CLAIMS
1. A compound of formula (I)
(Formula Removed)
or salt or N-oxide thereof,
wherein:
A is halogen, optionally substituted alkylthio, optionally substituted alkyl,
optionally substituted alkenyl or an optionally substituted 3-8 membered
carbocyclic ring;
X is azido, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulphinyl, optionally substituted alkylsulphonyl or NR5R6;
R5 is hydrogen, C2-4 alkenyl, SO2Rss, C(O)Ruu or optionally substituted
C1-4 alkyl; R6 is hydrogen, C2-4 alkenyl or optionally substituted C1-4;
each Rss is independently C1-4 alkyl or phenyl optionally
substituted by 1-3 groups Rzz;
each Ruu is independently C1-4 alkyl, phenyl optionally substituted
by 1-3 groups Rzz, C1-4 alkoxy, or NRacRad;
each Rzz is independently halogen, C1-4 alkyl, C1-4 alkoxy, or C1-4
alkylsulphonyl;
Rac and Rad are each independently hydrogen or C1-4 alkyl;
or R5 and R6 together form a group =C(Ri)ORj, =C(Rk)SRl, =C(Rm)NRnR°
wherein
R1 is hydrogen, C1-4 alkyl, C3-6 cycloalkyl, phenyl, C1-4 alkoxy, C1-4 alkylthio, or NRacRad wherein Rac and Rad are as defined above, Rj and RI are each independently C1-4 alkyl, Rk is hydrogen, C1-4 alkyl, C3-6cycloalkyl, phenyl, C1-4 alkylthio, or NRacRad wherein Rac: and Rad are as defined above,
Rm is hydrogen, C1-4 alkyl, C3-6 cycloalkyl, phenyl, or NRacRad
wherein Rac and Rad are as defined above, and
Rn and Ro are each independently hydrogen or C1-4 alkyl;
Y is optionally substituted alkyl, optionally substituted cycloalkyl, optionally
substituted alkenyl, or optionally substituted alkynyl; and,
Z is Om-(CHRw)n-C(O)Rcb, wherein m is an integer of 0 or 1, n is an integer of 0 or 1 and ≥m, Rw is hydrogen or C1-4 alkyl
Rcd is hydroxy, optionally substituted alkylthio, NH2, or ORco, Rco is C1-20 alkyl optionally substituted by 1-3 groups Rcq, or C1-20 haloalkyl optionally substituted by 1-3 groups Rcq;
each Rcq is independently C1-6 alkoxy, phenyl optionally substituted by 1-3 groups Rcr, or heteroaryl optionally substituted by 1-2 groups Rcs; each Rcr and each Rcs are independently halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C2-6 alkoxyalkyl, C1-4 alkoxy, C1-4 haloalkoxy, C1-4 alkylsulphonyl, or C1-4 alkoxycarbonyl; provided that:
i) when Y is C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxyalkyl, C2-4 alkythioalkyl, C2-4 alkenyl, C2-4 haloalkenyl, C2-4 alkoxyalkenyl, C2-4 thioalkylaikenyl, C2-4 alkynyl, C2-4 haloalkynyl, C2-4 alkylcarbonyl or C2-4 haloalkylcarbonyl; X is NR5R6;
R5 is H, C1-4 alkyl, C3-4 alkenyl, C1-4 alkylsulfonyl or C1-4 acyl; R6 is H, C1-4 alkyl or C3-4 alkenyl;
A is C1-C6 alkyl, cyclopropyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl or a group of the formula
(Formula Removed)
W1 represents H or halogen;
X, represents H, halogen, nitro, cyano, formyl, C1-6 alkyl, C2-6 alkenyl, C2-6
alkynyl, C1-6 alkoxy, C2-4 alkoxyalkyl, C1-6 alkylcarbonyl, C1-6 alkythio, C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, C2-4 alkenyloxy, C2-4 alkynyloxy, C2-4 alkenylthio, C2-4 alkynylthio, C1-6 haloalkyl, C2-6 halo- alkenyl, C2-6 haloalkynyl, C1-6 haloalkoxy, C2-4 haloalkoxyalkyl, C2-6 haloalkylcarbonyl, C1-6 haloalkylthio, C1-6 haloalkylsulfinyl, C1-6 halo- alkylsulfonyl, C3-6, trialkylsilyl, C2-4 haloalkenyloxy, C2-4 haloalkynyloxy, C2-4 haloalkenylthio, C2-4 haloalkynylthio, -C(O)OR7', -C(O)NR6R7'1 -CR8NOR7', -NR6R7', -NR6OR7', -NR6SO2R7', -NR6C(O)R7', -NR6'C(O)OR7', -NR6,C(O)NR6'R7 or -NCR6NR6R7'; R6' represents H, C1-4. alkyl or C1-4 haloalkyl; R7' represents C1-4 alkyl or C1-4 haloalkyl;
Y1 represents H, halogen, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C2-6 alkenyl or C2-6 haloalkenyl, or, X1 and Y1 taken together, represents -O(CH2)nnCH2-, or -O(CH2)nnO- wherein nn = 1 or 2; and Z1 represents H or halogen, then Z is other than CO2H, CO2Me, CO1Et, CO2nBu or CO2NHEt3+.
