Herbicidally active 2-(substituted-phenyl)-cyclopentane-1,3-dione compounds and
derivatives thereof
The present invention relates to novel, herbicidally active cyclopentanedione compounds,
specifically 2-(substituted-phenyl)-cyclopentane-1 ,3-dione compounds, and derivatives
thereof (e.g. enol ketone tautomer derivatives thereof), to processes for their preparation, to
herbicidal compositions comprising those compounds, and to their use in controlling weeds
such as grassy monocotyledonous weeds, especially in crops of useful plants, or in inhibiting
undesired plant growth.
US 4,338,122 (assignee Union Carbide Corp.) discloses 2-aryl-1 ,3-cyclopentanedione
compounds exhibiting acaricidal and herbicidal activity. WO 96/01798 (Bayer AG) and its
derived patent US 5,840,661 disclose 2-aryl-cyclopentane-1 ,3-dione derivatives and their
use as pesticides and herbicides. WO 96/03366 (Bayer AG) and its derived patent US
5,808,135 disclose fused 2-(2,4,6-trimethylphenyl)cyclopentane-1 ,3-dione derivatives and
their use as pesticides and herbicides.
WO 99/43649 A 1 (Bayer AG) discloses inter alia (4-aryl-phenyl)-substituted or (4-heteroarylphenyl)-
substituted cyclic keto-enols, including several types of cyclic diones and derivatives
thereof. WO 99/48869 A 1 (Bayer AG) discloses inter alia (3-aryl-phenyl)-substituted or (3-
heteroaryl-phenyl)-substituted cyclic keto-enols, including several types of cyclic diones and
derivatives thereof.
WO 01/17972 A2 (Syngenta Participations AG) discloses (4-methyl-phenyl)-substituted (such
as 4-methyl-2,6-diethyl-phenyl- substituted) heterocycles (e.g. heterocyclic diones) or
cyclopentane-1 ,3-dione derivatives, suitable for use as herbicides. WO 01/74770 (Bayer
AG), its equivalent US 2003/0216260 A 1, and its derived AU patent 782557 (AU
2001 4421 5C) disclose C2-phenyl-substituted cyclic ketoenols and their use as pesticides and
herbicides.
WO 03/013249 A 1 (Bayer AG) and its equivalent US 2005/0054535 A 1 disclose selective
herbicidal compositions comprising (a) a (substituted-phenyl)-substituted cyclic ketoenol and
(b) a compound which improves crop plant compatibility, in particular cloquintocet-mexyl or
mefenpyr-diethyl. In WO 03/013249 A 1 and US 2005/0054535 A 1, the cyclic ketoenol
(whose tautomer is a cyclic dione) can for example be a 2-(substituted-phenyl)-cyclopentane-
1,3-dione, or a derivative (e.g. ester or carbonate derivative) thereof.
WO 2007/068427 A2 (Bayer CropScience AG) and its equivalent US 2009/0227563 A 1
disclose a composition comprising (a) a (substituted-phenyl)-substituted cyclic ketoenol as a
herbicide, and (b) an ammonium and/or phosphonium salt to boost activity. In WO
2007/068427 A2 and US 2009/0227563 A 1, the cyclic ketoenol (whose tautomer is a cyclic
dione) can for example be a 2-(substituted-phenyl)-cyclopentane-1 ,3-dione or a derivative
(e.g. ester or carbonate derivative) thereof.
WO 2009/019005 A2 (Syngenta Limited) discloses fused bicyclic and oxygen-bridged
cyclopentanedione derivatives, specifically 10-oxatricyclo-[5.2.1 .02,6]decane-3,5-diones and
derivatives, which are substituted by substituted-phenyl and which have herbicidal activity.
WO 2010/000773 A 1 (Syngenta Limited) discloses 5-(heterocyclylalkyl)-3-hydroxy-2-phenylcyclopent-
2-enones and certain derivatives thereof as herbicides.
WO 2010/069834 A 1 (Syngenta Participations AG and Syngenta Limited) discloses
cyclopentane-1 ,3-diones having both heteroarylmethyl- and
2-(substituted-phenyl)- substituents on the cyclopentane ring, and derivatives thereof
containing latentiating groups; these compounds are disclosed as having herbicidal
properties.
WO 201 1/007146 A 1 (Syngenta Limited) discloses certain 2-(substituted-phenyl)-
cyclopentane-1 ,3-dione derivatives having herbicidal and/or plant-growth-inhibiting
properties, in which at the 4-position of the cyclopentane-1 ,3-dione there is a substituent
A-CHR4- in which A is unsubstituted or substituted C3-C7cycloalkyl or A is optionally
substituted phenyl.
Other cyclopentane-1 ,3-dione compounds substituted by substituted-phenyl and having
herbicidal activity are described in WO 2010/089210 A 1 and WO 2010/102848 A 1 (both
Syngenta Limited).
WO 2010/102758 A2 (Bayer CropScience AG) discloses (haloalkylmethoxy-)-phenylsubstituted
cyclic keto-enols as pest control agents and/or as herbicides.
Copending PCT application PCT/EP201 2/0741 18, filed on 30 November 2012 and published
on 6 June 2013 as WO 2013/079672 A 1 (Syngenta Limited and Syngenta Participations AG)
discloses that certain substituted spiroheterocyclic pyrrolidine dione compounds, having an
alkynyl-phenyl- headgroup, have herbicidal properties.
Copending PCT application PCT/EP201 2/0741 72, filed on 30 November 2012 and published
on 6 June 2013 as WO 2013/079708 A 1 (Syngenta Limited and Syngenta Participations AG)
discloses cyclopentane-1 ,3-dione compounds and derivatives (e.g. fused and/or spirocyclic
bicyclic derivatives) thereof, which are substituted at the 2-position of the cyclopentane-1 ,3-
dione by a phenyl which itself is substituted at the 4-position by (specifically) either
prop-1-ynyl or chloroethynyl and at the 2-position by (specifically) either methyl or chlorine,
and derivatives of the enol ketone tautomer of such cyclopentanediones, which have
herbicidal activity and/or plant-growth-inhibiting properties, especially in the control of grassy
monocotyledonous weeds and/or when used post-emergence.
2-(Substituted-phenyl)-cyclopentane-1 ,3-dione compounds, and derivatives of the enol
ketone tautomer of such cyclopentane-1 ,3-diones, which have an alkynyl-methyl- or similar
substituent on the cyclopentane-1 ,3-dione, and which have herbicidal activity and/or plantgrowth-
inhibiting properties, especially in the control of grassy monocotyledonous weeds
and/or when used post-emergence, have now been found, which are encompassed by the
present invention.
Some of the exemplified compounds within the following formula (I) according to the present
invention are efficacious vs grassy monocotyledonous weeds and appear to be selective for
grassy (e.g. warm-climate grassy) monocotyledonous weed control when applied postemergence
in crops of soybean and/or (in some cases) in crops of sugarbeet and/or winter
wheat (e.g. see Biological Examples 2 and 3 and the exemplified Compounds hereinafter for
details). That is: some of the exemplified compounds according to the invention appear to
have a lower post-emergence phytotoxicity on soybean and/or sugarbeet and/or winter
wheat than on certain warm-climate grassy monocotyledonous weeds (see e.g. Biological
Examples 2 and 3 for details).
Therefore, in a first aspect of the present invention, there is provided a compound of formula
(I):
wherein:
R is methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine, chlorine,
bromine, methoxy, difluoromethoxy or trifluoromethoxy; and
either (a): R2 is R2 and R3 is R ;
or (b): R2 is R2B and R3 is R B;
wherein:
R is hydrogen, methyl, fluorine or chlorine; and
R2 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, CrC 2fluoroalkyl, vinyl,
prop-1-enyl, -CºC-R2 , halogen, or (Ci-C2fluoroalkyl)-methoxy-; wherein R2 is hydrogen,
fluorine, trifluoromethyl, ethyl or cyclopropyl;
or R2 is phenyl optionally substituted by 1, 2 or 3 substituents independently being halogen,
CrC 2alkyl, CrC 2fluoroalkyl, methoxymethyl, vinyl, ethynyl, CrC 3alkoxy, CrC 2fluoroalkoxy,
methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that either one or none
(i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl,
methylthio, methylsulfinyl, methylsulfonyl or nitro;
or R2 is monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently
being halogen, C -C2alkyl, C -C2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C -C3alkoxy,
C -C2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
and wherein
R2B is hydrogen, methyl or fluorine; and
either R is phenyl optionally substituted by 1, 2 or 3 substituents independently being
halogen, CrC 2alkyl, CrC 2fluoroalkyl, methoxymethyl, vinyl, ethynyl, CrC 2alkoxy,
CrC 2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
or R B is monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently
being halogen, Ci-C 2alkyl, CrC 2fluoroalkyl, methoxymethyl, vinyl, ethynyl, Ci-C 2alkoxy,
CrC 2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
and wherein
R4 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine,
chlorine, bromine, C-i-C3alkoxy, C-i-C2fluoroalkoxy, or
C-ifluoroalkoxy-C-pCsalkoxy-; and
R5, R6 and R7, independently of each other, are hydrogen, C -C5alkyl (in particular C -C4alkyl,
e.g. CrC^alkyl), C2-C3 alkenyl (in particular ethenyl-CH 2-), C2-C3alkynyl (in particular
ethynyl-CH 2-), d-C^luoroalkyl or d-C^alkoxyCrC^alkyl;
provided that: either (i) at least two of R5, R6 and R7 are hydrogen, or (ii) two of R5, R6 and R7
are methyl and the remaining one of R5, R6 and R7 is hydrogen; and
R8 and R , independently of each other, are hydrogen, fluorine or C -C3alkyl; and
R 0 is hydrogen or methyl;
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group; or
G is -C(Xa)-Ra, -C(X )-X -R , -C(X )-N(R )-R , -S0 2-Re, -P(X e)(R )-R9, -CH2-X -Rh; or
phenyl-CH 2- or phenyl-CH(CrC 2alkyl)- (in each of which the phenyl is optionally substituted
by 1, 2 or 3 of, independently, C1-C2alkyl, CifluoroalkyI, C1-C2alkoxy, Cifluoroalkoxy, fluorine,
chlorine, bromine, cyano or nitro), or heteroaryl-CH 2- or heteroaryl-CH(Ci-C 2alkyl)- (in each
of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, Ci-C2alkyl,
CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or
phenyl-C(0)-CH 2- (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
CrC 2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or
nitro); or C C6alkoxy-C(0)-CH 2- , C C6alkyl-C(0)-CH 2- , C C6alkoxy-C(0)-CH=CH-,
C2-C7alken-1-yl-CH2- , C2-C7alken-1-yl-CH(C C2alkyl)-, C2-C4fluoroalken-1-yl-CH 2- ,
C2-C7alkyn-1-yl-CH2- , or C2-C7alkyn-1-yl-CH(C C2alkyl)-;
wherein Xa, X , X , X , Xe and X are independently of each other oxygen or sulfur (preferably
oxygen); and wherein
Ra is H, Ci-C 2ialkyl, C2-C2ialkenyl, C2-Ci 8alkynyl, Ci-Ci 0fluoroalkyl, Ci-Ci 0cyanoalkyl, C
C 0nitroalkyl, Ci-Ci 0aminoalkyl, Ci-C5alkylamino(Ci-C 5)alkyl, C2-C8dialkylamino(Ci-C 5)alkyl,
C3-C7cycloalkyl(Ci-C 5)alkyl, Ci-C 5alkoxy(Ci-C 5)alkyl, C3-C5alkenyloxy(Ci-C 5)alkyl, C3-
C5alkynyloxy (C C5)alkyl, Ci-C5alkylthio(Ci-C 5)alkyl, Ci-C 5alkylsulfinyl(Ci-C 5)alkyl, C
C5alkylsulfonyl(Ci-C 5)alkyl, C2-C8alkylideneaminoxy(Ci-C 5)alkyl, Ci-C5alkylcarbonyl(Cr
C5)alkyl, Ci-C 5alkoxycarbonyl(Ci-C 5)alkyl, aminocarbonyl(Ci-C 5)alkyl, -
C5alkylaminocarbonyl(Ci-C 5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C 5)alkyl, C
C5alkylcarbonylamino(Ci-C 5)alkyl, /V-(Ci-C5)alkylcarbonyl-/V-(Ci-C5)alkylamino(Ci-C 5)alkyl,
C3-C6trialkylsilyl(Ci-C 5)alkyl, phenyl(Ci-C 5)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, Ci-C 3alkyl, Ci-C3fluoroalkyl, Ci-C 3alkoxy, Ci-C3fluoroalkoxy,
Ci-C 3alkylthio, Ci-C 3alkylsulfinyl, Ci-C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Cr
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C
C3alkyl, Ci-C 3fluoroalkyl, Ci-C3alkoxy, CrC 3fluoroalkoxy, Ci-C 3alkylthio, Ci-C 3alkylsulfinyl,
Ci-C 3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, Ci-C3alkyl, Ci-C 3fluoroalkyl, Ci-C 3alkoxy,
CrC 3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
of, independently, Ci-C 3 alkyl, CrC 3fluoroalkyl, Ci-C 3alkoxy, Ci-C 3fluoroalkoxy, halogen,
cyano or nitro;
R is Ci-Ci 8alkyl, C3-Ci 8alkenyl, C3-Ci 8alkynyl, C2-Ci 0fluoroalkyl, Ci-Ciocyanoalkyl, -
Ci0nitroalkyl, C2-Ci 0aminoalkyl, Ci-C5alkylamino(Ci-C 5)alkyl, C2-C8dialkylamino(Ci-C 5)alkyl,
C 3-C7cycloalkyl(C1-C5)alkyl C1-C5alkoxy(C1-C5)alkyl, C 3-C5alkenyloxy(C1-C5)alkyl C3-
C5alkynyloxy(Ci-C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, C
C5alkylsulfonyl(Ci-C5)alkyl, C2-C8alkylideneaminoxy(Ci-C5)alkyl, d-dalkylcarbonyl(d-
