional active ingredient will depend upon the intended utility
of the composition. Examples of suitable pesticides include the
following: [0176] a) Pyrethroids, such as permethrin, cypermethrin,
fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in
particular lambda-cyhalothrin), bifenthrin, fenpropathrin,
cyfluthrin, tefluthrin, fish safe pyrethroids (for example
ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin,
fenfluthrin, prallethrin or
5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidene-
methyl)cyclopropane carboxylate; [0177] b) Organophosphates, such
as, profenofos, sulprofos, acephate, methyl parathion,
azinphos-methyl, demeton-s-methyl, heptenophos, thiometon,
fenamiphos, monocrotophos, profenofos, triazophos, methamidophos,
dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone,
terbufos, fensulfothion, fonofos, phorate, phoxim,
pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or
diazinon; [0178] c) Carbamates (including aryl carbamates), such as
pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb,
ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb,
fenobucarb, propoxur, methomyl or oxamyl; [0179] d) Benzoyl ureas,
such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or
chlorfluazuron; [0180] e) Organic tin compounds, such as cyhexatin,
fenbutatin oxide or azocyclotin; [0181] f) Pyrazoles, such as
tebufenpyrad and fenpyroximate; [0182] g) Macrolides, such as
avermectins or milbemycins, for example abamectin, emamectin
benzoate, ivermectin, milbemycin, spinosad or azadirachtin; [0183]
h) Hormones or pheromones; [0184] i) Organochlorine compounds such
as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;
[0185] j) Amidines, such as chlordimeform or amitraz; [0186] k)
Fumigant agents, such as chloropicrin, dichloropropane, methyl
bromide or metam; [0187] l) Chloronicotinyl compounds such as
imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam;
[0188] m) Diacylhydrazines, such as tebufenozide, chromafenozide or
methoxyfenozide; [0189] n) Diphenyl ethers, such as diofenolan or
pyriproxifen; [0190] o) Indoxacarb; [0191] p) Chlorfenapyr; or
[0192] q) Pymetrozine.
[0193] In addition to the major chemical classes of pesticide
listed above, other pesticides having particular targets may be
employed in the composition, if appropriate for the intended
utility of the composition. For instance, selective insecticides
for particular crops, for example stemborer specific insecticides
(such as cartap) or hopper specific insecticides (such as
buprofezin) for use in rice may be employed. Alternatively
insecticides or acaricides specific for particular insect
species/stages may also be included in the compositions (for
example acaricidal ovo-larvicides, such as clofentezine,
flubenzimine, hexythiazox or tetradifon; acaricidal motilicides,
such as dicofol or propargite; acaricides, such as bromopropylate
or chlorobenzilate; or growth regulators, such as hydramethylnon,
cyromazine, methoprene, chlorfluazuron or diflubenzuron).
[0194] Examples of fungicidal compounds which may be included in
the composition of the invention are
(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoaceta-
mide (SSF-129),
4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamid-
e,
.alpha.-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-.gamma.-butyrolacto-
ne, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide
(IKF-916, cyamidazosulfamid),
3-5-dichloro-N--(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide
(RH-7281, zoxamide),
N-allyl4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide
(MON65500),
N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide
(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,
acibenzolar (CGA245704), alanycarb, aldimorph, anilazine,
azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol,
bitertanol, blasticidin S, bromuconazole, bupirimate, captafol,
captan, carbendazim, carbendazim chlorhydrate, carboxin,
carpropamid, carvone, CGA41396, CGA41397, chinomethionate,
chlorothalonil, chlorozolinate, clozylacon, copper containing
compounds such as copper oxychloride, copper oxyquinolate, copper
sulphate, copper tallate and Bordeaux mixture, cymoxanil,
cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide
1,1'-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb,
difenoconazole, difenzoquat, diflumetorim,
O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole,
dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap,
dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine,
doguadine, edifenphos, epoxiconazole, ethirimol,
ethyl(Z)-N--benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]-
thio)-.beta.-alaninate, etridiazole, famoxadone, fenamidone
(RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid
(KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,
fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,
flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil,
flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine,
hexaconazole, hydroxyisoxazole, hymexazole, imazalil,
imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole,
iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl
carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,
LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim,
mepronil, metalaxyl, metconazole, metiram, metiram-zinc,
metominostrobin, myclobutanil, neoasozin, nickel
dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,
organomercury compounds, oxadixyl, oxasulifuron, oxolinic acid,
oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron,
phenazin oxide, phosetyl-A1, phosphorus acids, phthalide,
picoxystrobin (ZA1963), polyoxin D, polyram, probenazole,
prochloraz, procymidone, propamocarb, propiconazole, propineb,
propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
pyroxyfur, pyrrolnitrin, quatemary ammnonium compounds,
quinomethionate, quinoxyfen, quintozene, sipconazole (F-155),
sodium pentachlorophenate, spiroxamine, streptomycin, sulphur,
tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,
thifluzamid, 2-(thiocyanomethylthio)benzothiazole,
thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl,
tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide,
tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine,
triflumizole, triticonazole, validamycin A, vapam, vinclozolin,
zineb and ziram.
[0195] The compounds of formula (I) may be mixed with soil, peat or
other rooting media for the protection of plants against
seed-borne, soil-borne or foliar fungal diseases.
[0196] Examples of suitable synergists for use in the compositions
include piperonyl butoxide, sesamex, safroxan and dodecyl
imidazole.
[0197] Suitable herbicides and plant-growth regulators for
inclusion in the compositions will depend upon the intended target
and the effect required.
[0198] An example of a rice selective herbicide which may be
included is propanil. An example of a plant growth regulator for
use in cotton is PIX.TM..
[0199] Some mixtures may comprise active ingredients which have
significantly different physical, chemical or biological properties
such that they do not easily lend themselves to the same
conventional formulation type. In these circumstances other
formulation types may be prepared. For example, where one active
ingredient is a water insoluble solid and the other a water
insoluble liquid, it may nevertheless be possible to disperse each
active ingredient in the same continuous aqueous phase by
dispersing the solid active ingredient as a suspension (using a
preparation analogous to that of an SC) but dispersing the liquid
active ingredient as an emulsion (using a preparation analogous to
that of an EW). The resultant composition is a suspoemulsion (SE)
formulation.
[0200] The invention is illustrated by the following Examples:
EXAMPLE 1
[0201] This Example illustrates the preparation of compound V-22,
1-Acetyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4+-p-
iperidine] ##STR45##
Step 1: Preparation of 4-methoxymethylenepiperidine-1-carboxylic
acid tert-butyl ester
[0202] Potassium tert-butoxide (21.3 g) was added in portions to a
stirred solution of methoxymethyltriphenylphosphonium chloride
(65.3 g) in anhydrous THF (500 ml) under an atmosphere of nitrogen
at 4.degree. C. A vivid orange colour was noted and the reaction
was left as such for 1 h. 4-Oxopiperidine-1-carboxylic acid
tert-butyl ester 1 (25 g) was added slowly not letting the
temperature rise above 10.degree. C. and the mixture was then
allowed to warn to room temperature overnight.
[0203] The reaction mixture was poured onto water (150 ml),
extracted three times with ethyl acetate (100 ml) and the combined
organics were washed with brine (300 ml), dried over anhydrous
sodium sulphate and concentrated in vacuo to yield a brown oil (50
g). Flash chromatography [SiO.sub.2; hexane, then ethyl
acetate-hexane (10:90)] yielded 26.4 g (77%) of the desired enol
ether. .sup.1H NMR (400 MHz, CDCl.sub.3) 1.5 (9H, m), 2.0-2.2 (m,
4H), 3.4 (m, 4H), 3.5 (s, 3H), 5.9 (s, 1H). MS (ES+) 228
(M+H.sup.+), 172 (M-.sup.ibutene+H.sup.+)
Step 2: Preparation of
5-chlorospiro[indoline-3,4'-piperidine]-1'-carboxylic acid
tert-butyl ester
[0204] Trifluoroacetic acid (12 ml) was added to a stirred solution
of 4-methoxymethylene-piperidine-1-carboxylic acid tert-butyl ester
(12.5 g), 4-chlorophenylhydrazine hydrochloide (9.75 g) and ethanol
(1 ml) in chloroform (1200 ml) at 4.degree. C. under an atmosphere
of nitrogen. The mixture was then stirred at 50.degree. C.
overnight, turning a dark green colour. The reaction was quenched
with concentrated ammonia solution (200 ml) in ice water (500 ml),
the organic layer turning orange. The organic layer was separated
and the aqueous was further extracted twice with dichloromethane.
The combined organics were washed with brine (300 ml), dried over
anhydrous sodium sulphate and concentrated in vacuo to yield 13 g
of the crude imine
5-chlorospiro[3H-indole-3,4'-piperidine]-1'-carboxylic acid
tert-butyl ester (purity approximately 80% by NMR). .sup.1H NMR
(400 MHz, CDCl.sub.3) 1.5 (9H, m), 1.70 (m, 2H), 1.85 (m, 2H), 3.50
(m, 2H), 4.05 (m, 2H), 7.35 (m, 2H), 7.60 (s, 1H), 8.35 (s, 1H). MS
(ES+) 321/323 (M+H.sup.+), 265/267 (M-.sup.ibutene+H.sup.+),
221/223 (M-Boc+H.sup.+).
