WO2015004282A1 - Sulfonamide-heterocyclic herbicidal compounds - Google Patents
Sulfonamide-heterocyclic herbicidal compounds Download PDFInfo
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- WO2015004282A1 WO2015004282A1 PCT/EP2014/064983 EP2014064983W WO2015004282A1 WO 2015004282 A1 WO2015004282 A1 WO 2015004282A1 EP 2014064983 W EP2014064983 W EP 2014064983W WO 2015004282 A1 WO2015004282 A1 WO 2015004282A1
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- 0 *OC(C(CCCCC*(CC1)N)C1N)=O Chemical compound *OC(C(CCCCC*(CC1)N)C1N)=O 0.000 description 2
- HRTBNWCLDPBKSF-UHFFFAOYSA-N CC(CCN1Cc2c(NS(C(F)(F)F)(=O)=O)nc[s]2)CC1=O Chemical compound CC(CCN1Cc2c(NS(C(F)(F)F)(=O)=O)nc[s]2)CC1=O HRTBNWCLDPBKSF-UHFFFAOYSA-N 0.000 description 1
- UBJQAHARFFBLGH-UHFFFAOYSA-N CCOC(c1c(NS(C)(=O)=O)[n](C)nc1)=O Chemical compound CCOC(c1c(NS(C)(=O)=O)[n](C)nc1)=O UBJQAHARFFBLGH-UHFFFAOYSA-N 0.000 description 1
- YSJRVNLBEIPCHK-UHFFFAOYSA-N C[n]1ncc(CO)c1NS(C)(=O)=O Chemical compound C[n]1ncc(CO)c1NS(C)(=O)=O YSJRVNLBEIPCHK-UHFFFAOYSA-N 0.000 description 1
- NGDHTQYNBQJMCF-UHFFFAOYSA-N O=C1N(Cc2c(NS(C(F)(F)F)(=O)=O)nccc2)CCOC1 Chemical compound O=C1N(Cc2c(NS(C(F)(F)F)(=O)=O)nccc2)CCOC1 NGDHTQYNBQJMCF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Definitions
- the present invention relates to herbicidal sulfonanilide derivatives.
- haloalkylsulfonanilide derivatives are known to have herbicidal activities - see EP 2 420 493 and EP 2 336 104.
- the object of the present invention is to provide new herbicides, which are highly effective against various weeds at low doses.
- the present invention provides a compound of formula (I) or an agrochemically acceptable salt thereof:
- A is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not
- n is an integer selected from 0, 1 , 2 or 3
- p is an integer selected from 0, 1 , 2 or 3; with the proviso that 0 ⁇ n + p ⁇ 3
- W is oxygen or sulphur
- X is oxygen, sulphur, SO, S0 2 or CR 3 R 4 ;
- Z is oxygen, sulphur, CR 8 R 9 or NR 0 ;
- R is Ci- 6 alkyl or d- 6 haloalkyl;
- R is H, Ci- 4 alkyl, C 3 . 5 alkenyl, propargyl, Ci_ 4 haloalkoxyCi. 2 alkyl, cyanoCi_ 2 alkyl, Ci_
- Ci_ 2 alkoxyCi_ 2 alkoxy hydroxy, phenyl or phenoxy
- R 2 is halogen, nitrile, C 1 _ 4 alkyl, C-
- R 3 and R 4 are, independently, H, C 1 _ 4 alkyl, C-
- R 5 and R 6 are, independently, H, Ci_ 5 alkyl, Ci_ 4 haloalkyl, C 3 . 6 cycloalkyl optionally substituted with 1-3 groups selected from halogen, d_ 4 alkyl or phenyl, Ci_ 4 alkoxyCi_ 4 alkyl, Ci_ 4 alkoxycarbonylaminoCi.
- each R 2 is, independently, halogen, cyano, d_ 4 alkyl, Ci- 4 haloalkyl, Ci_ 4 alkoxy, Ci_ 4 haloalkoxy, Ci_ 2 alkoxyCi_ 2 alkoxy, hydroxy, phenyl or phenoxy or two R 2 groups together form OCH 2 0 or OCH 2 CH 2 0;
- R 8 and R 9 are, independently, H, halogen, cyano, d_ 4 alkyl, C-
- R 0 is H, Ci- 4 alkyl, C 2 - 5 alkenyl, aryl optionally substituted by 1-3 groups R 22 , arylCi_ 2 alkyl optionally substituted by 1-3 groups R 22 , heteroaryl optionally substituted by 1-3 groups R 22 , Ci_ 4 alkylcarbonyl, Ci_ 4 alkoxycarbonyl, Ci_ 4 haloalkoxycarbonyl, Ci. 4 alkoxyCi. 2 alkoxycarbonyl, C 3 .
- R and R 2 are, independently, H, halogen, hydroxy, d_ 4 alkyl, C-
- the preferred groups for A, W, X, Z, m, n, p, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 0 , R 11 , R 2 , R 20 , R 2 , R 22 and R 24 , in any combination thereof, are as set out below.
- A is a 5-membered heteroaromatic ring containing 1 to 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not
- the 5-membered ring is a pyrrole, furan, thiophene (other than the thiophene above), pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3- oxadiazole, 1 ,2,5-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,5-thiadiazole or tetrazole ring.
- the 5-membered ring is a thiophene (other than the thiophene above), pyrazole, thiazole, 1 ,2,4-triazole or tetrazole ring.
- the 5-membered ring is a thiophene ring (other than the thiophene above).
- A is a 6-membered heteroaromatic ring containing 1 to 3 nitrogen atoms.
- the 6-membered ring is a pyridine, pyridazine, pyrimidine, pyrazine, 1 ,2,3-triazine or 1 ,2,4- triazine ring. More preferably, the 6-membered ring is a pyridazine, pyrimidine or pyrazine ring. Most preferably, the 6-membered ring is a pyrimidine ring.
- W is oxygen.
- X is oxygen or CR 3 R 4 .
- Z is oxygen, CR 8 R 9 or NR 0 .
- n is 0 or 1. Most preferably, m is 0.
- n is 0, 1 or 2 and p is 0, 1 or 2 with the proviso that 1 ⁇ n + p ⁇ 2.
- R is Ci-C 6 alkyl.
- R is d- 4 haloalkyl. More preferably, R is trifluoromethyl.
- R is H
- arylCi- 2 alkyl optionally substituted by 1-3 groups R 20 , arylCi- 2 alkoxyCi- 2 alkyl optionally substituted by 1-3 groups R 20 , C-i ⁇ alkylcarbonyloxyC-i ⁇ alkyl, arylcarbonyloxyCi_ 2 alkyl optionally substituted by 1-3 groups R 20 , Ci- 4 alkoxycarbonyloxyCi- 2 alkyl, Ci_ 8 alkylcarbonyl, Ci_ 4 haloalkylcarbonyl,
- R is H, Ci_ 5 alkylcarbonyl, Ci_ 4 haloalkylcarbonyl, Ci_ 5 alkoxycarbonyl, Ci_ 4 haloalkoxycarbonyl or Ci_ 4 haloalkylsulphonyl. Most preferably, R is H, d- 5 alkylcarbonyl or Ci_ 5 alkoxycarbonyl.
- R 2 is halogen, C 1 _ 4 alkyl, C-
- R 3 and R 4 are, independently, H, halogen or C 1 _ 4 alkyl. Most preferably, R 3 and R 4 are, independently, H or methyl.
- R 5 and R 6 are, independently, H, Ci_ 5 alkyl, Ci_ 4 haloalkyl, C 3 . 6 cycloalkyl, Ci. 4 alkoxyCi_ 4 alkyl, arylCi_ 2 alkyl optionally substituted by 1-3 groups R 2 , C 2 - 4 alkenyl, Ci_ 4 alkoxy, Ci_ 4 alkylthio, aryl optionally substituted by 1-3 groups R 2 , aryloxy optionally substituted by 1-3 groups R 2 , arylthio optionally substituted by 1-3 groups R 2 , heteroaryl optionally substituted by 1-3 groups R 2 or R 5 and R 6 together form a C 2 - 5 alkylene chain optionally containing an oxygen atom, and each R 2 is, independently, halogen, cyano, C 1 _ 4 alkyl, C-
- R 5 and R 6 are, independently, H, d_ 4 alkyl, C-
- R 5 and R 6 are, independently, H, Ci_ 3 alkyl, trifluoromethyl, cyclopropyl, Ci_ 3 alkoxy, aryl optionally substituted by 1-2 groups R 2 or R 5 and R 6 together form a C 3 . 5 alkylene chain, and each R 2 is, independently, halogen, methyl or methoxy.
- R 8 and R 9 are, independently, H, halogen, d_ 4 alkyl, d. 4 haloalkyl, Ci_ 4 alkoxy, d- 4 alkylthio, aryl optionally substituted by 1-3 groups R 24 , aryloxy optionally substituted by 1-3 groups R 24 or arylthio optionally substituted by 1-3 groups R 24 , and each R 24 is, independently, halogen, cyano, d_ 4 alkyl, d- 4 haloalkyl, Ci_ 4 alkoxy or d. 4 haloalkoxy.
- R 8 and R 9 are, independently, H, halogen, Ci- 4 alkyl, Ci_ 4 haloalkyl, d- 4 alkoxy, Ci_ 4 alkylthio, aryl optionally substituted by 1-2 groups R , and each R 24 is, independently, halogen, methyl or methoxy. Most preferably, R 8 and R 9 are, independently, H, halogen, Ci_ 3 alkyl, Ci_ 3 alkoxy or Ci_ 3 alkylthio.
- R 0 is H, C 1 _ 4 alkyl, aryl optionally substituted by 1-3 groups R 22 , heteroaryl optionally substituted by 1-3 groups R 22 , Ci_ 4 alkylcarbonyl, Ci_ 4 alkoxycarbonyl, Ci_ 4 alkylsulphonyl or Ci_
- each R 22 is, independently, halogen, cyano, C 1 _ 4 alkyl, C-
- R 0 is H, Ci_ 3 alkyl or aryl optionally substituted by 1-3 groups R 22
- each R 22 is, independently, halogen, methyl or methoxy.
- R and R 2 are, independently, H, hydroxy, C 1 _ 4 alkyl, C-
- R and R 2 together form an oxo group.
- R and R 2 are each H.
- Table 1 below provides 801 compounds designated compounds 1-1 to 1-801 respectively, of formula (I), wherein ring A is A1.
- 801 compounds are described, designated compounds 5-1 to 5-801 respectively, of formula (I) wherein ring A is A5, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 6-1 to 6-801 respectively, of formula (I) wherein ring A is A6, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 14-1 to 14-801 respectively, of formula (I) wherein ring Ais A14, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 15-1 to 15-801 respectively, of formula (I) wherein ring Ais A15, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 19-1 to 19-801 respectively, of formula (I) wherein ring Ais A19, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 20-1 to 20-801 respectively, of formula (I) wherein ring Ais A20, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 24-1 to 24-801 respectively, of formula (I) wherein ring Ais A24, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 25-1 to 25-801 respectively, of formula (I) wherein ring Ais A25, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 30-1 to 30-801 respectively, of formula (I) wherein ring Ais A30, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 31-1 to 31-801 respectively, of formula (I) wherein ring Ais A31, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 35-1 to 35-801 respectively, of formula (I) wherein ring Ais A35, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 36-1 to 36-801 respectively, of formula (I) wherein ring Ais A36, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 40-1 to 40-801 respectively, of formula (I) wherein ring Ais A40, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 41-1 to 41-801 respectively, of formula (I) wherein ring Ais A41, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 46-1 to 46-801 respectively, of formula (I) wherein ring Ais A46, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 47-1 to 47-801 respectively, of formula (I) wherein ring Ais A47, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 51-1 to 51-801 respectively, of formula (I) wherein ring Ais A51, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 52-1 to 52-801 respectively, of formula (I) wherein ring Ais A52, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 56-1 to 56-801 respectively, of formula (I) wherein ring Ais A56, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 57-1 to 57-801 respectively, of formula (I) wherein ring Ais A57, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 62-1 to 62-801 respectively, of formula (I) wherein ring A is A62, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- 801 compounds are described, designated compounds 63-1 to 63-801 respectively, of formula (I) wherein ring A is A63, and the values of R, R , W, (CR R 2 ) n , X, (CR 5 R 6 ) P and Z are as defined in Table 1.
- the herbicidal compounds of formula (I) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.
- the herbicidal compounds of this invention may contain an asymmetric carbon atom and some of the compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to stereochemistry, the present invention includes such optical isomers and diastereomers; as well as the racemic mixture and resolved, enantiomerically pure R and S stereoisomers; as well as other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that one optical isomer, including diastereomer and enantiomer, or stereoisomer may have favorable properties over the other. Thus when disclosing and claiming the invention, when one racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers and enantiomers, or stereoisomers substantially free of the other are disclosed and claimed as well.
- hydroxy or hydroxyl refers to the group -OH.
- Nitro refers to the group -N0 2 .
- Carboxy refers to the group -C(0)OH.
- Alkyl refers to an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.
- Alkenyl refers to an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1-enyl, but-2-enyl, but-3-enyl, 2- methypropenyl.
- Alkynyl refers to an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl) but-1-ynyl, but-2-ynyl and but-3-ynyl.
- Alkylene as used herein, means a branched or linear divalent hydrocarbon radical. Examples of alkylene are methylene, 1 , 1-ethylene, 1 ,2-ethylene, 1 ,1-propylene, 1 ,2-propylene, 1 ,3-propylene and 2,2- propylene etc.
- Cycloalkyl refers to a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms.
- Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
- Alkylthio refers to the group -SR, wherein R is alkyl as defined above.
- Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.
- Cyanoalkyl refers to an alkyl group substituted with one or more cyano groups.
- Alkoxy refers to the group -OR, wherein R is alkyl as defined above.
- alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.
- Alkoxyalkyl refers to the group -ROR, wherein each R is independently alkyl group as defined herein.
- Alkoxyalkoxy refers to the group -OROR, wherein each R is independently alkyl as defined herein.
- Alkoxyalkoxyalkyl refers to the group -ROROR, wherein each R is independently alkyl as defined herein.
- Alkylthioalkyl refers to the group -RSR, wherein each R is independently alkyl as defined herein.
- Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.
- Haloalkyl refers to an alkyl group as defined herein wherein at least one hydrogen atom has been replaced with a halogen atom as defined above.
- haloalkyl groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl.
- Haloalkylthio refers to the group -SR, wherein R is haloalkyl as defined herein.
- Haloalkoxy refers to the group -OR, wherein R is haloalkyl as defined herein.
- Haloalkoxyalkyl refers to the group -ROR', wherein R is alkyl as defined herein and R' is haloalkyl as defined herein.
- Alkylcarbonyl refers to the group -C(0)R, wherein R is alkyl as defined herein.
- alkylcarbonyl groups examples include ethanoyl, propanoyl, n-butanoyl, etc.
- Alkenylcarbonyl refers to the group -C(0)R, wherein R is alkenyl as defined herein.
- Cycloalkylcarbonyl refers to the group -C(0)R, wherein R is cycloalkyl as defined herein.
- Haloalkylcarbonyl refers to the group -C(0)R, wherein R is haloalkyl as defined herein.
- Alkoxycarbonyl refers to the group -C(0)OR, wherein R is alkyl as defined herein.
- Alkenyloxycarbonyl refers to the group -C(0)OR, wherein R is alkenyl as defined herein.
- Propargyloxycarbonyl refers to the group -C(0)OCH 2 C ⁇ CH.
- Haloalkoxycarbonyl refers to the group -C(0)OR, wherein R is haloalkyl as defined herein.
- Alkylcarbonylalkyl refers to the group -RC(0)R, wherein each R is independently alkyl as defined herein.
- Alkoxycarbonylalkyl refers to the group -RC(0)OR, wherein each R is independently alkyl as defined herein.
- Alkoxyalkylcarbonyl refers to the group -C(0)ROR, wherein each R is independently alkyl as defined herein.
- Alkoxyalkoxycarbonyl refers to the group -C(0)OROR, wherein each R is independently alkyl as defined herein.
- Alkoxycarbonylalkylcarbonyl refers to the group -C(0)RC(0)OR, wherein each R is independently alkyl as defined herein.
- Aminocarbonyl refers to the group -C(0)NH 2 .
- Alkylaminocarbonyl refers to the group -C(0)NHR, wherein R is alkyl as defined herein.
- Dialkylaminocarbonyl refers to the group -C(0)NRR, wherein each R is independently alkyl as defined herein.
- Alkylthiocarbonyl refers to the group -C(0)SR, wherein R is alkyl as defined herein.
- Alkoxycarbonylaminoalkyl refers to the group -RNHC(0)OR, wherein each R is independently alkyl as defined herein.
- Alkylcarbonyloxy refers to the group -OC(0)R, wherein R is alkyl as defined herein.
- Alkylcarbonyloxyalkyl refers to the group -ROC(0)R, wherein each R is independently alkyl as defined herein.
- Alkoxycarbonyloxyalkyl refers to the group -ROC(0)OR, wherein each R is independently alkyl as defined herein.
- Alkylsulfonyl refers to the group -S(0) 2 R, wherein R is alkyl as defined herein.
- Haloalkylsulphonyl refers to the group -S(0) 2 R, wherein R is haloalkyl as defined herein.
- AlkylsulphonylalkyI refers to the group -RS(0) 2 R, wherein each R is independently alkyl as defined herein.
- Aryl refers to an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl).
- Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.
- Aryloxy refers to the group -OAr, wherein Ar is aryl as defined herein.
- Preferred aryloxy groups include phenoxy, naphthyloxy and the like.
- Arylalkyl refers to the group -RAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Preferred arylalkyl groups include phenylmethyl (benzyl).
- Aryloxyalkyl refers to the group -ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Arylthio refers to the group -SAr, wherein Ar is aryl as defined herein.
- Arylthioalkyl refers to the group -RSAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Arylalkylthioalkyl refers to the group -RSRAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein.
- Arylalkoxyalkyl refers to the group -RORAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein.
- Arylcarbonyl refers to the group -C(0)Ar, wherein Ar is aryl as defined herein.
- Arylcarbonylalkyl refers to the group -RC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Aryloxycarbonyl refers to the group -C(0)OAr, wherein Ar is aryl as defined herein.
- Aryloxyalkylcarbonyl refers to the group -C(0)ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Arylalkoxycarbonyl refers to the group -C(0)ORAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Arylcarbonyloxyalkyl refers to the group -ROC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Aryloxycarbonyloxyalkyl refers to the group -ROC(0)OAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
- Arylsulphonyl as used herein refers to the group -S(0) 2 Ar, wherein Ar is aryl as defined herein.
- Heteroaryl/heteroaromatic ring refers to a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic.
- single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur.
- Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.
- bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5- a] pyrimidinyl.
- Heteroarylalkyl refers to the group -RHet, wherein R is alkyl as defined herein and Het is heteroaryl as defined herein.
- Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter.
- one or more hydrogen atoms are replaced by the radicals listed thereafter.
- halogenated groups for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.
- Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
- Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N + (R 29 R 30 R 3 R 32 ) wherein R 29 , R 30 , R 3 and R 32 are independently selected from hydrogen, Ci-C 6 alkyl and Ci-C 6 hydroxyalkyl.
- Salts of the compounds of formula (I) can be prepared by treatment of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
- a metal hydroxide such as sodium hydroxide
- an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
- Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.
- Acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.
- organic and inorganic acids for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluene
- sulphonanilide derivatives of the present invention may be made as the skilled person will appreciate by applying and/or adapting, as appropriate, the methods described in the prior art (see for example, EP2336104 and WO 2010/119906).
- the starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods.
- the starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
- a compound of formula (A) may be heated with a compound of formula (B) in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example toluene or chlorobenzene.
- a catalyst for example an acid, such as para-toluene sulphonic acid
- a suitable solvent for example toluene or chlorobenzene.
- the process may conveniently be carried out using microwave heating or conventional heating in an apparatus for the removal of water, for example a Dean-Stark trap.
- Compounds of formula (B) are commercially available or can be made by standard methods well known in the chemical literature.
- Compounds of formula (A) may be prepared from compounds of formula (C) as shown in reaction scheme 2.
- a compound of formula (C) may be treated with a reducing agent such as lithium aluminium hydride in a suitable solvent such as tetrahydrofuran.
- a reducing agent such as lithium aluminium hydride
- a suitable solvent such as tetrahydrofuran.
- a compound of formula (D) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
- a sulphonylating reagent for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride
- a base for example an organic base such as triethylamine
- a suitable solvent for example dichloromethane.
- a compound of formula (E) in which LG' is a halogen, for example a chlorine atom may be treated with a sulphonamide RS0 2 NH 2 in the presence of a base, for example an inorganic base such as caesium carbonate or sodium hydride, in a suitable solvent such as dioxane.
- a base for example an inorganic base such as caesium carbonate or sodium hydride
- a suitable solvent such as dioxane.
- the reaction may be performed in the presence of a suitable catalyst, for example a metal catalyst such as a palladium dibenzylidene acetone complex, and optionally a ligand, for example a phosphine ligand such as XantPhos.
- Compounds of formula (E) may be prepared from compounds of formula (F) and compounds of formula (B) as shown in reaction scheme 5.
- a compound of formula (F) in which LG and LG' are halogens, for example chlorine atoms may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
- a base for example an inorganic base such as sodium hydride
- a suitable solvent for example tetrahydrofuran.
- a compound of formula (G) may be treated with a halogenating agent, for example /V-bromosuccinimide, in a suitable solvent, for example carbon tetrachloride, optionally in the presence of a reaction initiator, for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
- a halogenating agent for example /V-bromosuccinimide
- a suitable solvent for example carbon tetrachloride
- a reaction initiator for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
- compounds of formula (F) may be prepared from compounds of formula (H) as shown in reaction scheme 7.
- a compound of formula (H) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.
- a halogenating agent for example, thionyl chloride
- a compound of formula (J) may be treated with a carbonylating agent such as triphosgene, in the presence of a base, for example an organic base such as 2-tert-butyl-1 , 1 ,3,3- tetramethylguanidine (Barton's base), in a suitable solvent, for example dichloromethane.
- a carbonylating agent such as triphosgene
- a base for example an organic base such as 2-tert-butyl-1 , 1 ,3,3- tetramethylguanidine (Barton's base)
- a suitable solvent for example dichloromethane.
- a compound of formula (J) may be formed by the reaction of an aldehyde of formula (K) with an amine of formula (L) in the presence of a reducing agent, for example a hydride reducing agent such as sodium borohydride, in a suitable solvent, for example an alcohol such as ethanol.
- a reducing agent for example a hydride reducing agent such as sodium borohydride
- a suitable solvent for example an alcohol such as ethanol.
- Amines of formula (L) are commercially available or can be made by standard methods well known in the chemical literature.
- Aldehydes of formula (K) may be prepared from compounds of formula (M), as shown in reaction scheme 10.
- an aldehyde of formula (M) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
- a sulphonylating reagent for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride
- a base for example an organic base such as triethylamine
- a suitable solvent for example dichloromethane.
- Aldehydes of formula (M) are commercially available or can be made by standard methods well known in the chemical literature.
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Abstract
The present invention relates sulfonanilide derivatives of the formula (I) wherein A, W, X, Z, m, n, p, R, R1, R2, R5, R6, R11 and R12 are as defined in the specification. Furthermore, the present invention relates to herbicidal compositions comprising these compounds and to methods of using these compounds to control plant growth.
Description
SULFONAMIDE-HETEROCYCLIC HERBICIDAL COMPOUNDS The present invention relates to herbicidal sulfonanilide derivatives.
Some haloalkylsulfonanilide derivatives are known to have herbicidal activities - see EP 2 420 493 and EP 2 336 104.
The object of the present invention is to provide new herbicides, which are highly effective against various weeds at low doses.
Accordingly, the present invention provides a compound of formula (I) or an agrochemically acceptable salt thereof:
wherein:
A is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not
Z is oxygen, sulphur, CR8R9 or NR 0;
R is Ci-6alkyl or d-6haloalkyl;
R is H, Ci-4alkyl, C3.5alkenyl, propargyl,
Ci_ 4haloalkoxyCi.2alkyl,
cyanoCi_2alkyl, Ci_
4alkoxycarbonylCi.2alkyl,
arylCi_2alkyl optionally substituted by 1-3 groups R20, heteroarylCi_2alkyl optionally substituted by 1-3 groups R20, arylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkoxyCi_2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylcarbonylCi_2alkyl optionally substituted by 1-3 groups R20, d. 4alkylcarbonyloxyCi_2alkyl, arylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci_
4alkoxycarbonyloxyCi_2alkyl, aryloxycarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci_ 8alkylcarbonyl, C2.5alkenylcarbonyl, Ci_4haloalkylcarbonyl, Ci_4alkoxyCi_2alkylcarbonyl, C3.
6cycloalkylcarbonyl, Ci_4alkoxycarbonylCi_2alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R20, aryloxyCi-2alkylcarbonyl optionally substituted by 1-3 groups R20, Ci_i0alkoxycarbonyl, Ci_
4haloalkoxycarbonyl, C3.5alkenyloxycarbonyl, propargyloxycarbonyl, Ci_4alkoxyCi_2alkoxycarbonyl, Ci_ 4alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, Ci.4alkylaminocarbonyl, di(Ci_
4alkyl)aminocarbonyl, Ci_6alkylsulphonyl, Ci_6haloalkylsulphonyl or arylsulphonyl optionally substituted by 1-3 groups R20, and each R20 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_
4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, phenyl or phenoxy;
R2 is halogen, nitrile, C1_4alkyl, C-|.4haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4alkynyl, Ci_4alkoxy, Ci_ 4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, Ci_4alkylcarbonyl, Ci_4alkylsulphonyl or phenyl or two R2 groups together form -OCH20- or -OCH2CH20-;
R3 and R4 are, independently, H, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxycarbonyl or aryl optionally substituted by 1-3 groups R23 or R3 and R4 together form a C2.5alkylene chain or an oxo group or R3 together with one of R5, R8 or R forms a bond or R3 and R8 together form a C2.5alkylene chain and each R23 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, phenyl or phenoxy;
R5 and R6 are, independently, H, Ci_5alkyl, Ci_4haloalkyl, C3.6cycloalkyl optionally substituted with 1-3 groups selected from halogen, d_4alkyl or phenyl, Ci_4alkoxyCi_4alkyl, Ci_4alkoxycarbonylaminoCi. 4alkyl, Ci_4alkylcarbonyloxyCi_2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R2 , aryloxyCi_2alkyl optionally substituted by 1-3 groups R2 , arylCi_2alkoxyCi_2alkyl optionally substituted by 1-3 groups R2 , C2.4alkenyl, hydroxy, Ci_4alkoxy, Ci_4alkylthio, Ci_4alkylcarbonyloxy, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1-3 groups R2 or R5 and R6 together form an oxo group or a C2. 6alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen or Ci_2alkyl or R5 together with together with one of R3, R8 or R forms a bond or R5 and R together form a C2.5alkylene chain and each R2 is, independently, halogen, cyano, d_4alkyl, Ci-4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, phenyl or phenoxy or two R2 groups together form OCH20 or OCH2CH20;
R8 and R9 are, independently, H, halogen, cyano, d_4alkyl, C-|.4haloalkyl, C2.5alkenyl, C2.5alkynyl, Ci-4alkoxy, Ci_4alkylthio, Ci_4alkoxycarbonyl, aryl optionally substituted by 1-3 groups R24, aryloxy
optionally substituted by 1-3 groups R24 or arylthio optionally substituted by 1-3 groups R24 or R8 and R9 together form a C2-5alkylene chain or an oxo group or R8 together with one of R3 or R5 forms a bond or R8 and R3 together form a C2-5alkylene chain and each R24 is, independently, halogen, cyano, C1_4alkyl, C-|. 4haloalkyl, d-4alkoxy, Ci_4haloalkoxy,
hydroxy, phenyl or phenoxy;
R 0 is H, Ci-4alkyl, C2-5alkenyl, aryl optionally substituted by 1-3 groups R22, arylCi_2alkyl optionally substituted by 1-3 groups R22, heteroaryl optionally substituted by 1-3 groups R22, Ci_4alkylcarbonyl, Ci_ 4alkoxycarbonyl, Ci_4haloalkoxycarbonyl, Ci.4alkoxyCi.2alkoxycarbonyl, C3.5alkenyloxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R22, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R22, aminocarbonyl, Ci_4alkylaminocarbonyl, di(Ci_4alkyl)aminocarbonyl, Ci_6alkylsulphonyl or Ci_6haloalkylsulphonyl and each R22 is, independently, halogen, nitro, cyano, Ci_4alkyl, Ci_4haloalkyl, Ci_ 4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, Ci_4alkylthio, Ci_4haloalkylthio, Ci_4alkylsulphonyl, Ci_4alkoxycarbonyl, phenyl or phenoxy;
R and R 2 are, independently, H, halogen, hydroxy, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, carboxy, Ci_4alkoxycarbonyl or R and R 2 together form an oxo group or R together with one of R3 or R5 forms a bond or R and R5 together form a C2.5alkylene chain.
In particularly preferred embodiments of the invention, the preferred groups for A, W, X, Z, m, n, p, R, R1, R2, R3, R4, R5, R6, R8, R9, R 0, R11, R 2, R20, R2 , R22 and R24, in any combination thereof, are as set out below.
In one embodiment, A is a 5-membered heteroaromatic ring containing 1 to 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not
Preferably, the 5-membered ring is a pyrrole, furan, thiophene (other than the thiophene above), pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3- oxadiazole, 1 ,2,5-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,5-thiadiazole or tetrazole ring. More preferably, the 5-membered ring is a thiophene (other than the thiophene above), pyrazole, thiazole, 1 ,2,4-triazole or tetrazole ring. Most preferably, the 5-membered ring is a thiophene ring (other than the thiophene above).
In another embodiment, A is a 6-membered heteroaromatic ring containing 1 to 3 nitrogen atoms. Preferably, the 6-membered ring is a pyridine, pyridazine, pyrimidine, pyrazine, 1 ,2,3-triazine or 1 ,2,4- triazine ring. More preferably, the 6-membered ring is a pyridazine, pyrimidine or pyrazine ring. Most preferably, the 6-membered ring is a pyrimidine ring.
Preferably, W is oxygen. Preferably, X is oxygen or CR3R4.
Preferably, Z is oxygen, CR8R9 or NR 0.
Preferably, m is 0 or 1. Most preferably, m is 0.
Preferably, n is 0, 1 or 2 and p is 0, 1 or 2 with the proviso that 1 < n + p < 2. In one embodiment, R is Ci-C6 alkyl.
In another embodiment, R is d-4haloalkyl. More preferably, R is trifluoromethyl.
Preferably, R is H,
arylCi-2alkyl optionally substituted by 1-3 groups R20, arylCi-2alkoxyCi-2alkyl optionally substituted by 1-3 groups R20, C-i^alkylcarbonyloxyC-i^alkyl, arylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci-4alkoxycarbonyloxyCi-2alkyl, Ci_8alkylcarbonyl, Ci_4haloalkylcarbonyl,
Ci-i0alkoxycarbonyl, Ci_4haloalkoxycarbonyl,
aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R20, Ci_ 6alkylsulphonyl or Ci_6haloalkylsulphonyl, and each R20 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or Ci_4haloalkoxy. More preferably, R is H, Ci_5alkylcarbonyl, Ci_4haloalkylcarbonyl, Ci_ 5alkoxycarbonyl, Ci_4haloalkoxycarbonyl or Ci_4haloalkylsulphonyl. Most preferably, R is H, d- 5alkylcarbonyl or Ci_5alkoxycarbonyl.
Preferably, R2 is halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or Ci_4alkylsulphonyl. Most preferably, R2 is halogen or methyl.
Preferably, R3 and R4 are, independently, H, halogen or C1_4alkyl. Most preferably, R3 and R4 are, independently, H or methyl.
Preferably, R5 and R6 are, independently, H, Ci_5alkyl, Ci_4haloalkyl, C3.6cycloalkyl, Ci.4alkoxyCi_ 4alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R2 , C2-4alkenyl, Ci_4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1-3 groups R2 or R5 and R6 together form a C2-5alkylene chain optionally containing an oxygen atom, and each R2 is, independently, halogen, cyano, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or Ci.4haloalkoxy. More preferably, R5 and R6 are, independently, H, d_4alkyl, C-|.3haloalkyl, cyclopropyl, Ci_3alkoxy, Ci_3alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1-3 groups R2 or R5 and R6 together form a C3.5alkylene chain, and each R2 is, independently, halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or d- 4haloalkoxy Most preferably, R5 and R6 are, independently, H, Ci_3alkyl, trifluoromethyl, cyclopropyl, Ci_ 3alkoxy, aryl optionally substituted by 1-2 groups R2 or R5 and R6 together form a C3.5alkylene chain, and each R2 is, independently, halogen, methyl or methoxy.
Preferably, R8 and R9 are, independently, H, halogen, d_4alkyl, d.4haloalkyl, Ci_4alkoxy, d- 4alkylthio, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1-3 groups R24 or arylthio optionally substituted by 1-3 groups R24, and each R24 is, independently, halogen, cyano, d_4alkyl, d-4haloalkyl, Ci_4alkoxy or d.4haloalkoxy. More preferably, R8 and R9 are, independently, H, halogen,
Ci-4alkyl, Ci_4haloalkyl, d-4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-2 groups R , and each R24 is, independently, halogen, methyl or methoxy. Most preferably, R8 and R9 are, independently, H, halogen, Ci_3alkyl, Ci_3alkoxy or Ci_3alkylthio.
Preferably, R 0 is H, C1_4alkyl, aryl optionally substituted by 1-3 groups R22, heteroaryl optionally substituted by 1-3 groups R22, Ci_4alkylcarbonyl, Ci_4alkoxycarbonyl, Ci_4alkylsulphonyl or Ci_
4haloalkylsulphonyl, and each R22 is, independently, halogen, cyano, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy or Ci_4alkylsulphonyl. Most preferably, R 0 is H, Ci_3alkyl or aryl optionally substituted by 1-3 groups R22, and each R22 is, independently, halogen, methyl or methoxy.
Preferably, R and R 2 are, independently, H, hydroxy, C1_4alkyl, C-|.4alkoxy, carboxy, Ci_
4alkoxycarbonyl or R and R 2 together form an oxo group. Most preferably, R and R 2 are each H.
The compounds described below are illustrative of compounds of the invention. In the tables the different values of rin A are as follows:
A1 A2 A3 A4 A5 A6
A7 A8 A9 A10 A1 1 A12
A13 A14 A15 A16 A17 A18
A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30
A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42
A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54
A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65
Table 1 below provides 801 compounds designated compounds 1-1 to 1-801 respectively, of formula (I), wherein ring A is A1.