2. The compound according to claim 1, wherein
A is halogen, C1-4 alkylthio, phenyl optionally substituted by 1-3 groups R1, or C3-6 cycloalkyl optionally substituted by 1-4 groups R2;
R1 is halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, C1-4 alkylthio, C1-4 haloalkylthio, amino, C1-4 alkylamino, di(C1-4)alkylamino or two adjacent groups R1 together with the atoms to which they are joined form a 6-membered aromatic ring, said ring being optionally substituted by 1-2 groups selected from: halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, C1-4 alkylthio, C1-4 haloalkylthio;
R2 is halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C3-6 cycloalkyl, C1-4 alkoxy, C1-4haloalkoxy, C1-4 alkoxycarbonyl, or C1-4 alkylaminocarbonyl; or any two geminal R2 groups together form a group selected from oxo, =CRmmRnn, or =NOR∞; or two groups R2 together with the atoms to which they are joined form a 3-6-membered ring system, said ring system being optionally substituted by 1-2 groups selected from: halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, or C1-4 haloalkoxy; Rmm and Rm are each independently hydrogen, halogen, cyano, nitro, C1-4 alkyl, or C1-4 alkoxycarbonyl; R∞ is hydrogen, C1-4 alkyl, C3-6cycloalkyl (C1-2)alkyl or C3-6cycloalkyl;
X is azido, halogen, C1-3 alkoxy, C1-4 alkoxycarbonylC1-3alkoxy, C1-4 alkylthio, C1-4 alkylsulphinyl, C1-4 alkylsulphonyl or NR5R6 wherein R5 is hydrogen, C1-4 alkyl optionally substituted with 1 or 2 C1-4 alkoxy groups, C1-4 haloalkyl optionally substituted with 1 or 2 C1-4 alkoxy groups, C2-4 alkenyl, SO2Rss, or C(O)RUU;
R6 is hydrogen, C1-4 alkyl optionally substituted with 1 or 2 C1-4 alkoxy groups, or C1-4 haloalkyl optionally substituted with 1 or 2 C1-4 alkoxy groups, C2-4 alkenyl; Rss and Ruu are C1-3 alkyl,
Y is C1-6 alkyl optionally substituted by 1-3 groups Rba, C1-6 haloalkyl optionally substituted by 1-3 groups Rba, C3-6cycloalkyl optionally substituted by 1-3 groups Rbc, C2-6alkenyl optionally substituted by 1-3 groups Rbd, C2-6
alkynyl optionally substituted by 1-3 groups Rbe, wherein each Rba is independently cyano, nitro, hydroxyl, C3-6cycloalkyl, C1-4 alkoxy, C1-4alkylthio, C1-4alkylcarbonyl or C1-4alkoxycarbonyl, or two geminal Rba together form an oxo or oximino group; Rbc is halogen, cyano, C1-4alkyl, C1-4alkoxy, or C1-4alkoxycarbonyl; Rbd is halogen, cyano, C3-6cycloalkyl, C1-4alkylcarbonyl, or C1-4 alkoxycarbonyl; Rbe is halogen, cyano, hydroxyl, C1-4alkoxycarbonyl, or C3-12 trialkylsilyl;
and,
Z is Om-(CH2)n-C(O)Rcb, wherein n is an integer of 0 or 1, m is an integer of 0 or 1, and n=m Rcb is hydroxyl, C1-10 alkoxy, phenyl C1-2 alkoxy or NH2.