C5)alkyl, Ci-C5alkoxycarbonyl(Ci-C5)alkyl, aminocarbonyl(CrC 5)alkyl, d -
C5alkylaminocarbonyl(Ci-C5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C5)alkyl, d -
dalkylcarbonylamino(d-d)alkyl, /V-(d-d)alkylcarbonyl-/V-(Ci-d)alkylamino(Ci-d)alkyl,
d-dtrialkylsilyl(d-d)alkyl, phenyl(d-d)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy,
d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), heteroarylddalkyl
(wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, d -
dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkyl-thio, d-dalkylsulfinyl,
d-dalkylsulfonyl, halogen, cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy,
d-dfluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
of, independently, d-d alkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen,
cyano or nitro; and
R and R are each independently of each other hydrogen, d-d 0alkyl, C3-d 0alkenyl, d -
doalkynyl, C2-d 0fluoroalkyl, d-d 0cyanoalkyl, d-d 0nitroalkyl, d-d 0aminoalkyl, d -
dalkylamino(C 1-d)alkyl, d-ddialkylamino(C 1-C5)alkyl, d-dcycloalkyl(d-d)alkyl, d -
dalkoxy(d-d)alkyl, d-dalkenyloxy(d-d)alkyl, C3-dalkynyloxy(d-d)alkyl, C
dalkylthio(d-d)alkyl, C1-dalkylsulfinyl(C 1-C5)alkyl, C1-dalkylsulfonyl(C 1-d)alkyl, d -
dalkylideneaminoxy(C 1-d)alkyl, C1-dalkylcarbonyl(C 1-C5)alkyl, d-dalkoxycarbonyl(dd)
alkyl, aminocarbonyl(d-d)alkyl, C1-dalkylaminocarbonyl(C 1-d)alkyl, C2-
ddialkylaminocarbonyl(C -d)alkyl, C -dalkylcarbonylamino(C -d)alkyl, /V-(dd)
alkylcarbonyl-/V-(C 2-d)alkylaminoalkyl, C3-C6trialkylsilyl(C -C5)alkyl, phenyl(d-d)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d -
dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d -
dalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d-C 5)alkyl (wherein the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d -
dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen,
cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, d-dalkyl,
CrC 3fluoroalkyl, CrCsalkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, -C3alkyl, CrC 3fluoroalkyl, -
C3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
substituted by 1, 2 or 3 of, independently, CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, Cr
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
of, independently, CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen,
cyano or by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently,
CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; or C3-
C7cycloalkylamino, di(C3-C7cycloalkyl)amino or C3-C7cycloalkoxy;
or R and R , together with the nitrogen to which they are bonded, to form an unsubstituted 4,
5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom selected from O
or S; and
Re is CrC 10alkyl, C2-C10alkenyl, C2-C10alkynyl, CrC 10fluoroalkyl, CrC 10cyanoalkyl, Cr
C10nitroalkyl, CrC 10aminoalkyl, CrC 5alkylamino (CrC 5)alkyl, C2-C8dialkylamino (CrC 5)alkyl,
C3-C7cycloalkyl(CrC 5)alkyl, CrC 5alkoxy (CrC 5)alkyl, C3-C5alkenyloxy(CrC 5)alkyl, C3-
C5alkynyloxy(CrC 5)alkyl, CrC 5alkylthio (CrC 5)alkyl, CrC 5alkylsulfinyl (CrC 5)alkyl, Cr
C5alkylsulfonyl(CrC 5)alkyl, C 2-C8alkylideneaminoxy(CrC 5)alkyl, CrC 5alkylcarbonyl(Cr
C5)alkyl, Ci-C 5alkoxycarbonyl(CrC 5)alkyl, aminocarbonyl(Ci-C 5)alkyl, -
C5alkylaminocarbonyl(CrC 5)alkyl, C2-C8dialkylaminocarbonyl (CrC 5)alkyl, Cr
C5alkylcarbonylamino(CrC 5)alkyl, /V-(CrC 5)alkylcarbonyl-/V-(CrC 5)alkylamino(CrC 5)alkyl,
C3-C6trialkylsilyl(CrC 5)alkyl, phenyl(CrC 5)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy,
CrC 3alkylthio, CrC 3alkylsulfinyl, CrC 3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Cr
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, Cr
C3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, CrC 3alkylthio, CrC 3alkylsulfinyl,
CrC 3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy,
CrC 3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of,
independently, CrC 3alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano
or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, CrC 3
alkyl, CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro;
diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, CrC 3alkyl,
CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; phenylamino or
phenylamino substituted by 1, 2 or 3 of, independently, -C3alkyl, Crdfluoroalkyl, d -
C3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino
substituted by 1, 2 or 3 of, independently, CrC 3alkyl, CrC 3fluoroalkyl, Ci-C3alkoxy, Ci-
Csfluoroalkoxy, halogen, cyano or nitro; or C3-C7cycloalkylamino, di(C3-C7cycloalkyl)amino,
C3-C7cycloalkoxy, CrCi 0alkoxy, Ci-Ci 0fluoroalkoxy, Ci-C 5alkylamino or di(Ci-C 4alkyl)amino;
R and R9 are are each independently of each other Ci-Ci 0alkyl, C2-Ci 0alkenyl, C2-Ci 0alkynyl,
Ci-Ci 0alkoxy, Ci-Ci 0fluoroalkyl, Ci-Ciocyanoalkyl, CrCi 0nitroalkyl, Ci-Ci 0aminoalkyl, d -
C5alkylamino(Ci-C 5)alkyl, C 2-C8dialkylamino(Ci-C 5)alkyl, C3-C7cycloalkyl(Ci-C 5)alkyl, d -
C5alkoxy(Ci-C 5)alkyl, C3-C5alkenyloxy(Ci-C 5)alkyl, C3-C5alkynyloxy(Ci-C 5)alkyl, Cr
C5alkylthio(d-C5)alkyl, C1-C5alkylsulfinyl(C 1-C5)alkyl, C1-C5alkylsulfonyl(C 1-C5)alkyl, C2-
C8alkylideneaminoxy(C 1-C5)alkyl, C1-C5alkylcarbonyl(C 1-C5)alkyl, CrC 5alkoxycarbonyl(Cr
C5)alkyl, aminocarbonyl(d-C 5)alkyl, C1-C5alkylaminocarbonyl(C 1-C5)alkyl, C2-
C8dialkylaminocarbonyl(C -C5)alkyl, C -C5alkylcarbonylamino(C -C5)alkyl, /V-(d-
C5)alkylcarbonyl-/V-(C2-C5)alkylaminoalkyl, C3-C6trialkylsilyl(C 1-C5)alkyl, phenyl(d-C 5)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, d-C 3alkyl, d -
C3fluoroalkyl, d-C 3alkoxy, d-C 3fluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d -
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Ci-C 5)alkyl (wherein the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, d-C 3alkyl, Ci-C 3fluoroalkyl, d -
C3alkoxy, d-dfluoroalkoxy, d-dalkylthio, d-C 3alkylsulfinyl, d-dalkylsulfonyl, halogen,
cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, d-dfluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, d-C 3 alkyl,
CrCsfluoroalkyl, CrCsalkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, d-C 3 alkyl, Crdfluoroalkyl, Cr
C3alkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
substituted by 1, 2 or 3 of, independently, d-C 3 alkyl, Crdfluoroalkyl, d-dalkoxy, d -
dfluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
of, independently, d-C 3alkyl, Crdfluoroalkyl, d-C 3alkoxy, d-C 3fluoroalkoxy, halogen,
cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, d -
dalkyl, Crdfluoroalkyl, d-C 3alkoxy, d-C 3fluoroalkoxy, halogen, cyano or nitro; or C3-
C7cycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, d-Ciofluoroalkoxy, d -
C5alkylamino or di(CrC 4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and
phenyl groups are in turn optionally substituted by 1, 2 or 3 of, independently, -C3alkyl, d -
C3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; and
Rh is Ci-Ci 0alkyl, C3-Ci 0alkenyl, C3-Ci 0alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d -
C 0nitroalkyl, C2-Ci 0aminoalkyl, Ci-C5alkylamino(Ci-C 5)alkyl, C2-C8dialkylamino(Ci-C 5)alkyl,
C3-C7cycloalkyl(Ci-C 5)alkyl, Ci-C 5alkoxy(Ci-C 5)alkyl, C3-C5alkenyloxy(Ci-C 5)alkyl, C3-
C5alkynyloxy(Ci-C 5)alkyl, Ci-C5alkylthio(Ci-C 5)alkyl, Ci-C 5alkylsulfinyl(Ci-C 5)alkyl, d -
C5alkylsulfonyl(Ci-C 5)alkyl, C2-C8alkylideneaminoxy(Ci-C 5)alkyl, CrC 5alkylcarbonyl(Cr
C5)alkyl, Ci-C 5alkoxycarbonyl(Ci-C 5)alkyl, aminocarbonyl(Ci-C 5)alkyl, d -
dalkylaminocarbonyl(Ci-d)alkyl, d-ddialkylaminocarbonyl(d-d)alkyl, d -
C5alkylcarbonylamino(d-C 5)alkyl, /V-(C -d)alkylcarbonyl-/V-(C -d)alkylamino(C -d)alkyl,
C3-C6trialkylsilyl(CrC 5)alkyl, phenyl(C -d)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, d-dfluoroalkoxy,
Crdalkylthio, Ci-C 3alkylsulfinyl, Ci-C3 alkylsulfonyl, halogen, cyano or nitro), heteroaryl(dd)
alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, d -
C3alkyl, Ci-C 3fluoroalkyl, Ci-C3alkoxy, d-dfluoroalkoxy, Crdalkylthio, d-C 3alkylsulfinyl,
d-C 3 alkylsulfonyl, halogen, cyano or nitro), phenoxy(d-C 5)alkyl (wherein the phenyl is
optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d-C 3fluoroalkyl, d -
dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-d alkylsulfonyl, halogen,
cyano or nitro), heteroaryloxy(C -d)alkyl (wherein the heteroaryl is optionally substituted by
1, 2 or 3 of, independently, d-dalkyl, d-C 3fluoroalkyl, Crdalkoxy, d-dfluoroalkoxy, d -
dalkylthio, Ci-C 3alkylsulfinyl, d-C 3 alkylsulfonyl, halogen, cyano or nitro), C3-
dfluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently,
d-dalkyl, d-C 3fluoroalkyl, Crdalkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro;
heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, d-C 3alkyl, d -
dfluoroalkyl, d-C 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; CrC 6alkyl-C(0)-; or
phenyl-C(O)- wherein the phenyl is optionally substituted by 1 or 2 of, independently, d -
dalkyl, CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro;
wherein "heteroaryl" means an aromatic ring system containing at least one ring heteroatom
and consisting either of a single ring or of two fused rings;
and wherein the compound of formula (I) is optionally present (e.g. where chemically
possible) as an agrochemically acceptable salt (e.g. agriculturally acceptable metal,
sulfonium or ammonium salt) thereof.
In the substituent definitions of the compounds of the formula I , each alkyl moiety either
alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl,
alkylaminocarbonyl, or dialkylaminocarbonyl, et al.) can be straight-chained or branched.
Typically, the alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, ierf-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl groups can e.g. be CrC 6alkyl
groups (except where already defined more narrowly), but are preferably CrC 4alkyl or -
C3alkyl groups (except where already defined more narrowly), and, more preferably, are
CrC 2alkyl groups such as methyl.
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 (£)- or (Z)-configuration. The
alkenyl or alkynyl are typically C2-C3alkenyl or C2-C3alkynyl such as vinyl, allyl, ethynyl,
propargyl or prop-1-ynyl. Alkenyl and alkynyl moieties can contain one or more double
and/or triple bonds in any combination; but preferably contain only one double bond (for
alkenyl) or only one triple bond (for alkynyl).
Halogen is fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine, chlorine or
bromine. More preferably, in various aspects and/or embodiments of the invention, halogen
is fluorine or chlorine.
FluoroalkyI groups are alkyl groups which are substituted with one or more (e.g. 1, 2, 3, 4 or
5; in particular 1, 2 or 3; e.g. 1 or 2) fluorine atoms. FluoroalkyI is typically C -C3fluoroalkyl or
Ci-C 2fluoroalkyl (preferably dfluoroalkyl), such as CF3, CHF2, CH2F, CH3CHF-, CF3CH2- ,
CHF2CH2- , CH2FCH2- , CHF2CF2- or (CH3)2CF-. Fluoroalkoxy is typically C C3fluoroalkoxy
or Ci-C 2fluoroalkoxy (preferably Cifluoroalkoxy), such as CF30 , CHF20 , CH2FO, CH3CHFO-,
CF3CH20-, CHF2CH20 - or CH2FCH20-.
In the context of the present specification the term "aryl" means phenyl or naphthyl. A
preferred aryl group is phenyl.
The term "heteroaryl" as used herein means an aromatic ring system containing at least one
ring heteroatom and consisting either of a single ring or of two fused rings. Preferably, single
rings will contain 1, 2 or 3 ring heteroatoms and bicyclic systems 1, 2, 3 or 4 ring
heteroatoms which will preferably be selected from nitrogen, oxygen and sulfur. Typically, a
"heteroaryl" is furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl,
oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 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, 2,1 ,3-
benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl,
naphthyridinyl, benzotriazinyl, purinyl, pteridinyl or indolizinyl; optionally present, where
chemically possible, as an agrochemically acceptable salt thereof.