[0205] Sodium borohydride (6.0 g) was added to a stirred solution
of crude imine (12 g) in absolute ethanol (500 ml) under an
atmosphere of nitrogen. The reaction was stirred for 15 min and
left to stand overnight. The mixture was concentrated in vacuo and
the residue re-dissolved in dichloromethane (100 ml). The organics
were washed with water (100 ml) and brine (100 ml), dried over
anhydrous sodium sulphate and concentrated in vacuo to yield a
brown solid. Flash chromatography [SiO.sub.2: ethyl
acetate-hexane-triethylamine (25:75:1)) yielded 9.8 g (56%, over
both steps) of the desired indoline. M.p. 165-166.degree. C.
.sup.1H NMR (400 MHz, CDCl.sub.3) 1.5 (9H, s), 1.70 (m, 4H), 2.9
(m, 2H), 3.50 (s, 2H), 3.75 (br s, 1H), 4.05 (m, 2H), 6.55 (d, J=6
Hz, 1H), 7.00 (m, 2H). MS (ES+) 323/325 (M+H.sup.+), 267/269
(M-.sup.ibutene+H.sup.+), 223/225 (M-Boc+H.sup.+).
Step 3: Preparation of
1-acetyl-5-chlorospiro[indoline-3,4'-piperidine]-1'-carboxylic acid
tert-butyl ester
[0206] Acetyl chloride (2.8 ml) was added dropwise to a stirred
solution of 5-chlorospiro[indoline-3,4'-piperidine]-1'-carboxylic
acid tert-butyl ester (9.8 g) and triethylamine (15 ml) in
anhydrous dichloromethane (400 ml) under an atmosphere of nitrogen.
The reaction was stirred for 1 h and was then quenched with
saturated sodium bicarbonate solution (200 ml). The organic layer
was dried over anhydrous sodium sulphate and concentrated in vacuo
to yield 9.8 g (87%) of the desired amide as an off-white solid.
M.p. 64-66.degree. C. .sup.1H NMR (400 MHz, CDCl.sub.3) a 6:1
mixture of rotamers. Major rotamer 1.5 (9H, s), 1.70 (m, 2H), 1.85
(m, 2H), 2.25 (s, 3H), 2.85 (m, 2H), 3.90 (s, 2H), 4.2 (m, 2H),
6.97 (d, J=1 Hz, 1H), 7.20 (dd, J=7 & 1 Hz, 1H), 8.15 (d, J=7
Hz, 1H). Minor rotamer 1.5 (9H, s), 1.70 (m, 2H), 1.85 (m, 2H),
2.45 (s, 3H), 2.85 (m, 2H), 4.05 (s, 2H), 4.2 (m, 2H), 7.2 (d, J=1
Hz, 1H), 7.25 (dd, J=7 & 1 Hz, 1H), 7.48 (d, J=7 Hz, 1H).
Step 4: Preparation of
1-acetyl-5-chlorospiro[indoline-3,4'-piperidine]
[0207] Trifluoroacetic acid (25 ml) was added to a stirred solution
of 1-acetyl-5-chlorospiro[indoline-3,4'-piperidine]-1'-carboxylic
acid tert-butyl ester (8 g) in anhydrous dichloromethane (250 ml)
under an atmosphere of nitrogen. The reaction was left as such for
3 h. The reaction was washed with saturated bicarbonate solution
(200 ml) and dried over sodium sulphate and concentrated in vacuo
to yield an off white solid. Flash chromatography [SiO.sub.2:
methanol-dichloromethane-triethylamine (90:5:5)] yielded 5.6 g
(61%) of the desired
1-Acetyl-5-chlorospiro[indoline-3,4'-piperidine]. .sup.1H NMR (400
MHz, CDCl.sub.3) a 6:1 mixture of rotamers. Major rotamer 1.70 (m,
2H), 1.80 (m, 2H), 2.27 (s, 3H), 2.75 (t, J=12 Hz, 2H), 3.15 (m,
2H), 3.90 (s, 2H), 7.12 (d, J=1 Hz, 1H), 7.18 (dd, J=7& 1 Hz,
1H), 8.15 (d, J=7 Hz, 1H). Minor rotamer (partial data) 2.44 (s,
3H), 2.86 (m, 2H), 3.10 (m, 2H), 4.05 (s, 2H). MS (ES+) 265/267
(M+H.sup.+).
Step 5: Preparation of
1-acetyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-p-
iperidine]
[0208] A solution of 4-chlorocinnamyl chloride (4.0 g) in
chloroform (120 ml) was added slowly to a stirred mixture of
1-acetyl-5-chlorospiro[indoline-3,4'-piperidine] (5.3 g) and
diisopropylethylamine (6.7 ml) in chloroform (120 ml) under an
atmosphere of nitrogen at room. The reaction was heated to
50.degree. C. for 30 h. The reaction mixture was concentrated in
vacuo to yield a red oil. Flash chromatography [SiO.sub.2; ethyl
acetate-hexane-triethylamine (50:50:1)] yielded 5.1 g (68%) of the
desired compound. .sup.1H NMR (400 MHz, CDCl.sub.3) a 5:1 mixture
of rotamers. Major rotamer 1.70 (d, J=12 Hz, 2H), 2.0 (td, J=12
& 2 Hz), 2.08 (t, J=12 Hz, 2H), 2.25 (s, 3H), 3.03 (d, J=12 Hz,
2H), 3.20 (d, J=7 Hz, 2H), 3.96 (s, 2H), 6.28 (dt, J=12 & 5 Hz,
1H), 6.50 (d, J=12 Hz, 1H), 7.13 (d, J=1 Hz, 1H), 7.18 (dd, J=7
& 1 Hz, 1H), 7.3 (m, 4H), 8.15 (d, J=7 Hz, 1H). Minor rotamer
(partial data) 2.42 (s, 3H), 4.00 (s, 2H). MS (ES+) 415/417/419
(M+H.sup.+).
[0209] Compounds II-301, V-21, XXIX-49, V-192, V-62, V-202 XXX-1,
XXX-11, XXX1-1, XXX-118, XXX-12, XXX-13, XXX-14, XXX-15, XXX-16,
XXX-17, XXX-18, XXX-19, XXX-2, XXX-20, XXX-21, XXX-22, XXX-23,
XXX-24, XXX-25, XXX-26, XXX-27, XXX-28, XXX-29, XXX-3, XXX-4,
XXX-5, XXX-6, XXX-7, XXXII-7, XXX-8, XXXI-2, XXXI-8, XXXII-1,
XXXII-10, XXXII-2, XXXII-3, XXXII-4, XXXII-5, XXXII-6, XXXII-8 and
XXXII-9 were prepared according to procedures analogous to those
described in Example 1.
EXAMPLE 2
[0210] This Example illustrates the preparation of compound I-1,
1-(2-Chloropyridin-4-1'-[trans-3-phenylallyl]spiro[indoline-3,4'-piperidi-
ne] ##STR46## Spiro[indoline-3,4'-piperidine]-1'-carboxylic acid
tert-butyl ester was prepared according to a procedure analogous to
that described in steps 1 and 2 of Example 1.
Step 1:
1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]-1'-
-carboxylic acid tert-butyl ester
[0211] Thionyl chloride (20 ml) was added to 2-chloroisonicotinic
acid (1.2 g) at room temperature. DMF (2 drops) was added and the
mixture was heated to reflux for 1 hour. The excess thionyl
chloride was evaporated and the residue was dissolved in
dichloromethane (50 ml). Triethylamine (2 ml) was added followed by
dropwise addition of a solution of
spiro[indoline-3,4'-piperidine]-1'-carboxylic acid tert-butyl ester
(1.7 g) dissolved in dichloromethane (20 ml). The mixture was
stirred for 48 hours. The reaction mixture was washed with pH 9.4
buffer (100 ml) and the aqueous layer was extracted with
dichloromethane. The combined organic layers were dried (magnesium
sulfate), filtered and evaporated. The crude product was purified
by chromatography [SiO.sub.2; ethyl acetate-hexane-triethylamine
(50:50:1), increasing polarity to (100:0:1)] to give 2.4 g (94%) of
the desired amide. M.p. 212.degree. C; .sup.1H NMR (400 MHz,
d.sub.6-DMSO) 1.50 (s, 9H), 1.6-1.8 (m, 4H), 2.8 (br s, 2H), 3.9
(br s, 2H), 4.08 (d, 2H), 7.0-7.2 (m, 3H), 7.30 (d, J=6 Hz, 1H),
8.43 (d, J=6 Hz, 1H), 7.40 (s, 1H), 8.0-8.2 (br m, 1H); MS (ES+)
428/430 (M+H.sup.+), 372/374 (M+H.sup.+-isobutene).