TABLE 1
Cpd
No R R1 W (CR11R12)n X (CR5R6)P Z
1 Me H 0 CH2 CH2 CH2
2 Me COEt 0 CH2 CH2 CH2
3 Me C02Et 0 CH2 CH2 CH2
4 Me S02Me 0 CH2 CH2 CH2
5 CF3 H 0 CH2 CH2 CH2
6 CF3 COEt 0 CH2 CH2 CH2
7 CF3 C02Et 0 CH2 CH2 CH2
8 CF3 S02CF3 0 CH2 CH2 CH2
9 CF3 S02Me 0 CH2 CH2 CH2
10 Me H 0 CH2 CHMe CH2
11 Me COEt 0 CH2 CHMe CH2
12 Me C02Et 0 CH2 CHMe CH2
13 Me S02Me 0 CH2 CHMe CH2
14 CF3 H 0 CH2 CHMe CH2
15 CF3 COEt 0 CH2 CHMe CH2
16 CF3 C02Et 0 CH2 CHMe CH2
CF3 S02CF3 0 CH2 CHMe CH2
CF3 S02Me 0 CH2 CHMe CH2
Me H 0 CH2 CMe2 CH2
Me COEt 0 CH2 CMe2 CH2
Me C02Et 0 CH2 CMe2 CH2
Me S02Me 0 CH2 CMe2 CH2
CF3 H 0 CH2 CMe2 CH2
CF3 COEt 0 CH2 CMe2 CH2
CF3 C02Et 0 CH2 CMe2 CH2
CF3 S02CF3 0 CH2 CMe2 CH2
CF3 S02Me 0 CH2 CMe2 CH2
Me H 0 CH2 CHPh CH2
Me COEt 0 CH2 CHPh CH2
Me C02Et 0 CH2 CHPh CH2
Me S02Me 0 CH2 CHPh CH2
CF3 H 0 CH2 CHPh CH2
CF3 COEt 0 CH2 CHPh CH2
CF3 C02Et 0 CH2 CHPh CH2
CF3 S02CF3 0 CH2 CHPh CH2
CF3 S02Me 0 CH2 CHPh CH2
Me H 0 CHMe CH2 CH2
Me COEt 0 CHMe CH2 CH2
Me C02Et 0 CHMe CH2 CH2
Me S02Me 0 CHMe CH2 CH2
CF3 H 0 CHMe CH2 CH2
CF3 COEt 0 CHMe CH2 CH2
CF3 C02Et 0 CHMe CH2 CH2
CF3 S02CF3 0 CHMe CH2 CH2
CF3 S02Me 0 CHMe CH2 CH2
Me H 0 CMe2 CH2 CH2
Me COEt 0 CMe2 CH2 CH2
Me C02Et 0 CMe2 CH2 CH2
Me S02Me 0 CMe2 CH2 CH2
CF3 H 0 CMe2 CH2 CH2
CF3 COEt 0 CMe2 CH2 CH2
CF3 C02Et 0 CMe2 CH2 CH2
CF3 S02CF3 0 CMe2 CH2 CH2
CF3 S02Me 0 CMe2 CH2 CH2
Me H 0 CH2 CH2 CH2 CH2
Me COEt 0 CH2 CH2 CH2 CH2
Me C02Et 0 CH2 CH2 CH2 CH2
Me S02Me 0 CH2 CH2 CH2 CH2
CF3 H 0 CH2 CH2 CH2 CH2
CF3 COEt 0 CH2 CH2 CH2 CH2
CF3 C02Et 0 CH2 CH2 CH2 CH2
CF3 S02CF3 0 CH2 CH2 CH2 CH2
CF3 S02Me 0 CH2 CH2 CH2 CH2
Me H 0 CH2 CH2 CHMe CH2
Me COEt 0 CH2 CH2 CHMe CH2
Me C02Et 0 CH2 CH2 CHMe CH2
Me S02Me 0 CH2 CH2 CHMe CH2
CF3 H 0 CH2 CH2 CHMe CH2
CF3 COEt 0 CH2 CH2 CHMe CH2
CF3 C02Et 0 CH2 CH2 CHMe CH2
CF3 S02CF3 0 CH2 CH2 CHMe CH2
CF3 S02Me 0 CH2 CH2 CHMe CH2
Me H 0 CH2 CH2 CMe2 CH2
Me COEt 0 CH2 CH2 CMe2 CH2
Me C02Et 0 CH2 CH2 CMe2 CH2
Me S02Me 0 CH2 CH2 CMe2 CH2
CF3 H 0 CH2 CH2 CMe2 CH2
CF3 COEt 0 CH2 CH2 CMe2 CH2
CF3 C02Et 0 CH2 CH2 CMe2 CH2
CF3 S02CF3 0 CH2 CH2 CMe2 CH2
CF3 S02Me 0 CH2 CH2 CMe2 CH2
Me H 0 CH2 CH2 C(Me)(Et) CH2
Me COEt 0 CH2 CH2 C(Me)(Et) CH2
Me C02Et 0 CH2 CH2 C(Me)(Et) CH2
Me S02Me 0 CH2 CH2 C(Me)(Et) CH2
CF3 H 0 CH2 CH2 C(Me)(Et) CH2
87 CF3 COEt 0 CH2 CH2 C(Me)(Et) CH2
88 CF3 C02Et 0 CH2 CH2 C(Me)(Et) CH2
89 CF3 S02CF3 0 CH2 CH2 C(Me)(Et) CH2
90 CF3 S02Me 0 CH2 CH2 C(Me)(Et) CH2
91 Me H 0 CH2 CH2 CH2 CHSMe
92 Me COEt 0 CH2 CH2 CH2 CHSMe
93 Me C02Et 0 CH2 CH2 CH2 CHSMe
94 Me S02Me 0 CH2 CH2 CH2 CHSMe
95 CF3 H 0 CH2 CH2 CH2 CHSMe
96 CF3 COEt 0 CH2 CH2 CH2 CHSMe
97 CF3 C02Et 0 CH2 CH2 CH2 CHSMe
98 CF3 S02CF3 0 CH2 CH2 CH2 CHSMe
99 CF3 S02Me 0 CH2 CH2 CH2 CHSMe
100 Me H 0 CHMe CH2 CH2 CH2
101 Me COEt 0 CHMe CH2 CH2 CH2
102 Me C02Et 0 CHMe CH2 CH2 CH2
103 Me S02Me 0 CHMe CH2 CH2 CH2
104 CF3 H 0 CHMe CH2 CH2 CH2
105 CF3 COEt 0 CHMe CH2 CH2 CH2
106 CF3 C02Et 0 CHMe CH2 CH2 CH2
107 CF3 S02CF3 0 CHMe CH2 CH2 CH2
108 CF3 S02Me 0 CHMe CH2 CH2 CH2
109 Me H 0 CHMe CH2 CMe2 CH2
110 Me COEt 0 CHMe CH2 CMe2 CH2
111 Me C02Et 0 CHMe CH2 CMe2 CH2
112 Me S02Me 0 CHMe CH2 CMe2 CH2
113 CF3 H 0 CHMe CH2 CMe2 CH2
114 CF3 COEt 0 CHMe CH2 CMe2 CH2
115 CF3 C02Et 0 CHMe CH2 CMe2 CH2
116 CF3 S02CF3 0 CHMe CH2 CMe2 CH2
117 CF3 S02Me 0 CHMe CH2 CMe2 CH2
118 Me H 0 CMe2 CH2 CH2 CH2
119 Me COEt 0 CMe2 CH2 CH2 CH2
120 Me C02Et 0 CMe2 CH2 CH2 CH2
121 Me S02Me 0 CMe2 CH2 CH2 CH2
122 CF3 H 0 CMe2 CH2 CH2 CH2
123 CF3 COEt 0 CMe2 CH2 CH2 CH2
124 CF3 C02Et 0 CMe2 CH2 CH2 CH2
125 CF3 S02CF3 0 CMe2 CH2 CH2 CH2
126 CF3 S02Me 0 CMe2 CH2 CH2 CH2
127 Me H 0 CMe2 CH2 CHMe CH2
128 Me COEt 0 CMe2 CH2 CHMe CH2
129 Me C02Et 0 CMe2 CH2 CHMe CH2
130 Me S02Me 0 CMe2 CH2 CHMe CH2
131 CF3 H 0 CMe2 CH2 CHMe CH2
132 CF3 COEt 0 CMe2 CH2 CHMe CH2
133 CF3 C02Et 0 CMe2 CH2 CHMe CH2
134 CF3 S02CF3 0 CMe2 CH2 CHMe CH2
135 CF3 S02Me 0 CMe2 CH2 CHMe CH2
136 Me H 0 CH2 CH2 CHEt CH2
137 Me COEt 0 CH2 CH2 CHEt CH2
138 Me C02Et 0 CH2 CH2 CHEt CH2
139 Me S02Me 0 CH2 CH2 CHEt CH2
140 CF3 H 0 CH2 CH2 CHEt CH2
141 CF3 COEt 0 CH2 CH2 CHEt CH2
142 CF3 C02Et 0 CH2 CH2 CHEt CH2
143 CF3 S02CF3 0 CH2 CH2 CHEt CH2
144 CF3 S02Me 0 CH2 CH2 CHEt CH2
145 Me H 0 CH2 CH2 CHnPr CH2
146 Me COEt 0 CH2 CH2 CHnPr CH2
147 Me C02Et 0 CH2 CH2 CHnPr CH2
148 Me S02Me 0 CH2 CH2 CHnPr CH2
149 CF3 H 0 CH2 CH2 CHnPr CH2
150 CF3 COEt 0 CH2 CH2 CHnPr CH2
151 CF3 C02Et 0 CH2 CH2 CHnPr CH2
152 CF3 S02CF3 0 CH2 CH2 CHnPr CH2
153 CF3 S02Me 0 CH2 CH2 CHnPr CH2
154 Me H 0 CH2 CH2 CHcPr CH2
155 Me COEt 0 CH2 CH2 CHcPr CH2
156 Me C02Et 0 CH2 CH2 CHcPr CH2
157 Me S02Me 0 CH2 CH2 CHcPr CH2
158 CF3 H 0 CH2 CH2 CHcPr CH2
159 CF3 COEt 0 CH2 CH2 CHcPr CH2
160 CF3 C02Et 0 CH2 CH2 CHcPr CH2
161 CF3 S02CF3 0 CH2 CH2 CHcPr CH2
162 CF3 S02Me 0 CH2 CH2 CHcPr CH2
163 Me H 0 CH2 CH2 C(CH2)4 CH2
164 Me COEt 0 CH2 CH2 C(CH2)4 CH2
165 Me C02Et 0 CH2 CH2 C(CH2)4 CH2
166 Me S02Me 0 CH2 CH2 C(CH2)4 CH2
167 CF3 H 0 CH2 CH2 C(CH2)4 CH2
168 CF3 COEt 0 CH2 CH2 C(CH2)4 CH2
169 CF3 C02Et 0 CH2 CH2 C(CH2)4 CH2
170 CF3 S02CF3 0 CH2 CH2 C(CH2)4 CH2
171 CF3 S02Me 0 CH2 CH2 C(CH2)4 CH2
172 Me H 0 CHMe CH2 CHMe CH2
173 Me COEt 0 CHMe CH2 CHMe CH2
174 Me C02Et 0 CHMe CH2 CHMe CH2
175 Me S02Me 0 CHMe CH2 CHMe CH2
176 CF3 H 0 CHMe CH2 CHMe CH2
177 CF3 COEt 0 CHMe CH2 CHMe CH2
178 CF3 C02Et 0 CHMe CH2 CHMe CH2
179 CF3 S02CF3 0 CHMe CH2 CHMe CH2
180 CF3 S02Me 0 CHMe CH2 CHMe CH2
181 Me H 0 CH2 CHMe CH2 CH2
182 Me COEt 0 CH2 CHMe CH2 CH2
183 Me C02Et 0 CH2 CHMe CH2 CH2
184 Me S02Me 0 CH2 CHMe CH2 CH2
185 CF3 H 0 CH2 CHMe CH2 CH2
186 CF3 COEt 0 CH2 CHMe CH2 CH2
187 CF3 C02Et 0 CH2 CHMe CH2 CH2
188 CF3 S02CF3 0 CH2 CHMe CH2 CH2
189 CF3 S02Me 0 CH2 CHMe CH2 CH2
190 Me H 0 CH2 CHEt CH2 CH2
191 Me COEt 0 CH2 CHEt CH2 CH2
192 Me C02Et 0 CH2 CHEt CH2 CH2
193 Me S02Me 0 CH2 CHEt CH2 CH2
194 CF3 H 0 CH2 CHEt CH2 CH2
195 CF3 COEt 0 CH2 CHEt CH2 CH2
196 CF3 C02Et 0 CH2 CHEt CH2 CH2
197 CF3 S02CF3 0 CH2 CHEt CH2 CH2
198 CF3 S02Me 0 CH2 CHEt CH2 CH2
199 Me H 0 CH2 CMe2 CH2 CH2
200 Me COEt 0 CH2 CMe2 CH2 CH2
201 Me C02Et 0 CH2 CMe2 CH2 CH2
202 Me S02Me 0 CH2 CMe2 CH2 CH2
203 CF3 H 0 CH2 CMe2 CH2 CH2
204 CF3 COEt 0 CH2 CMe2 CH2 CH2
205 CF3 C02Et 0 CH2 CMe2 CH2 CH2
206 CF3 S02CF3 0 CH2 CMe2 CH2 CH2
207 CF3 S02Me 0 CH2 CMe2 CH2 CH2
208 Me H 0 CH2 CMe2 CH2 CHMe
209 Me COEt 0 CH2 CMe2 CH2 CHMe
210 Me C02Et 0 CH2 CMe2 CH2 CHMe
211 Me S02Me 0 CH2 CMe2 CH2 CHMe
212 CF3 H 0 CH2 CMe2 CH2 CHMe
213 CF3 COEt 0 CH2 CMe2 CH2 CHMe
214 CF3 C02Et 0 CH2 CMe2 CH2 CHMe
215 CF3 S02CF3 0 CH2 CMe2 CH2 CHMe
216 CF3 S02Me 0 CH2 CMe2 CH2 CHMe
217 Me H 0 CH2 CH2 CH2 CHMe
218 Me COEt 0 CH2 CH2 CH2 CHMe
219 Me C02Et 0 CH2 CH2 CH2 CHMe
220 Me S02Me 0 CH2 CH2 CH2 CHMe
221 CF3 H 0 CH2 CH2 CH2 CHMe
222 CF3 COEt 0 CH2 CH2 CH2 CHMe
223 CF3 C02Et 0 CH2 CH2 CH2 CHMe
224 CF3 S02CF3 0 CH2 CH2 CH2 CHMe
225 CF3 S02Me 0 CH2 CH2 CH2 CHMe
226 Me H 0 CH2 CH2 CH2 CMe2
227 Me COEt 0 CH2 CH2 CH2 CMe2
228 Me C02Et 0 CH2 CH2 CH2 CMe2
229 Me S02Me 0 CH2 CH2 CH2 CMe2
230 CF3 H 0 CH2 CH2 CH2 CMe2
231 CF3 COEt 0 CH2 CH2 CH2 CMe2
232 CF3 C02Et 0 CH2 CH2 CH2 CMe2
233 CF3 S02CF3 0 CH2 CH2 CH2 CMe2
234 CF3 S02Me 0 CH2 CH2 CH2 CMe2
235 Me H 0 CH2 CHMe CH2 CMe2
236 Me COEt 0 CH2 CHMe CH2 CMe2
237 Me C02Et 0 CH2 CHMe CH2 CMe2
238 Me S02Me 0 CH2 CHMe CH2 CMe2
239 CF3 H 0 CH2 CHMe CH2 CMe2
240 CF3 COEt 0 CH2 CHMe CH2 CMe2
241 CF3 C02Et 0 CH2 CHMe CH2 CMe2
242 CF3 S02CF3 0 CH2 CHMe CH2 CMe2
243 CF3 S02Me 0 CH2 CHMe CH2 CMe2
244 Me H 0 CH2 CH2 CH2 CHEt
245 Me COEt 0 CH2 CH2 CH2 CHEt
246 Me C02Et 0 CH2 CH2 CH2 CHEt
247 Me S02Me 0 CH2 CH2 CH2 CHEt
248 CF3 H 0 CH2 CH2 CH2 CHEt
249 CF3 COEt 0 CH2 CH2 CH2 CHEt
250 CF3 C02Et 0 CH2 CH2 CH2 CHEt
251 CF3 S02CF3 0 CH2 CH2 CH2 CHEt
252 CF3 S02Me 0 CH2 CH2 CH2 CHEt
253 Me H 0 CH2 CH2 CHPh CH2
254 Me COEt 0 CH2 CH2 CHPh CH2
255 Me C02Et 0 CH2 CH2 CHPh CH2
256 Me S02Me 0 CH2 CH2 CHPh CH2
257 CF3 H 0 CH2 CH2 CHPh CH2
258 CF3 COEt 0 CH2 CH2 CHPh CH2
259 CF3 C02Et 0 CH2 CH2 CHPh CH2
260 CF3 S02CF3 0 CH2 CH2 CHPh CH2
261 CF3 S02Me 0 CH2 CH2 CHPh CH2
262 Me H 0 CH2 CH2 CH2 CHPh
263 Me COEt 0 CH2 CH2 CH2 CHPh
264 Me C02Et 0 CH2 CH2 CH2 CHPh
265 Me S02Me 0 CH2 CH2 CH2 CHPh
266 CF3 H 0 CH2 CH2 CH2 CHPh
267 CF3 COEt 0 CH2 CH2 CH2 CHPh
268 CF3 C02Et 0 CH2 CH2 CH2 CHPh
269 CF3 S02CF3 0 CH2 CH2 CH2 CHPh
270 CF3 S02Me 0 CH2 CH2 CH2 CHPh
271 Me H 0 CH2CH2 CH2 CH2 CH2
272 Me COEt 0 CH2CH2 CH2 CH2 CH2
273 Me C02Et 0 CH2CH2 CH2 CH2 CH2
274 Me S02Me 0 CH2CH2 CH2 CH2 CH2
275 CF3 H 0 CH2CH2 CH2 CH2 CH2
276 CF3 COEt 0 CH2CH2 CH2 CH2 CH2
277 CF3 C02Et 0 CH2CH2 CH2 CH2 CH2
278 CF3 S02CF3 0 CH2CH2 CH2 CH2 CH2
279 CF3 S02Me 0 CH2CH2 CH2 CH2 CH2
280 Me H 0 CH2CH2 CH2 CHMe CH2
281 Me COEt 0 CH2CH2 CH2 CHMe CH2
282 Me C02Et 0 CH2CH2 CH2 CHMe CH2
283 Me S02Me 0 CH2CH2 CH2 CHMe CH2
284 CF3 H 0 CH2CH2 CH2 CHMe CH2
285 CF3 COEt 0 CH2CH2 CH2 CHMe CH2
286 CF3 C02Et 0 CH2CH2 CH2 CHMe CH2
287 CF3 S02CF3 0 CH2CH2 CH2 CHMe CH2
288 CF3 S02Me 0 CH2CH2 CH2 CHMe CH2
289 Me H 0 CH2CH2 CHMe CH2 CH2
290 Me COEt 0 CH2CH2 CHMe CH2 CH2
291 Me C02Et 0 CH2CH2 CHMe CH2 CH2
292 Me S02Me 0 CH2CH2 CHMe CH2 CH2
293 CF3 H 0 CH2CH2 CHMe CH2 CH2
294 CF3 COEt 0 CH2CH2 CHMe CH2 CH2
295 CF3 C02Et 0 CH2CH2 CHMe CH2 CH2
296 CF3 S02CF3 0 CH2CH2 CHMe CH2 CH2
297 CF3 S02Me 0 CH2CH2 CHMe CH2 CH2
298 Me H 0 CH2CH2 CMe2 CH2 CH2
299 Me COEt 0 CH2CH2 CMe2 CH2 CH2
300 Me C02Et 0 CH2CH2 CMe2 CH2 CH2
301 Me S02Me 0 CH2CH2 CMe2 CH2 CH2
302 CF3 H 0 CH2CH2 CMe2 CH2 CH2
303 CF3 COEt 0 CH2CH2 CMe2 CH2 CH2
304 CF3 C02Et 0 CH2CH2 CMe2 CH2 CH2
305 CF3 S02CF3 0 CH2CH2 CMe2 CH2 CH2
306 CF3 S02Me 0 CH2CH2 CMe2 CH2 CH2
307 Me H 0 CH2 CH2 N(2,6-dichlorophenyl)
308 Me COEt 0 CH2 CH2 N(2,6-dichlorophenyl)
309 Me C02Et 0 CH2 CH2 N(2,6-dichlorophenyl)
310 Me S02Me 0 CH2 CH2 N(2,6-dichlorophenyl)
311 CF3 H 0 CH2 CH2 N(2,6-dichlorophenyl)
312 CF3 COEt 0 CH2 CH2 N(2,6-dichlorophenyl)
313 CF3 C02Et 0 CH2 CH2 N(2,6-dichlorophenyl)
314 CF3 S02CF3 0 CH2 CH2 N(2,6-dichlorophenyl)
315 CF3 S02Me 0 CH2 CH2 N(2,6-dichlorophenyl)
316 Me H 0 CH2 CH2 CH2 NH
317 Me COEt 0 CH2 CH2 CH2 NH
318 Me C02Et 0 CH2 CH2 CH2 NH
319 Me S02Me 0 CH2 CH2 CH2 NH
320 CF3 H 0 CH2 CH2 CH2 NH
321 CF3 COEt 0 CH2 CH2 CH2 NH
322 CF3 C02Et 0 CH2 CH2 CH2 NH
323 CF3 S02CF3 0 CH2 CH2 CH2 NH
324 CF3 S02Me 0 CH2 CH2 CH2 NH
325 Me H 0 CH2 CH2 CH2 NMe
326 Me COEt 0 CH2 CH2 CH2 NMe
327 Me C02Et 0 CH2 CH2 CH2 NMe
328 Me S02Me 0 CH2 CH2 CH2 NMe
329 CF3 H 0 CH2 CH2 CH2 NMe
330 CF3 COEt 0 CH2 CH2 CH2 NMe
331 CF3 C02Et 0 CH2 CH2 CH2 NMe
332 CF3 S02CF3 0 CH2 CH2 CH2 NMe
333 CF3 S02Me 0 CH2 CH2 CH2 NMe
334 Me H 0 CH2 CH2 CH2 NC02Et
335 Me COEt 0 CH2 CH2 CH2 NC02Et
336 Me C02Et 0 CH2 CH2 CH2 NC02Et
337 Me S02Me 0 CH2 CH2 CH2 NC02Et
338 CF3 H 0 CH2 CH2 CH2 NC02Et
339 CF3 COEt 0 CH2 CH2 CH2 NC02Et
340 CF3 C02Et 0 CH2 CH2 CH2 NC02Et
341 CF3 S02CF3 0 CH2 CH2 CH2 NC02Et
342 CF3 S02Me 0 CH2 CH2 CH2 NC02Et
343 Me H 0 CH2 CH2 CMe2 NH
344 Me COEt 0 CH2 CH2 CMe2 NH
345 Me C02Et 0 CH2 CH2 CMe2 NH
346 Me S02Me 0 CH2 CH2 CMe2 NH
347 CF3 H 0 CH2 CH2 CMe2 NH
348 CF3 COEt 0 CH2 CH2 CMe2 NH
349 CF3 C02Et 0 CH2 CH2 CMe2 NH
350 CF3 S02CF3 0 CH2 CH2 CMe2 NH
351 CF3 S02Me 0 CH2 CH2 CMe2 NH
352 Me H 0 CH2 CH2 CMe2 NMe
353 Me COEt 0 CH2 CH2 CMe2 NMe
354 Me C02Et 0 CH2 CH2 CMe2 NMe
355 Me S02Me 0 CH2 CH2 CMe2 NMe
356 CF3 H 0 CH2 CH2 CMe2 NMe
357 CF3 COEt 0 CH2 CH2 CMe2 NMe
358 CF3 C02Et 0 CH2 CH2 CMe2 NMe
359 CF3 S02CF3 0 CH2 CH2 CMe2 NMe
360 CF3 S02Me 0 CH2 CH2 CMe2 NMe
361 Me H 0 CH2 CH2 CMe2 NC02Et
362 Me COEt 0 CH2 CH2 CMe2 NC02Et
363 Me C02Et 0 CH2 CH2 CMe2 NC02Et
364 Me S02Me 0 CH2 CH2 CMe2 NC02Et
365 CF3 H 0 CH2 CH2 CMe2 NC02Et