The term "heterocyclyl" as used herein, except where explicitly stated otherwise, means a 4,
5, 6 or 7 (in particular 5, 6 or 7) membered monocyclic organic ring or a 8, 9, 10 or 11 (in
particular 8, 9 or 10) membered fused bicyclic organic ring system, which is fully saturated,
and which has one or two (preferably one) ring heteroatoms independently selected from
oxygen, sulfur and nitrogen. Where the heterocyclyl has two ring heteroatoms, preferably,
the two ring heteroatoms are separated by at least two ring carbon atoms. Preferably, the
heterocyclyl is attached at a ring carbon atom within the heterocyclyl. In particular, the
heterocyclyl can be tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, 1,4-dioxanyl,
1,4-dithianyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, piperidinyl or piperazinyl; more
particularly tetrahydrofuranyl (e.g. tetrahydrofuran-2-yl or particularly tetrahydrofuran-3-yl),
tetrahydropyranyl (e.g. tetrahydropyran-2-yl, tetrahydropyran-3-yl or particularly
tetrahydropyran-4-yl), morpholinyl, pyrrolidinyl (e.g. pyrrolidin-2-yl or particularly pyrrolidin-3-
yl), piperidinyl (e.g. piperidin-2-yl, piperidin-3-yl or particularly piperidin-4-yl) or piperazinyl. In
a particular embodiment, the heterocyclyl, when optionally substituted, is optionally
substituted by 1 or 2 (e.g. 1) ring-carbon substituents independently being CrC 3alkyl (e.g.
CrC 2alkyl), CrC 2fluoroalkyl or oxo (=0), and/or is optionally substituted by one CrC 3alkyl
(e.g. CrC 2alkyl), CrC 2fluoroalkyl or -C3alkoxy (e.g. Ci-C2alkyl or Ci-C2fluoroalkyl)
substituent on a ring nitrogen if present, and/or is optionally substituted by one or two oxo
(=0) substituents on a ring sulfur if present.
Preferably, a cycloalkyi is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. (Cycloalkyl)alkyl
is preferably (cycloalkyl)methyl such as (C3-C6cycloalkyl)methyl in particular
cyclopropylmethyl. Preferably, cycloalkenyl is cyclopentenyl or cyclohexenyl.
The invention relates also to the agriculturally acceptable salts which the compounds of
formula I are able to form with transition metal, alkali metal and alkaline earth metal bases,
amines, quaternary ammonium bases or tertiary sulfonium bases.
Among the transition metal, alkali metal and alkaline earth metal salt formers, special
mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium,
magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of
sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as
primary, secondary and tertiary C-i-C-isalkylamines, C -C4hydroxyalkylamines and
C2-C4alkoxyalkyl-amines, for example methylamine, ethylamine, n-propylamine,
isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine,
heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,
heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,
methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine,
ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine,
dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-namylamine,
di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, npropanolamine,
isopropanolamine, L/,/V-diethanolamine, /V-ethylpropanolamine, Nbutylethanolamine,
allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut-2-
enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine,
triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-secbutylamine,
tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines,
for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline,
quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines,
ethoxyanilines, , m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and
0-, m- and p-chloroanilines; but especially triethylamine,
isopropylamine and di-isopropylamine.
Preferred quaternary ammonium bases suitable for salt formation correspond, for example,
to the formula [N(Ra R Rc Rd)]OH , wherein Ra, R , Rc and Rd are each independently of the
others hydrogen, CrC 4alkyl. Further suitable tetraalkylammonium bases with other anions
can be obtained, for example, by anion exchange reactions.
Preferred tertiary sulfonium bases suitable for salt formation correspond , for example, to the
formula [SReRfRg]OH , wherein Re, Rf and Rg are each independently of the others C C4
alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable sulfonium bases may be
obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides,
followed by conversion to a suitable base, for example a hydroxide, by anion exchange
reactions.
It should be understood that in those compounds of formula I, where G is a metal,
ammonium or sulfonium as mentioned above and as such represents a cation, the
corresponding negative charge is largely delocalised across the 0-C=C-C=0 unit.
The compounds of formula I according to the invention also include hydrates which may be
formed during the salt formation .
The latentiating groups (i.e. leaving or removeable groups) within G (for example, without
limitation , the latentiating groups where G is -C(Xa)-Ra or -C(X )-X -R , et al.) are generally
selected to allow their removal, typically by one or a combination of biochemical, chemical or
physical processes, to afford the corresponding compound of formula ( I) where G is H,
before, during or following (preferably during or following) application of the compound of
formula ( I) to the treated area (e.g. field) or to plants. Examples of these processes include
enzymatic cleavage or other in/on-plant cleavage (e.g. cleavage of ester and/or carbonate
moieties), chemical hydrolysis, and/or photolysis. Some compounds bearing such groups G
occasionally offer certain advantages or different technical properties, such as improved
and/or more consistent and/or different penetration of the cuticula of the plants treated ,
increased and/or different tolerance of certain crops, improved and/or different compatibility
or stability in formulated mixtures containing other herbicides, herbicide safeners, plant
growth regulators, fungicides or insecticides, or reduced and/or different leaching properties
in soils.
The preferred (including more preferred, most preferred, et al.), suitable and/or particular
values of the substituents in, or other features of, the compound of formula (I), in particular
(and without limitation): G, R , R2, R2 , R , R2B, R3, R , R B, R4, R4 , R4B, R4C, R5, R6, R7,
2 2A 12AA 12B 13 13A 13AA 13B 14 14A 14B 15 16 a
R , R , R , Re, R , R9, Rh, Xa, X , X , X , Xe, and/or X ; are set out below (and/or generally
herein), and can be either taken alone or taken together with one or more of any other
preferred (including more preferred, most preferred, et al.), suitable and/or particular values
of the substituents in, or other features of, the compound of formula (I), in any and all
possible combination(s) thereof.
Preferably, e.g. in all aspects and/or embodiments of the invention, G is hydrogen; an
agriculturally acceptable metal (e.g. an agriculturally acceptable alkali metal or alkaline earth
metal), or an agriculturally acceptable sulfonium or ammonium group; or G is -C(Xa)-Ra
or -C(X )-X -R , wherein Xa, Ra, X , X and R are as defined herein. More preferably, G is
hydrogen, or an agriculturally acceptable alkali metal (e.g. lithium, sodium or potassium) or
an agriculturally acceptable alkaline earth metal (e.g. calcium or magnesium), or -C(Xa)-Ra
or -C(X )-X -R .
In a particular embodiment, G is a group -C(Xa)-Ra or -C(X )-X -R , wherein Xa, Ra, X , X
and R are as defined herein.
Preferably, Xa, X , X , X , Xe and/or X are oxygen; and/or X is sulfur. More preferably, Xa,
X , X , X , Xe and Xf are oxygen; and/or X is sulfur.
Preferably, Ra is CrCi 0alkyl (e.g. CrC 6alkyl), C2-C6alkenyl (e.g. C2-C4alkenyl), C2-C6alkynyl
(e.g. C2-C4alkynyl), C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-, Ci-C 4alkoxyCrC 4alkyl,
phenyl-methyl- (in which the phenyl is optionally substituted by 1 or 2 of, independently,
Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano); phenyl or
phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano; or monocyclic heteroaryl or monocyclic heteroaryl
substituted by 1 or 2 of, independently, C1-C2alkyl, CifluoroalkyI, C1-C2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano.
More preferably, Ra is CrCi 0alkyl (e.g. CrC 6alkyl), C2-C6alkenyl (e.g. C2-C4alkenyl), C2-
C6alkynyl (e.g. C2-C4alkynyl), C3-C6cycloalkyl, or Ci-C 4alkoxyCrC 4alkyl.
Preferably, R is C C 0alkyl (e.g. C C6alkyl), C2-C5alkenyl-CH 2- (e.g. C2-C3alkenyl-CH 2-),
C2-C4alkenyl-CH(Me)- (e.g. C2-C3alkenyl-CH(Me)-), C2-C5alkynyl-CH 2- (e.g.
C2-C3alkynyl-CH 2-), C2-C4alkynyl-CH(Me)- (e.g. C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl,
C3-C6cycloalkyl-methyl-, Ci-C 4alkoxyCi-C 4alkyl, phenyl-methyl- (in which the phenyl is
optionally substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano); phenyl or phenyl substituted by 1 or 2 of,
independently, C -C2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or
cyano; or monocyclic heteroaryl or monocyclic heteroaryl substituted by 1 or 2 of,
independently, C -C2alkyl, CifluoroalkyI, C-i-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine or
cyano.
More preferably, R is C C 0alkyl (e.g. C C6alkyl), C2-C5alkenyl-CH 2- (e.g.
C2-C3alkenyl-CH 2-), C2-C4alkenyl-CH(Me)- (e.g. C2-C3alkenyl-CH(Me)-),
C2-C5alkynyl-CH 2- (e.g. C2-C3alkynyl-CH 2-), C2-C4alkynyl-CH(Me)- (e.g.
C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl, or Ci-C 4alkoxyCi-C 4alkyl.
Preferably, Xa, X and X are oxygen (and/or X is sulfur); and
Ra is Ci-Ci 0alkyl (e.g. Ci-C 6alkyl), C2-C6alkenyl (e.g. C2-C4alkenyl), C2-C6alkynyl (e.g. C2-
C4alkynyl), C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-, Ci-C 4alkoxyCi-C 4alkyl,
phenyl-methyl- (in which the phenyl is optionally substituted by 1 or 2 of, independently,
Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano); phenyl or
phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano; or monocyclic heteroaryl or monocyclic heteroaryl
substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano;
and
R is - oalkyl (e.g. C C6alkyl), C2-C5alkenyl-CH 2- (e.g. C2-C3alkenyl-CH 2-),
C2-C4alkenyl-CH(Me)- (e.g. C2-C3alkenyl-CH(Me)-), C2-C5alkynyl-CH 2- (e.g.
C2-C3alkynyl-CH2-), C2-C4alkynyl-CH(Me)- (e.g. C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl,
C3-C6cycloalkyl-methyl-, Ci-C 4alkoxyCrC 4alkyl, phenyl-methyl- (in which the phenyl is
optionally substituted by 1 or 2 of, independently, CrC 2alkyl, CifluoroalkyI, CrC 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano); phenyl or phenyl substituted by 1 or 2 of,
independently, CrC 2alkyl, CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or
cyano; or monocyclic heteroaryl or monocyclic heteroaryl substituted by 1 or 2 of,
independently, CrC 2alkyl, CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or
cyano.
In a particularly preferable embodiment, G is hydrogen, -C(Xa)-Ra or -C(X )-X -R .
In another preferable embodiment, G is hydrogen, or an agriculturally acceptable alkali metal
or alkaline earth metal, or an agriculturally acceptable sulfonium or ammonium group. In a
particular embodiment, G is hydrogen, or an agriculturally acceptable alkali metal (e.g.
lithium, sodium or potassium) or an agriculturally acceptable alkaline earth metal (e.g.
calcium or magnesium).
Most preferably, G is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R is methyl, ethyl,
cyclopropyl, ethynyl, fluorine, chlorine, bromine, methoxy, difluoromethoxy or
trifluoromethoxy.
Preferably, e.g. in all aspects and/or embodiments of the invention, R is methyl, ethyl,
ethynyl, fluorine, chlorine, bromine, methoxy, difluoromethoxy or trifluoromethoxy.
More preferably, e.g. in all aspects and/or embodiments of the invention, R is methyl,
fluorine, chlorine, bromine, difluoromethoxy or trifluoromethoxy.
Even more preferably, R is methyl, fluorine, chlorine or bromine.
Still more preferably, R is methyl, fluorine or chlorine.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R is fluorine or
chlorine.
In the invention, either (a): R2 is R2 and R3 is R ; or (b): R2 is R2B and R3 is R B.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R2 is R2 and R3 is
R3A .
Preferably, e.g. in all aspects and/or embodiments of the invention, R is hydrogen or
methyl.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R is hydrogen.
When R2 is halogen, then preferably it is chlorine or bromine.
When R2 is (Ci-C 2fluoroalkyl)-methoxy-, then preferably it is Cifluoroalkyl-methoxy-, such as
CF3CH20 or CHF2CH20 .
R2 can be -CºC-R2 . Preferably, R2 is hydrogen, fluorine or trifluoromethyl. More
preferably, R2 is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is hydrogen, methyl, ethyl, vinyl, prop-1-enyl, -CºC-R2 (in particular, -CºC-R2 wherein
R2 is hydrogen), halogen (in particular chlorine or bromine), or Cifluoroalkyl-methoxy- (in
particular, CF3CH20 or CHF2CH20);
or R2 is phenyl optionally substituted by 1, 2 or 3 (preferably 1 or 2) substituents
independently being halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C2alkyl, CrC 2fluoroalkyl, Ci-C2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro, provided that either one or none (i.e. no more than one) of these optional substituents
are Ci-C2alkyl, Ci-C2alkoxy or nitro;
or R2 is monocyclic 6-membered or 5-membered heteroaryl (e.g. pyridin-2-yl, pyridin-3-yl,
pyrimidin-2-yl, pyrimidin-5-yl, pyridazin-3-yl, or pyrazol-1-yl) optionally substituted by 1, 2 or 3
(preferably 1 or 2) substituents independently being halogen (in particular fluorine, chlorine or
bromine, more particularly fluorine or chlorine), CrC 2alkyl, Ci-C2fluoroalkyl, CrC 2alkoxy,
CrC 2fluoroalkoxy, cyano or nitro, provided that either one or none (i.e. no more than one) of
these optional substituents are CrC 2alkyl, Ci-C2alkoxy or nitro.
Preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is methyl, ethyl, vinyl, prop-1-enyl, -CºC-R2 (in particular, -CºC-R2 wherein R2 is
hydrogen), halogen (in particular chlorine or bromine), or Cifluoroalkyl-methoxy- (in
particular, CF3CH20 or CHF2CH20);
or R2 is phenyl optionally substituted by 1, 2 or 3 (preferably 1 or 2) substituents
independently being halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C2alkyl, Ci-C2fluoroalkyl, d-C^alkoxy, CrC^luoroalkoxy, cyano or
nitro, provided that either one or none (i.e. no more than one) of these optional substituents
are Ci-C2alkyl, CrC 2alkoxy or nitro;
or R2 is monocyclic 6-membered or 5-membered heteroaryl (e.g. pyridin-2-yl, pyridin-3-yl,
pyrimidin-2-yl, pyrimidin-5-yl, pyridazin-3-yl, or pyrazol-1-yl) optionally substituted by 1, 2 or 3
(preferably 1 or 2) substituents independently being halogen (in particular fluorine, chlorine or
bromine, more particularly fluorine or chlorine), CrC 2alkyl, Ci-C2fluoroalkyl, Ci-C2alkoxy,
CrC 2fluoroalkoxy, cyano or nitro, provided that either one or none (i.e. no more than one) of
these optional substituents are C -C2alkyl, C-i-C2alkoxy or nitro.
More preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is methyl, -CºC-R2 (in particular, -CºC-R2 wherein R2 is hydrogen), chlorine or
bromine;
or R2 is phenyl optionally substituted by 1, 2 or 3 (preferably 1 or 2) substituents
independently being halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), C-ifluoroalkyl, C-ifluoroalkoxy or cyano;
or R2 is monocyclic 6-membered or 5-membered heteroaryl (e.g. pyridin-2-yl, pyridin-3-yl,
pyrimidin-2-yl, pyrimidin-5-yl, pyridazin-3-yl, or pyrazol-1-yl) optionally substituted by 1, 2 or 3
(preferably 1 or 2) substituents independently being halogen (in particular fluorine, chlorine or
bromine, more particularly fluorine or chlorine), C-ifluoroalkyl, dfluoroalkoxy or cyano.
Still more preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is methyl or -CºC-R2 wherein R2 is hydrogen;
or R is phenyl substituted by 1, 2 or 3 (preferably 1 or 2) substituents independently being
fluorine, chlorine or bromine (preferably independently being fluorine or chlorine);
or R2 is monocyclic 6-membered or 5-membered heteroaryl (e.g. pyridin-2-yl, pyridin-3-yl,
pyrimidin-2-yl, pyrimidin-5-yl, pyridazin-3-yl, or pyrazol-1-yl) substituted by 1, 2 or 3
(preferably 1 or 2) substituents independently being fluorine, chlorine or bromine (preferably
independently being fluorine or chlorine).
Preferably, e.g. in all aspects and/or embodiments of the invention, when R2 is optionally
substituted phenyl, then R2 is of sub-formula (a) or (a1 ) :
(a) (a1 )
, in which:
R is hydrogen, fluorine or chlorine;
R 2 is halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or
chlorine), CrC 2alkyl, CrC 2fluoroalkyl, CrC 2alkoxy, CrC 2fluoroalkoxy, cyano or nitro;
R 3 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly fluorine
or chlorine), C -C2alkyl, C -C2fluoroalkyl, C -C2alkoxy, C -C2fluoroalkoxy, cyano or nitro; and
R 4 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly fluorine
or chlorine), -C2alkyl, C -C2fluoroalkyl, CrC 2alkoxy, Crdfluoroalkoxy, cyano or nitro;
provided that one or more (preferably two or more) of R , R 3 and R 4 are hydrogen; and
provided that either one or none (i.e. no more than one) of R 2 , R 3 and R 4 are C -C2alkyl,
Ci -C2alkoxy or nitro; and
R 2 is hydrogen, fluorine or chlorine (in particular hydrogen or fluorine);
R is fluorine or chlorine (in particular fluorine); and
R 6 is hydrogen, fluorine or chlorine (in particular hydrogen or fluorine);
provided that when R 2 is fluorine or chlorine, then R 6 is fluorine or chlorine; and
provided that either one or none (i.e. no more than one) of R and R 6 are chlorine.
More preferably, when R is optionally substituted phenyl, then R is of sub-formula (a).
R2 being of sub-formula (a1) is less preferred than sub-formula (a).
In the above-mentioned preferred or more preferred embodiment wherein R2 is of subformula
(a), preferably, two or more of R , R 3 and R 4 are hydrogen.
Most preferably, R is hydrogen.
Preferably, R 2 is halogen (in particular fluorine, chlorine or bromine) or Cifluoroalkyl (e.g.
trifluoromethyl), Cifluoroalkoxy (e.g. difluoromethoxy or trifluoromethoxy), or cyano. More
preferably, R 2 is halogen; even more preferably fluorine, chlorine or bromine.
Most preferably, R 2 is fluorine or chlorine.
Preferably, R 3 is hydrogen, fluorine or chlorine; more preferably hydrogen or fluorine.
Most preferably, R 3 is hydrogen.
Preferably, R 4 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more
particularly fluorine or chlorine), or Cifluoroalkyl (e.g. trifluoromethyl).
More preferably, R 4 is hydrogen or halogen; even more preferably hydrogen, fluorine,
chlorine or bromine.
Most preferably, R 4 is hydrogen, fluorine or chlorine; in particular hydrogen or fluorine.
For the above preferred R , R 2 , R 3 and/or R 4 features, then, e.g. as previously mentioned:
one or more (preferably two or more) of R , R 3 and R 4 are hydrogen; and
either one or none (i.e. no more than one) of R 2 , R 3 and R 4 are CrC 2alkyl, CrC 2alkoxy or
nitro.
Preferably, e.g. in all aspects and/or embodiments of the invention, when R2 is optionally
substituted monocyclic heteroaryl (e.g. monocyclic 6-membered or 5-membered heteroaryl,
in particular pyridin-2-yl, pyridin-3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridazin-3-yl, or pyrazol-
1-yl)), then R2 is of sub-formula (b), (c), (d), (e), (f) or (g):
, in which:
R 2 is halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or
chlorine), C1-C2alkyl, C1-C2fluoroalkyl, C1-C2alkoxy, C1-C2fluoroalkoxy, cyano or nitro;
R is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C 2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro; and
R 4 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C 2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro;
provided that either one or none (i.e. no more than one) of R 2 , R and R 4 are Ci-C 2alkyl,
C-i-C2alkoxy or nitro;
and R 5 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), methyl, C-ifluoroalkyl (e.g. trifluoromethyl), C-ifluoroalkoxy (e.g.
difluoromethoxy or trifluoromethoxy), or cyano.
In the above-mentioned preferred embodiments wherein R2 is of sub-formula (b), (e) or (f),
preferably, one or both of R and R 4 are hydrogen.
Preferably, R 2 is halogen (in particular fluorine, chlorine or bromine) or C-ifluoroalkyl (e.g.
trifluoromethyl), C-ifluoroalkoxy (e.g. difluoromethoxy or trifluoromethoxy), or cyano. More
preferably, R 2 is halogen; even more preferably fluorine, chlorine or bromine.
Most preferably, R 2 is fluorine or chlorine; in particular chlorine.
Preferably, R is hydrogen, fluorine or chlorine; more preferably hydrogen or fluorine.
Most preferably, R is hydrogen.
Preferably, R 4 is hydrogen, halogen (in particular fluorine, chlorine or bromine, more
particularly fluorine or chlorine), or Cifluoroalkyl (e.g. trifluoromethyl).
More preferably, R 4 is hydrogen or halogen; even more preferably hydrogen, fluorine,
chlorine or bromine.
Most preferably, R 4 is hydrogen, fluorine or chlorine; in particular hydrogen or fluorine.
For the above preferred R 2 , R and/or R 4 features, then, e.g. as previously mentioned:
either one or none (i.e. no more than one), more preferably none, of R 2 , R and R 4 are
C -C2alkyl, C -C2alkoxy or nitro.
Preferably, R 5 is hydrogen, fluorine, chlorine, methyl, Cifluoroalkyl (e.g. trifluoromethyl), or
C-ifluoroalkoxy (e.g. difluoromethoxy or trifluoromethoxy).
Most preferably R 5 is fluorine or chlorine, in particular chlorine.
More preferably, e.g. in all aspects and/or embodiments of the invention, when R2 is
optionally substituted monocyclic heteroaryl (e.g. monocyclic 6-membered or 5-membered
heteroaryl, in particular optionally substituted pyridin-2-yl, pyrimidin-2-yl, or pyrazol-1-yl)),
then R2 is of sub-formula (b), (c) or (g), in particular (b) or (c), as defined herein.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R2 is of subformula
(a), (b), (c) or (g), in particular of sub-formula (a), (b) or (c), as defined herein. Most
preferably, in this embodiment, R2 is R2 and R3 is R .
ln another particular embodiment (b) of the invention, R2 is R2B and R3 is R B.
Preferably, e.g. in all aspects and/or embodiments of the invention, R2B is hydrogen or
methyl.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R2B is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention,
either R B is phenyl optionally substituted by 1, 2 or 3 (preferably 1 or 2) substituents
independently being halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), C1-C2alkyl, C1-C2fluoroalkyl, C1-C2alkoxy, C1-C2fluoroalkoxy, cyano or
nitro, provided that either one or none (i.e. no more than one) of these optional substituents
are -C2alkyl, Ci-C 2alkoxy or nitro;
or R B is monocyclic 6-membered heteroaryl (e.g. pyridin-2-yl, or pyrimidin-2-yl) optionally
substituted by 1, 2 or 3 (preferably 1 or 2) substituents independently being halogen (in
particular fluorine, chlorine or bromine, more particularly fluorine or chlorine), CrC 2alkyl,
CrC 2fluoroalkyl, Ci-C 2alkoxy, CrC 2fluoroalkoxy, cyano or nitro, provided that either one or
none (i.e. no more than one) of these optional substituents are C -C2alkyl, C-i-C2alkoxy or
nitro.
More preferably, e.g. in all aspects and/or embodiments of the invention,
either R B is phenyl optionally substituted by 1, 2 or 3 (preferably 1 or 2) substituents
independently being halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), methyl, CifluoroalkyI, methoxy, Cifluoroalkoxy or cyano, provided that
either one or none (i.e. no more than one) of these optional substituents are methyl or
methoxy;
or R B is monocyclic 6-membered heteroaryl (e.g. pyridin-2-yl, or pyrimidin-2-yl) optionally
substituted by 1, 2 or 3 (preferably 1 or 2) substituents independently being halogen (in
particular fluorine, chlorine or bromine, more particularly fluorine or chlorine), methyl,
CifluoroalkyI, methoxy, Cifluoroalkoxy or cyano, provided that either one or none (i.e. no
more than one) of these optional substituents are methyl or methoxy.
Still more preferably, e.g. in all aspects and/or embodiments of the invention,
either R B is phenyl substituted by 1, 2 or 3 (preferably 1 or 2) substituents independently
being fluorine, chlorine or bromine (preferably independently being fluorine or chlorine);
or R B is monocyclic 6-membered heteroaryl (e.g. pyridin-2-yl or pyrimidin-2-yl) substituted by
1, 2 or 3 (preferably 1 or 2) substituents independently being fluorine, chlorine or bromine
(preferably independently being fluorine or chlorine).
Preferably, e.g. in all aspects and/or embodiments of the invention, when R B is optionally
substituted phenyl, then R is of sub-formula (a2): (a2)
in which
R B is hydrogen, fluorine, chlorine, methyl, dfluoroalkyl, methoxy or dfluoroalkoxy;
R 2B is halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or
chlorine), C1-C2alkyl, C1-C2fluoroalkyl, C1-C2alkoxy, C1-C2fluoroalkoxy, cyano or nitro;
R B is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C 2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro; and
R 4B is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C 2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro;
provided that one or more (preferably two or more) of R B, R B and R 4B are hydrogen; and
provided that either one or none (i.e. no more than one) of R 2B, R B and R 4B are CrC 2alkyl,
C -C2alkoxy or nitro.
Preferably, R B is hydrogen, fluorine, chlorine, methyl or methoxy; most preferably hydrogen,
fluorine or chlorine.
Preferably, R 2B is fluorine, chlorine, C-ifluoroalkyl, methoxy or C-ifluoroalkoxy; more
preferably fluorine or chlorine; most preferably chlorine.
Preferably, R B is hydrogen or fluorine; most preferably hydrogen.
Preferably, R is hydrogen or fluorine; most preferably hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, when R B is optionally
substituted monocyclic heteroaryl (e.g. monocyclic 6-membered heteroaryl, in particular
pyridin-2-yl or pyrimidin-2-yl), then R B is of sub-formula (b1) or (c1):
(b1 ) ( )
, in which:
R 2B is halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or
chlorine), C1-C2alkyl, C1-C2fluoroalkyl, C1-C2alkoxy, C1-C2fluoroalkoxy, cyano or nitro;
R B is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), CrC^alkyl, d-C^luoroalkyl, d-C^alkoxy, CrC^luoroalkoxy, cyano or
nitro; and
R 4B is hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly
fluorine or chlorine), Ci-C 2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy, cyano or
nitro;
provided that either one or none (i.e. no more than one) of R 2B, R B and R 4B are C -C2alkyl,
C -C2alkoxy or nitro.