Step 2: preparation of
1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]trifluoroa-
cetic acid salt
[0212] Trifluoroacetic acid (30 ml) was added to a solution of
solution of
1-(2-chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]-1'-car-
boxylic acid tert-butyl ester (2.3 g) in anhydrous dichloromethane
(50 ml), the solution darkening upon addition. The reaction was
left as such for 15 min. The reaction mixture was evaporated in
vacuo and the dark residue re-suspended in dry ether (100 ml). The
residue was triturated until it became a free-flowing beige
precipitate. The precipitate was collected by filtration and dried
in a stream of nitrogen to give 2.28 g (96%) of the desired amine
salt. M.p. 245.degree. C. (decomposition). .sup.1H NMR (400 MHz,
d.sub.6-DMSO) 1.8 (m, 2H), 1.9 (m, 2H), 2.9 (m, 2H), 3.25 (m, 2H),
3.98 (s, 2H), 7.15-7.3 (m, 2H), 7.24 (d, J=8 Hz, 1H), 7.56 (d, J=7
Hz, 1H), 7.62 (s, 1H), 8.1 (br s, 1H), 8.56 (d, J=7 HZ, 1H), 8.8
(br s, 2H). MS (ES+) 328/330 (M+H.sup.+).
Step 3: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-1'-[trans-3-phenylallyl]spiro[indoline-3-
,4'-piperidine]
[0213]
1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]
trifluoroacetic acid salt (0.44 g) and trans-cinnamaldehyde (0.29
g) were suspended in tetrahydrofuran (8 ml) and ethanol (6 ml).
Borane-pyridine complex (0.26 ml) was added and the reaction
stirred vigorously overnight at room temperature. The mixture was
evaporated and partitioned between dichloromethane and water. The
organics were dried over anhydrous magnesium sulfate and evaporated
in vacuo. Flash chromatography [SiO.sub.2; ethyl
acetate-hexane-triethylamine (25:75:1), increasing polarity to
(50:50:1)] yielded 0.42 g (94%) of the desired product.
[0214] .sup.1H NMR (400 MHz, CDCl.sub.3) a 3:1 mixture of rotamers.
Major rotamer 1.70 (m, 2H), 1.8-2.1 (m, 4H), 3.0 (m, 2H), 3.20 (m,
2H), 3.75 (m, 2H), 6.3 (m, 1H), 6.52 (d, J=12 Hz, 1H), 7.1-7.4 (m,
9H), 7.46 (d, J=2 Hz, 1H), 8.2 (br m, 1H), 8.6 (m, 1H). MS (ES+)
444/446 (M+H.sup.+).
[0215] Compounds I-5, I-4, XXIX-7, XXIX-13, I-182, I-142, I-132,
XXII-22, VI-1, VI-101, I-22, XXX-96, XXIX-31 (with an alkylation as
the final step), XXIX-37 (with an alkylation as the final step),
XXIX-43 (with an alkylation as the final step), XXVII-1 (followed
by treatment with HCl in ether), XXVII-2 (followed by treatment
with HCl in ether), XXVII-22 (followed by treatment with HCl in
ether), XXVI-1 (followed by treatment with hydrogen peroxide in
methanol) and XXIX-25 (with an acylation as the final step) were
prepared according to procedures analogous to those described in
Example 2.
EXAMPLE 3
[0216] This Example illustrates the preparation of compound VI-22,
1-(Pyridin-4-yl)-carbonyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spir-
o[indoline-3,4'-piperidine] ##STR47##
1-Acetyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-p-
iperidine] was prepared according to the procedures described in
Example 1.
Step 1: Preparation of
5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
]
[0217]
1-Acetyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-
-3,4'-piperidine] (5.0 g) was dissolved in 6 N hydrochloric acid
(100 ml) and heated to reflux for 3 hours. The mixture was cooled
and the aqueous layer was basified with solid NaOH pellets (CARE!
Exotherm) to pH 12 and triethylamine (20 ml) was added. The mixture
was extracted three times with chloroform. The organic layers were
dried over anhydrous sodium sulfate, filtered and evaporated in
vacuo to give a crude brown oil which was purified by column
chromatography (SiO2, ethyl acetate:hexane: triethylamine,
1:1:0.01) to give 3.94 g (88%) of the desired indoline. MS (ES+)
373/375/377 (M+H.sup.+).
Step 2: Preparation of
1-(pyridin-4-yl)carbonyl-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro-
[indoline-3,4'-piperidine]
[0218] Isonicotinic acid (0.022 g) and DMF (1 drop) were dissolved
in thionyl chloride (2 ml) and the mixture was heated to reflux for
1 hour. The mixture was allowed to cool and the excess thionyl
chloride was evaporated in vacuo. The residue was dissolved in
chloroform (4 ml) and triethylamine (0.1 ml) was added. A solution
of
5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
] (0.055 g) in chloroform (1 ml) was added and the reaction was
allowed to stir at room temperature for 18 hours. Aqueous sodium
carbonate solution (1M, 20 ml) was added and the mixture was
extracted into chloroform (3.times.20 ml). The combined organic
layers were dried (magnesium sulfate), filtered and evaporated in
vacuo to give a crude brown oil which was purified by
chromatography (SiO2, ethyl acetate:hexane:triethylamine 0:1:0.01
to 1:0:0.01) to give 0.034 g (49%) of the desired amide. MS (ES+)
478/480/482 (M+H.sup.+).
[0219] Compounds XXV-62, I-192, I-202, XXIX-189, VI-202 and VI-62
were prepared according to procedures analogous to those described
in Example 3.
EXAMPLE 4
[0220] This Example illustrates the preparation of compound
XIX-202,
1-(4-cyanobenzoyl)-5-methyl-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indol-
ine-3,4'-piperidine] ##STR48##
Step 1: Preparation of
8-[trans-3-(4-chlorophenyl)allyl]-1,4-dioxa-8-azaspiror4.5]decane
[0221] 1,4-Dioxa-8-azaspiro[4.5]decane (0.88 g) was dissolved in
chloroform (5 ml) and diisopropylethylamine (2.1 ml) was added. A
solution of 4-chlorocinnamyl chloride (1.2 g) dissolved in
chloroform (2 ml) was added and mixture was heated to 70.degree. C.
overnight. The solvents were evaporated in vacuo and flash
chromatography [SiO.sub.2; ethyl acetate-hexane-triethylamine
(50:50:2)] yielded 1.38 g (76%) of the desired ketal as a yellow
oil. .sup.1H NMR (400 MHz, CDCl.sub.3) 1.78 (t, J=4 Hz, 4H), 2.60
(br s, 4H), 3.18 (d, J=5 Hz, 2H), 3.96 (s, 4H), 6.27 (dt, J=12
& 5 Hz, 1H) 6.47 (d, J=12 Hz, 2H), 7.28, m, 4H). MS (ES+)
294/296 M+H.sup.+.
Step 2: Preparation of
1-[trans-3-(4-chlorophenyl)allyl]-4-oxopiperidine
[0222]
8-[trans-3-(4-Chlorophenyl)allyl]-1,4-dioxa-8-azaspiro[4.5]decane
(1.38 g) was dissolved in methanol (40 ml) and 6 N hydrochloric
acid (120 ml) was added. The mixture was heated to reflux for 4 h.
The mixture cooled and was basified to pH 14 with solid sodium
hydroxide pellets (CARE! Exotherm), the solution becoming opaque.
The aqueous was extracted three times with ether. The organics were
washed with brine, dried over anhydrous MgSO.sub.4 and evaporated
to give 1.17g (100%) of the desired ketone .sup.1H NMR (400 MHz,
CDCl.sub.3) 2.38 (m, 4H), 2.70 (m, 4H), 3.15 (d, J=5 Hz, 2H), 3.96
(s, 4H), 6.17 (dt, J=12 & 5 Hz, 1H), 6.40 (d, J=12 Hz, 1H),
7.20 (m, 4H). MS (ES+) 250/252 M+H.sup.+.
Step 3: Preparation of
1-[trans-3-(4-chlorophenyl)allyl]-4-methoxymethylenepiperidine
[0223] Methoxymethyltriphenylphosphonium chloride (2.4 g) was
dissolved in tetrahydrofuran (20 ml) and was cooled to 4.degree. C.
Potassium tert-butoxide (0.78 g) was added, turning the solution a
bright orange colour. The reaction was left as such for 30 min. A
solution of 1-[trans-3-(4-chlorophenyl)allyl]-4-oxopiperidine (0.85
g) dissolved in tetrahydrofuran (10 ml) was added and the mixture
was stirred for 10 min. The solvents were evaporated in vacuo and
the residue re-suspended in ether. The organics were washed with
water and dried over anhydrous magnesium sulfate. Flash
chromatography [SiO.sub.2; ethyl acetate-hexane-triethylamine
(50:50:2)] gave 0.85 g (89%) of the desired enol ether. .sup.1H NMR
(400 MHz, CDCl.sub.3) 2.10 (t, J=6 Hz, 2H), 2.35 (t, J=6 Hz, 2H),
2.4 (m, 4H), 3.13 (d, J=5 Hz, 2H), 3.55 (s, 3H), 5.80 (s, 1H), 6.30
(dt, J=11 & 5 Hz, 1H), 6.45 (d, J=11 Hz, 1H), 7.28 (m, 4H). MS
(ES+) 278/280 (M+H.sup.+).