366 CF3 COEt 0 CH2 CH2 CMe2 NC02Et
367 CF3 C02Et 0 CH2 CH2 CMe2 NC02Et
368 CF3 S02CF3 0 CH2 CH2 CMe2 NC02Et
369 CF3 S02Me 0 CH2 CH2 CMe2 NC02Et
370 Me H 0 CH2CH2 CH2 CH2 NH
371 Me COEt 0 CH2CH2 CH2 CH2 NH
372 Me C02Et 0 CH2CH2 CH2 CH2 NH
373 Me S02Me 0 CH2CH2 CH2 CH2 NH
374 CF3 H 0 CH2CH2 CH2 CH2 NH
375 CF3 COEt 0 CH2CH2 CH2 CH2 NH
376 CF3 C02Et 0 CH2CH2 CH2 CH2 NH
377 CF3 S02CF3 0 CH2CH2 CH2 CH2 NH
378 CF3 S02Me 0 CH2CH2 CH2 CH2 NH
379 Me H 0 CH2 0 CH2 NMe
380 Me COEt 0 CH2 0 CH2 NMe
381 Me C02Et 0 CH2 0 CH2 NMe
382 Me S02Me 0 CH2 0 CH2 NMe
383 CF3 H 0 CH2 0 CH2 NMe
384 CF3 COEt 0 CH2 0 CH2 NMe
385 CF3 C02Et 0 CH2 0 CH2 NMe
386 CF3 S02CF3 0 CH2 0 CH2 NMe
387 CF3 S02Me 0 CH2 0 CH2 NMe
388 Me H 0 CH2 CH2 0
389 Me COEt 0 CH2 CH2 0
390 Me C02Et 0 CH2 CH2 0
391 Me S02Me 0 CH2 CH2 0
392 CF3 H 0 CH2 CH2 0
393 CF3 COEt 0 CH2 CH2 0
394 CF3 C02Et 0 CH2 CH2 0
395 CF3 S02CF3 0 CH2 CH2 0
396 CF3 S02Me 0 CH2 CH2 0
397 Me H 0 CH2 CMe2 0
398 Me COEt 0 CH2 CMe2 0
399 Me C02Et 0 CH2 CMe2 0
400 Me S02Me 0 CH2 CMe2 0
401 CF3 H 0 CH2 CMe2 0
402 CF3 COEt 0 CH2 CMe2 0
403 CF3 C02Et 0 CH2 CMe2 0
404 CF3 S02CF3 0 CH2 CMe2 0
405 CF3 S02Me 0 CH2 CMe2 0
406 Me H 0 CH2 C(Me)( cPr) 0
407 Me COEt 0 CH2 C(Me)( cPr) 0
408 Me C02Et 0 CH2 C(Me)( cPr) 0
409 Me S02Me 0 CH2 C(Me)( cPr) 0
410 CF3 H 0 CH2 C(Me)( cPr) 0
411 CF3 COEt 0 CH2 C(Me)( cPr) 0
412 CF3 C02Et 0 CH2 C(Me)( cPr) 0
413 CF3 S02CF3 0 CH2 C(Me)( cPr) 0
414 CF3 S02Me 0 CH2 C(Me)( cPr) 0
415 Me H 0 CH2 C(Me)( CF3) 0
416 Me COEt 0 CH2 C(Me)( CF3) 0
417 Me C02Et 0 CH2 C(Me)( CF3) 0
418 Me S02Me 0 CH2 C(Me)( CF3) 0
419 CF3 H 0 CH2 C(Me)( CF3) 0
420 CF3 COEt 0 CH2 C(Me)( CF3) 0
421 CF3 C02Et 0 CH2 C(Me)( CF3) 0
422 CF3 S02CF3 0 CH2 C(Me)( CF3) 0
423 CF3 S02Me 0 CH2 C(Me)( CF3) 0
C(Me)(2-
424 Me H 0 CH2 fluorophenyl) 0
C(Me)(2-
425 Me COEt 0 CH2 fluorophenyl) 0
C(Me)(2-
426 Me C02Et 0 CH2 fluorophenyl) 0
C(Me)(2-
427 Me S02Me 0 CH2 fluorophenyl) 0
C(Me)(2-
428 CF3 H 0 CH2 fluorophenyl) 0
C(Me)(2-
429 CF3 COEt 0 CH2 fluorophenyl) 0
C(Me)(2-
430 CF3 C02Et 0 CH2 fluorophenyl) 0
C(Me)(2-
431 CF3 S02CF3 0 CH2 fluorophenyl) 0
C(Me)(2-
432 CF3 S02Me 0 CH2 fluorophenyl) 0
433 Me H 0 CMe2 CH2 0
434 Me COEt 0 CMe2 CH2 0
435 Me C02Et 0 CMe2 CH2 0
436 Me S02Me 0 CMe2 CH2 0
437 CF3 H 0 CMe2 CH2 0
438 CF3 COEt 0 CMe2 CH2 0
439 CF3 C02Et 0 CMe2 CH2 0
440 CF3 S02CF3 0 CMe2 CH2 0
441 CF3 S02Me 0 CMe2 CH2 0
442 Me H 0 CH2 CH2 CH2 0
443 Me COEt 0 CH2 CH2 CH2 0
444 Me C02Et 0 CH2 CH2 CH2 0
445 Me S02Me 0 CH2 CH2 CH2 0
446 CF3 H 0 CH2 CH2 CH2 0
447 CF3 COEt 0 CH2 CH2 CH2 0
448 CF3 C02Et 0 CH2 CH2 CH2 0
449 CF3 S02CF3 0 CH2 CH2 CH2 0
450 CF3 S02Me 0 CH2 CH2 CH2 0
451 Me H 0 CH2 CH2 CHMe 0
452 Me COEt 0 CH2 CH2 CHMe 0
453 Me C02Et 0 CH2 CH2 CHMe 0
454 Me S02Me 0 CH2 CH2 CHMe 0
455 CF3 H 0 CH2 CH2 CHMe 0
456 CF3 COEt 0 CH2 CH2 CHMe 0
457 CF3 C02Et 0 CH2 CH2 CHMe 0
458 CF3 S02CF3 0 CH2 CH2 CHMe 0
459 CF3 S02Me 0 CH2 CH2 CHMe 0
460 Me H 0 CH2 CH2 CHEt 0
461 Me COEt 0 CH2 CH2 CHEt 0
462 Me C02Et 0 CH2 CH2 CHEt 0
463 Me S02Me 0 CH2 CH2 CHEt 0
464 CF3 H 0 CH2 CH2 CHEt 0
465 CF3 COEt 0 CH2 CH2 CHEt 0
466 CF3 C02Et 0 CH2 CH2 CHEt 0
467 CF3 S02CF3 0 CH2 CH2 CHEt 0
468 CF3 S02Me 0 CH2 CH2 CHEt 0
469 Me H 0 CH2 CH2 CHnPr 0
470 Me COEt 0 CH2 CH2 CHnPr 0
471 Me C02Et 0 CH2 CH2 CHnPr 0
472 Me S02Me 0 CH2 CH2 CHnPr 0
473 CF3 H 0 CH2 CH2 CHnPr 0
474 CF3 COEt 0 CH2 CH2 CHnPr 0
475 CF3 C02Et 0 CH2 CH2 CHnPr 0
476 CF3 S02CF3 0 CH2 CH2 CHnPr 0
477 CF3 S02Me 0 CH2 CH2 CHnPr 0
478 Me H 0 CH2 CH2 CMe2 0
479 Me COEt 0 CH2 CH2 CMe2 0
480 Me C02Et 0 CH2 CH2 CMe2 0
481 Me S02Me 0 CH2 CH2 CMe2 0
482 CF3 H 0 CH2 CH2 CMe2 0
483 CF3 COEt 0 CH2 CH2 CMe2 0
484 CF3 C02Et 0 CH2 CH2 CMe2 0
485 CF3 S02CF3 0 CH2 CH2 CMe2 0
486 CF3 S02Me 0 CH2 CH2 CMe2 0
487 Me H 0 CH2 CH2 C(Me)( CF3) 0
488 Me COEt 0 CH2 CH2 C(Me)( CF3) 0
489 Me C02Et 0 CH2 CH2 C(Me)( CF3) 0
490 Me S02Me 0 CH2 CH2 C(Me)( CF3) 0
491 CF3 H 0 CH2 CH2 C(Me)( CF3) 0
492 CF3 COEt 0 CH2 CH2 C(Me)( CF3) 0
493 CF3 C02Et 0 CH2 CH2 C(Me)( CF3) 0
494 CF3 S02CF3 0 CH2 CH2 C(Me)( CF3) 0
495 CF3 S02Me 0 CH2 CH2 C(Me)( CF3) 0
496 Me H 0 CH2 CH2 C(Et)( CF3) 0
497 Me COEt 0 CH2 CH2 C(Et)( CF3) 0
498 Me C02Et 0 CH2 CH2 C(Et)( CF3) 0
499 Me S02Me 0 CH2 CH2 C(Et)( CF3) 0
500 CF3 H 0 CH2 CH2 C(Et)( CF3) 0
501 CF3 COEt 0 CH2 CH2 C(Et)( CF3) 0
502 CF3 C02Et 0 CH2 CH2 C(Et)( CF3) 0
503 CF3 S02CF3 0 CH2 CH2 C(Et)( CF3) 0
504 CF3 S02Me 0 CH2 CH2 C(Et)( CF3) 0
505 Me H 0 CH2 CH2 CEt2 0
506 Me COEt 0 CH2 CH2 CEt2 0
507 Me C02Et 0 CH2 CH2 CEt2 0
508 Me S02Me 0 CH2 CH2 CEt2 0
509 CF3 H 0 CH2 CH2 CEt2 0
510 CF3 COEt 0 CH2 CH2 CEt2 0
511 CF3 C02Et 0 CH2 CH2 CEt2 0
512 CF3 S02CF3 0 CH2 CH2 CEt2 0
513 CF3 S02Me 0 CH2 CH2 CEt2 0
514 Me H 0 CH2 CH2 C( cPr)(Me) 0
515 Me COEt 0 CH2 CH2 C( cPr)(Me) 0
516 Me C02Et 0 CH2 CH2 C( cPr)(Me) 0
517 Me S02Me 0 CH2 CH2 C( cPr)(Me) 0
518 CF3 H 0 CH2 CH2 C( cPr)(Me) 0
519 CF3 COEt 0 CH2 CH2 C( cPr)(Me) 0
520 CF3 C02Et 0 CH2 CH2 C( cPr)(Me) 0
521 CF3 S02CF3 0 CH2 CH2 C( cPr)(Me) 0
522 CF3 S02Me 0 CH2 CH2 C( cPr)(Me) 0
523 Me H 0 CH2 CH2 C(CH2)4 0
524 Me COEt 0 CH2 CH2 C(CH2)4 0
525 Me C02Et 0 CH2 CH2 C(CH2)4 0
526 Me S02Me 0 CH2 CH2 C(CH2)4 0
527 CF3 H 0 CH2 CH2 C(CH2)4 0
528 CF3 COEt 0 CH2 CH2 C(CH2)4 0
529 CF3 C02Et 0 CH2 CH2 C(CH2)4 0
530 CF3 S02CF3 0 CH2 CH2 C(CH2)4 0
531 CF3 S02Me 0 CH2 CH2 C(CH2)4 0
532 Me H 0 CH2 CH2 CH(2-fluorophenyl) 0
533 Me COEt 0 CH2 CH2 CH(2-fluorophenyl) 0
534 Me C02Et 0 CH2 CH2 CH(2-fluorophenyl) 0
535 Me S02Me 0 CH2 CH2 CH(2-fluorophenyl) 0
536 CF3 H 0 CH2 CH2 CH(2-fluorophenyl) 0
537 CF3 COEt 0 CH2 CH2 CH(2-fluorophenyl) 0
538 CF3 C02Et 0 CH2 CH2 CH(2-fluorophenyl) 0
539 CF3 S02CF3 0 CH2 CH2 CH(2-fluorophenyl) 0
540 CF3 S02Me 0 CH2 CH2 CH(2-fluorophenyl) 0
541 Me H 0 CH2 CHMe CH2 0
542 Me COEt 0 CH2 CHMe CH2 0
543 Me C02Et 0 CH2 CHMe CH2 0
544 Me S02Me 0 CH2 CHMe CH2 0
545 CF3 H 0 CH2 CHMe CH2 0
546 CF3 COEt 0 CH2 CHMe CH2 0
547 CF3 C02Et 0 CH2 CHMe CH2 0
548 CF3 S02CF3 0 CH2 CHMe CH2 0
549 CF3 S02Me 0 CH2 CHMe CH2 0
550 Me H 0 CH2 CMe2 CH2 0
551 Me COEt 0 CH2 CMe2 CH2 0
552 Me C02Et 0 CH2 CMe2 CH2 0
553 Me S02Me 0 CH2 CMe2 CH2 0
554 CF3 H 0 CH2 CMe2 CH2 0
555 CF3 COEt 0 CH2 CMe2 CH2 0
556 CF3 C02Et 0 CH2 CMe2 CH2 0
557 CF3 S02CF3 0 CH2 CMe2 CH2 0
558 CF3 S02Me 0 CH2 CMe2 CH2 0
559 Me H 0 CHMe CH2 CH2 0
560 Me COEt 0 CHMe CH2 CH2 0
561 Me C02Et 0 CHMe CH2 CH2 0
562 Me S02Me 0 CHMe CH2 CH2 0
563 CF3 H 0 CHMe CH2 CH2 0
564 CF3 COEt 0 CHMe CH2 CH2 0
565 CF3 C02Et 0 CHMe CH2 CH2 0
566 CF3 S02CF3 0 CHMe CH2 CH2 0
567 CF3 S02Me 0 CHMe CH2 CH2 0
568 Me H 0 CMe2 CH2 CH2 0
569 Me COEt 0 CMe2 CH2 CH2 0
570 Me C02Et 0 CMe2 CH2 CH2 0
571 Me S02Me 0 CMe2 CH2 CH2 0
572 CF3 H 0 CMe2 CH2 CH2 0
573 CF3 COEt 0 CMe2 CH2 CH2 0
574 CF3 C02Et 0 CMe2 CH2 CH2 0
575 CF3 S02CF3 0 CMe2 CH2 CH2 0
576 CF3 S02Me 0 CMe2 CH2 CH2 0
577 Me H 0 CH2CH2 CH2 CH2 0
578 Me COEt 0 CH2CH2 CH2 CH2 0
579 Me C02Et 0 CH2CH2 CH2 CH2 0
580 Me S02Me 0 CH2CH2 CH2 CH2 0
581 CF3 H 0 CH2CH2 CH2 CH2 0
582 CF3 COEt 0 CH2CH2 CH2 CH2 0
583 CF3 C02Et 0 CH2CH2 CH2 CH2 0
584 CF3 S02CF3 0 CH2CH2 CH2 CH2 0
585 CF3 S02Me 0 CH2CH2 CH2 CH2 0
586 Me H 0 CH2CH2 CHMe CH2 0
587 Me COEt 0 CH2CH2 CHMe CH2 0
588 Me C02Et 0 CH2CH2 CHMe CH2 0
589 Me S02Me 0 CH2CH2 CHMe CH2 0
590 CF3 H 0 CH2CH2 CHMe CH2 0
591 CF3 COEt 0 CH2CH2 CHMe CH2 0
592 CF3 C02Et 0 CH2CH2 CHMe CH2 0
593 CF3 S02CF3 0 CH2CH2 CHMe CH2 0
594 CF3 S02Me 0 CH2CH2 CHMe CH2 0
595 Me H 0 CH2CH2 CMe2 CH2 0
596 Me COEt 0 CH2CH2 CMe2 CH2 0
597 Me C02Et 0 CH2CH2 CMe2 CH2 0
598 Me S02Me 0 CH2CH2 CMe2 CH2 0
599 CF3 H 0 CH2CH2 CMe2 CH2 0
600 CF3 COEt 0 CH2CH2 CMe2 CH2 0
601 CF3 C02Et 0 CH2CH2 CMe2 CH2 0
602 CF3 S02CF3 0 CH2CH2 CMe2 CH2 0
603 CF3 S02Me 0 CH2CH2 CMe2 CH2 0
604 Me H 0 CH2 0 CH2 CH2
605 Me COEt 0 CH2 0 CH2 CH2
606 Me C02Et 0 CH2 0 CH2 CH2
607 Me S02Me 0 CH2 0 CH2 CH2
608 CF3 H 0 CH2 0 CH2 CH2
609 CF3 COEt 0 CH2 0 CH2 CH2
610 CF3 C02Et 0 CH2 0 CH2 CH2
611 CF3 S02CF3 0 CH2 0 CH2 CH2
612 CF3 S02Me 0 CH2 0 CH2 CH2
613 Me H 0 CH2 0 CHMe CH2
614 Me COEt 0 CH2 0 CHMe CH2
615 Me C02Et 0 CH2 0 CHMe CH2
616 Me S02Me 0 CH2 0 CHMe CH2
617 CF3 H 0 CH2 0 CHMe CH2
618 CF3 COEt 0 CH2 0 CHMe CH2
619 CF3 C02Et 0 CH2 0 CHMe CH2
620 CF3 S02CF3 0 CH2 0 CHMe CH2
621 CF3 S02Me 0 CH2 0 CHMe CH2
622 Me H 0 CH2 0 CMe2 CH2
623 Me COEt 0 CH2 0 CMe2 CH2
624 Me C02Et 0 CH2 0 CMe2 CH2
625 Me S02Me 0 CH2 0 CMe2 CH2
626 CF3 H 0 CH2 0 CMe2 CH2
627 CF3 COEt 0 CH2 0 CMe2 CH2
628 CF3 C02Et 0 CH2 0 CMe2 CH2
629 CF3 S02CF3 0 CH2 0 CMe2 CH2
630 CF3 S02Me 0 CH2 0 CMe2 CH2
631 Me H 0 CH2 0 C(Me)( CF3) CH2
632 Me COEt 0 CH2 0 C(Me)( CF3) CH2
633 Me C02Et 0 CH2 0 C(Me)( CF3) CH2
634 Me S02Me 0 CH2 0 C(Me)( CF3) CH2
635 CF3 H 0 CH2 0 C(Me)( CF3) CH2
636 CF3 COEt 0 CH2 0 C(Me)( CF3) CH2
637 CF3 C02Et 0 CH2 0 C(Me)( CF3) CH2
638 CF3 S02CF3 0 CH2 0 C(Me)( CF3) CH2
639 CF3 S02Me 0 CH2 0 C(Me)( CF3) CH2
640 Me H 0 CH2 0 C(CH2)3 CH2
641 Me COEt 0 CH2 0 C(CH2)3 CH2
642 Me C02Et 0 CH2 0 C(CH2)3 CH2
643 Me S02Me 0 CH2 0 C(CH2)3 CH2
644 CF3 H 0 CH2 0 C(CH2)3 CH2
645 CF3 COEt 0 CH2 0 C(CH2)3 CH2
646 CF3 C02Et 0 CH2 0 C(CH2)3 CH2
647 CF3 S02CF3 0 CH2 0 C(CH2)3 CH2
648 CF3 S02Me 0 CH2 0 C(CH2)3 CH2
649 Me H 0 CH2 0 C(CH2)4 CH2
650 Me COEt 0 CH2 0 C(CH2)4 CH2
651 Me C02Et 0 CH2 0 C(CH2)4 CH2
652 Me S02Me 0 CH2 0 C(CH2)4 CH2
653 CF3 H 0 CH2 0 C(CH2)4 CH2
654 CF3 COEt 0 CH2 0 C(CH2)4 CH2
655 CF3 C02Et 0 CH2 0 C(CH2)4 CH2
656 CF3 S02CF3 0 CH2 0 C(CH2)4 CH2
657 CF3 S02Me 0 CH2 0 C(CH2)4 CH2
658 Me H 0 CHMe 0 CH2 CH2
659 Me COEt 0 CHMe 0 CH2 CH2
660 Me C02Et 0 CHMe 0 CH2 CH2
661 Me S02Me 0 CHMe 0 CH2 CH2
662 CF3 H 0 CHMe 0 CH2 CH2
663 CF3 COEt 0 CHMe 0 CH2 CH2
664 CF3 C02Et 0 CHMe 0 CH2 CH2
665 CF3 S02CF3 0 CHMe 0 CH2 CH2
666 CF3 S02Me 0 CHMe 0 CH2 CH2
667 Me H 0 CHMe 0 CMe2 CH2
668 Me COEt 0 CHMe 0 CMe2 CH2
669 Me C02Et 0 CHMe 0 CMe2 CH2
670 Me S02Me 0 CHMe 0 CMe2 CH2
671 CF3 H 0 CHMe 0 CMe2 CH2
672 CF3 COEt 0 CHMe 0 CMe2 CH2
673 CF3 C02Et 0 CHMe 0 CMe2 CH2
674 CF3 S02CF3 0 CHMe 0 CMe2 CH2
675 CF3 S02Me 0 CHMe 0 CMe2 CH2
676 Me H 0 CH2CH2 0 CH2
677 Me COEt 0 CH2CH2 0 CH2
678 Me C02Et 0 CH2CH2 0 CH2
679 Me S02Me 0 CH2CH2 0 CH2
680 CF3 H 0 CH2CH2 0 CH2
681 CF3 COEt 0 CH2CH2 0 CH2
682 CF3 C02Et 0 CH2CH2 0 CH2
683 CF3 S02CF3 0 CH2CH2 0 CH2
684 CF3 S02Me 0 CH2CH2 0 CH2
685 Me H 0 CH2CHMe 0 CH2
686 Me COEt 0 CH2CHMe 0 CH2
687 Me C02Et 0 CH2CHMe 0 CH2
688 Me S02Me 0 CH2CHMe 0 CH2
689 CF3 H 0 CH2CHMe 0 CH2
690 CF3 COEt 0 CH2CHMe 0 CH2
691 CF3 C02Et 0 CH2CHMe 0 CH2
692 CF3 S02CF3 0 CH2CHMe 0 CH2
693 CF3 S02Me 0 CH2CHMe 0 CH2
694 Me H 0 CH2CHEt 0 CH2
695 Me COEt 0 CH2CHEt 0 CH2
696 Me C02Et 0 CH2CHEt 0 CH2
697 Me S02Me 0 CH2CHEt 0 CH2
698 CF3 H 0 CH2CHEt 0 CH2
699 CF3 COEt 0 CH2CHEt 0 CH2
700 CF3 C02Et 0 CH2CHEt 0 CH2
701 CF3 S02CF3 0 CH2CHEt 0 CH2
702 CF3 S02Me 0 CH2CHEt 0 CH2
703 Me H 0 CH2CMe2 0 CH2
704 Me COEt 0 CH2CMe2 0 CH2
705 Me C02Et 0 CH2CMe2 0 CH2
706 Me S02Me 0 CH2CMe2 0 CH2
707 CF3 H 0 CH2CMe2 0 CH2
708 CF3 COEt 0 CH2CMe2 0 CH2
709 CF3 C02Et 0 CH2CMe2 0 CH2
710 CF3 S02CF3 0 CH2CMe2 0 CH2
711 CF3 S02Me 0 CH2CMe2 0 CH2
712 Me H 0 CHMeCH2 0 CH2
713 Me COEt 0 CHMeCH2 0 CH2
714 Me C02Et 0 CHMeCH2 0 CH2
715 Me S02Me 0 CHMeCH2 0 CH2
716 CF3 H 0 CHMeCH2 0 CH2
717 CF3 COEt 0 CHMeCH2 0 CH2
718 CF3 C02Et 0 CHMeCH2 0 CH2
719 CF3 S02CF3 0 CHMeCH2 0 CH2
720 CF3 S02Me 0 CHMeCH2 0 CH2
721 Me H 0 CH2CH2 0 CHMe
722 Me COEt 0 CH2CH2 0 CHMe
723 Me C02Et 0 CH2CH2 0 CHMe
724 Me S02Me 0 CH2CH2 0 CHMe
725 CF3 H 0 CH2CH2 0 CHMe
726 CF3 COEt 0 CH2CH2 0 CHMe
727 CF3 C02Et 0 CH2CH2 0 CHMe
728 CF3 S02CF3 0 CH2CH2 0 CHMe
729 CF3 S02Me 0 CH2CH2 0 CHMe
730 Me H 0 CH2CH2 0 CMe2
731 Me COEt 0 CH2CH2 0 CMe2