Preferably, in sub-formula (b1) or (c1), R 2B is fluorine, chlorine, C-ifluoroalkyl, methoxy or
Cifluoroalkoxy; more preferably fluorine or chlorine; most preferably chlorine. Preferably, in
sub-formula (b1) or (c1 ) , R B is hydrogen or fluorine; most preferably hydrogen. Preferably,
in sub-formula (b1) or (c1 ) , R 4B is hydrogen, fluorine or chlorine; most preferably hydrogen
or fluorine.
More preferably, e.g. in all aspects and/or embodiments of the invention, R is optionally
substituted phenyl. In this embodiment, then, even more preferably, R B is of sub-formula
(a 2 ) , in which R B, R 2B, R B and R 4B are as defined herein.
In the invention, R4 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl,
ethynyl, fluorine, chlorine, bromine, CrC 3alkoxy (e.g. methoxy, ethoxy, n-propoxy or
isopropoxy), CrC 2fluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or
trifluoromethoxy; or more particularly dfluoroalkyl-methoxy- such as
trifluoromethyl-methoxy- or difluoromethyl-methoxy-), Ci-C 2alkoxy-Ci-C 3alkoxy-, or
C fIuoroa Ikoxy-C -C3aIkoxy- .
Preferances for R4 follow. Most of the following R4 preferences are particularly preferred
and/or particularly applicable when R2 is R2 and R3 is R (which is particularly preferred).
Preferably, when R4 is Ci-C 2alkoxy-Ci-C 3alkoxy- or Cifluoroalkoxy-CrC 3alkoxy-, then R4 is
R4 0-CH(R 4B)-CH(R 4C)-0-;
wherein R4 is CrC 2alkyl (in particular methyl) or dfluoroalkyl (such as trifluoromethyl);
and R4B and R4C are independently hydrogen or methyl, provided that one or both of R4B and
R4C are hydrogen.
Preferably, R4 is methyl or C-ifluoroalkyl, more preferably methyl.
Preferably, both of R4B and R4C are hydrogen.
More preferably, when R4 is C -C2alkoxy-C-i-C3alkoxy- or C-ifluoroalkoxy-C-i-Caalkoxy- (in
particular when R4 is R4 0-CH(R 4B)-CH(R4C)-0-), then R4 is MeO-CH2-CH2-0-.
Preferably, e.g. in all aspects and/or embodiments of the invention, R4 is hydrogen, methyl,
ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, methoxy, ethoxy,
n-propoxy, CrC 2fluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy;
or more particularly dfluoroalkyl-methoxy- such as trifluoromethyl-methoxy- or
difluoromethyl-methoxy-), or R4 0-CH(R 4B)-CH(R4C)-0- (in particular MeO-CH2-CH2-0-).
Preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methyl, ethyl, npropyl,
cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, methoxy, ethoxy, n-propoxy,
CrC 2fluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy; or more
particularly C-ifluoroalkyl-methoxy- such as trifluoromethyl-methoxy- or
difluoromethyl-methoxy-), or R4 0-CH(R 4B)-CH(R4C)-0- (in particular MeO-CH2-CH2-0-).
Alternatively or additionally, preferably, e.g. in all aspects and/or embodiments of the
invention, R4 is hydrogen, methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, n-propoxy,
C -C2fluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy; or more
particularly C-ifluoroalkyl-methoxy- such as trifluoromethyl-methoxy- or
difluoromethyl-methoxy-), or R4 0-CH(R 4B)-CH(R4C)-0- (in particular MeO-CH2-CH2-0-).
More preferably, R4 is not hydrogen. This is especially preferred when R2 is R2 and R3 is R3
(which is preferred).
More preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methyl, ethyl,
ethynyl, fluorine, chlorine, methoxy, ethoxy, n-propoxy, C -C2fluoroalkoxy (e.g.
monofluoromethoxy, difluoromethoxy or trifluoromethoxy; or more particularly
C-ifluoroalkyl-methoxy- such as trifluoromethyl-methoxy- or difluoromethyl-methoxy-), or
MeO-CH2-CH2-0-.
Even more preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methyl,
fluorine, chlorine, methoxy, ethoxy, C-ifluoroalkyl-methoxy- (in particular
trifluoromethyl-methoxy- or difluoromethyl-methoxy-), or MeO-CH2-CH2-0-.
Still more preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methyl,
chlorine or methoxy.
Yet more preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methyl or
methoxy.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R4 is methoxy.
Preferances for R4 , which are particularly preferred and/or particularly applicable when R2 is
R2B and R3 is R B (which is less preferred), follow. In this embodiment, preferably, R4 is
hydrogen, methyl, fluorine or chlorine, in particular hydrogen, methyl or fluorine. In this
embodiment, most preferably, R4 is hydrogen.
Particularly preferably, e.g. in all aspects and/or embodiments of the invention:
R is methyl, fluorine, chlorine, bromine, difluoromethoxy or trifluoromethoxy (or more
preferably, R is methyl, fluorine, chlorine or bromine; or even more preferably, R is methyl,
fluorine or chlorine); and
either (a): R2 is R2 and R3 is R ;
or (b): R2 is R2B and R3 is R B;
and wherein:
R is hydrogen or methyl (or more preferably, R is hydrogen); and
R2 is methyl, -CºC-R2 (in particular, -CºC-R2 wherein R2 is hydrogen), chlorine or
bromine (or more preferably, R2 is methyl or -CºC-R2 wherein R2 is hydrogen);
or R2 is of sub-formula (a) or (a1 ) as defined herein e.g. hereinabove (more preferably with
the preferances as defined herein e.g. hereinabove);
or R2 is of sub-formula (b), (c), (d), (e), (f) or (g) as defined herein e.g. hereinabove (more
preferably with the preferences as defined herein e.g. hereinabove);
(or, even more preferably, R is of sub-formula (a), (b), (c) or (g), still more preferably of subformula
(a), (b) or (c), as defined herein e.g. hereinabove, in particular with the preferences
as defined herein e.g. hereinabove);
and R2B is hydrogen or methyl (or more preferably, R2B is hydrogen); and
either R B is of sub-formula (a2) as defined herein e.g. hereinabove (more preferably with the
preferances as defined herein e.g. hereinabove);
or R B is of sub-formula (b1 ) or (c1 ) as defined herein e.g. hereinabove (more preferably with
the preferances as defined herein e.g. hereinabove);
(or, even more preferably, R B is of sub-formula (a2) as defined herein e.g. hereinabove, in
particular with the preferences as defined herein e.g. hereinabove);
and wherein:
when R2 is R2 and R3 is R (which is particularly preferred), then R4 is methyl, ethyl,
ethynyl, fluorine, chlorine, methoxy, ethoxy, n-propoxy, CrC 2fluoroalkoxy (e.g.
monofluoromethoxy, difluoromethoxy or trifluoromethoxy; or more particularly
Cifluoroalkyl-methoxy- such as trifluoromethyl-methoxy- or difluoromethyl-methoxy-), or
MeO-CH2-CH2-0-;
(or, more preferably, when R2 is R2 and R3 is R (which is particularly preferred), then R4 is
methyl, fluorine, chlorine, methoxy, ethoxy, Cifluoroalkyl-methoxy- (in particular
trifluoromethyl-methoxy- or difluoromethyl-methoxy-), or MeO-CH2-CH2-0-;
or, even more preferably, when R2 is R2 and R3 is R (which is particularly preferred), then
R4 is methyl, chlorine or methoxy;)
and, when R2 is R2B and R3 is R B (which is less preferred), then R4 is hydrogen, methyl,
fluorine or chlorine, in particular hydrogen, methyl or fluorine
(or more preferably, when R2 is R2B and R3 is R B, then R4 is hydrogen).
As discussed before, most preferably, e.g. in all aspects and/or embodiments of the
invention, R2 is R2 and R3 is R .
In the invention, R5, R6 and R7, independently of each other, are hydrogen, C -C5alkyl (in
particular C1-C4alkyl, e.g. C1-C2alkyl), C2-C3 alkenyl (in particular ethenyl-CH2-), C2-C3alkynyl
(in particular ethynyl-CH 2-), C -C2fluoroalkyl or C -C2alkoxyC -C2alkyl (in particular
methoxymethyl);
provided that: either (i) at least two of R5, R6 and R7 are hydrogen, or (ii) two of R5, R6 and R7
are methyl and the remaining one of R5, R6 and R7 is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R5, R6 and R7,
independently of each other, are hydrogen, C -C2alkyl, ethynyl-CH 2- , C-ifluoroalkyl or
methoxymethyl;
provided that: either (i) at least two of R5, R6 and R7 are hydrogen, or (ii) two of R5, R6 and R7
are methyl and the remaining one of R5, R6 and R7 is hydrogen.
More preferably, e.g. in all aspects and/or embodiments of the invention, R5, R6 and R7,
independently of each other, are hydrogen or methyl;
provided that: either (i) at least two of R5, R6 and R7 are hydrogen, or (ii) two of R5, R6 and R7
are methyl and the remaining one of R5, R6 and R7 is hydrogen.
Most preferably, e.g. in all aspects and/or embodiments of the invention, all of R5, R6 and R7
are hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R8 and R , independently
of each other, are hydrogen or methyl.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R8 and R are both
hydrogen.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R 0 is hydrogen.
In a more particularly preferable embodiment of the invention (which e.g. can apply to all
aspects and/or embodiments of the invention), the compound of formula (I) is any of (e.g.
any one of) compounds A 1 to A29 or A30 to A41 , as described and/or illustrated herein,
present either as a free compound (i.e. a compound not substantially in the form of a salt)
and/or (e.g. where chemically possible) present as an agrochemically acceptable salt (e.g.
agriculturally acceptable metal, sulfonium or ammonium salt) thereof. Alternatively, in an
also more particularly preferable embodiment of the invention (which e.g. can apply to all
aspects and/or embodiments of the invention), the compound of formula (I) is any of (e.g.
any one of) compounds A42 or A45, as described and/or illustrated herein, present either as
a free compound (i.e. a compound not substantially in the form of a salt) and/or (e.g. where
chemically possible) present as an agrochemically acceptable salt (e.g. agriculturally
acceptable metal, sulfonium or ammonium salt) thereof.
In another preferable embodiment of the invention (which e.g. can apply to all aspects and/or
embodiments of the invention), the compound of formula (I) is any of (e.g. any one of) the
compounds disclosed in any of Tables 1 to 60, as described and/or illustrated herein, present
either as a free compound (i.e. a compound not substantially in the form of a salt) and/or
(e.g. where chemically possible) present as an agrochemically acceptable salt (e.g.
agriculturally acceptable metal, sulfonium or ammonium salt) thereof.
In all embodiments or aspects of the invention, it is preferred that the compound of formula
(I) is a compound of formula (IC):
wherein R , R2, R3, R4, R5, R6, R7, R8, R9, R 0 , and G are as defined herein,
and wherein 40% or more (in particular 45% or more) by molarity of the compound of formula
(IC) has the indicated stereochemistry at the ring-carbon atom bonded to R5
and -CR R -CºC-R 0 . For example, this broadest definition of formula (IC) includes
compounds which are substantially racemic at the ring-carbon atom bonded to R5
and -CR R -C=C-R 0 , and also includes compounds enriched with isomer(s) having the
stereochemistry indicated at the ring-carbon atom bonded to R5 and -CR R -CºC-R 0 .
More preferably, more than 50% (still more preferably more than 70% or more than 80%,
most preferably more than 90% or more than 95%) by molarity of the compound of formula
(IC) has the indicated stereochemistry at the ring-carbon atom bonded to R5
and -CR R -CºC-R 0 . This more preferred definition of formula (IC) includes compounds
enriched with isomer(s) having the stereochemistry indicated at the ring-carbon atom bonded
to R5 and -CR R -CºC-R10 .
Depending on the nature of the substituents G, R , R2, R3, R4, R5, R6, R7, R8, R9, and R 0 ,
compounds of formula (I) may exist in different isomeric or tautomeric forms.
For example, when G is hydrogen, compounds of formula (I) may exist in different tautomeric
forms (of formulae (A), (A1 ) and (A2)), as shown below:
Also, when substituents contain double bonds, cis- and trans-isomers can exist.
This invention covers all such isomers and/or tautomers and/or mixtures thereof in all
proportions. These isomers and/or tautomers are within the scope of the claimed
compounds of formula (I).
According to a further aspe compound of formula (II):
wherein:
X is methyl or chlorine;
R is methoxy, ethoxy, Cifluoroalkoxy (e.g. difluoromethoxy or trifluoromethoxy), ethyl, npropyl,
cyclopropyl or ethynyl;
R4 is hydrogen, methoxy, ethoxy, Cifluoroalkoxy (e.g. difluoromethoxy or trifluoromethoxy),
or ethyl; and
G is hydrogen, an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group; or G is -CiO^R^ or -C(0)-X cc-RBB;
wherein Xcc is oxygen or sulfur;
R is CrCioalkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-,
Ci-C 3alkoxyCi-C 3alkyl; phenyl or phenyl substituted by 1 or 2 of, independently, C1-C2alkyl,
CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; monocyclic heteroaryl
or monocyclic heteroaryl substituted by 1 or 2 of, independently, Ci-C2alkyl, CifluoroalkyI,
CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; or phenyl-methyl- in which the
phenyl is optionally substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI,
CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; and
RBB is Ci-Cioalkyl, C2-C5alkenyl-CH2- , C2-C4alkenyl-CH(Me)-, C2-C5alkynyl-CH2- ,
C2-C4alkynyl-CH(Me)-, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-, Ci-C 3alkoxyCi-C 3alkyl;
phenyl or phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI,
Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; monocyclic heteroaryl or monocyclic
heteroaryl substituted by 1 or 2 of, independently, C1-C2alkyl, CifluoroalkyI, C1-C2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano; or phenyl-methyl- in which the phenyl is optionally
substituted by 1 or 2 of, independently, CrC 2alkyl, CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano;
and wherein the compound of formula (II) is optionally present as an agrochemically
acceptable salt (e.g. agriculturally acceptable metal, sulfonium or ammonium salt) thereof.