Step 4: Preparation of
5-methyl-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
]
[0224] Trifluoroacetic acid (0.75 ml) was added to a stirred
solution of
1-[trans-3-(4-chlorophenyl)allyl]-4-methoxymethylenepiperidine-and
4-tolylhydrazine hydrochloride (28 mg) in chloroform (5 ml) and the
reaction was heated to 50.degree. C. for 5 h. Triethylsilane (2 ml)
was added and the reaction was heated at 50.degree. C. for a
further 5 h. The mixture was allowed to cool and was quenched in
concentrated ammonia solution/ice chips (20 ml). The aqueous phase
was extracted twice with chloroform and the combined organics were
dried over anhydrous magnesium sulphate and concentrated in vacuo
to yield 0.04 g (63%) of the desired indoline. .sup.1H NMR (400
MHz, CDCl.sub.3) 1.75 (d, J=9 Hz, 2H), 1.96 (td, J=8 & 2, 2H),
2.13 (t, J=9 Hz, 2H), 2.25 (s, 3H), 2.95 (d, J=10 Hz, 2H), 3.19 (d,
J=5 Hz, 2H), 3.42 (s, 2H), 6.30 (dt, J=11 & 5 Hz, 1H), 6.48 (d,
J=11 Hz, 1H), 6.58 (d, J=7 Hz, 1H), 6.85 (d, J=7 Hz, 1H), 6.9 (s,
1H), 7.30 (m, 4H). MS (ES+) 353/355 (M+H.sup.+), 203
(M-4-chlorocinnamyl+H.sup.+).
Step 5: Preparation of
1-(4-cyanobenzoyl)-5-methyl-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indol-
ine-3,4'-piperidine]
[0225] This step was achieved using a Zymark XP2 synthetic
chemistry robot. A solution of
5-methyl-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
] (2 ml of a solution derived from dissolving 1.43 g in 100 ml of
THF) was added to a robot tube and the solvent was removed in
vacuo. 4-Cyanobenzoic acid (28 mg) was weighed into a different
robot tube. A solution of 2-chloro-1,3-dimethyl-2-imidazolinium
hexafluorophosphate (2 ml of a solution derived from dissolving
4.80 g in 180 ml of chloroform) and a solution of triethylamine (2
ml of a solution derived from dissolving 8.68 ml in 250 ml of
chloroform) were added to the acid and the tube was agitated and
allowed to stand for 30 minutes. A 2 ml aliquot of the acid
solution was added to the tube containing the dry amine. This tube
was agitated and allowed to stand overnight. The reaction mixture
was washed with 1M aqueous sodium carbonate solution and the
solvents were evaporated. The crude mixture was purified by MS
directed liquid chromatography to give the desired amide, 2.9 mg.
MS (ES+) 482/484 (M+H.sup.+).
[0226] Compounds I-61, I-171, XXVIII-97, XIX-22, XXVIII-67,
XXVIII-7, XX-22, XXIX-69, XXIX-75, XVIII-22, XXVIII-217, XXIX-81,
XXIX-87, XV-22, XXIX-93, XXIX-99, XXVIII-187, XXI-22, XXIX-105,
XXIX-111, XXIX-117, XXIX-123, XIII-22, XXIX-129, X-22, XXIX-135,
XXIX-141, XXIX-147, XXIX-153, XII-22, XXIX-196, II-22, XXIX-159,
XXVIII-252, XXVIII-27, XXVIII-42, XVIII-202, XX-62, XXIX-165,
XXVIII-162, XXVIII-132, XXIX-171, XXIX-177, XXI-62, XVII-62,
XIII-62, X-62, XXIX-183, XI-62, IX-62, XXIX-207, XXIX-195, II-62,
I-92, 1-112, I-12, I-32, I-52, I-72, I-152, I-162, I-82, I-252,
I-242, I-262, I-292, I-62 XXX-10, XXX-116, XXX-117, XXX-30, XXX-33,
XXX-34, XXX-35, XXX-36, XXX-37, XXX-38, XXX-39, XXX-40, XXX-41,
XXX-42, XXX-43, XXX-44, XXX-45, XXX-46, XXX-47, XXX-48, XXX-49,
XXX-50, XXX-9 and XXX-93 were prepared according to procedures
analogous to those described in Example 4.
EXAMPLE5
[0227] This example illustrates the preparation of compound XIV-22,
1-(2-Pyrazinyl)-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-
-3,4'-piperidine] ##STR49##
[0228]
5-Chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pip-
eridine] was prepared according to the procedures described in
Example 3.
[0229] Sodium hydride (50 mg) was added to a stirred solution of
5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
] (35 mg) and 2-chloropyrazine (43 mg) in anhydrous DMSO (5 ml)
under an atmosphere of nitrogen. The reaction was heated to
60.degree. C. overnight. The reaction mixture was diluted with
brine (20 ml) and extracted four times with dichloromethane (20
ml). The combined organics were dried over magnesium sulphate and
concentrated in vacuo (1 mmHg) to yield a brown oil. Flash
chromatography [SiO.sub.2, ethyl acetate-hexane-triethylamine
gradient (0:98:2) to (98:0:2)] yielded 25 mg (55%) of the desired
product. .sup.1H NMR (400 MHz, CDCl.sub.3) 1.75 (m, 2H), 2.05 (td,
J=8 & 2, 2H), 2.18 (t, J=9 Hz, 2H), 3.05 (d, J=9 Hz, 2H), 3.22
(d, J=5 Hz, 2H), 3.94 (s, 2H), 6.30 (dt, J=11 & 5 Hz, 1H), 6.51
(d, J=11 Hz, 1H), 7.18 (m, 2H), 7.30 (m, 4H), 8.05 (d, J=1Hz, 1H),
8.17 (d, J=6 Hz, 1H), 8.25 (m, 2H). MS (ES+) 451/453/455
M+H.sup.+.
[0230] Compounds XXIX-57 and XXIX-63 were prepared according to
procedures analogous to those described in Example 5.
EXAMPLE 6
[0231] This Example illustrates the preparation of compound XXII-3,
1-(2-Chloropyridin-4-yl)carbonyl-1'-[trans-3-(4fluorophenyl)allyl]spiro[i-
ndoline-3,4'-piperidine] ##STR50##
[0232]
1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]tri-
fluoroacetic acid salt was prepared according to the procedures
described in Example 2.
[0233]
1-(2-Chloropyridin-4-yl)carbonylspiro[indoline-3,4'-piperidine]tri-
fluoroacetic acid salt (0.25 g) was suspended in dioxane (2 ml) and
paraformaldehyde (0.08 g) was added. The mixture was stirred and
heated to 90.degree. C. for 20 minutes.
2-(4-fluorophenyl)vinylboronic acid (0.10 g) was dissolved in
dioxane (2 ml) and the resulting solution was added to the
salt/paraformaldehyde mixture and the resulting mixture was heated
to 90.degree. C. for 24 hours. The mixture was allowed to cool and
evaporated to dryness in vacuo. The residue was partitioned between
dichloromethane and water, and the organic layer was washed with
aqueous sodium carbonate solution (1M) and evaporated. The crude
product was purified by column chormatography (SiO.sub.2, first
column in dichloromethane:triethylamine 95:5, then a second column
starting with neat dichloromethane, then a gradient from ethyl
acetate:hexane: triethylamine 25:75:1 to 95:0:5) to give 0.20 g
(76%) of the desired product. MS (ES+) 462/464 M+H.sup.+.
[0234] Compounds I-23, XXIX-1, I-21, I-2, XXVI-2 (followed by
treatment with hydrogen peroxide in methanol) and XXVI-22 (followed
by treatment with hydrogen peroxide in methanol), were prepared
according to procedures analogous to those described in Example
6.
EXAMPLE 7
[0235] This Example illustrates the preparation of compound I-212,
5-Cyano-1-(2-chloropyridin-4-yl)carbonyl-1'-[trans-3-(4-chlorophenyl)ally-
l]spiro[indoline-3,4'-piperidine] ##STR51##
[0236]
5-Iodo-1-(2-chloropyridin-4-yl)carbonyl-1'-[trans-3-(4-chloropheny-
l)allyl]spiro[indoline-3,4'-piperidine] was prepared by procedures
analogous to those described in Example 2.
[0237]
5-Iodo-1-(2-chloropyridin-4-yl)carbonyl-1'-[trans-3-(4-chloropheny-
l)allyl]spiro[indoline-3,4'-piperidine] (0.05 g) was dissolved in
anhydrous THF (5 ml) under an atmosphere of dry nitrogen. Potassium
cyanide (0.011 g) and copper (I) iodide (0.016 g) were added and
the mixture was degassed for 15 minutes.
Tetrakis(triphenylphosphine) palladium (0.005 g) was added and the
mixture was heated to reflux for 28 hours. The reaction mixture was
diluted with dichloromethane (50 ml) and washed with water (30 ml).