732 Me C02Et 0 CH2CH2 0 CMe2
733 Me S02Me 0 CH2CH2 0 CMe2
734 CF3 H 0 CH2CH2 0 CMe2
735 CF3 COEt 0 CH2CH2 0 CMe2
736 CF3 C02Et 0 CH2CH2 0 CMe2
737 CF3 S02CF3 0 CH2CH2 0 CMe2
738 CF3 S02Me 0 CH2CH2 0 CMe2
739 Me H 0 CH2CH2 0 CHPh
740 Me COEt 0 CH2CH2 0 CHPh
741 Me C02Et 0 CH2CH2 0 CHPh
742 Me S02Me 0 CH2CH2 0 CHPh
743 CF3 H 0 CH2CH2 0 CHPh
744 CF3 COEt 0 CH2CH2 0 CHPh
745 CF3 C02Et 0 CH2CH2 0 CHPh
746 CF3 S02CF3 0 CH2CH2 0 CHPh
747 CF3 S02Me 0 CH2CH2 0 CHPh
748 Me H 0 CH2CH2 s CH2
749 Me COEt 0 CH2CH2 s CH2
750 Me C02Et 0 CH2CH2 s CH2
751 Me S02Me 0 CH2CH2 s CH2
752 CF3 H 0 CH2CH2 s CH2
753 CF3 COEt 0 CH2CH2 s CH2
754 CF3 C02Et 0 CH2CH2 s CH2
755 CF3 S02CF3 0 CH2CH2 s CH2
756 CF3 S02Me 0 CH2CH2 s CH2
757 Me H 0 CH2CH2 0 CH2 CH2
758 Me COEt 0 CH2CH2 0 CH2 CH2
759 Me C02Et 0 CH2CH2 0 CH2 CH2
760 Me S02Me 0 CH2CH2 0 CH2 CH2
761 CF3 H 0 CH2CH2 0 CH2 CH2
762 CF3 COEt 0 CH2CH2 0 CH2 CH2
763 CF3 C02Et 0 CH2CH2 0 CH2 CH2
764 CF3 S02CF3 0 CH2CH2 0 CH2 CH2
765 CF3 S02Me 0 CH2CH2 0 CH2 CH2
766 Me H 0 0 CMe2 CH2
767 Me COEt 0 0 CMe2 CH2
768 Me C02Et 0 0 CMe2 CH2
769 Me S02Me 0 0 CMe2 CH2
770 CF3 H 0 0 CMe2 CH2
771 CF3 COEt 0 0 CMe2 CH2
772 CF3 C02Et 0 0 CMe2 CH2
773 CF3 S02CF3 0 0 CMe2 CH2
774 CF3 S02Me 0 0 CMe2 CH2
775 Me H 0 0 CH2CH2 CH2
776 Me COEt 0 0 CH2CH2 CH2
777 Me C02Et 0 0 CH2CH2 CH2
778 Me S02Me 0 0 CH2CH2 CH2
779 CF3 H 0 0 CH2CH2 CH2
780 CF3 COEt 0 0 CH2CH2 CH2
781 CF3 C02Et 0 0 CH2CH2 CH2
782 CF3 S02CF3 0 0 CH2CH2 CH2
783 CF3 S02Me 0 0 CH2CH2 CH2
784 Me H 0 0 CH2CHEt 0
785 Me COEt 0 0 CH2CHEt 0
786 Me C02Et 0 0 CH2CHEt 0
787 Me S02Me 0 0 CH2CHEt 0
788 CF3 H 0 0 CH2CHEt 0
789 CF3 COEt 0 0 CH2CHEt 0
790 CF3 C02Et 0 0 CH2CHEt 0
791 CF3 S02CF3 0 0 CH2CHEt 0
792 CF3 S02Me 0 0 CH2CHEt 0
793 Me H 0 0 CH2CH2CMe2 CH2
794 Me COEt 0 0 CH2CH2CMe2 CH2
795 Me C02Et 0 0 CH2CH2CMe2 CH2
796 Me S02Me 0 0 CH2CH2CMe2 CH2
797 CF3 H 0 0 CH2CH2CMe2 CH2
798 CF3 COEt 0 0 CH2CH2CMe2 CH2
799 CF3 C02Et 0 0 CH2CH2CMe2 CH2
800 CF3 S02CF3 0 0 CH2CH2CMe2 CH2
801 CF3 S02Me 0 0 CH2CH2CMe2 CH2
801 compounds are described, designated compounds 2-1 to 2-801 respectively, of formula (I) wherein ring A is A2, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 3-1 to 3-801 respectively, of formula (I) wherein ring A is A3, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 4-1 to 4-801 respectively, of formula (I) wherein ring A is A4, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 5-1 to 5-801 respectively, of formula (I) wherein ring A is A5, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 6-1 to 6-801 respectively, of formula (I) wherein ring A is A6, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 7-1 to 7-801 respectively, of formula (I) wherein ring A is A7, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 8-1 to 8-801 respectively, of formula (I) wherein ring A is A8, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 9-1 to 9-801 respectively, of formula (I) wherein ring A is A9, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1. compounds are described, designated compounds 10-1 to 10-801 respectively, of formula (I)
wherein ring Ais A10, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 11-1 to 11-801 respectively, of formula (I) wherein ring Ais A11, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 12-1 to 12-801 respectively, of formula (I) wherein ring Ais A12, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 13-1 to 13-801 respectively, of formula (I) wherein ring Ais A13, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 14-1 to 14-801 respectively, of formula (I) wherein ring Ais A14, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 15-1 to 15-801 respectively, of formula (I) wherein ring Ais A15, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 16-1 to 16-801 respectively, of formula (I) wherein ring Ais A16, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 17-1 to 17-801 respectively, of formula (I) wherein ring Ais A17, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 18-1 to 18-801 respectively, of formula (I) wherein ring Ais A18, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 19-1 to 19-801 respectively, of formula (I) wherein ring Ais A19, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 20-1 to 20-801 respectively, of formula (I) wherein ring Ais A20, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 21-1 to 21-801 respectively, of formula (I) wherein ring Ais A21, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 22-1 to 22-801 respectively, of formula (I) wherein ring Ais A22, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 23-1 to 23-801 respectively, of formula (I) wherein ring Ais A23, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 24-1 to 24-801 respectively, of formula (I) wherein ring Ais A24, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 25-1 to 25-801 respectively, of formula (I) wherein ring Ais A25, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 26-1 to 26-801 respectively, of formula (I)
wherein ring Ais A26, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 27-1 to 27-801 respectively, of formula (I) wherein ring Ais A27, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 28-1 to 28-801 respectively, of formula (I) wherein ring Ais A28, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 29-1 to 29-801 respectively, of formula (I) wherein ring Ais A29, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 30-1 to 30-801 respectively, of formula (I) wherein ring Ais A30, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 31-1 to 31-801 respectively, of formula (I) wherein ring Ais A31, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 32-1 to 32-801 respectively, of formula (I) wherein ring Ais A32, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 33-1 to 33-801 respectively, of formula (I) wherein ring Ais A33, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 34-1 to 34-801 respectively, of formula (I) wherein ring Ais A34, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 35-1 to 35-801 respectively, of formula (I) wherein ring Ais A35, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 36-1 to 36-801 respectively, of formula (I) wherein ring Ais A36, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 37-1 to 37-801 respectively, of formula (I) wherein ring Ais A37, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 38-1 to 38-801 respectively, of formula (I) wherein ring Ais A38, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 39-1 to 39-801 respectively, of formula (I) wherein ring Ais A39, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 40-1 to 40-801 respectively, of formula (I) wherein ring Ais A40, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 41-1 to 41-801 respectively, of formula (I) wherein ring Ais A41, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. compounds are described, designated compounds 42-1 to 42-801 respectively, of formula (I)
wherein ring Ais A42, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 43-1 to 43-801 respectively, of formula (I) wherein ring Ais A43, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 44-1 to 44-801 respectively, of formula (I) wherein ring Ais A44, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 45-1 to 45-801 respectively, of formula (I) wherein ring Ais A45, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 46-1 to 46-801 respectively, of formula (I) wherein ring Ais A46, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 47-1 to 47-801 respectively, of formula (I) wherein ring Ais A47, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 48-1 to 48-801 respectively, of formula (I) wherein ring Ais A48, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 49-1 to 49-801 respectively, of formula (I) wherein ring Ais A49, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 50-1 to 50-801 respectively, of formula (I) wherein ring Ais A50, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 51-1 to 51-801 respectively, of formula (I) wherein ring Ais A51, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 52-1 to 52-801 respectively, of formula (I) wherein ring Ais A52, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 53-1 to 53-801 respectively, of formula (I) wherein ring Ais A53, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 54-1 to 54-801 respectively, of formula (I) wherein ring Ais A54, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 55-1 to 55-801 respectively, of formula (I) wherein ring Ais A55, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 56-1 to 56-801 respectively, of formula (I) wherein ring Ais A56, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 57-1 to 57-801 respectively, of formula (I) wherein ring Ais A57, and the values of R, R , W, (CR R2)n, X, (CR5R6)P and Z are as defined in Table 1. compounds are described, designated compounds 58-1 to 58-801 respectively, of formula (I)
wherein ring A is A58, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 59-1 to 59-801 respectively, of formula (I) wherein ring A is A59, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 60-1 to 60-801 respectively, of formula (I) wherein ring A is A60, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 61-1 to 61-801 respectively, of formula (I) wherein ring A is A61 , and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 62-1 to 62-801 respectively, of formula (I) wherein ring A is A62, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1. 801 compounds are described, designated compounds 63-1 to 63-801 respectively, of formula (I) wherein ring A is A63, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 64-1 to 64-801 respectively, of formula (I) wherein ring A is A64, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
801 compounds are described, designated compounds 65-1 to 65-801 respectively, of formula (I) wherein ring A is A65, and the values of R, R , W, (CR R 2)n, X, (CR5R6)P and Z are as defined in Table 1.
The herbicidal compounds of formula (I) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.
The herbicidal compounds of this invention may contain an asymmetric carbon atom and some of the compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to stereochemistry, the present invention includes such optical isomers and diastereomers; as well as the racemic mixture and resolved, enantiomerically pure R and S stereoisomers; as well as other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that one optical isomer, including diastereomer and enantiomer, or stereoisomer may have favorable properties over the other. Thus when disclosing and claiming the invention, when one racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers and enantiomers, or stereoisomers substantially free of the other are disclosed and claimed as well.
Hydroxy or hydroxyl, as used herein, refers to the group -OH. Cyano, or nitrile, as used herein, refers to the group -CN.
Nitro, as used herein, refers to the group -N02.
Oxo, as used herein, refers to the group =0.
Carboxy, as used herein, refers to the group -C(0)OH.
Alkyl, as used herein, refers to an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.
Alkenyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1-enyl, but-2-enyl, but-3-enyl, 2- methypropenyl.
Alkynyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl) but-1-ynyl, but-2-ynyl and but-3-ynyl.