3. The compound according to claim 1 or claim 2, wherein
A is CI, phenyl optionally substituted by 1-3 groups R1, cyclopropyl optionally
substituted by 1-2 groups R2;
each R1 is independently halogen, cyano, C1-2 alkyl, C1-2 haloalkyl, C1-2
alkoxy, C1-2 haloalkoxy, amino, C1-4 alkylamino, or di(C1-4)alkylamino;
each R2is independently halogen, cyano, C1-2alkyl, C1-2 haloalkyl, C1-2
alkoxy, C1-2 haloalkoxy or C2-4 alkoxycarbonyl; X is N3, CI, OCH3, OCH2CO2CH3, NH2, NHCH3, N(CH3)2, NH-i-propyl, SMe,
SOMe, SO2Me, NHCOCH3, NHC(O)OCH3, NHSO2CH3, NCH3COCH3,
NCH3C(O)OCH3, or NCH3SO2CH3;
Y is C1-3 alkyl, C1-3 haloalkyl, C2-5alkoxyalkyl, cyclopropyl optionally substituted
by 1 or 2 groups Rbc, 2-4 alkenyl, C2-4 haloalkenyl, or C2-4 alkynyl
optionally substituted by 1 or 2 groups Rbe, wherein
each Rbc is independently halogen or C1-2 alkyl, and each Rbe is
independently halogen or C3-9 trialkylsilyl; and Z is selected from the group consisting of CO2H, CO2CH3, CO2CH2CH3, CO2-
i-propyl, CO2-n-propyl, CO2CH2-i-propyl, CO2CH2Phenyl, CONH2,
OCH2CO2H, OCH2CO2CH3.
4. The compound according to any one of the preceding claims wherein A is selected from the group consisting of:
CI, methylthio, isopropyl, cyclopropyl, 2-methylcyclopropyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 2,4-dimethoxyphenyl, 2,4-dichlorophenyl, 2-chloro-4-methylphenyl, 2-chloro-4-trifluoromethylphenyl, 2-fluoro-4-methylphenyl, 2-fluoro-3-methoxyphenyl, 2-fluoro-4-methoxyphenyl, 2,4-bis(trifluoromethyl)phenyl, 3,4-dimethylphenyl, 3,4-dimethoxyphenyl, 3-chloro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3,4-dichlorophenyl, 3-chloro-4-fluorophenyl, 3-chloro-4-trifluoromethylphenyl, 3-fluoro-4-methylphenyl, 3-fluoro-4-methoxyphenyl, 4-methyl-3-nitrophenyl, 4-methoxy-2-methylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-methylphenyl, 4-chloro-2-methoxyphenyl, 4-chloro-3-methoxyphenyl, 4-chloro-3-nitrophenyl, 4-chloro-3-cyanophenyl, 4-chloro-2-fluorophenyl, 4-chloro-3-fluorophenyl, 4-chloro-2-trifluoromethylphenyl, 4-chloro-3-trifluoromethylphenyl, 4-fluoro-3-methylphenyl, 4-fluoro-3-methoxyphenyl, 4-fluoro-3-trifluoromethylphenyl, 2,4,5-trimethylphenyl, 2,3,4-trimethoxyphenyl, 2,3,4-trichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, 2.3,4-trifluorophenyl, 2,4-dichloro-3-fluorophenyl, 3,4-dichloro-2-fluorophenyl, 4-chloro-2,3-difluorophenyl, 4-chloro-2,6-difluorophenyl, 4-chloro-3,5-difluorophenyl, 2,4-dichloro-6-fluorophenyl, 4-chloro-2-fluoro-3-methoxyphenyl, 4-chloro-2-fluoro-3-trifluoromethylphenyl, 4-chloro-3-dimethylamino-2-fluorophenyl, and 2-fluoro-3-methoxy-4-methylphenyl;
Y is selected from the group consisting of:
methyl, ethyl, isopropyl, n-propyl, prop-1-en-2-yl, prop-1-enyl, prop-2-enyl, but-1-enyl, pent-1-enyl, difluoromethyl, trifluoromethyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-methylprop-1-enyl, 2-methylprop-1-enyl, 1,2-dimethylprop-1-
enyl, 3-methylbut-1-ynyl, 3-methylbut-2-enyl, 3,3-dimethylbut-1-ynyl, acetyl, formyl, methoxymethyl, 2-methoxyethyl, hydroxyiminomethyl, methoxyiminomethyl, 1-(hydroxyimino)ethyl, 1-(methoxyimino)ethyl, cyclopropyl, 1-methylcyclopropyl, 2,2-dichlorocyclopropyl, vinyl, 2-cydopropylvinyl, 1-ethoxyvinyl, 2,2-dichlorovinyl, ethynyl, prop-1-ynyl, 2-bromoethynyl, 2-chloroethynyl, and 2-trimethylsilylethynyl.
5. A compound according to any one of claims 1, 2 or 4 wherein A is optionally substituted alkylthio.
6. A compound according to any preceding claim wherein X is azido, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulphinyl or optionally substituted alkylsulphonyl.
7. A compound according to any preceding claim wherein n is 1.
8. A herbicidal composition comprising a compound as defined in any one of the preceding claims and at least one agriculturally acceptable formulation adjuvant or diluent.