The aqueous layer was extracted with dichloromethane (2.times.40
ml) and the combined organic layers were dried (magnesium sulfate),
filtered and evaporated in vacuo to give a colourless oil that was
purified by prep. TLC (SiO.sub.2, EtOAc:Hexane:Et.sub.3N 1:1:0.01)
to give 0.041 g (95%) of the desired product. MS (ES+) 503/505/507
M+H.sup.+.
[0238] Compounds XXIX-201, I-282, I-232 were prepared according to
standard procedures analogous to those described in Example 7.
Compound XXV-222 was prepared by treating compound XXIX-201 with
potassium carbonate in methanol. Compound I-222 was prepared by
re-acylation of compound XXV-222 under standard conditions.
EXAMPLE 8
[0239] This example illustrates the preparation of compound XXX-51
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(E)-3-(4-trifluoromethyl-ph-
enyl) allyl]spiro[indolin-3,4'-piperidine] ##STR52##
Step 1: Preparation of (E)-3-(4-trifluoromethyl-phenyl)-acrylic
acid ethyl ester
[0240] Ethyl diethylphosphonoacetate (84 g) in 1,2-dimethoxyethane
(100 ml) was added dropwise to a suspension of sodium hydride (55%
in oil, 15 g) in 1,2-dimethoxyethane (500 ml) at room temperature.
4-Trifluorobenzaldehyde (43.5 g) dissolved in 1,2-dimethoxyethane
(100 ml) was then added and the resulting mixture was stirred at
room temperature for 4 h. The reaction was quenched by addition of
water (400 ml), diluted with diethyl ether (700 ml), the organic
phase was separated, washed with brine, dried over sodium sulfate
and concentrated in vacuo. The crude product was recrystallised
from hexane to give 37 g of the desired product (61%) which was
characterized by its mass and NMR spectra.
Step 2: Preparation of
(E)-3-(4-trifluoromethyl-phenyl)-prop-2-en-1-ol
[0241] To a solution of the ester obtained in step 1 (37.1 g) in
toluene (310 ml) at 0.degree. C. was added dropwise
diisobutylaluminium hydride (1.2M in toluene, 317 ml) and the
solution was stirred at 0.degree. C. for 1 h. Water (47.6 ml) was
carefully added at 0.degree. C. followed by sodium hydroxide 2M
(47.6 ml) and finally water (95.1 ml). The mixture was allowed to
stir at room temperature for 1 h. After filtration, the solution
was washed with hydrochloric acid 2N, water and brine, dried over
sodium sulfate and concentrated in vacuo to give 29.5 g of the
desired alcohol as a solid (96%) which was characterized by its
mass and NMR spectra.
Step 3: Preparation of
1-((E)-3-bromo-propenyl)-4-trifluoromethyl-benzene
[0242] To a solution of the alcohol obtained in step 2 (10 g) in
dimethylacetamide (100 ml) at room temperature were added
triphenylphosphine (23 g) and carbon tetrabromide (29 g). The
resulting solution was stirred at room temperature for 1 h, poured
into water and extracted with ethyl acetate. The organic phase was
washed with water and brine, dried over sodium sulfate and filtered
over silica gel to give 13 g of the desired product as a white
solid (95%) which was characterized by its mass and NMR
spectra.
Step 4: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(E)-3-(4-trifluoromethyl-ph-
enyl)allyl]spiro[indolin-3,4'-piperidine]
[0243] To a stirred suspension of
-(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4'-piperidine]
(20 g) and diisopropylethylamine (18.2 ml) in acetonitrile (200 ml)
was added the allylic bromide obtained in step 3 (11.6 g) and the
reaction mixture was stirred overnight at room temperature. The
solution was diluted with ethyl acetate (200 ml), washed with brine
(3.times.100 ml), dried over sodium sulfate and concentrated in
vacuo. The residue was purified by column chromatography
(SiO.sub.2, ethyl acetate:hexane:triethylamine 95:5:0.1 to ethyl
acetate:methanol:triethylamine 95:5:0.1) to give 18.9 g of the
desired product (82%). Mp=130.degree. C.
[0244] Compounds XXX-82, XXX-83, XXX-84, XXX-85, XXX-86, XXX-87,
XXX-91 and XXX-92 were prepared according to standard procedures
analogous to those described in Example 8.
EXAMPLE 9
[0245] This example illustrates the preparation of compound
XXX-113
[0246]
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chloropheny-
l)-2-fluoro-allyl]spiro[indolin-3,4'-piperidine] ##STR53##
Step 1: Preparation of (Z)-3-(4-chloro-phenyl)-2-fluoro-acrylic
acid methyl ester
[0247] By analogy with: Cousseau, J. et al. Tetrahedron Lett. 1993,
43, 6903
[0248] 4-Chlorobenzaldehyde (0.66 g) was added to a suspension of
diethylfluorooxalacetate, sodium salt (1 g, prepared from diethyl
oxalate, ethylfluoroacetate and sodium hydride according to Alberg
et al. J. Am. Chem. Soc. 1992, 3542) in tetrahydrofuran (20 ml) at
0.degree. C., and the resulting: mixture was stirred 1 h at
0.degree. C. then 3 h at 80.degree. C. The reaction mixture was
concentrated in vacuo, diluted with diethyl ether, washed with
aqueous sodium bicarbonate, water and brine, dried over sodium
sulfate and concentrated in vacuo to afford a crude residue (1.2 g)
which was used diretly in the next step.
Step 2: Preparation of
(Z)-3-(4-chloro-phenyl)-2-fluoro-prop-2-en-1-ol
Step 3: Preparation of
1-((Z)-3-bromo-2-fluoro-propenyl)-4-chloro-benzene
Step 4: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chlorophenyl)-2-fl-
uoro-allyl]spiro[indolin-3,4'-piperidine]
[0249] Step 2 to 4 were carried out following the procedure
described in Example 8, step 2-4 to give 0.17 g of the desired
product (41%) which was characterized by its mass and NMR spectra.
MS (ES+) 530.
[0250] Compound XXX-114 was prepared according to standard
procedures analogous to those described in Example 9.
EXAMPLE 10
[0251] This example illustrates the preparation of I-25
[0252]
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[trans-3-(4-methoxyph-
enyl) allyl]spiro[indolin-3,4'-piperidine] ##STR54##
Step 1: Preparation of 1-(4-Methoxy-phenyl)-prop-2-en-1-ol
[0253] To a solution of p-anisaldehyde (1.54 ml) in tetrahydrofuran
(20 ml) at -10.degree. C. under argon was added dropwise vinyl
magnesium bromide (1M in THF, 12.5 ml). The solution was stirred
overnight at room temperature and quenched by addition of saturated
aqueous ammonium chloride (20 ml). The organic phase was separated,
dried over sodium sulfate and concentrated in vacuo. The residue
was purified by column chromatography (SiO.sub.2, ethyl
acetate:cyclohexan 7:3) to give 1.05 g of the desired product as a
colorless oil (51%) which was characterized by its mass and NMR
spectra.
Step 2: Preparation of
1-((E)-3-Chloro-propenyl)-4-methoxy-benzene
[0254] To a solution of the allylic alcohol obtained in step 1 (200
mg) in diethyl ether (3 ml) was added thionyl chloride (0.087 ml)
and the solution was stirred at room temperature for 1 h. The
solution was concentrated in vacuo to give 221 mg of the desired
product (100%) as a colorless solid. Mp=70.degree. C.
Step 3: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[trans-3-(4-methoxy-phenyl)a-
llyl]spiro[indolin-3,4'-piperidine]
[0255] Alkylation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4'-piperidine]
(0.43 g) with 1-((E)-3-chloro-propenyl)-4-methoxy-benzene obtained
in step 2 (0.22 g) was carried out following the procedure
described in example 101, step 4 to afford 0.36 g of the title
compound (59%) which was characterized by its mass and NMR spectra.
MS (ES+) 509. Mp=83-85.degree. C.
EXAMPLE 11
[0256] This example illustrates the preparation of XXX-115
[0257]
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chloropheny-
l)-3-chloro-allyl]spiro[indolin-3,4'-piperidine] ##STR55##
Step 1: Preparation of (Z)-3-chloro-3-(4-chloro-phenyl)-acrylic
acid methyl ester
[0258] By analogy with: Tanaka, M. et al. J. Am. Chem. Soc. 1998,
120, 12365 To a solution of 4-chlorophenylacetylene (100 mg) and
Rh(CO)(PPh.sub.3).sub.2Cl (5 mg) in toluene (3 ml) was added methyl
chloroformate (0.17 ml) and the mixture was stirred in a sealed
tube at 110.degree. C. for 10 h. The reaction mixture was
concentrated in vacuo and subjected to column chromatography
(SiO.sub.2, ethyl acetate:cyclohexan 1:9) to give 104 mg of the
desired product as a brown solid (61%) which was characterized by
its mass and NMR spectra. Mp=40.degree. C.
Step 2: Preparation of
(Z)-3-chloro-3-(4-chloro-phenyl)-prop-2-en-1-ol
[0259] Following the procedure described in Example 8, step 2,
(Z)-3-chloro-3-(4-chloro-phenyl)-acrylic acid methyl ester ( 462
mg) was converted into the desired product (391 mg, 96%) which was
characterized by its mass and NMR spectra.