Preferably, X is methyl. This is strongly preferred.
Preferably, R is methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, ethyl or n-propyl.
More peferably, R is methoxy, ethyl or n-propyl. Even more preferably, R is methoxy or
ethyl. Most preferably, R is methoxy.
Preferably, R4 is hydrogen, methoxy or ethyl. More preferably, R4 is hydrogen or
methoxy. Most preferably, R4 is hydrogen.
Preferably, R is Ci-C 6alkyl, C3-C6cycloalkyl, Ci-C 2alkoxyCi-C 2alkyl; or phenyl or phenyl
substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano.
Preferably, RBB is C C6alkyl, C2-C5alkenyl-CH2- , C2-C5alkynyl-CH2- , C3-C6cycloalkyl; or
phenyl or phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI,
CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano.
Preferably, G is hydrogen, an agriculturally acceptable metal (e.g. an agriculturally
acceptable alkali metal or alkaline earth metal), or an agriculturally acceptable sulfonium or
ammonium group. Most preferably, G is hydrogen.
Particularly preferably, in the compound of formula (II):
X is methyl;
R is methoxy, ethyl or n-propyl (more preferably, R is methoxy or ethyl; or most
preferably methoxy);
R4 is hydrogen, methoxy or ethyl (more preferably, R4 is hydrogen or methoxy; or most
preferably hydrogen); and
G is hydrogen, an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group (most preferably, G is hydrogen).
Particularl preferably, the compound of formula (II) is one of the following compounds:
in each case optionally present as an agrochemically acceptable salt (e.g. agriculturally
acceptable metal, sulfonium or ammonium salt) thereof.
Preferably, the compound of formula (II) is a compound of formula (IIC):
wherein X, R , R , and G are as defined herein,
and wherein 40% or more (in particular 45% or more, preferably more than 50%, more
preferably more than 70% or more than 90%) by molarity of the compound of formula (IIC)
has the indicated stereochemistry at the ring-carbon atom bonded to -CH 2-CºC-H.
A further aspect of the invention provides a herbicidal composition which comprises:
(i) a compound of formula (II), as defined herein, and
(ii) an agrochemically acceptable carrier, diluent and/or solvent; and
(iii) optionally one or more further herbicides and/or optionally a safener.
A further aspect of the invention provides a method of controlling grassy monocotyledonous
weeds in crops of useful plants, comprising applying (e.g. post-emergence) a compound of
formula (II), as defined herein, or a herbicidal composition comprising such a compound (e.g.
as defined herein), to the weeds and/or to the plants and/or to the locus thereof. In this
aspect, preferably, the crops of useful plants comprise wheat, barley, rye, triticale,
sugarcane, soybean, peanut, pulse crops, cotton, rape, sunflower, linseed, sugarbeet, fodder
beet, potato, and/or dicotyledonous vegetables. In this aspect, preferably, the grassy
monocotyledonous weeds comprise (e.g. are) the preferred or particular grassy
monocotyledonous weeds as defined herein e.g. for the compounds of formula (I).
Processes for preparation of compounds, e.g. compounds of formula (I)
Processes for preparation of compounds, e.g. a compound of formula (I) (which optionally
can be an agrochemically acceptable salt thereof), are now described, and form further
aspects of the present invention.
A compound of formula I , wherein G is:
-C(Xa)-Ra, -C(X )-X -R , -C(X )-N(R )-R , -S0 2-Re, -P(Xe)(R )-R9, -CH2-X -Rh; or
phenyl-CH 2- or phenyl-CH(Ci-C 2alkyl)- (in each of which the phenyl is optionally substituted
by 1, 2 or 3 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine,
chlorine, bromine, cyano or nitro), or heteroaryl-CH 2- or heteroaryl-CH(Ci-C 2alkyl)- (in each
of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, Ci-C 2alkyl,
CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or
phenyl-C(0)-CH 2- (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
CrC 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or
nitro); or C C6alkoxy-C(0)-CH 2- , C C6alkyl-C(0)-CH 2- , C C6alkoxy-C(0)-CH=CH-,
C2-C7alken-1-yl-CH 2- , C2-C7alken-1-yl-CH(C C2alkyl)-, C2-C4fluoroalken-1-yl-CH 2- ,
C2-C7alkyn-1-yl-CH 2- , or C2-C7alkyn-1-yl-CH(C C2alkyl)-;
may be prepared by treating a compound of formula (A), which is a compound of formula I
wherein G is H,
(a) with a reagent G1-Z, wherein G1-Z is an alkylating agent (wherein G 1 is an organic group
according to G within the compound of formula (I) and which is linked by a non-carbonyl,
non-thiocarbonyl carbon atom) such as an organic halide (in which Z = halogen such as
chlorine, bromine or iodine); wherein the organic halide (e.g. chloride) can typically be a
substituted alkyl halide (e.g. chloride) such as a chloromethyl alkyl ether CI—CH2-X -Rh
wherein X is oxygen, a chloromethyl alkyl sulfide CI—CH2-X -Rh wherein X is sulphur, a
suitable optionally substituted benzyl halide (e.g. chloride) such as CI-CH2-[optionally
substituted phenyl], [optionally substituted phenyl]-C(0)-CH 2-[halogen e.g. CI],
C C6alkoxy-C(0)-CH 2-[halogen e.g. CI], C C6alkoxy-C(0)-CH=CH-[halogen e.g. CI], a
suitable alkenyl or alkynyl halide (e.g. chloride) such as C2-C7alken-1-yl-CH 2-[halogen e.g.
CI] or C2-C7alkyn-1-yl-CH 2-[halogen e.g. CI], or another organic halide suitable for preparing
a (non-carbonyl, non-thiocarbonyl carbon)-linked G (or G1) group; or
(b) [e.g. to prepare carbonyl-carbon-linked or thiocarbonyl-carbon-linked G groups] with an
acylating agent such as a carboxylic acid, HO-C(Xa)Ra, wherein Xa is oxygen, an acid
chloride, CI-C(Xa)Ra, wherein Xa is oxygen, or an acid anhydride, [RaC(Xa)]20 , wherein Xa is
oxygen, or an isocyanate, R N=C=0, or a carbamoyl chloride, CI-C(X )-N(R )-R (wherein X
is oxygen and with the proviso that neither R or R is hydrogen), or a thiocarbamoyi chloride
CI-(X )-N(R )-R (wherein X is sulfur and with the proviso that neither R or R is hydrogen),
or a chloroformate, CI-C(X )-X -R (wherein X and X are oxygen), or a chlorothioformate Cl-
C(X )-X -R (wherein X is oxygen and X is sulfur), or a chlorodithioformate CI-C(X )-X -R
(wherein X and X are sulfur), or an isothiocyanate, R N=C=S; or
(c) by sequential treatment with carbon disulfide and an alkylating agent; or
(d) with a phosphorylating agent such as a phosphoryl chloride, CI-P(Xe)(R )-R9; or
(e) with a sulfonylating agent such as a sulfonyl chloride Cl-S0 2—Re, preferably in the
presence of at least one equivalent of base.
Where substituents R6 and R7 are not equal to substituents R5 and -CR R -CºC-R 0 , the
above-described reactions may produce, in addition to a compound of formula (I), a second
compound of formula (IA).
This invention covers both a compound of formula (I) and a compound of formula (IA),
to ether with mixtures of these compounds in any ratio.
formula (A) formula I formula (IA)
The O-alkylation of cyclic 1,3-diones is known; suitable methods are described, for example,
by T. Wheeler, US4436666. Alternative procedures have been reported by M. Pizzorno and
S. Albonico, Chem. Ind. (London), (1972), 425-426; H. Born et al., J. Chem. Soc, (1953),
1779-1782; M. G. Constantino et al., Synth. Commun., (1992), 22 (19), 2859-2864; Y. Tian et
ai, Synth. Commun., (1997), 27 (9), 1577-1582; S. Chandra Roy et al., Chem. Letters,
(2006), 35 ( 1 ) , 16-17; and/or P. K. Zubaidha et al., Tetrahedron Lett., (2004), 45, 7187-7188.
The O-acylation of cyclic 1,3-diones may be effected e.g. by procedures similar to those
described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870,
US4659372 and US4436666. Typically diones of formula (A) may be treated with an
acylating agent preferably in the presence of at least one equivalent of a suitable base, and
optionally in the presence of a suitable solvent. The base may be inorganic, such as an alkali
metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary
amine or metal alkoxide. Examples of suitable inorganic bases include sodium carbonate,
sodium or potassium hydroxide, or sodium hydride, and suitable organic bases include
trialkylamines, such as trimethylamine or triethylamine, pyridines or other amine bases such
as 1,4-diazobicyclo[2.2.2]-octane or 1,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases
include triethylamine and pyridine. Suitable solvents for this reaction are selected to be
compatible with the reagents and include ethers such as tetrahydrofuran or 1,2-
dimethoxyethane or halogenated solvents such as dichloromethane or chloroform. Certain
bases, such as pyridine or triethylamine, may be employed successfully as both base and
solvent. For cases where the acylating agent is a carboxylic acid, acylation is preferably
effected in the presence of a known coupling agent such as 2-chloro-1-methylpyridinium
iodide, L/,L/'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide or
L/,L/'-carbodiimidazole, and optionally in the presence of a base such as triethylamine or
pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile.
Suitable procedures are described, for example, by W. Zhang and G. Pugh, Tetrahedron
Lett., (1999), 40 (43), 7595-7598; T. Isobe and T. Ishikawa, J. Org. Chem., (1999), 64 (19),
6984-6988 and/or K. Nicolaou, T. Montagnon, G. Vassilikogiannakis, C. Mathison, J. Am.
Chem. Soc, (2005), 127(24), 8872-8888.
Phosphorylation of cyclic 1,3-diones may be effected e.g. using a phosphoryl halide or
thiophosphoryl halide and a base e.g. by procedures analogous to those described by L.
Hodakowski, US4409153.
Sulfonylation of a compound of formula (A) may be achieved e.g. using an alkyl or aryl
sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by
the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981 ) , 46, 197-201 .
A compound of formula (A) may be prepared via the cyclisation of a compound of formula (B),
preferably in the presence of an acid or base, and optionally in the presence of a suitable solvent,
by analogous methods to those described by T. Wheeler, US4209532. Compounds of formula (B)
have been particularly designed as intermediates in the synthesis of the compounds of formula I .
Compounds of formula (B) wherein R is hydrogen or C -C4alkyl, (especially methyl, ethyl and tertbutyl)
may be cyclised under acidic conditions, preferably in the presence of a strong acid such
as sulfuric acid, polyphosphoric acid or Eaton's reagent, optionally in the presence of a suitable
solvent such as acetic acid, toluene or dichloromethane. A compound of formula (B) wherein R is
alkyl (preferably methyl or ethyl) may also be cyclised under basic conditions in the presence of
at least one equivalent of a strong base in a solvent such as tetrahydrofuran, toluene,
dimethylsulfoxide or , -dimethylformamide. Suitable bases include potassium fert-butoxide,
lithium diisopropylamide, sodium bis(trimethylsilyl)amide or sodium hydride. A compound of
formula (B), wherein R is alkyl, may be produced from a compound of formula (B), wherein R is
H, by esterification under known conditions, for example by treatment with an alcohol, R-OH, in
the presence of an acid catalyst.