9. The herbicidal composition according to claim 8, further comprising a crop safener.
10. A compound as defined in any one of claims 1 to 7, or a herbicidal composition according to claim 8 or claim 9, in admixture with at least one active ingredient selected from the group consisting of: an insecticide, an acaricide, a nematocide, a molluscicide, an herbicide, a fungicide, and a plant growth regulator.
11. Use of a compound according to any one of claims 1 to 7 as a herbicide.
12. A method of controlling weeds in crops of useful plants which comprises applying to said weeds or to the locus of said weeds, or to said crop of useful plants, a compound as defined in any one of claims 1 to 7, or a herbicidal composition according to claim 8 or claim 9, or a mixture according to claim 10.
13. A compound of formula (II)
(Formula Removed)
wherein
R7 is methyl, Br, or CI;
R8 is H, F, CI, OR10, or N(R10)2;
R9 is H, F, or CI; and
each R10 is independently H or C1-4alkyl,
provided that
(i) R8 and R9 are not both hydrogen,
(ii) when R7 is methyl and R9 is hydrogen, then R8 is not F, CI, or NH2,
(iii) when R7 is CI and R8 is hydrogen, R9 is not CI,
(iv) when R7 is CI and R8 is CI, R9 is not hydrogen, and
(v) when R7 is Br and R9 is hydrogen, R8 is not F.
14. A process for the preparation of a compound of formula (T)
(Formula Removed)
or salt or N-oxide thereof,
wherein:
A is halogen, optionally substituted alkylthio, optionally substituted alkyl,
optionally substituted alkenyl or an optionally substituted 3-8 membered
carbocyclic ring;
Y' is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl,
optionally substituted alkenyl, or optionally substituted alkynyl; and,
Z' is hydroxyl or CHRw)n-C(O)Rcd wherein
n is an integer of 0 or 1
Rw is hydrogen or C1-4 alkyl
Rcb is hydroxy, optionally substituted alkylthio, NH2l or OR™,
Rco is C1-20 alkyl optionally substituted by 1-3 groups Rcq, or C1-20 haloalkyl
optionally substituted by 1-3 groups Rcq;
each Rcq is independently C1-6 alkoxy, phenyl optionally substituted by 1-3
groups Rcr, or heteroaryl optionally substituted by 1-2 groups Rcs; each Rcr and each Rcs are independently halogen, cyano, C1-4 alkyl, C1-4 haloalkyl, C2-6 alkoxyalkyl, C1-4 alkoxy, C1-4 haloalkoxy, C1-4 alkylsulphonyl, or C1-4 alkoxycarbonyl comprising reacting an amidine of formula (N)
(Formula Removed)
wherein A is as defined above, or a salt form thereof, with a keto ester of the formula (U)
(Formula Removed)
or a salt form thereof,
wherein Y' and Z' are as defined above, or Z' is OR, and R is selected from hydrogen or
alkyl.
15. A process according to claim 14 comprising the further step or steps of converting the compound of formula (T) to a compound of formula (I)
(Formula Removed)
wherein A, Z and Y are as defined in claim 14, and
X is azido, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulphyl, optionally substituted alkylsulphonyl or NR5R6;
R5 is hydrogen, C2-4 alkenyl, SO2Rss, C(O)Ruu or optionally substituted
C1-4 alkyl; R6 is hydrogen, C2-4 alkenyl or optionally substituted C1-4 alkyl; each Rss is independently C1-4 alkyl or phenyl optionally substituted by 1 -3 groups Rzz;
each Ruu is independently C1-4 alkyl, phenyl optionally substituted by 1-3 groups R21, C1-4 alkoxy, or NRacRad; each Rzz is independently halogen, C1-4 alkyl, C1-4 alkoxy, or C1-4 alkylsulphonyl; Rac and Rad are each independently hydrogen or C1-4 alkyl;
or R5 and R6 together form a group -C(Ri)ORj, =C(Rk)SRl, =C(Rm)NRnRo
wherein
R1 is hydrogen, C1-4 alkyl, C3-6 cycloalkyl, phenyl, C1-4 alkoxy, C1-4 alkylthio, or NRacRad wherein Rac and Rad are as defined above, Rj and R' are each independently C1-4 alkyl, Rk is hydrogen, C1-4 alkyl, C3-6 cycloalkyl, phenyl. C1-4 alkylthio, or NRacRad wherein Rac and Rad are as defined above, Rm is hydrogen, C1-4 alkyl, C3-6 cycloalkyl, phenyl, or NRacRad wherein Rac and Rad are as defined above, and Rn and Ro are each independently hydrogen or C1-4 alkyl, or a salt form thereof.