Step 3: Preparation of
1-chloro-4-((Z)-1,3-dichloro-propenyl)-benzene
[0260] To a solution of
(Z)-3-chloro-3-(4-chloro-phenyl)-prop-2-en-1-ol (101 mg) in toluene
(3 ml) was added thionyl chloride (0.11 ml) and one drop of
dimethylformamide. After 1 h, the solution was concentrated in
vacuo to afford 120 mg of the desired allylic chloride (100%) as a
colorless oil.
Step 4: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chlorophenyl)-3-ch-
loro-allyl]spiro[indolin-3,4'-piperidine]
[0261] Alkylation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-spiro[indolin-3,4'-piperidine]
(0.18 g) with 1-chloro-4-((Z)-1,3-dichloro-propenyl)-benzene
obtained in step 3 (0.11 g) was carried out following the procedure
described in example 101, step 4 to afford 0.17 g of the title
compound (64%) as a foam which was characterized by its mass and
NMR spectra. MS (ES+) 548.
EXAMPLE 12
[0262] This example illustrates the preparation of XXX-90
[0263]
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chloropheny-
l)-3-fluoro-allyl]spiro[indolin-3,4'-piperidine] ##STR56##
Step 1: Preparation of (Z)-3-(4-Chloro-phenyl)-3-fluoro-acrylic
acid methyl ester
[0264] By analogy with: Cousseau, J. J. Chem. Soc. Chem. Commun.
1989, 1493
[0265] To a solution of (4-chloro-phenyl)-propynoic acid methyl
ester (5.36 g) in dimethylformamide (60 ml) was added cesium
fluoride (11.4 g) and potassium hydrogen fluoride (2.73 g) in water
(5.4 ml) and the mixture was stirred at 80.degree. C. for 8 h. The
reaction mixture was cooled to room temperature, diluted with ethyl
acetate (50 ml), the organic phase washed with water (3.times.50
ml) and brine (3.times.20 ml), dried over sodium sulfate and
concentrated in vacuo. The residue was purified by column
chromatography (SiO.sub.2, ethyl acetate:cyclohexan 1:9) to give
1.06 g of the desired product (20%) which was characterized by its
mass and NMR spectra.
Step 2: Preparation of
(Z)-3-(4-chloro-phenyl)-3-fluoro-prop-2-en-1-ol
Step 3: Preparation of
1-Chloro-4-((Z)-3-chloro-1-fluoro-propenyl)-benzene
Step 4: Preparation of
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-chlorophenyl)-3-fl-
uoro-allyl]spiro[indolin-3,4'-piperidine]
[0266] Step 2 to 4 were carried out following the procedure
described in Example 11, step 2-4 to give 163 mg of the desired
product (42%) which was characterized by its mass and NMR spectra.
MS (ES+) 531.
[0267] Compounds XXX-88 and XXX-90 were prepared according to
standard procedures analogous to those described in Example 12.
EXAMPLE 13
[0268] This example illustrates the preparation of compound XXX-121
and XXX-94, 1-carboxylic acid
(4-chloro-phenyl)-amide-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[-
indoline-3,4'-piperidine]. ##STR57##
[0269]
5-Fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pip-
eridine] was prepared according to a procedure analogous to that
described in steps 1 to 4 of Example 4.
Step 1: Preparation of Compound XXX-121.
1-nitroso-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'--
piperidine]
[0270] A solution of
5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperidine-
] (5 g) in dichloromethane (15 ml) was added to a suspension of wet
silica gel (50% w/w in water, 2.9 g) and zinc chloride (5.73 g) in
dichloromethane (15 ml) and the resulting mixture was stirred for
3.5 hours at room temperature. The reaction mixture was diluted
with ethyl acetate and the insoluble residues were removed by
filtration. The filtrate was washed with saturated aqueous sodium
bicarbonate solution, water and brine, dried over sodium sulfate
and the solvents were evaporated in vacuo to afford 5.13 g (95%) of
the desired nitroso-amine as a solid. MS (ES+) 386.
Step 2: Preparation of
1-amino-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pi-
peridine]
[0271] A solution of
1-nitroso-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'--
piperidine] (5 g) in tetrahydrofuran (60 ml) was added dropwise to
a suspension of lithium aluminium hydride (1.47 g) in
tetrahydrofuran (60 ml) at 0.degree. C. and the resulting mixture
was stirred at room temperature for 2.5 hours. Water (4.8 ml) was
carefully added, followed by 15 % aqueous sodium hydroxide (4.8
ml), and finally water (14.4 ml). The mixture was stirred for 0.5
hours, diluted with ethyl acetate, dried over sodium sulfate, and
filtered. The solvents were evaporated in vacuo to afford 5.1 g
(100%) of the desired amino-indoline as a solid. MS (ES+) 372.
Step 3: Preparation of 1-carboxylic acid
(4-chloro-phenyl)-amide-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[-
indoline-3,4'-piperidine]
[0272] 2-Chloroisonicotinoyl chloride (1.2 g) was added to a
stirred solution of
1-amino-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pi-
peridine] (0.2 g) and triethylamine (0.3 ml) in dichloromethane (4
ml) at room temperature. The mixture was stirred for 2 hours.
[0273] The reaction mixture was washed with water and the aqueous
layer was extracted with dichloromethane. The combined organic
layers were dried (sodium sulfate), filtered and evaporated. The
crude product was purified by chromatography [SiO.sub.2; ethyl
acetate-methanol (96:4) to give 0.13 g (48%) of the desired
product. MS (ES+) 511.
[0274] Compounds XXX-95, XXX-97, XXX-98 and XXX-99 were prepared
according to standard procedures analogous to those described in
Example 13
EXAMPLE 14
[0275] This example illustrates the preparation of compound
XXX-119,
1-(4-chloro-phenyl)-urea-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro-
[indoline-3,4'-piperidine]. ##STR58##
[0276] To a solution of
1-amino-5-fluoro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pi-
peridine] (0.2 g) in tetrahydrofuran (2 ml) was added
4-chlorophenyl isocyanate (70 mg) and the mixture was stirred at
room temperature for 10 min. The solvent was evaporated in vacuo
and the residue purified by preparative HPLC to afford the title
compound (49%) as a solid. MS (ES+) 525.
[0277] Compounds XXX-100, XXX-101, XXX-102 and XXX-103 were
prepared according to standard procedures analogous to those
described in Example 14.
EXAMPLE 15
[0278] This example illustrates the preparation of compound XXX-102
N'-[5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-piperi-
dine]-1-yl]-N,N-dimethylacetamidine ##STR59##
[0279] To a solution of
1-amino-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pi-
peridine] (0.15 g) in tetrahydrofuran (2 ml) was added
N,N-dimethylacetamide dimethyl acetal (0.2 g) and the mixture was
stirred at 70.degree. C. for 24 hours. The solvent was evaporated
in vacuo and the residue purified by chromatography [SiO.sub.2;
ethyl acetate-methanol (9:1) to give 35 mg (20%) of the desired
product. MS (ES+) 457.
EXAMPLE 16
[0280] This example illustrates the preparation of compound XXX-105
1-[carboxylic acid
(2-methoxy-ethyl)-amide]-5-chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro-
[indoline-3,4'-piperidine]. ##STR60##
[0281]
5-Chloro-1'-[trans-3-(4-chlorophenyl)allyl]spiro[indoline-3,4'-pip-
eridine] (2.5 g) was added to a suspension of sodium bicarbonate
(1.7 g) in acetonitrile (45 ml) and the resulting mixture cooled to
0.degree. C. 4-Nitrophenyl chloroformate (2.54 g) was then added
dropwise and the resulting solution stirred at 0.degree. C. for 2
hours. 3 ml of the solution was added to a solution of
2-methoxy-ethylamine (315 mg) and triethylamine (0.3 ml) in
dimethylformamide (10 ml) and the resulting mixture was stirred at
50.degree. C. for 3 hours. The solution was cooled to room
temperature, poured into water, extracted three times with ethyl
acetate. The organic phase was dried over sodium sulfate, filtered,
and the solvents were removed in vacuo. The residue was purified by
reverse-phase HPLC to afford the desired product (57% yield). MS
(ES+) 458.
[0282] Compounds XXX-104, XXX-106, XXX-107, XXX-108, XXX-109,
XXX-110, XXX-111 and XXX-112 were prepared according to standard
procedures analogous to those described in Example 16.
EXAMPLE 17
[0283] Preparation of compound XXVI-1
--1,2-Dihydro-1-(4-nitrobenzoyl)-1'-(3-phenyl-2-propenyl)-spiro[3H-indole-
-3-4'-piperidine] ##STR61## ##STR62##
[0284] In the experimental details to follow, standard wash will
refer to the following washing sequence: dimethylformamide,
dichloromethane, dimethylformamide, dichloromethane, methanol,
dichloromethane, methanol (X2), tert-butyl methyl ether (X2) and
resin swelling protocol will be based on a standard of 10 ml of
solvent per gram of resin. Compound identities and purities were
determined using High Performance Liquid Chromatography lo coupled
Mass Spectrometry (HPLC-MS) and Proton Nuclear Magnetic Resonance
(1H NMR) on selected compounds. REM resin was prepared from
commercially available (hydroxymethyl)polystyrene resin and
acryloyl chloride. The loading of the resins were assumed to be
constant at 1.2 mmolg.sup.-1 throughout the synthesis.