Alkylene, as used herein, means a branched or linear divalent hydrocarbon radical. Examples of alkylene are methylene, 1 , 1-ethylene, 1 ,2-ethylene, 1 ,1-propylene, 1 ,2-propylene, 1 ,3-propylene and 2,2- propylene etc.
Cycloalkyl, as used herein, refers to a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Alkylthio, as used herein, refers to the group -SR, wherein R is alkyl as defined above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.
Cyanoalkyl, as used herein, refers to an alkyl group substituted with one or more cyano groups.
Alkoxy, as used herein, refers to the group -OR, wherein R is alkyl as defined above. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.
Alkoxyalkyl, as used herein, refers to the group -ROR, wherein each R is independently alkyl group as defined herein.
Alkoxyalkoxy, as used herein, refers to the group -OROR, wherein each R is independently alkyl as defined herein.
Alkoxyalkoxyalkyl, as used herein, refers to the group -ROROR, wherein each R is independently alkyl as defined herein.
Alkylthioalkyl, as used herein, refers to the group -RSR, wherein each R is independently alkyl as defined herein.
Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.
Haloalkyl, as used herein, refers to an alkyl group as defined herein wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyl groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl.
Haloalkylthio, as used herein, refers to the group -SR, wherein R is haloalkyl as defined herein.
Haloalkoxy, as used herein, refers to the group -OR, wherein R is haloalkyl as defined herein.
Haloalkoxyalkyl, as used herein, refers to the group -ROR', wherein R is alkyl as defined herein and R' is haloalkyl as defined herein. Alkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is alkyl as defined herein.
Examples of alkylcarbonyl groups include ethanoyl, propanoyl, n-butanoyl, etc.
Alkenylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is alkenyl as defined herein.
Cycloalkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is cycloalkyl as defined herein.
Haloalkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is haloalkyl as defined herein.
Alkoxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is alkyl as defined herein.
Alkenyloxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is alkenyl as defined herein.
Propargyloxycarbonyl, as used herein, refers to the group -C(0)OCH2C≡CH.
Haloalkoxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is haloalkyl as defined herein.
Alkylcarbonylalkyl, as used herein, refers to the group -RC(0)R, wherein each R is independently alkyl as defined herein.
Alkoxycarbonylalkyl, as used herein, refers to the group -RC(0)OR, wherein each R is independently alkyl as defined herein.
Alkoxyalkylcarbonyl, as used herein, refers to the group -C(0)ROR, wherein each R is independently alkyl as defined herein. Alkoxyalkoxycarbonyl, as used herein, refers to the group -C(0)OROR, wherein each R is independently alkyl as defined herein.
Alkoxycarbonylalkylcarbonyl, as used herein, refers to the group -C(0)RC(0)OR, wherein each R is independently alkyl as defined herein.
Aminocarbonyl, as used herein, refers to the group -C(0)NH2. Alkylaminocarbonyl, as used herein, refers to the group -C(0)NHR, wherein R is alkyl as defined herein.
Dialkylaminocarbonyl, as used herein, refers to the group -C(0)NRR, wherein each R is independently alkyl as defined herein.
Alkylthiocarbonyl, as used herein, refers to the group -C(0)SR, wherein R is alkyl as defined herein. Alkoxycarbonylaminoalkyl, as used herein, refers to the group -RNHC(0)OR, wherein each R is independently alkyl as defined herein.
Alkylcarbonyloxy, as used herein, refers to the group -OC(0)R, wherein R is alkyl as defined herein.
Alkylcarbonyloxyalkyl, as used herein, refers to the group -ROC(0)R, wherein each R is independently alkyl as defined herein.
Alkoxycarbonyloxyalkyl, as used herein, refers to the group -ROC(0)OR, wherein each R is independently alkyl as defined herein.
Alkylsulfonyl, as used herein, refers to the group -S(0)2R, wherein R is alkyl as defined herein.
Haloalkylsulphonyl, as used herein, refers to the group -S(0)2R, wherein R is haloalkyl as defined herein.
AlkylsulphonylalkyI, as used herein, refers to the group -RS(0)2R, wherein each R is independently alkyl as defined herein.
Aryl, as used herein, refers to an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.
Aryloxy, as used herein, refers to the group -OAr, wherein Ar is aryl as defined herein. Preferred aryloxy groups include phenoxy, naphthyloxy and the like.
Arylalkyl, as used herein, refers to the group -RAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein. Preferred arylalkyl groups include phenylmethyl (benzyl).
Aryloxyalkyl, as used herein, refers to the group -ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Arylthio, as used herein, refers to the group -SAr, wherein Ar is aryl as defined herein.
Arylthioalkyl, as used herein, refers to the group -RSAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Arylalkylthioalkyl, as used herein, refers to the group -RSRAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein.
Arylalkoxyalkyl, as used herein, refers to the group -RORAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein.
Arylcarbonyl, as used herein, refers to the group -C(0)Ar, wherein Ar is aryl as defined herein.
Arylcarbonylalkyl, as used herein, refers to the group -RC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Aryloxycarbonyl, as used herein, refers to the group -C(0)OAr, wherein Ar is aryl as defined herein.
Aryloxyalkylcarbonyl, as used herein, refers to the group -C(0)ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Arylalkoxycarbonyl, as used herein, refers to the group -C(0)ORAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Arylcarbonyloxyalkyl, as used herein, refers to the group -ROC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.
Aryloxycarbonyloxyalkyl, as used herein, refers to the group -ROC(0)OAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein. Arylsulphonyl as used herein refers to the group -S(0)2Ar, wherein Ar is aryl as defined herein.
Heteroaryl/heteroaromatic ring, as used herein, refers to a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. When a ring system contains a sulphur atom, the sulphur atom may be present in any one of its oxidation states e.g. -S-, -S(=0)- or -S(=0)2-. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5- a] pyrimidinyl.
Heteroarylalkyl, as used herein, refers to the group -RHet, wherein R is alkyl as defined herein and Het is heteroaryl as defined herein.
Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter. For most groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For halogenated groups, for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.
Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N+(R29R30R3 R32) wherein R29, R30, R3 and R32 are independently selected from hydrogen, Ci-C6 alkyl and Ci-C6 hydroxyalkyl. Salts of the compounds of formula (I) can be prepared by treatment
of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.
Acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.
The sulphonanilide derivatives of the present invention may be made as the skilled person will appreciate by applying and/or adapting, as appropriate, the methods described in the prior art (see for example, EP2336104 and WO 2010/119906).
In addition, general methods for the production of compounds of formula (I) are described below. Unless otherwise stated in the text, the substituents R, R , R2, R5, R6, R , R 2, m, n, p, A, W, X and Z are as defined hereinbefore. The abbreviations LG and LG' as used herein refer to any suitable leaving group, and includes halogen and sulphonate groups. The abbreviation R' as used herein refers to an alkyl group, typically a methyl or ethyl group.
The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
Compounds of formula (I) in which R is H may be prepared from compounds of formula (A) and compounds of formula (B) as shown in reaction scheme 1.
Reaction scheme 1
w (B) (I)
For example, A compound of formula (A) may be heated with a compound of formula (B) in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example toluene or chlorobenzene. The process may conveniently be carried out using microwave heating or conventional heating in an apparatus for the removal of water, for example a Dean-Stark trap.
Compounds of formula (B) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (A) may be prepared from compounds of formula (C) as shown in reaction scheme 2.
Reaction scheme 2
For example, a compound of formula (C) may be treated with a reducing agent such as lithium aluminium hydride in a suitable solvent such as tetrahydrofuran.
Compounds of formula (C) may be prepared from compounds of formula (D) as shown in reaction scheme 3.
Reaction scheme 3
For example, a compound of formula (D) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Compounds of formula (D) are commercially available or can be made by standard methods well
known in the chemical literature.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (E) as shown in reaction scheme 4.
Reaction scheme 4
(E) (I)
For example, a compound of formula (E) in which LG' is a halogen, for example a chlorine atom, may be treated with a sulphonamide RS02NH2 in the presence of a base, for example an inorganic base such as caesium carbonate or sodium hydride, in a suitable solvent such as dioxane. Optionally the reaction may be performed in the presence of a suitable catalyst, for example a metal catalyst such as a palladium dibenzylidene acetone complex, and optionally a ligand, for example a phosphine ligand such as XantPhos.
Compounds of formula (E) may be prepared from compounds of formula (F) and compounds of formula (B) as shown in reaction scheme 5.
Reaction scheme 5
' (B) (E)
For example, a compound of formula (F) in which LG and LG' are halogens, for example chlorine atoms, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
Compounds of formula (F) are commercially available or can be made by standard methods well known in the chemical literature. For example, compounds of formula (F) may be prepared from compounds of formula (G) as shown in reaction scheme 6.
Reaction scheme 6
(G) (F)
For example, a compound of formula (G) may be treated with a halogenating agent, for example /V-bromosuccinimide, in a suitable solvent, for example carbon tetrachloride, optionally in the presence of a reaction initiator, for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
Alternatively, compounds of formula (F) may be prepared from compounds of formula (H) as shown in reaction scheme 7.
Reaction scheme 7
(H) (F)
For example, a compound of formula (H) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (J) as shown in reaction scheme 8.
Reaction scheme 8
For example, a compound of formula (J) may be treated with a carbonylating agent such as triphosgene, in the presence of a base, for example an organic base such as 2-tert-butyl-1 , 1 ,3,3- tetramethylguanidine (Barton's base), in a suitable solvent, for example dichloromethane.
Compounds of formula (J) may be prepared from aldehydes of formula (K) and amines of formula (L) as shown in reaction scheme 9.
Reaction scheme 9
For example, a compound of formula (J) may be formed by the reaction of an aldehyde of formula (K) with an amine of formula (L) in the presence of a reducing agent, for example a hydride reducing agent such as sodium borohydride, in a suitable solvent, for example an alcohol such as ethanol.
Amines of formula (L) are commercially available or can be made by standard methods well known in the chemical literature.
Aldehydes of formula (K) may be prepared from compounds of formula (M), as shown in reaction scheme 10.
Reaction scheme 10
(K)
For example, an aldehyde of formula (M) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Aldehydes of formula (M) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (N) as shown in reaction scheme 11.
Reaction scheme 11
(N)
For example, a compound of formula (N) in which LG is a halogen atom, for example a chlorine atom, may be treated with a base, for example an inorganic base such as sodium hydride, in a suitable solvent, such as dimethylformamide.
Compounds of formula (N) may be made from amines of formula (O) and acylating agents of compound (P), as shown in reaction scheme 12.
Reaction scheme 12
(P)
(N)
For example, an amine of formula (O) may be reacted with an acylating agent of formula (P) in which LG and LG' are halogen atom, for example chlorine atoms, in the presence of a suitable base, for example an organic base such as pyridine, in a suitable solvent, for example dichloromethane. Compounds of formula (P) are commercially available or can be made by standard methods well known in the chemical literature.
Amines of formula (O) may be prepared from nitriles of formula (P) as shown in reaction scheme
13.
Reaction scheme 13
For example, a nitrile of formula (Q) may be treated with a reducing agent, for example a hydride reducing agent such as lithium aluminium hydride, in a suitable solvent, for example tetrahydrofuran.
Nitriles of formula (Q) may be prepared from compounds of formula (R), as shown in reaction scheme 14.
Reaction scheme 14
(R)
(Q)
For example, a nitrile of formula (R) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Compounds of formula (R) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (S) as shown in reaction scheme 15
Reaction scheme 15
(S) (I)
For example, a compound of formula (S) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Compounds of formula (S) may be prepared from compounds of formula (T) as shown in reaction scheme 16.
Reaction scheme 16
For example, a compound of formula (T) may be treated with a reducing agent, for example a dissolving metal such as iron and ammonium chloride, in a suitable solvent, for example a mixture of water and ethanol.
Compounds of formula (T) may be made from compounds of formula (U) and compounds of formula (B), as shown in reaction scheme 17.
Reaction scheme 17
For example, a compound of formula (U) in which LG is a halogen, for example a bromine atom, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride or caesium carbonate, in a suitable solvent, for example dimethylformamide.
Compounds of formula (U) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which R is not H may be prepared from compounds of formula (I) in which R is H as shown in reaction scheme 18.
Reaction scheme 18
For example, a compound of formula (I) in which R is H may be treated with a base, for example an inorganic base such as sodium hydride or an organic base such as triethylamine, and an electrophilic reagent LG-R , in a suitable solvent, for example dichloromethane.
One skilled in the art will realise that it is often possible to alter the order in which the
transformations described above are conducted, or to combine them in alternative ways to prepare a wide range of compounds of formula (I). Multiple steps may also be combined in a single reaction. All such variations are contemplated within the scope of the invention. The skilled man will also be aware that some reagents will be incompatible with certain values or combinations of the substituents R, R , R2, R5, R6, R , R 2, m, n, p, A, W, X and Z as defined herein, and any additional steps, such as protection and/or deprotection steps, which are necessary to achieve the desired transformation will be clear to the skilled man.
The compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. Therefore, the invention also relates to a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) in addition to formulation adjuvants. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo- emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal
origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl- hexanol, ethylene carbonate, 1 ,1 , 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N- methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d).
A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-
active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium
dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.
Further adjuvants that can usually be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralizing or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilizers.
The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of Ci2-Ci8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS- 112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the oil additives can be further improved by combination with surface- active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non- ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone
surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).
If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say, without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US-A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.
The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
Preferred formulations have especially the following compositions (% = percent by weight): Emulsifiable concentrates:
active ingredient: 1 to 95 %, preferably 60 to 90 %
surface-active agent: 1 to 30 %, preferably 5 to 20 %
liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
Formulation Examples for herbicides of formula (I) (% = % by weight)
F1. Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide)
octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide)
NMP - - 10 % 20 % arom. hydrocarbon mixture 85 % 78 % 55 % 16 %
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c) d)
active ingredient 5% 10% 50% 90%
1-methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 %
polyethylene glycol MW 400 20 % 10%
NMP - - 30% 10%
arom. hydrocarbon mixture 75% 60%
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
active ingredient 5% 25% 50% 80%
sodium lignosulfonate 4 % - 3 %
sodium lauryl sulfate 2 % 3 % - 4 %
sodium diisobutylnaphthalene- sulfonate - 6 % 5 % 6 %
octylphenol polyglycol ether - 1 % 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 1 % 3% 5% 10%
kaolin 88% 62% 35%
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated qranules a) b) c)
active ingredient 0.1 % 5% 15%
highly dispersed silicic acid 0.9 % 2 % 2 %
inorganic carrier 99.0 % 93 % 83 %
(diameter 0.1 -1 mm)
e.g. CaC03 or Si02
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
F5. Coated qranules a) b) c)
active ingredient 0.1 % 5 % 15 %
polyethylene glycol MW 200 1.0 % 2 % 3 %
highly dispersed silicic acid 0.9 % 1 % 2 %
inorganic carrier 98.0 % 92 % 80 %
(diameter 0.1 - 1 mm)
e.g. CaC03 or Si02
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder qranules a) b) c) d)
active ingredient 0.1 % 3 % 5 % 15 %
sodium lignosulfonate 1.5 % 2 % 3 % 4 %
carboxymethylcellulose 1.4 % 2 % 2 % 2 %
kaolin 97.0 % 93 % 90 % 79 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c)
active ingredient 0.1 % 1 % 5 %
talcum 39.9 % 49 % 35 %
kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
active ingredient 3 % 10 % 25 % 50 %
ethylene glycol 5 % 5 % 5 % 5 %
nonylphenol polyglycol ether - 1 % 2 % -
(15 mol of ethylene oxide)
sodium lignosulfonate 3 % 3 % 4 % 5 %
carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 %
solution
silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 %
water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension
concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
The invention also provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).
The invention also provides a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).
The invention also provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful crop plants, a compound or a composition of the invention.
The invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I).
The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example: killing, retardation, leaf burn, albinism, dwarfing and the like. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation and includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation with respect to crops of useful plants. "Areas under cultivation" include land on which the crop plants are already growing and land intended for cultivation with such crop plants. The term "weeds" as used herein means any undesired plant, and thus includes not only agronomically important weeds as described below, but also volunteer crop plants.
The compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence application), and are particularly effective when applied pre-emergence.
Crops of useful plants in which the composition according to the invention can be used include, but are not limited to, perennial crops, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf
and vegetables, especially cereals, maize, rice and soy beans.
The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eriochloa, Lolium, Monochoria, Panicum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium, Polygonum, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®, respectively.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and
Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor). Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (I) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein).
The compounds of formula (I) according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different
compounds of formula (I). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I).