CLAIMS
wherein:
R is methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine, chlorine,
bromine, methoxy, difluoromethoxy or trifluoromethoxy; and
either (a): R2 is R2 and R3 is R ;
or (b): R2 is R2B and R3 is R B;
R is hydrogen, methyl, fluorine or chlorine; and
R is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, CrC 2fluoroalkyl, vinyl,
prop-1-enyl, -CºC-R2 , halogen, or (Ci-C2fluoroalkyl)-methoxy-; wherein R2 is hydrogen,
fluorine, trifluoromethyl, ethyl or cyclopropyl;
or R2 is phenyl optionally substituted by 1, 2 or 3 substituents independently being halogen,
CrC 2alkyl, Ci-C2fluoroalkyl, methoxymethyl, vinyl, ethynyl, CrC 3alkoxy, CrC 2fluoroalkoxy,
methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that either one or none
(i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl,
methylthio, methylsulfinyl, methylsulfonyl or nitro;
or R2 is monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently
being halogen, C -C2alkyl, C -C2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C -C3alkoxy,
C -C2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
and wherein
R2B is hydrogen, methyl or fluorine; and
either R B is phenyl optionally substituted by 1, 2 or 3 substituents independently being
halogen, CrC 2alkyl, CrC 2fluoroalkyl, methoxymethyl, vinyl, ethynyl, CrC 2alkoxy,
CrC 2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
or R B is monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently
being halogen, Ci-C 2alkyl, CrC 2fluoroalkyl, methoxymethyl, vinyl, ethynyl, Ci-C 2alkoxy,
C -C2fluoroalkoxy, methylthio, methylsulfinyl, methylsulfonyl, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are methoxymethyl,
vinyl, ethynyl, methylthio, methylsulfinyl, methylsulfonyl or nitro;
and wherein
R4 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine,
chlorine, bromine, CrC 3alkoxy, Ci-C 2fluoroalkoxy, Ci-C 2alkoxy-CrC 3alkoxy-, or
Cifluoroalkoxy-CrC 3alkoxy-; and
R5, R6 and R7, independently of each other, are hydrogen, -C5alkyl, C2-C3 alkenyl,
C2-C3alkynyl, Ci-C 2fluoroalkyl or Ci-C 2alkoxyCrC 2alkyl;
provided that: either (i) at least two of R5, R6 and R7 are hydrogen, or (ii) two of R5, R6 and R7
are methyl and the remaining one of R5, R6 and R7 is hydrogen; and
R8 and R , independently of each other, are hydrogen, fluorine or Ci-C 3alkyl; and
R 0 is hydrogen or methyl;
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group; or
G is -C(Xa)-Ra, -C(X )-X -R , -C(X )-N(R )-R , -S0 2-Re, -P(Xe)(R )-R9, -CH2-X -Rh; or
phenyl-CH2- or phenyl-CH(Ci-C 2alkyl)- (in each of which the phenyl is optionally substituted
by 1, 2 or 3 of, independently, Ci-C 2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy, fluorine,
chlorine, bromine, cyano or nitro), or heteroaryl-CH 2- or heteroaryl-CH(Ci-C 2alkyl)- (in each
of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, Ci-C2alkyl,
CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or
phenyl-C(0)-CH 2- (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
CrC 2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or
nitro); or C C6alkoxy-C(0)-CH 2- , C C6alkyl-C(0)-CH 2- , C C6alkoxy-C(0)-CH=CH-,
C2-C7alken-1-yl-CH 2- , C2-C7alken-1-yl-CH(C C2alkyl)-, C2-C4fluoroalken-1-yl-CH 2- ,
C2-C7alkyn-1-yl-CH2- , or C2-C7alkyn-1-yl-CH(Ci-C 2alkyl)-;
wherein Xa, X , X , X , Xe and X are independently of each other oxygen or sulfur; and
wherein
Ra is H, C -C2ialkyl, C2-C2ialkenyl, C2-Ci 8alkynyl, Ci-Ci 0fluoroalkyl, Ci-Ci 0cyanoalkyl, C
C 0nitroalkyl, Ci-Ci 0aminoalkyl, C -C5alkylamino(Ci-C 5)alkyl, C2-C8dialkylamino(Ci-C 5)alkyl,
C3-C7cycloalkyl(Ci-C 5)alkyl, C i -C5alkoxy(Ci-C 5)alkyl, C3-C5alkenyloxy(Ci-C 5)alkyl, C3-
C5alkynyloxy (C C5)alkyl, C i -C5alkylthio(Ci-C 5)alkyl, C i -C5alkylsulfinyl(Ci-C 5)alkyl, C
C5alkylsulfonyl(Ci-C 5)alkyl, C2-C8alkylideneaminoxy(Ci-C 5)alkyl, C -C5alkylcarbonyl(d-
C5)alkyl, C -C5alkoxycarbonyl(Ci-C 5)alkyl, aminocarbonyl(Ci-C 5)alkyl, C
C5alkylaminocarbonyl(Ci-C 5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C 5)alkyl, C
C5alkylcarbonylamino(Ci-C 5)alkyl, /V-(Ci-C5 )alkylcarbonyl-/V-(Ci-C5)alkylamino(Ci-C 5)alkyl,
C3-C6trialkylsilyl(Ci-C 5)alkyl, phenyl(Ci-C 5)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, C -C3alkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy,
C -C3alkylthio, C -C3alkylsulfinyl, C -C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Cr
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C
C3alkyl, C i -C3fluoroalkyl, C i -C3alkoxy, C i -C3fluoroalkoxy, C i -C3alkylthio, CrC 3alkylsulfinyl,
CrC 3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, C i -C3alkyl, C i -C3fluoroalkyl, C i -C3alkoxy,
CrC 3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
of, independently, C i -C3 alkyl, CrC 3fluoroalkyl, C i -C3alkoxy, C i -C3fluoroalkoxy, halogen,
cyano or nitro;
R is C -C 8alkyl, C3-C18alkenyl, C3-C18alkynyl, C2-C10fluoroalkyl, d-docyanoalkyl, C
Cionitroalkyl, d-doaminoalkyl, d-C 5alkylamino(d-C 5)alkyl, d-ddialkylamino(d-d)alkyl,
d-dcycloalkyl(Ci-d)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, d-dalkenyloxy(d-d)alkyl, C3-
dalkynyloxy(Ci-d)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, -
dalkylsulfonyl(d-d)alkyl, d-dalkylideneaminoxy(d-d)alkyl, d-dalkylcarbonyl(dd)
alkyl, Ci-dalkoxycarbonyl(d-d)alkyl, aminocarbonyl(d-d)alkyl, d -
dalkylaminocarbonyl(Ci-d)alkyl, d-ddialkylaminocarbonyl(d-d)alkyl, d -
dalkylcarbonylamino(d-d)alkyl, /V-(d-d)alkylcarbonyl-/V-(Ci-d)alkylamino(Ci-d)alkyl,
d-dtrialkylsilyl(d-d)alkyl, phenyl(d-d)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy,
d-dalkylthio, Ci-C3alkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), heteroarylddalkyl
(wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, d -
dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkyl-thio, d-dalkylsulfinyl,
Crdalkylsulfonyl, halogen, cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy,
d-dfluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
of, independently, d-d alkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen,
cyano or nitro; and
R and R are each independently of each other hydrogen, d-C 10alkyl, C3-d 0alkenyl, d -
d 0alkynyl, C2-d 0fluoroalkyl, d-d 0cyanoalkyl, d-d 0nitroalkyl, d-d 0aminoalkyl, d -
dalkylamino(C 1-d)alkyl, d-ddialkylamino(C 1-C5)alkyl, d-dcycloalkyl(d-d)alkyl, d -
dalkoxy(d-d)alkyl, d-dalkenyloxy(d-d)alkyl, C3-dalkynyloxy(d-d)alkyl, C
dalkylthio(d-d)alkyl, C1-dalkylsulfinyl(C 1-C5)alkyl, C1-dalkylsulfonyl(C 1-d)alkyl, d -
dalkylideneaminoxy(C 1-d)alkyl, C1-dalkylcarbonyl(C 1-C5)alkyl, d-dalkoxycarbonyl(dd)
alkyl, aminocarbonyl(d-d)alkyl, C1-dalkylaminocarbonyl(C 1-d)alkyl, C2-
ddialkylaminocarbonyl(C -d)alkyl, C -dalkylcarbonylamino(C -d)alkyl, /V-(dd)
alkylcarbonyl-/V-(C2-d)alkylaminoalkyl, d-dtrialkylsilyl(d-d)alkyl, phenyl(d-C 5)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d -
dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d -
dalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d-C 5)alkyl (wherein the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d -
dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen,
cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
of, independently, -C3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, CrCsfluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, CrC 3alkyl,
CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, C -C3alkyl, C -C3fluoroalkyl, d -
C3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
substituted by 1, 2 or 3 of, independently, C -C3alkyl, C -C3fluoroalkyl, C -C3alkoxy, d -
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
of, independently, C -C3alkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy, halogen,
cyano or by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently,
d-dalkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy, halogen, cyano or nitro; or C3-
dcycloalkylamino, di(C3-C7cycloalkyl)amino or C3-C7cycloalkoxy;
or R and R , together with the nitrogen to which they are bonded, to form an unsubstituted 4,
5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom selected from O
or S; and
Re is d-C 10alkyl, C2-C10alkenyl, C2-C10alkynyl, d-C 10fluoroalkyl, d-C 10cyanoalkyl, d -
C10nitroalkyl, d-C 10aminoalkyl, C1-C5alkylamino(C 1-C5)alkyl, C2-C8dialkylamino(C 1-C5)alkyl,
C3-C7cycloalkyl (Ci -C5)alkyl, C -C5alkoxy(Ci -C5)alkyl, C3-C5alkenyloxy (Ci -C5)alkyl, C3-
C5alkynyloxy (Ci -C5)alkyl, C -C5alkylthio (Ci -C5)alkyl, C -C5alkylsulfinyl (Ci -C5)alkyl, d -
C5alkylsulfonyl(d-C5)alkyl, C2-C8alkylideneaminoxy(C 1-C5)alkyl, CrC 5alkylcarbonyl(Cr
C5)alkyl, C1-C5alkoxycarbonyl(C 1-C5)alkyl, aminocarbonyl(d-C 5)alkyl, d -
C5alkylaminocarbonyl(d-C 5)alkyl, C2-C8dialkylaminocarbonyl(d-C 5)alkyl, d -
C5alkylcarbonylamino(C -C5)alkyl, /V-(C -C5 )alkylcarbonyl-/V-(C -C5)alkylamino(C -C5)alkyl,
C3-C6trialkylsilyl(C -C5)alkyl, phenyl(C -C5)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, CrCsfluoroalkoxy,
CrC 3alkylthio, CrC 3alkylsulfinyl, CrC 3alkylsulfonyl, halogen , cyano, or nitro), heteroaryl(d-
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, d -
C3alkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy, C -C3alkylthio, C -C3alkylsulfinyl,
C -C3alkylsulfonyl, halogen , cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, C -C3alkyl, C -C3fluoroalkyl, C -C3alkoxy,
CrC 3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of,
independently, C -C3alkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy, halogen, cyano
or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, CrC 3
alkyl, C -C3fluoroalkyl, C -C3alkoxy, C -C3fluoroalkoxy, halogen, cyano or nitro;
diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, Ci-C3alkyl,
CrC 3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; phenylamino or
phenylamino substituted by 1, 2 or 3 of, independently, Ci-C3alkyl, CrC 3fluoroalkyl, d -
C3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino
substituted by 1, 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, d -
C3fluoroalkoxy, halogen, cyano or nitro; or C3-C7cycloalkylamino, di(C3-C7cycloalkyl)amino,
C3-C7cycloalkoxy, CrCi 0alkoxy, Ci-Ci 0fluoroalkoxy, Ci-C5alkylamino or di(Ci-C 4alkyl)amino;
R and R9 are are each independently of each other CrCi 0alkyl, C2-Ci 0alkenyl, C2-Ci 0alkynyl,
Ci-Ci 0alkoxy, Ci-Ci 0fluoroalkyl, Ci-Ciocyanoalkyl, CrCi 0nitroalkyl, Ci-Ci 0aminoalkyl, d -
C5alkylamino(C1-C5)alkyl, C2-C8dialkylamino(C1-C5)alkyl, C3-C7cycloalkyl(C1-C5)alkyl, d -
C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-C5)alkyl, C3-C5alkynyloxy(C1-C5)alkyl, C
C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C 1-C5)alkyl, C2-
C8alkylideneaminoxy(C 1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl, CrC 5alkoxycarbonyl(Cr
d)alkyl, aminocarbonyl(d-d)alkyl, C1-dalkylaminocarbonyl(C 1-d)alkyl, C2-
ddialkylaminocarbonyl(C -d)alkyl, d-C 5alkylcarbonylamino(d-C 5)alkyl, /V-(dd)
alkylcarbonyl-/V-(C 2-d)alkylaminoalkyl, C3-C6trialkylsilyl(C -C5)alkyl, phenyl(d-C 5)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, d-C 3alkyl, d -
dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-C 3alkylsulfinyl, d -
dalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C -d)alkyl (wherein the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d -
dalkoxy, Crdfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen,
cyano, or nitro), C2-dfluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, d-d alkyl,
d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, d-C 3 alkyl, d-C 3fluoroalkyl, d -
dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
substituted by 1, 2 or 3 of, independently, Ci-C3 alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, d -
dfluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, Crdfluoroalkoxy, halogen,
cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, d -
dalkyl, d-C 3fluoroalkyl, d-C 3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; or C3-
dcycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, d-Ciofluoroalkoxy, d -
C5alkylamino or di(C -C4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and
phenyl groups are in turn optionally substituted by 1, 2 or 3 of, independently, -C3alkyl, d -
C3fluoroalkyl, CrC 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro; and
Rh is Ci-Ci 0alkyl, C3-Ci 0alkenyl, C3-Ci 0alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d -
C 0nitroalkyl, C2-Ci 0aminoalkyl, Ci-C5alkylamino(Ci-C 5)alkyl, C2-C8dialkylamino(Ci-C 5)alkyl,
C3-C7cycloalkyl(Ci-C 5)alkyl, Ci-C 5alkoxy(Ci-C 5)alkyl, C3-C5alkenyloxy(Ci-C 5)alkyl, C3-
C5alkynyloxy(Ci-C 5)alkyl, Ci-C5alkylthio(Ci-C 5)alkyl, Ci-C 5alkylsulfinyl(Ci-C 5)alkyl, Cr
C5alkylsulfonyl(Ci-C 5)alkyl, C2-C8alkylideneaminoxy(Ci-C 5)alkyl, CrC 5alkylcarbonyl(Cr
C5)alkyl, Ci-C 5alkoxycarbonyl(Ci-C 5)alkyl, aminocarbonyl(Ci-C 5)alkyl, d -
dalkylaminocarbonyl(d-d)alkyl, d-ddialkylaminocarbonyl(d-d)alkyl, d -
dalkylcarbonylamino(C -d)alkyl, /V-(C -d)alkylcarbonyl-/V-(C -d)alkylamino(C -d)alkyl,
C3-C6trialkylsilyl(CrC 5)alkyl, phenyl(d-C 5)alkyl (wherein the phenyl is optionally substituted
by 1, 2 or 3 of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, Crdfluoroalkoxy,
Crdalkylthio, d-C 3alkylsulfinyl, d-d alkylsulfonyl, halogen, cyano or nitro), heteroaryl(dd)
alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, d -
dalkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, Crdalkylthio, d-C 3alkylsulfinyl,
C alkylsulfonyl, halogen, cyano or nitro), phenoxy(d-C 5)alkyl (wherein the phenyl is
optionally substituted by 1, 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d -
dalkoxy, Crdfluoroalkoxy, Crdalkylthio, d-dalkylsulfinyl, d-C 3 alkylsulfonyl, halogen,
cyano or nitro), heteroaryloxy(CrC 5)alkyl (wherein the heteroaryl is optionally substituted by
1, 2 or 3 of, independently, d-C 3alkyl, d-C 3fluoroalkyl, d-C 3alkoxy, CrC 3fluoroalkoxy, d -
C3alkylthio, CrC 3alkylsulfinyl, d-C 3 alkylsulfonyl, halogen, cyano or nitro), C3-
C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently,
d-dalkyl, d-C 3fluoroalkyl, d-C 3alkoxy, CrC 3fluoroalkoxy, halogen, cyano or nitro;
heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, d-C 3alkyl, d -
dfluoroalkyl, d-C 3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; CrC 6alkyl-C(0)-; or
phenyl-C(O)- wherein the phenyl is optionally substituted by 1 or 2 of, independently, d -
dalkyl, CifluoroalkyI, d-dalkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro;
wherein "heteroaryl" means an aromatic ring system containing at least one ring heteroatom
and consisting either of a single ring or of two fused rings;
and wherein the compound of formula (I) is optionally present as an agrochemically
acceptable salt thereof.