Step A: Loading of 4-Formylpiperidine dimethyl acetal onto REM
resin (Resin A)
[0285] REM resin (10 g, 12 mmol) was swollen in dimethylformamide
(100 ml). A solution of 4-formylpiperidine dimethyl acetal (2.86 g,
18 mmol) in dimethylformamide (10 ml) was then added. The reaction
was left to shake at room temperature for 18 hours. The resulting
resin was then filtered, washed according to the standard procedure
and dried in vacuo to afford 11.83 g (96% yield) of the desired
resin A.
Step B: Preparation of Solid supported 4-Formylpiperidine (Resin
B)
[0286] A 100 ml solution of trifluoroacetic
acid/dichloromethane/water (49:49:2) was added to resin A (10 g, 12
mmol) and the mixture was then shaken at room temperature for 2
hours. The resulting resin was then filtered, washed using
dichloromethane (.times.3), methanol, dichloromethane, methanol,
tert-butyl methyl ether (.times.2) and dried in vacuo to afford
9.48 g of the desired resin B, which was stored at -50.degree. C.
under nitrogen.
Step C: Preparation of Solid supported
Spiro[3H-indole-3,4'-piperidine) (Resin C)
[0287] To resin B (1 g, 1.2 mmol) was added a solution of 5%
trifluoroacetic acid in dichloromethane (10 ml) followed by
addition of anisole (0.0026 g, 0.024 mmol). The mixture was
degassed with nitrogen for 10 minutes, and phenylhydrazine (0.39 g,
3.6 mmol) was added. The reaction mixture was stirred under
nitrogen and heated to reflux for 36 hours. The mixture was then
filtered, washed according to the standard wash cycle and dried in
vacuo to afford 1.09 g of the desired resin C, which was used
immediately in Step D.
Step D: Preparation of Solid supported
1,2-Dihydro-spiro[3H-indole-3,4'-piperidine] (Resin D)
[0288] To resin C (1 g, 1.2 mmol), swollen in anhydrous
dichloromethane (10 ml) was added sodium triacetoxyborohydride
(0.51 g, 2.4 mmol) as a solid. The reaction mixture was stirred at
room temperature under nitrogen for 2 hours. The resin was then
filtered, washed according to the standard wash cycle and dried in
vacuo to afford 0.95 g of the desired resin D, which was stored at
-50.degree. C. under nitrogen.
Step E: Preparation of Solid supported
1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4'-piperidine]
(Resin E)
[0289] Resin D (0.5 g, 0.6 mmol) was swollen in anhydrous
dichloromethane (5 ml). To the mixture was added 4-nitrobenzoyl
chloride (0.33 g, 1.8 mmol) and N,N-diisopropylethylamine (0.42 ml,
2.4 mmol). After shaking at room temperature for 18 hours, the
resin was filtered, washed according to the standard wash cycle and
dried in vacuo to afford 0.53 g of the desired resin E.
Step F: Quaternization of Solid supported
1,2-Dihydro-1-(4-nitrobenzoyl)-spiro[3H-indole-3,4'-piperidine]
(Resin F)
[0290] To resin E (0.1 g, 0.12 mmol) in anhydrous dimethylformamide
(1 ml) was added cinnamyl bromide (0.12 g, 0.6 mmol). The reaction
mixture was shaken at room temperature for 48 hours. The resulting
resin was then washed according to the standard wash cycle to
afford 0.11 g of the desired resin F, which was used immediately in
Step G.
Step G: Preparation of
1,2-Dihydro-1-(4-nitrobenzoyl)-1'-(3-phenyl-2-propenyl)-spiro[3H-indole-3-
,4'-piperidine]
[0291] To resin F (0.11 g, 0.132 mmol) in anhydrous
dimethylformamide (1.1 ml) was added Amberlite IRA-93 (previously
washed with 10% N,N-diisopropylethylamine/dimethylformamide) (0.11
g). The mixture was shaken at room temperature for 36 hours. The
dimethylformamide filtrate was then collected and concentrated
under reduced pressure. The resin was further washed with
dichloromethane and methanol. All filtrates were then combined and
concentrated in vacuo to afford 0.052 g (88% yield) of the desired
compound as a pale yellow oil.
[0292] By an analogous procedure other compounds were prepared
including compound XVI-21,
5-Chloro-1,2-dihydro-1-(4-nitrobenzoyl)-1'-(3-phenyl-2-propenyl)-spiro[3H-
-indole-3-4'-piperidine]
EXAMPLE 18
[0293] This example illustrates the preparation of compound XXX-72,
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(Z)-3-(4-methylthiophenyl)
allyl]spiro[indolin-3,4'-piperidine] ##STR63##
[0294] To 13.1 mg 4-thiomethylboronic acid in a "Zisser-block" were
added 14.5 mg
1-(2-chloropyridin-4-yl)carbonyl-5-chloro-1'-[(E/Z)-3-bromo-allyl-
]spiro[indolin-3,4'-piperidine] in 0.05ml dimethoxyethane, 8 mg
sodium bicarbonate in 0.3 ml H2O and 2 mg
bis-(triphenylphosphin)palladium(II) dichloride. The mixture was
stirred at 75.degree. C. for 13 hours.
[0295] The organic layer was separated and evaporated in vacuo and
the residue purified by chromatography (H2O-acetonitrile gradient)
to yield the desired product MS (ES+) 525.
[0296] By an analogous procedure other compounds were prepared
including compounds XXX1-4, XXX-51, XXX-52, XXX-53, XXX-54, XXX-55,
XXX-56, XXX-57, XXX-58, XXX-59, XXX-60, XXX-61, XXX-62, XXX-63,
XXX-64, XXX-65, XXX-66, XXX-67, XXX-68, XXX-69, XXX-70, XXX-71,
XXX-73, XXX-74, XXX-75, XXX-76, XXX-77, XXX-78, XXX-79, XXX-80,
XXX-81, XXXI-3, XXXI-5, XXXI-6 and XXXI-7.
EXAMPLE 19
[0297] This Example illustrates the pesticidal/insecticidal
properties of compounds of formula (I).
[0298] Test against were performed as follows:
Spodoptera littoralis (Egyptian Cotton Leafworm)
[0299] Cotton leaf discs were placed on agar in a 24-well
microtiter plate and sprayed with test solutions at an application
rate of 200 ppm. After drying, the leaf discs were infested with 5
L.sub.1 larvae. The samples were checked for mortality, repellent
effect, feeding behaviour, and growth regulation 3 days after
treatment (DAT). The following compounds gave at least 80% control
of Spodoptera littoralis: I-2, I-12, I-21, I-22, I-23, I-32, I-52,
I-61, I-62, I-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162,
I-182, I-192, I-202, I-212, I-222, I-232, I-242, I-252, I-262,
I-282, II-62, V-22, VI-22, VI-62, VI-202, X-22, X-62, XI-62,
XII-22, XIII-62, XIV-22, XV-22, XVII-62, XVIII-22, XIX-22, XIX-202,
XX-22, XX-62, XXI-22, XXI-62, XXII-22, XXVI-2, XXVI-22, XXVII-2,
XXVII-22, XXIX-43, XXIX-93, XXIX-195, XXIX-196, XXIX-201, XXX-10,
XXX-106, XXX-107, XXX-118, XXX-15, XXX-16, XXX-18, XXX-24, XXX-26,
XXX-28, XXX-3, XXX-36, XXX-43, XXX-48, XXX-49, XXX-52, XXX-55,
XXX-57, XXX-60, XXX-67, XXX-83, XXX-84, XXX-87, XXX-88, XXX-99,
XXXI-8, XXXII4, XXX-104, XXX-105, XXX-109, XXX-112, XXX-113,
XXX-114, XXX-117, XXX-12, XXX-13, XXX1-4, XXX-19, XXX-2, XXX-20,
XXX-30, XXX-38, XXX-39, XXX-40, XXX-41, XXX-42, XXX-44, XXX-45,
XXX-50, XXX-53, XXX-59, XXX-6, XXX-61, XXX-62, XXX-65, XXX-7,
XXX-70, XX-8, XXX-82, XXX-89, XXX-95, XXXI-2, XXXI-7, XXX-11,
XXX1-1, XXX-110, XXX-111, XXX-31, XXX-51, XXX-66, XXX-86, XXX-93
and XXXI-5.