When a compound of formula (I) is combined with at least one additional herbicide, the following mixtures of the compound of formula (I) are preferred: compound of formula (I) + acetochlor, compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I) + alachlor, compound of formula (I) + alloxydim, compound of formula (I) + allyl alcohol, compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of formula (I) + amidosulfuron, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + aminopyralid, compound of formula (I) + amitrole, compound of formula (I) + ammonium sulfamate, compound of formula (I) + anilofos, compound of formula (I) + asulam, compound of formula (I) + atrazine, compound of formula (I) + aviglycine, compound of formula (I) + azafenidin, compound of formula (I) + azimsulfuron, compound of formula (I) + BCPC, compound of formula (I) + beflubutamid, compound of formula (I) + benazolin, compound of formula (I) + bencarbazone, compound of formula (I) + benfluralin, compound of formula (I) + benfuresate, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + bensulide, compound of formula (I) + bentazone, compound of formula (I) + benzfendizone, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bicyclopyrone, compound of formula (I) + bifenox, compound of formula (I) + bilanafos, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + borax, compound of formula (I) + bromacil, compound of formula (I) + bromobutide, compound of formula (I) + bromophenoxim, compound of formula (I) + bromoxynil, compound of formula (I) + butachlor, compound of formula (I) + butafenacil, compound of formula (I) + butamifos, compound of formula (I) + butralin, compound of formula (I) + butroxydim, compound of formula (I) + butylate, compound of formula (I) + cacodylic acid, compound of formula (I) + calcium chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carbetamide, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) + chlorflurenol, compound of formula (I) + chlorflurenol-methyl, compound of formula (I) + chloridazon, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + chloroacetic acid, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) + chlorthal, compound of formula (I) + chlorthal-dimethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) + cinmethylin, compound of formula (I) + cinosulfuron, compound of formula (I) + cisanilide, compound of formula (I) + clethodim, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + clopyralid, compound of formula (I) + cloransulam, compound of formula (I) + cloransulam-methyl, compound of formula (I) + CMA, compound of formula (I) + 4-CPB, compound of formula (I) + CPMF, compound of formula (I) + 4-CPP, compound of formula (I) + CPPC, compound of formula (I) + cresol, compound of formula (I) + cumyluron, compound of formula (I) + cyanamide, compound of formula (I) + cyanazine, compound of formula (I) + cycloate, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cycloxydim, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 3,4-DA,
compound of formula (I) + daimuron, compound of formula (I) + dalapon, compound of formula (I) + dazomet, compound of formula (I) + 2,4-DB, compound of formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB, compound of formula (I) + desmedipham, formula (I) + desmetryn, compound of formula (I) + dicamba, compound of formula (I) + dichlobenil, compound of formula (I) + ortho-dichlorobenzene, compound of formula (I) + para-dichlorobenzene, compound of formula (I) + dichlorprop, compound of formula (I) + dichlorprop-P, compound of formula (I) + diclofop, compound of formula (I) + diclofop-m ethyl, compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + diflufenzopyr, compound of formula (I) + dimefuron, compound of formula (I) + dimepiperate, compound of formula (I) + dimethachlor, compound of formula (I) + dimethametryn, compound of formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + dimethipin, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + dinitramine, compound of formula (I) + dinoterb, compound of formula (I) + diphenamid, formula (I) + dipropetryn, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of formula (I) + DNOC, compound of formula (I) + 3,4-DP, compound of formula (I) + DSMA, compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) + EPTC, compound of formula (I) + esprocarb, compound of formula (I) + ethalfluralin, compound of formula (I) + ethametsulfuron, compound of formula (I) + ethametsulfuron-methyl, compound of formula (I) + ethephon, compound of formula (I) + ethofumesate, compound of formula (I) + ethoxyfen, compound of formula (I) + ethoxysulfuron, compound of formula (I) + etobenzanid, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fenoxasulfone, compound of formula (I) + fentrazamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + flamprop- M, compound of formula (I) + flazasulfuron, compound of formula (I) + florasulam, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, formula (I) + fluazolate, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flucetosulfuron, compound of formula (I) + fluchloralin, compound of formula (I) + flufenacet, compound of formula (I) + flufenpyr, compound of formula (I) + flufenpyr-ethyl, compound of formula (I) + flumetralin, compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac, compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumioxazin, compound of formula (I) + flumipropin, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen, compound of formula (I) + f I uoroglycof en-ethyl, formula (I) + fluoxaprop, compound of formula (I) + flupoxam, compound of formula (I) + flupropacil, compound of formula (I) + flupropanate, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + flurenol, compound of formula (I) + fluridone, compound of formula (I) + flurochloridone, compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-methyl, compound of formula (I) + fomesafen, compound of formula (I) + foramsulfuron, compound of formula (I) + fosamine, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + halauxifen, compound of formula (I) + haloauxifen- methyl, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl,
compound of formula (I) + haloxyfop, compound of formula (I) + haloxyfop-P, compound of formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) + imazosulfuron, compound of formula (I) + indanofan, compound of formula (I) and indaziflam, compound of formula (I) + iodomethane, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + iofensulfuron, compound of formula (I) + ioxynil, compound of formula (I) and ipfencarbazone, compound of formula (I) + isoproturon, compound of formula (I) + isouron, compound of formula (I) + isoxaben, compound of formula (I) + isoxachlortole, compound of formula (I) + isoxaflutole, formula (I) + isoxapyrifop, compound of formula (I) + karbutilate, compound of formula (I) + lactofen, compound of formula (I) + lenacil, compound of formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA, compound of formula (I) + MCPA, compound of formula (I) + MCPA-thioethyl, compound of formula (I) + MCPB, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop-P, compound of formula (I) + mefenacet, compound of formula (I) + mefluidide, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) + metamifop, compound of formula (I) + metamitron, compound of formula (I) + metazachlor, compound of formula (I) and metazosulfuron, compound of formula (I) + methabenzthiazuron, compound of formula (I) + methazole, compound of formula (I) + methiozolin, compound of formula (I) + methylarsonic acid, compound of formula (I) + methyldymron, compound of formula (I) + methyl isothiocyanate, compound of formula (I) +
metobenzuron, compound of formula (I) + metobromuron, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metosulam, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + MK-616, compound of formula (I) + molinate, compound of formula (I) + monolinuron, a compound of formula (I) +monosulfuron, compound of formula (I) + monosulfuron-ester, compound of formula (I) + MSMA, compound of formula (I) + naproanilide, compound of formula (I) + napropamide, compound of formula (I) + naptalam, compound of formula (I) + NDA-402989, compound of formula (I) + neburon, compound of formula (I) + nicosulfuron, compound of formula (I) + nipyraclofen, compound of formula (I) + n-methyl glyphosate, compound of formula (I) + nonanoic acid, compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids), compound of formula (I) + orbencarb, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + oxasulfuron, compound of formula (I) + oxaziclomefone, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquat dichloride, compound of formula (I) + pebulate, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pentachlorophenol, compound of formula (I) + pentanochlor, compound of formula (I) + pentoxazone, compound of formula (I) + pethoxamid, compound of formula (I) + petroleum oils, compound of formula (I) + phenmedipham, compound of formula (I) + phenmedipham- ethyl, compound of formula (I) + picloram, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + piperophos, compound of formula (I) + potassium arsenite,
compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor, compound of formula (I) + primisulfuron, compound of formula (I) + primisulfuron-methyl, compound of formula (I) + prodiamine, compound of formula (I) + profluazol, compound of formula (I) + profoxydim, compound of formula (I) + prohexadione-calcium, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propachlor, compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of formula (I) + propazine, compound of formula (I) + propham, compound of formula (I) + propisochlor, compound of formula (I) + propoxycarbazone, compound of formula (I) + propoxycarbazone-sodium, compound of formula (I) + propyzamide, compound of formula (I) + prosulfocarb, compound of formula (I) + prosulfuron, compound of formula (I) + pyraclonil, compound of formula (I) + pyraflufen, compound of formula (I) + pyraflufen-ethyl, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributicarb, compound of formula (I) + pyridafol, compound of formula (I) + pyridate, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + pyrithiobac, compound of formula (I) + pyrithiobac-sodium, compound of formula (I) + pyroxasulfone, compound of formula (I) + pyroxulam, compound of formula (I) + quinclorac, compound of formula (I) + quinmerac, compound of formula (I) + quinoclamine, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-P, compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P-ethyl, compound of formula (I) + rimsulfuron, compound of formula (I) + saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) + siduron, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) + sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium chlorate, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone, compound of formula (I) + sulfometuron, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + sulfosate, compound of formula (I) + sulfosulfuron, compound of formula (I) + sulfuric acid, compound of formula (I) + tar oils, compound of formula (I) + 2,3,6-TBA, compound of formula (I) + TCA, compound of formula (I) + TCA-sodium, compound of formula (I) + tebutam, compound of formula (I) + tebuthiuron, compound of formula (I) + tefuryltrione, compound of formula (I) + tembotrione, compound of formula (I) + tepraloxydim, compound of formula (I) + terbacil, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + thenylchlor, compound of formula (I) + thiazafluron, compound of formula (I) + thiazopyr, compound of formula (I) + thifensulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + thiobencarb, compound of formula (I) + tiocarbazil, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, a compound of formula (I) and triafamone, compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound of formula (I) + triaziflam, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + tricamba, compound of formula (I) + triclopyr, compound of formula (I) + trietazine, compound of formula (I) + trifloxysulfuron, compound of formula (I) +
trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I) + triflusulfuron, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + trifop, compound of formula (I)
+ trifop-methyl, compound of formula (I) + trihydroxytriazine, compound of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione and the compound of formula (I) + VX-573.
In particular, the following mixtures are important:
Mixtures of a compound of the formula (I) with a triazine (e.g. compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + cyanazine, compound of formula (I) + dimethametryn, compound of formula (I) + metribuzin, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propazine, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + trietazine).
Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole, compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of formula (I) + topramezone, compound of formula (I) + bicyclopyrone, compound of formula (I) + benzobicyclon or compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]1 ,3- cyclohexanedione (CAS RN 1342891-70-6)).
Mixtures of a compound of formula (I) with an auxin (e.g. compound of formula (I) + dicamba, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-DB, compound of formula (I) + MCPA, compound of formula (I) + fluroxypyr, compound of formula (I) + picloram, compound of formula (I) + triclopyr, compound of formula (I) + quinclorac, compound of formula (I) + clopyralid, compound of formula (I) + aminopyralid, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + halauxifen, compound of formula (I) + halauxifen-methyl). Mixtures of a compound of formula (I) with a VLCFA inhibitor (e.g. compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + dimethenamid-P, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + metazachlor, compound of formula (I) + napropamide, compound of formula (I) + pretilachlor). Mixtures of a compound of formula (I) with a triazolinone (e.g. compound of formula (I) + amicarbazone).
Mixtures of a compound of formula (I) with an ALS inhibitor (e.g. compound of formula (I) + chlorsulfuron, compound of formula (I) + cinosulfuron, compound of formula (I) + cloransulam, compound of formula (I) + ethametsulfuron, compound of formula (I) + flazasulfuron, compound of formula (I) + foramsulfuron, compound of formula (I) + flumetsulam, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazethapyr, compound of formula (I) + iodosulfuron, compound of
formula (I) + iofensulfuron, compound of formula (I) + metsulfuron, compound of formula (I) + nicosulfuron, compound of formula (I) + oxasulfuron, compound of formula (I) + primisulfuron, compound of formula (I) + prosulfuron, compound of formula (I) + pyrithiobac, compound of formula (I) + pyroxsulam, compound of formula (I) + rimsulfuron, compound of formula (I) + sulfosulfuron, compound of formula (I) +
thifensulfuron, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + trifloxysulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + tritosulfuron, compound of formula (I) + bispyribac-sodium, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) +flucarbazone-sodium, compound of formula (I) +bensulfuron-methyl, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + diclosulam, compound of formula (I) + florasulam, compound of formula (I) + penoxsulam).
Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (I) + fomesafen, compound of formula (I) + flumioxazin, compound of formula (I) + sulfentrazone, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + lactofen, compound of formula (I) + oxyfluorfen, compound of formula (I) + oxadiazon, compound of formula (I) + butafenacil, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoro- methyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester).
Mixtures of a compound of formula (I) with and ACCase inhibitor (i.e. compound of formula (I) + clodinafop, compound of formula (I) + fluazifop, compound of formula (I) + fenoxaprop, compound of formula (I) + clethodim, compound of formula (I) + quizalofop, compound of formula (I) + haloxyfop, compound of formula (I) + pinoxaden, compound of formula (I) + cycloxydim, compound of formula (I) + sethoxydim).
In addition, the following mixtures are also preferred: compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + diquat, compound of formula (I) + pendimethalin, compound of formula (I) + trifluralin, compound of formula (I) + metamitron, compound of formula (I) + clomazone, compound of formula (I) + prodiamine, compound of formula (I) + saflufenacil, compound of formula (I) + prosulfocarb, compound of formula (I) + diflufenican, compound of formula (I) + isoxaben, compound of formula (I) + beflubutamide, compound of formula (I) + flurtamone, compound of formula (I) + benfluralin, compound of formula (I) + chlorotoluron, compound of formula (I) +linuron, compound of formula (I) + isoproturon, compound of formula (I) + triallate, compound of formula (I) + hexazinone, compound of formula (I) + diuron, compound of formula (I) + propanil, compound of formula (I) + indaziflam.
Thus, in particular, the following mixtures are preferred: compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + cyanazine, compound of formula (I) + dimethametryn, compound of formula (I) + metribuzin, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propazine, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + trietazine, compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole,
compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of formula (I) + topramezone, compound of formula (I) + bicyclopyrone, compound of formula (I ) + benzobicyclon compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6), compound of formula (I) + dicamba, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-DB, compound of formula (I) + MCPA, compound of formula (I) + fluroxypyr, compound of formula (I) + picloram, compound of formula (I) + triclopyr, compound of formula (I) + quinclorac, compound of formula (I) + clopyralid, compound of formula (I) + aminopyralid, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + halauxifen, compound of formula (I) + halauxifen-methyl, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + dimethenamid-P, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + metazachlor, compound of formula (I) + napropamide, compound of formula (I) + pretilachlor, compound of formula (I) + amicarbazone, compound of formula (I) + chlorsulfuron, compound of formula (I) + cinosulfuron, compound of formula (I) + cloransulam, compound of formula (I) + ethametsulfuron, compound of formula (I) + flazasulfuron, compound of formula (I) + foramsulfuron, compound of formula (I) + flumetsulam, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazethapyr, compound of formula (I) + iodosulfuron, compound of formula (I) + iofensulfuron, compound of formula (I) + metsulfuron, compound of formula (I) + nicosulfuron, compound of formula (I) + oxasulfuron, compound of formula (I) + primisulfuron, compound of formula (I) + prosulfuron, compound of formula (I) + pyrithiobac, compound of formula (I) + pyroxsulam, compound of formula (I) + rimsulfuron, compound of formula (I) + sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + trifloxysulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + tritosulfuron, compound of formula (I) + bispyribac-sodium, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) +flucarbazone- sodium, compound of formula (I) +bensulfuron-methyl, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + diclosulam, compound of formula (I) + florasulam, compound of formula (I) + penoxsulam, compound of formula (I) + fomesafen, compound of formula (I) + flumioxazin, compound of formula (I) + sulfentrazone, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + lactofen, compound of formula (I) + oxyfluorfen, compound of formula (I) + oxadiazon, compound of formula (I) + butafenacil, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4- dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester, compound of formula (I) + clodinafop, compound of formula (I) + fluazifop, compound of formula (I) + fenoxaprop, compound of formula (I) + clethodim, compound of formula (I) + quizalofop, compound of formula (I) + haloxyfop, compound of formula (I) + pinoxaden, compound of formula (I) + cycloxydim, compound of formula (I) + sethoxydim, compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + diquat, compound of formula (I) + pendimethalin, compound of formula (I) + trifluralin, compound of formula (I) + metamitron, compound of formula (I) + clomazone, compound of formula (I) + prodiamine, compound of formula (I) + saflufenacil, compound of
formula (I) + prosulfocarb, compound of formula (I) + diflufenican, compound of formula (I) + isoxaben, compound of formula (I) + beflubutamide, compound of formula (I) + flurtamone, compound of formula (I) + benfluralin, compound of formula (I) + chlorotoluron, compound of formula (I) +linuron, compound of formula (I) + isoproturon, compound of formula (I) + triallate, compound of formula (I) + hexazinone, compound of formula (I) + diuron, compound of formula (I) + propanil, compound of formula (I) + indaziflam.
The following mixtures are particularly preferred: compound of formula (I) + atrazine, compound of formula (I) + terbuthylazine, compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + nicosulfuron, compound of formula (I) + fomesafen, compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + saflufenacil, compound of formula (I) + prosulfocarb.
For the avoidance of doubt, the present invention also includes three-way mixtures of a compound of formula (I), a herbicide as defined above and a further herbicide. In particular, the following three-way mixtures are preferred: compound of formula (I) + atrazine + mesotrione, compound of formula (I) + atrazine + S-metolachlor, compound of formula (I) + S-metolachlor + mesotrione, compound of formula (I) + glyphosate + mesotrione, compound of formula (I) + glufosinate + mesotrione, compound of formula (I) + atrazine + isoxaflutole, compound of formula (I) + S-metolachlor + isoxaflutole, compound of formula (I) + glyphosate + isoxaflutole, compound of formula (I) + glufosinate + isoxaflutole, compound of formula (I) + glyphosate + fomesafen.
In addition, the present invention also includes four-way mixtures of a compound of formula (I), a herbicide as defined above and two further herbicides. In particular, the following four-way mixtures is preferred: the compound of formula (I) + atrazine + mesotrione + S-metolachlor. The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to acifluorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to dimethenamid-P, the reference to glufosinate-ammonium also applies to glufosinate, the reference to bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam-methyl also applies to cloransulam, the reference to flamprop- M also applies to flamprop, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to
1000: 1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner). The mixtures according to the invention can also be used in combination with further active ingredients, e.g. further herbicides and/or insecticides and/or acaricides and/or nematocides and/or molluscicides and/or fungicides and/or plant growth regulators. Such mixtures, and the use of such
mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I).
The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (I) according to the invention with one or more further active ingredients, in particular with one or more further herbicides, can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds. Where a compound of formula (I) is combined with a safener, the following combinations of the compound of formula (I) and the safener are particularly preferred.
Compound of formula (I) + AD 67 (MON 4660), compound of formula (I) + benoxacor, compound of formula (I) + cloquintocet-mexyl, compound of formula (I) + cyometrinil and a compound of formula (I) + the corresponding (Z) isomer of cyometrinil, compound of formula (I) + cyprosulfamide (CAS RN 221667- 31-8), compound of formula (I) + dichlormid, compound of formula (I) and dicyclonon, compound of formula (I) and dietholate, compound of formula (I) + fenchlorazole-ethyl, compound of formula (I) + fenclorim, compound of formula (I) + flurazole, compound of formula (I) + fluxofenim, compound of formula (I) + furilazole and a compound of formula (I) + the corresponding R isomer or furilazome, compound of formula (I) + isoxad if en-ethyl, compound of formula (I) + mefenpyr-diethyl, compound of formula (I) and mephenate, compound of formula (I) + oxabetrinil, compound of formula (I) + naphthalic anhydride (CAS RN 81-84-5), compound of formula (I) and TI-35, compound of formula (I) + N-isopropyl- 4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and a compound of formula (I) + N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
In particular, the following compound/safener combinations are preferred: compound of formula (I) + cloquintocet-mexyl, compound of formula (I) + cyprosulfamide, compound of formula (I) + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, compound of formula (I) + isoxad if en-ethyl, compound of formula (I) + benoxacor, compound of formula (I) + dichlormid and the compound of formula (I) + fluxofenim .
The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener).
It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence. It is also possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence.
For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference.
Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.
EXAMPLES Example 1 : Synthesis of A -{2-methyl-4-[(2-oxo-1 -piperidyl)-methyl]-pyrazol-3-yl}- methanesulfonamide (Compound 15-55)
Step 1.1 Synthesis of ethyl 5-(methanesulfonamido)-1-methyl-pyrazole-4-carboxylate
Triethylamine (0.49 ml, 3.5 mmol) was added to a stirred solution of ethyl 5-amino-1-methyl-pyrazole-4- carboxylate (0.50 g, 3.0 mmol) in dichloromethane (30 ml) at 0°C. After 5 minutes methanesulfonyl chloride (0.23 ml, 3.0 mmol) was added dropwise. The resulting mixture was allowed to warm to room temperature over 18 hours and then partitioned between 1 M hydrochloric acid and dichloromethane. The phases were separated and the aqueous extracted with further dichloromethane. The combined organic phases were passed through a PhaseSep® cartridge and concentrated under reduced pressure to leave ethyl 5-(methanesulfonamido)-1-methyl-pyrazole-4-carboxylate, which was used without further purification.
Characterising data for the compound are as follows: H NMR (400 MHz, CDCI3) δ 7.97 (s, 1 H), 4.34 (t,
2H), 3.92 (s, 3H), 3.51 (s, 3H) and 1.36 (t, 3H) ppm.
Other compounds made using this general method are listed in Table 2 below.
TABLE 2 Compounds made according to the general method described in Step 1.1.