2. A compound as claimed in claim 1, wherein G is hydrogen; an agriculturally acceptable
metal, or an agriculturally acceptable sulfonium or ammonium group; or G is -C(Xa)-Ra
or -C(X )-X -R , wherein Xa, Ra, X , X and R are as defined in claim 1.
3. A compound as claimed in claim 1 or 2, wherein Xa, X and X are oxygen;
Ra is CrCioalkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-,
C -C4alkoxyC -C4alkyl, phenyl-methyl- (in which the phenyl is optionally substituted by 1 or 2
of, independently, CrC 2alkyl, CifluoroalkyI, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or
cyano); phenyl or phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI,
CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; or monocyclic heteroaryl or
monocyclic heteroaryl substituted by 1 or 2 of, independently, Ci-C 2alkyl, CifluoroalkyI,
CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano;
and
R is - oalkyl, C2-C5alkenyl-CH2- , C2-C4alkenyl-CH(Me)-, C2-C5alkynyl-CH2- ,
C2-C4alkynyl-CH(Me)-, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-, Ci-C4alkoxyCi-C 4alkyl,
phenyl-methyl- (in which the phenyl is optionally substituted by 1 or 2 of, independently,
Ci-C 2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano); phenyl or
phenyl substituted by 1 or 2 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano; or monocyclic heteroaryl or monocyclic heteroaryl
substituted by 1 or 2 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C 2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano.
4. A compound as claimed in claim 1, 2 or 3, wherein R is methyl, ethyl, ethynyl, fluorine,
chlorine, bromine, methoxy, difluoromethoxy or trifluoromethoxy.
5. A compound as claimed in claim 1, 2 or 3, wherein R is methyl, fluorine or chlorine.
6. A compound as claimed in any of claims 1, 2, 3, 4 or 5, wherein R2 is R2 and R3 is R .
7. A compound as claimed in any of claims 1, 2, 3, 4, 5 or 6, wherein R is hydrogen.
8. A compound as claimed in any of claims 1, 2, 3, 4, 5, 6 or 7, wherein:
R2 is methyl, ethyl, vinyl, prop-1-enyl, -CºC-R 2 , halogen, or dfluoroalkyl-methoxy-;
or R2 is phenyl optionally substituted by 1, 2 or 3 substituents independently being halogen,
CrC 2alkyl, CrC 2fluoroalkyl, CrC 2alkoxy, CrC 2fluoroalkoxy, cyano or nitro, provided that
either one or none (i.e. no more than one) of these optional substituents are CrC 2alkyl,
CrC 2alkoxy or nitro;
or R2 is monocyclic 6-membered or 5-membered heteroaryl optionally substituted by 1, 2 or
3 substituents independently being halogen, Ci-C2alkyl, CrC 2fluoroalkyl, Ci-C2alkoxy,
CrC 2fluoroalkoxy, cyano or nitro, provided that either one or none (i.e. no more than one) of
these optional substituents are CrC 2alkyl, Ci-C2alkoxy or nitro.
9. A compound as claimed in any of claims 1, 2, 3, 4, 5, 6, 7 or 8, wherein:
when R2 is optionally substituted phenyl, then R2 is of sub-formula (a) or (a1):
(a) (a1 )
, in which:
R is hydrogen, fluorine or chlorine;
R 2 is halogen, Ci-C2alkyl, CrC 2fluoroalkyl, Ci-C2alkoxy, Ci-C2fluoroalkoxy, cyano or nitro;
R 3 is hydrogen, halogen, Ci-C2alkyl, Ci-C2fluoroalkyl, d-C^alkoxy, CrC ^luoroalkoxy, cyano
or nitro; and
R 4 is hydrogen, halogen, Ci-C2alkyl, Ci-C2fluoroalkyl, Ci-C2alkoxy, CrC ^luoroalkoxy, cyano
or nitro;
provided that one or more of R , R 3 and R 4 are hydrogen; and provided that either one or
none (i.e. no more than one) of R 2 , R 3 and R 4 are C -C2alkyl, C -C2alkoxy or nitro; and
R 2 is hydrogen, fluorine or chlorine;
R is fluorine or chlorine; and
R 6 is hydrogen, fluorine or chlorine;
provided that when R 2 is fluorine or chlorine, then R 6 is fluorine or chlorine; and
provided that either one or none (i.e. no more than one) of R and R 6 are chlorine;
and wherein, when R is optionally substituted monocyclic heteroaryl, then R is of subformula
(b), (c), (d), (e), (f) or (g):
, in which:
R 2 is halogen, C1-C2alkyl, C1-C2fluoroalkyl, C1-C2alkoxy, C1-C2fluoroalkoxy, cyano or nitro;
R is hydrogen, halogen, -C2alkyl, Ci-C 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy,
cyano or nitro; and
R 4 is hydrogen, halogen, Ci-C 2alkyl, CrC 2fluoroalkyl, Ci-C 2alkoxy, Ci-C 2fluoroalkoxy,
cyano or nitro;
provided that either one or none (i.e. no more than one) of R 2 , R and R 4 are Ci-C 2alkyl,
CrC 2alkoxy or nitro;
and R 5 is hydrogen, halogen, methyl, CifluoroalkyI, Cifluoroalkoxy, or cyano.
10. A compound as claimed in claim 9, wherein:
when R2 is optionally substituted phenyl, then R2 is of sub-formula (a), wherein:
R is hydrogen;
R 2 is fluorine, chlorine, bromine, CifluoroalkyI, Cifluoroalkoxy, or cyano;
R 3 is hydrogen, fluorine or chlorine; and
R 4 is hydrogen, fluorine, chlorine, bromine, or CifluoroalkyI.
and when R2 is optionally substituted monocyclic heteroaryl, then R2 is of sub-formula (b),
(c), or (g), wherein:
R 2 is fluorine, chlorine, bromine, CifluoroalkyI, Cifluoroalkoxy, or cyano;
R is hydrogen, fluorine or chlorine; and
R 4 is hydrogen, fluorine, chlorine, bromine, or CifluoroalkyI; and
R 5 is hydrogen, fluorine, chlorine, methyl, CifluoroalkyI, or Cifluoroalkoxy.
11. A compound as claimed in any of claims 1 to 10, wherein:
when R B is optionally substituted phenyl, then R B is of sub-formula (a2):
(a2)
in which
R B is hydrogen, fluorine, chlorine, methyl or methoxy;
R 2B is fluorine, chlorine, CifluoroalkyI, methoxy or Cifluoroalkoxy;
R B is hydrogen or fluorine; and
R 4B is hydrogen or fluorine;
provided that one or more of R B, R B and R 4B are hydrogen;
and wherein, when R B is optionally substituted monocyclic heteroaryl, then R B is of subformula
(b1) or (c1):
(c1 )
, in which:
R 2B is fluorine, chlorine, CifluoroalkyI, methoxy or Cifluoroalkoxy;
R B is hydrogen or fluorine; and
R is hydrogen, fluorine or chlorine.
A compound as claimed in any of claims 1 to 11, wherein
R is of sub-formula (a2): (82) , in which R11B
defined in claim 11;
and R is hydrogen.
13. A compound as claimed in any of claims 1 to 12, wherein:
R1 is methyl, fluorine, chlorine, bromine, difluoromethoxy or trifluoromethoxy; and
either (a): R2 is R2 and R3 is R ;
or (b): R2 is R2B and R3 is R B;
and wherein:
R is hydrogen or methyl; and
R2 is methyl, -CºC-R2 , chlorine or bromine;
or R2 is of sub-formula (a) or (a1 ) as defined in claim 9 or 10;
or R2 is of sub-formula (b), (c), (d), (e), (f) or (g) as defined in claim 9 or 10;
and R2B is hydrogen or methyl; and
either R B is of sub-formula (a2) as defined in claim 11 or 12;
or R B is of sub-formula (b1 ) or (c1 ) as defined in claim 11;
and wherein:
when R2 is R2 and R3 is R , then R4 is methyl, ethyl, ethynyl, fluorine, chlorine, methoxy,
ethoxy, n-propoxy, CrC 2fluoroalkoxy, or MeO-CH2-CH2-0-;
and, when R2 is R2B and R3 is R B, then R4 is hydrogen, methyl, fluorine or chlorine.
14. A compound as claimed in claim 13, wherein:
when R2 is R2 and R3 is R , then R4 is methyl, chlorine or methoxy;
and when R2 is R2B and R3 is R B, then R4 is hydrogen.
15. A compound as claimed in any of claims 1 to 14, wherein all of R5, R6 and R7 are
hydrogen.
16. A compound as claimed in any of claims 1 to 15, wherein R8 and R are both hydrogen.
17. A compound as claimed in any of claims 1 to 16, wherein R 0 is hydrogen.
18. A compound as claimed in any of claims 1 to 17, wherein the compound of formula (I) is
a compound of formul
wherein R , R2, R3, R4, R5, R6, R7, R8, R9, R 0 , and G are as defined in any of claims 1 to 17,
and wherein 40% or more by molarity of the compound of formula (IC) has the indicated
stereochemistry at the ring-carbon atom bonded to R5 and -CR R -CºC-R 0 .
19. A compound as claimed in any of claims 1 to 18, which is any of compounds A 1 to A29
or A30 to A41 , as described and/or illustrated herein, present either as a free compound
and/or present as an agrochemically acceptable salt thereof.
20. A compound as claimed in any of claims 1 to 18, which is any of the compounds
disclosed in any of Tables 1 to 60, as described and/or illustrated herein, present either as a
free compound and/or present as an agrochemically acceptable salt thereof.
2 1. A herbicidal composition which comprises:
(i) a compound of formula (I), as defined in any of claims 1 to 20, and
(ii) an agrochemically acceptable carrier, diluent and/or solvent; and
(iii) optionally one or more further herbicides and/or optionally a safener.
22. A method of controlling grassy monocotyledonous weeds in crops of useful plants,
comprising applying a compound of formula (I), as defined in any of claims 1 to 20, or a
herbicidal composition comprising such a compound, to the weeds and/or to the plants
and/or to the locus thereof.
23. A method as claimed in claim 22, wherein the crops of useful plants comprise wheat,
barley, rye, triticale, sugarcane, soybean, peanut, pulse crops, cotton, rape, sunflower,
linseed, sugarbeet, fodder beet, potato, and/or dicotyledonous vegetables.
24. A compound of formula
wherein:
X is methyl or chlorine;
R is methoxy, ethoxy, Cifluoroalkoxy, ethyl, n-propyl, cyclopropyl or ethynyl;
R is hydrogen, methoxy, ethoxy, Cifluoroalkoxy or ethyl; and
G is hydrogen, an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group; or G is -0(0)-^ or -C(0)-X c c -RBB;
wherein Xc c is oxygen or sulfur;
R is Ci-Ci 0alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-,
Ci-C 3alkoxyCi-C 3alkyl; phenyl or phenyl substituted by 1 or 2 of, independently, CrC 2alkyl,
C-ifluoroalkyl, CrC 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; monocyclic heteroaryl
or monocyclic heteroaryl substituted by 1 or 2 of, independently, Ci-C2alkyl, Cifluoroalkyl,
Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; or phenyl-methyl- in which the
phenyl is optionally substituted by 1 or 2 of, independently, Ci-C 2alkyl, Cifluoroalkyl,
Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; and
RBB is Ci-Ci 0alkyl, C2-C5alkenyl-CH2- , C2-C4alkenyl-CH(Me)-, C2-C5alkynyl-CH2- ,
C2-C4alkynyl-CH(Me)-, C3-C6cycloalkyl, C3-C6cycloalkyl-methyl-, Ci-C 3alkoxyC C3alkyl;
phenyl or phenyl substituted by 1 or 2 of, independently, Ci-C 2alkyl, Cifluoroalkyl,
Ci-C 2alkoxy, Cifluoroalkoxy, fluorine, chlorine or cyano; monocyclic heteroaryl or monocyclic
heteroaryl substituted by 1 or 2 of, independently, Ci-C2alkyl, Cifluoroalkyl, Ci-C 2alkoxy,
Cifluoroalkoxy, fluorine, chlorine or cyano; or phenyl-methyl- in which the phenyl is optionally
substituted by 1 or 2 of, independently, Ci-C2alkyl, Cifluoroalkyl, Ci-C 2alkoxy, Cifluoroalkoxy,
fluorine, chlorine or cyano;
and wherein the compound of formula (II) is optionally present as an agrochemically
acceptable salt thereof.
25. A compound as claimed in claim 24, wherein
X is methyl;
R is methoxy, ethyl or n-propyl;
R4 is hydrogen, methoxy or ethyl; and
G is hydrogen, an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
ammonium group.