Heliothis virescens (Tobacco Budworm):
[0300] Eggs (0-24 h old) were placed in 24-well microtiter plate on
artificial diet and treated with test solutions at an application
rate of 200 ppm by pipetting. After an incubation period of 4 days,
samples were checked for egg mortality, larval mortality, and
growth regulation. The following compounds gave at least 80%
control of Heliothis virescen: I-1, I-2, I-3, I-4, I-5, I-12, I-21,
I-22, I-23, I-32, I-52, I-61, I-62, I-72, I-82, I-92, I-112, I-132,
I-142, I-152, I-162, I-171, I-182, I-192, I-202, I-212, I-222,
I-232, I-242, I-252, I-262, I-282, I-292, II-301, II-22, II-62,
V-21, V-22, V-62, V-192, V-202, VI-1, VI-22, VI-62, VI-101, VI-202,
IX-62, X-22, X-62, XI-62, XII-22, XIII-22, XIII-62, XIV-22, XV-22,
XVII-62, XVIII-22, XVIII-202, XIX-22, XIX-202, XX-22, XX-62,
XXI-22, XXI-62, XXII-22, XXV-222, XXVI-2, XXVI-22, XXVII-2,
XXVII-22, XXVIII-7, XXVIII-27, XXVIII-42, XXVIII-67, XXVIII-97,
XXVIII-132, XXVIII-187, XXVIII-217, XXVIII-252, XXIX-1, XXIX-7,
XXIX-13, XXIX-57, XXIX-63, XXIX-75, XXIX-81, XXIX-87, XXIX-93,
XXIX-111, XXIX-117, XXIX-123, XXIX-129, XXIX-141, XXIX-147,
XXIX-153, XXIX-159, XXIX-165, XXIX-171,XXIX-183,XXIX-195,XXIX-196,
XXIX-201,XXX-100, XXX-107, XXX-108, XXX-109, XXX-116, XXX-14,
XXX-15, XXX-17, XXX-23, XXX-32, XXX-35, XXX-4, XXX-43, XXX-46,
XXX-55, XXX-56, XXX-63, XXX-64, XXX-7, XXX-71, XXX-72, XXX-73,
XXX-76, XXX-77, XXX-78, XXX-79, XXX-80, XXX-81, XXX-85, XXX-88,
XXX-92, XXX-94, XXX-98, XXXII-1, XXXII-2, XXXII-3, XXXII-5,
XXXII-8, XXXII-9, XXX-1, XXX-10, XXX-105, XXX-106, XXX-112,
XXX-115, XXX-118, XXX-12, XXX-16, XXX-18, XXX-19, XXX-21, XXX-22,
XXX-24, XXX-26, XXX-28, XXX-29, XXX-33, XXX-34, XXX-37, XXX-50,
XXX-54, XXX-58, XXX-60, XXX-65, XXX-67, XXX-68, XXX-74, XXX-75,
XXX-83, XXX-87, XXX-9, XXX-91, XXX-93, XXX-96, XXX-99, XXXI-3,
XXXI-6, XXXII-10, XXXII-4, XXXII-6, XXX1-1, XXX-110, XXX-111,
XXX-113, XXX-114, XXX-117, XXX-13, XXX1-4, XXX-2, XXX-20, XXX-3,
XXX-30, XXX-31, XXX-36, XXX-38, XXX-40, XXX-41, XXX-44, XXX-45,
XXX-48, XXX-49, XXX-5, XXX-53, XXX-57, XXX-59, XXX-6, XXX-61,
XXX-62, XXX-7, XXX-8, XXX-82, XXX-89, XXX90, XXXI-2, XXX-120 and
XXXI-7.
Plutella xylostella (Diamond Back Moth):
[0301] 24-well microtiter plate (MTP) with artificial diet was
treated with test solutions at an application rate of 18.2 ppm by
pipetting. After drying, the MTP's were infested with larvae
(L2)(10-15 per well). After an incubation period of 5 days, samples
were checked for larval mortality, antifeedant and growth
regulation. The following compounds gave at least 80% control of
Plutella xylostella:
[0302] I-1, I-2, I-3, I-4, I-5, I-12, I-21, I-22, I-23, I-32, I-52,
I-61, I-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-171,
I-192, I-202, I-212, I-222, I-242, I-252, I-262, I-282, I-292,
II-22, II-62, V-22, V-62, V-202, VI-22, VI-62, IX-62, X-22, X-62,
XI-62, XII-22, XIII-62, XIV-22, XV-22, XVII-62, XX-22, XXI-62,
XXII-22, XXV-62, XXVI-2, XXVI-22, XXVII-1, XXVII-2, XXVII-22,
XXVIII-97, XXVIII-187, XXIX-129, XXIX-135, XXIX-159, XXIX-177,
XXIX-189, XXIX-195, XXIX-196, XXX-10, XXX-100, XXX-109, XXX-112,
XXX-117, XXX-16, XXX-18, XXX-19, XXX-21, XXX-28, XXX-34, XXX-36,
XXX-43, XXX-48, XXX-5, XXX-50, XXX-54, XXX-59, XXX-60, XXX-66,
XXX-68, XXX-69, XXX-75, XXX-83, XXX-90, XXX-91, XXX-98, XXXI-2,
XXXI-7, XXXII-4, XXXII-8, XXXII-9,
XXX-101,XXX-104,XXX-107,XXX-110,XXX-111,XXX-118,XXX-12,XXX-13,
XXXI-4, XXX-22, XXX-3, XXX-30, XXX-37, XXX-39, XXX-40, XXX-41,
XXX-42, XXX-44, XXX-49, XXX-57, XXX-61, XXX-7, XXX-89, XXX-105,
XXX-106, XXX1-1, XXX-113, XXX-114, XXX-31, XXX-35, XXX-38, XXX-45,
XXX-46, XXX-47, XXX-53, XXX-62, XXX-67, XXX-70, XXX-8, XXX-86,
XXXI-5, XXX-2, XXX-120 and XXX-51
Myzus persicae (Green Peach Aphid):
[0303] Sunflower leaf discs were placed on agar in a 24-well
microtiter plate and sprayed with test solutions at an application
rate of 200 ppm. After drying, the leaf discs were infested with an
aphid population of mixed ages. After an incubation period of 6
DAT, samples were checked for mortality. The following compounds
gave at least 80% control of Myzus persicae:
[0304] I-2,1-21, II-62, XI-62, XXVII-2, XXVIII-162, XXIX-49
XXX-111, XXX-13, XXX-29, XXX-34 and XXX-47.
Tetranychus urticae (Two-Spotted Spider Mite):
[0305] Bean leaf discs on agar in 24-well microtiter plates wer
sprayed with test solutions at an application rate of 200 ppm.
After drying, the leaf discs are infested with mite populations of
mixed ages. 8 days later, discs are checked for egg mortality,
larval mortality, and adult mortality. The following compounds gave
at least 80% control of Tetranychus urticae:
[0306] I-202, XIII-22, XIX-202, XXVI-1, XXVIII-162, XXIX-207,
XXX-57 and XXXI-2.
Aedes aegypti (Yellow Fever Mosquito):
[0307] 10-15 Aedes larvae (L2) together with a nutrition mixture
are placed in 96-well microtiter plates. Test solutions at an
application rate of 2ppm are pipetted into the wells. 2 days later,
insects were checked for mortality and growth inhibition. The
following compounds gave at least 80% control of Aedes aegypti
[0308] I-4, I-5, I-12, I-21, I-22, I-23, I-32, I-52, I-61, I-62,
1-72, I-82, I-92, I-112, I-132, I-142, I-152, I-162, I-202, I-212,
I-222, I-232, I-242, I-252, I-262, I-292, II-22, I-62, V-22, VI-22,
VI-62, VI-202, XIV-22, XV-22, XVII-62, XVIII-22, XIX-22, XX-22,
XXI-22, XXI-62, XXII-22, XXVI-2, XXVI-22, XXVII-22, XXVIII-7,
XXVIII-27, XXVIII-67, XXVIII-97, XXVIII-187, XXIX-13, XXIX-19,
XXIX-25, XXIX-31, XXIX-37, XXIX-69, XXIX-75, XXIX-93, XXIX-99,
XXIX-105, XXIX-117,XXIX-123, XXIX-129, XXIX-135, XXIX-159,
XXIX-183, XXX-102, XXX-105, XXX-11, XXX-110, XXX-117, XXX-24,
XXX-28, XXX-31, XXX-34, XXX-4, XXX-48, XXX-49, XXX-52, XXX-57,
XXX-59, XXX-60, XXX-61, XXX-67, XXX-68, XXX-7, XXX-70, XXX-75,
XXX-78, XXX-79, XXX-82, XXX-83, XXX-84, XXX-87, XXX-88, XXX90,
XXX-93, XXX-94, XXX-97, XXXI-2, XXXI-7, XXXI-8, XXXII-10, XXXII-4,
XXX-104, XXX-106, XXX1-1, XXX-111, XXX-113, XXX-114, XXX-118,
XXX-12, XXX-13, XXX1-4, XXX-16, XXX-17, XXX-18, XXX-19, XXX-2,
XXX-20, XXX-22, XXX-26, XXX-3, XXX-30, XXX-35, XXX-38, XXX-39,
XXX-44, XXX-46, XXX-47, XXX-5, XXX-50, XXX-53, XXX-62, XXX-86,
XXX-98, XXXI-5, XXX-109, XXX-45, XXX-51, XXX-6, XXX-66 XXX-121 and
XXX-8.
* * * * *