Step 1.2 Synthesis of A/-[4-(hvdroxymethvn-2-methyl-pyrazol-3-yll-methanesulfonamide
A solution of ethyl 5-(methanesulfonamido)-1 -methyl-pyrazole-4-carboxylate (0.55 g, 2.2 mmol) in tetrahydrofuran (6.7 ml) was added to a stirred suspension of lithium aluminium hydride (1 M solution in tetrahydrofuran; 5.6 ml, 5.6 mmol) at -20°C. The resulting mixture was allowed to warm to room temperature, stirred for 1 hour, then water added. The mixture was adjusted to pH 4 and extracted twice with ether. The aqueous phase was then further acidified to pH 1 and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and concentrated under reduced pressure to provide A/-[4-(hydroxymethyl)-2-methyl-pyrazol-3-yl]-methanesulfonamide (0.121 g, 27%). Characterising data for the compound are as follows: H NMR (400 MHz, d6-DMSO) δ 7.02 (s, 1 H), 4.09 (s, 2 H) and 3.46 (s, 6 H) ppm.
Other compounds made using this general method are listed in Table 3 below.
TABLE 3 Compounds made according to the general method described in Step 1.2.
Step 1.3 Synthesis of A/-{2-methyl-4-[(2-oxo-1-piperidvn-methyll-pyrazol-3-yl)-methanesulfonamide (Compound 15-55)
A mixture of A/-[4-(hydroxymethyl)-2-methyl-pyrazol-3-yl]-methanesulfonamide (0.121 g, 0.590 mmol), 4- methylbenzenesulfonic acid hydrate (0.1 12 g, 0.590 mmol), piperidin-2-one (0.058 g, 0.590 mmol) and toluene (2.95 ml) was heated at 140°C under microwave irradiation for 30 minutes. The mixture was allowed to cool, water and ethyl acetate added and the phases separated. The aqueous phase was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined organic phases were dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to give A/-{2-methyl-4-[(2-oxo-1-piperidyl)-methyl]-pyrazol-3-yl}-methanesulfonamide (43 mg, 25%).
Characterising data for the compound are as follows: 1 H NMR (400 MHz, CDCI3) δ 9.17 (br s, 1 H), 7.36
(s, 1 H), 4.13 (s, 2H), 3.67 (s, 3H), 3.13 (m, 2H), 2.99 (s, 3H), 2.17 (t, 2H) and 1.64 (m, 4H) ppm. compounds made using this general method are listed in Table 4 below.
TABLE 4 Compounds made according to the general method described in Step 1.3.
Characteristic data is melting point (°C) or 1H nmr data (400 MHz, CDCI3 unless otherwise stated) δΗ ppm.
Example 2: Synthesis of A -{4-[(4-methyl-2-oxo-1 -piperidyl)-methyl]-pyrimidin-5-yl}- methanesulfonamide (Compound 60-64) Step 2.1 Synthesis of 5-bromo-4-bromomethylpyrimidine
/V-Bromosuccinimide (5.96 g, 31.8 mmol) and azobisisobutyronitrile (0.50 g, 2.9 mmol) were added to a solution of 5-bromo-4-methyl-pyrimidine (5 g, 29 mmol) in carbon tetrachloride (72 ml). The resulting mixture was heated at reflux for 16 hours, then allowed to cool and filtered. The solid was washed with dichloromethane and the filtrate concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography (gradient elution: 5 - 100% ethyl acetate in /so-hexane) to provide 5- bromo-4-bromomethylpyrimidine (4.22 g, 58%). Characterising data for the compound are as follows: 1 H NMR (400 MHz, CDCI3) δ 9.10 (s, 1 H), 8.84 (s, 1 H) and 4.57 (s, 2H) ppm.
Other compounds made using this general method are listed in Table 5 below.
TABLE 5 Compounds made according to the general method described in Step 2.1.
Name Structure Ή nmr data (400 MHz, CDCI3) δΗ ppm
5-Bromomethyl-4- 8.95 (s, 1 H), 8.77 (s, 1 H), 4.53 (s,
CI
chloropyrimidine 2H)
Step 2.2 Synthesis of 1-[(5-bromopyrimidin-4-yl)-methyll-4-methyl-piperidin-2-one
Characterising data for the compound are as follows: 1 H NMR (400 MHz, CDCI3) δ 9.00 (s, 1 H), 8.71 (s, 1 H), 4.73 (ABq, 2H), 3.49 (m, 1 H), 3.40 (m, 1 H), 2.59 (m, 1 H), 2.1 1 (m, 2H), 1.90 (m, 1 H), 1.60 (m, 1 H) and 1 .09 (d, 3H) ppm.
Other compounds made using this general method are listed in Table 6 below.
TABLE 6 Compounds made according to the general method described in Step 2.2.
Name Structure Ή nmr data (400 MHz, CDCI3) δΗ ppm
4-[(5- 9.05 (s, 1 H), 8.77 (s, 1 H), 4.79 (s,
Br O
Bromopyrimidin- 2H), 4.30 (s, 2H), 4.00 (t, 2H), 3.55
4-yl)-methyl]- (t, 2H)
morpholin-3-one
1- 1(4- 8.90 (s, 1 H), 8.59 (s, 1 H), 4.70
Chloropyrimidin- (ABq, 2H), 3.40 (m, 2H), 2.60 (br d,
5-yl)-methyl]-4- 1 H), 2.04 (m, 3H), 1.56 (m, 1 H), methyl-piperidin- 1.08 (d, 3H)
2- one 0^0k
Step 2.3 Synthesis of /V-{4-[(4-methyl-2-oxo-1-piperidvn-methyll-pyrimidin-5-yl)-meth
(Compound 60-64)
methanesulfonamide (0.184 g, 1 .94 mmol), caesium carbonate (1.72 g, 5.28 mmol), XantPhos (0.157 g, 0.264 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.083 g, 0.088 mmol) and 1 ,4-dioxane (8.8 ml) was at 140°C under microwave irradiation for 2 hours. The reaction mixture was allowed to cool, then dilute hydrochloric acid added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a residue that was purified by silica gel chromatography (gradient elution: 30 - 100% ethyl acetate in /so-hexane) to provide A/-{4-[(4-methyl-2-oxo-1-piperidyl)-methyl]- pyrimidin-5-yl}-methanesulfonamide (280 mg, 53%).
Characterising data for the compound are as follows: melting point 117-121 °C; H NMR (400MHz, CDCI3) 5 = 10.40 (br s, 1 H), 8.96 (s, 1 H), 8.89 (s, 1 H), 4.72 (d, 1 H), 4.58 (d, 1 H), 3.66 (ddd, 1 H), 3.52 (dt, 1 H), 3.15 (s, 3H), 2.61 - 2.50 (m, 1 H), 2.06 - 1.86 (m, 3H), 1.52 - 1.39 (m, 1 H) and 1.01 (d, 3H) ppm.
Other compounds made using this general method are listed in Table 7 below.
TABLE 7 Compounds made according to the general method described in Step 2.3.
Characteristic data is melting point (°C) or 1H nmr data (400 MHz, CDCI3 unless otherwise stated) δΗ ppm.
-
(m, (m,
3.38
Example 3: Synthesis of A -{4-[(4-methyl-2-oxo-1 -piperidyl)-methyl]-pyrimidin-5-yl}-A - methylsulfonyl-propanamide (Compound 60-65)
Sodium hydride (0.032 g, 0.80 mmol) was added to a stirred solution of A/-[4-[(4-methyl-2-oxo-1- piperidyl)-methyl]-pyrimidin-5-yl]-methanesulfonamide (0.08 g, 0.27 mmol) in tetrahydrofuran (2.7 ml) at 0°C. The resulting mixture was stirred for 30 min then propanoyl chloride (0.070 ml, 0.80 mmol) was added. The reaction mixture was allowed to warm to ambient temperature and stirred for 3.5 hours. Water, followed by dilute hydrochloric acid, was added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with aqueous sodium hydroxide and brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (gradient elution: 25 - 100% ethyl acetate in /so-hexane) to provide A/-{4-[(4-methyl-2-oxo-1-piperidyl)-methyl]-pyrimidin-5-yl}-A/-methylsulfonyl-propanamide (77 mg, 81 %).
Characterising data for the compound are as follows: melting point 187-190°C; "Ή NMR (400MHz, CDCI3) 5 = 9.14 (d, 1 H), 8.52 (d, 1 H), 5.17 (dd, 1 H), 3.96 (dd, 1 H), 3.91 - 3.74 (m, 1 H), 3.57 (s, 3H), 3.55 - 3.48 (m, 1 H), 2.64 - 2.43 (m, 2H), 2.19 - 1.91 (m, 4H), 1.73 - 1.52 (m, 1 H), 1.16 (t, 3H), 1.04 (d, 3H) ppm. Example 4: Synthesis of 1,1 ,1 -trifluoro-A -{3-[(2-oxo-1 -piperidyl)-methyl]-2-pyridyl}- methanesulfonamide (Compound 55-59)
Step 4.1 Synthesis of 1 ,1 , 1-trifluoro-A/-[3-(hvdroxymethyl)-2-pyridyll-methanesulfonamide
Triethylamine (4.67 ml, 33.5 mmol) was added to a stirred solution of (2-amino-3-pyridyl)-methanol (3.33 g, 26.8 mmol) in dichloromethane (233 ml) at 0°C. After 5 minutes a solution of trifluoromethanesulfonic anhydride (5.76 ml, 33.5 mmol) in dichloromethane (6.7 ml) was added dropwise. The resulting mixture was stirred for 30 minutes, and then partitioned between water and dichloromethane. The phases were separated and the aqueous extracted with further dichloromethane. The combined organic phases were dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (gradient elution: 5 - 100% ethyl acetate in /so-hexane) to provide 1 , 1 ,1-trifluoro-A/-[3-(hydroxymethyl)-2-pyridyl]-methanesulfonamide (2.37 g, 34%) as an orange solid.
Characterising data for the compound are as follows: H NMR (400 MHz, CDCI3) δ 12.45 (br s, 1 H), 8.01 (d, 1 H), 7.73 (d, 1 H), 7.02 (t, 1 H), 4.70 (s, 2H) and 2.88 (br s, 1 H) ppm.
Step 4.2 Synthesis of A/-[3-(chloromethyl)-2-pyridyll-1 ,1 , 1-trifluoro-methanesulfonamide
Thionyl chloride (0.57 ml, 7.8 mmol) was added to a solution of 1 ,1 , 1-trifluoro-A/-[3-(hydroxymethyl)-2- pyridyl]-methanesulfonamide (1 .00 g, 3.90 mmol) in chloroform (19.5 ml). The resulting mixture was stirred at 50°C for 2 hours, allowed to cool and concentrated under reduced pressure to provide N-[3- (chloromethyl)-2-pyridyl]-1 , 1 ,1-trifluoro-methanesulfonamide (1.07 g, 100%) as a brown oil that was used without further purification.
Characterising data for the compound are as follows: H NMR (400 MHz, CDCI3) δ 12.50 (br s, 1 H), 8.12 (d, 1 H), 7.81 (d, 1 H), 7.04 (t, 1 H) and 4.64 (s, 2H) ppm. Step 4.3 Synthesis of 1 , 1 , 1-trifluoro-A/-{3-[(2-oxo-1-piperidyl)-methyll-2-pyridyl)-methanesulfonamide (Compound 55-59)
Sodium hydride (0.463 g, 11.6 mmol) was added to a stirred solution of piperidin-2-one (0.383 g, 3.86 mmol) in tetrahydrofuran (19 ml) at 0°C under nitrogen. After stirring for 30 minutes a solution of N-[3- (chloromethyl)-2-pyridyl]-1 , 1 ,1-trifluoromethanesulfonamide (1.06 g, 3.86 mmol) in tetrahydrofuran (9.6 ml) was added and the resulting mixture was stirred at ambient temperature for 115 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to give 1 ,1 , 1 -trifluoro-/V-{3-[(2- oxo-1-piperidyl)-methyl]-2-pyridyl}-methanesulfonamide (50 mg, 11 %) as a white solid.
Characterising data for the compound are as follows: 1 H NMR (400MHz, CDCI3) 5 = 12.46 (br s, 1 H), 8.02 (d, 1 H), 7.66-7.58 (m, 1 H), 6.95 (t, 1 H), 4.52 (s, 2H), 3.54 - 3.44 (m, 2H), 2.47-2.36 (m, 2H) and 1.89 - 1.76 (m, 4H) ppm.
Other compounds made using this general method are listed in Table 8 below.
TABLE 8 Compounds made according to the general method described in Step 4.3.
Example 5: Synthesis of 1,1,1 -trifluoro-A -[3-{[6-(2-fluorophenyl)-2-oxo-1,3-oxazinan-3-yl]-methyl}- 2-pyridyl]-methanesulfonamide (Compound 55-536)
Step 5.1 Synthesis of 1 ,1 , 1-trifluoro-A/-(3-formyl-2-pyridyl)-methanesulfonamide
A solution of trifluoromethanesulfonic anhydride (1 .5 ml, 8.9 mmol) in dichloromethane (20 ml) was added dropwise to a stirred solution of 2-aminopyridine-3-carbaldehyde (1.0 g, 8.2 mmol) and diisopropylethyl amine (1 .57 ml, 9.0 mmol) in dichloromethane (50 ml) at 0°C. The resulting mixture was stirred for 2 hours at 0°C, then allowed to warm to ambient temperature and stirred for a further 1 hour. Water was added and the solid removed by filtration. The filtrate was extracted with dichloromethane and the combined organic extracts evaporated under reduced pressure to leave a sticky solid which was triturated with dichloromethane to provide a solid that was removed by filtration. The solids were combined to provide 1 , 1 , 1-trifluoro-A/-(3-formyl-2-pyridyl)-methanesulfonamide (0.87 g, 42%).
Characterising data for the compound are as follows: 1 H NMR (400MHz, d6-DMSO) δ = 10.2 (s, 1 H), 8.49 (d, 1 H), 8.45 (d, 1 H) and 7.39 (t, 1 H) ppm.
Other compounds made using this general method are listed in Table 9 below.
TABLE 9 Compounds made according to the general method described in Step 5.1.
Step 5.2 Synthesis of 1 ,1 , 1 rifluoro-/V-{3-[|[3-(2-fluorophenvn-3-hvdroxy-propyll-amino)-methyll-2- pyridvD-methanesulfonamide
A solution of 3-amino-1-(2-fluorophenyl)-propan-1-ol (prepared as described in Example 6.3; 146 mg, 0.87 mmol) in ethanol (2 ml) was added slowly to a stirred solution of 1 , 1 ,1-trifluoro-A/-(3-formyl-2-pyridyl)- methanesulfonamide (200 mg, 0.79 mmol) in ethanol (3 ml). A few activated molecular sieves were added, the mixture stirred at ambient temperature for 17 hours and then filtered. The filtrate was cooled to 0°C and sodium borohydride (33 mg, 0.87 mmol) added portionwise. The resulting mixture was stirred for 3 hours at ambient temperature, then methanol (3 ml) added and stirring continued for a further hour. Water and ethyl acetate were added, the phases separated and the aqueous extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulphate, filtered and evaporated under reduced pressure to provide 1 ,1 ,1-trifluoro-A/-{3-[{[3-(2-fluorophenyl)-3-hydroxy- propyl]-amino}-methyl]-2-pyridyl}-methanesulfonamide (445 mg) as a brown gum which was used without further purification.
Other compounds made using this general method are listed in Table 10 below.
TABLE 10 Compounds made according to the general method described in Step 5.2.
Name Structure Characteristic Data
1 , 1 , 1-Trifluoro-/V- Used without characterisation
{3-[{[3-(2- fluorophenyl)-3- ¥
hydroxy-propyl]- amino}methyl]-4- pyridyl}- methanesulfona
mide
Step 5.3 Synthesis of 1 , 1 ,1-trifluoro-A/-[3-|[6-(2-fluorophenyl)-2-oxo-1 ,3-oxazinan-3-yll-methyl)-2- pyridyll-methanesulfonamide (Compound 55-536)
2-ieri-Butyl-1 , 1 ,3,3-tetramethylguanidine (0.75 ml, 3.18 mmol), followed by triphosgene (156 mg, 0.53 mmol), was added to a stirred solution of 1 , 1 ,1-trifluoro-A/-{3-[{[3-(2-fluorophenyl)-3-hydroxy-propyl]- amino}-methyl]-2-pyridyl}-methanesulfonamide (215 mg, 0.53 mmol) in dichloromethane (5 ml) at 0°C. The resulting mixture was allowed to warm to ambient temperature, stirred for 17 hours, and then poured into iced dilute hydrochloric acid. The resulting mixture was extracted with dichloromethane and the combined organic extracts dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a brown gum which was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to provide 1 , 1 ,1-trifluoro-A/-[3-{[6-(2- fluorophenyl)-2-oxo-1 ,3-oxazinan-3-yl]-methyl}-2-pyridyl]-methanesulfonamide as a brown solid. Characterising data for the compound are as follows: 1 H NMR (400MHz, d6-DMSO) δ = 13.45 (br s, 1 H), 8.00 (t, 2H), 7.49 (d, 1 H), 7.38 (m, 1 H), 7.19 (m, 3H), 5.67 (m, 1 H), 4.37 (ABq, 2H), 3.58 (m, 1 H), 3.28 (m, 1 H) and 2.19 (m, 2H) ppm.
Other compounds made using this general method are listed in Table 11 below.
TABLE 11 Compounds made according to the general method described in Step 5.3.
Compound Structure Ή nmr data (400 MHz, d6-DMSO)
Number δΗ ppm
53-536 8.20 (m, 2H), 7.59 (d, 1 H), 7.44 (m,
1 H), 7.38 (m, 1 H), 7.20 (m, 2H), 5.60 (t, 1 H), 4.30 (ABq, 2H), 3.60 (m, 1 H), 3.27 (m, 1 H) and 2.16 (m, 2H)
Example 6: Synthesis of starting materials
Example 6.1 Synthesis of 5-chloro-4-(chloromethvn-1-methyl-3-(trifluoromethvn-pyrazole
Thionyl chloride (1.0 ml, 14.0 mmol) was added dropwise to a solution of [5-chloro-1-methyl-3- (trifluoromethyl)-pyrazol-4-yl]-methanol (2.50 g, 11.7 mmol) in dichloromethane (58 ml). The resulting mixture was stirred at room temperature for 30 minutes, then concentrated under reduced pressure to provide 5-chloro-4-(chloromethyl)-1-methyl-3-(trifluoromethyl)-pyrazole (2.66 g, 98%).
Characterising data for the compound are as follows: H NMR (400MHz, CDCI3) δ = 4.53 (s, 2H) and 3.90 (s, 3H) ppm.
Example 6.2 Synthesis of ethyl 4-(trifluoromethylsulfonylamino)-thiazole-5-carboxylate
A mixture of ethyl 4-chlorothiazole-5-carboxylate (0.5 g, 2.6 mmol), trifluoromethanesulfonamide (0.43 g 2.9 mmol), caesium carbonate (2.6 g, 7.8 mmol), XantPhos (0.23 g, 0.39 mmol),
tris(dibenzylideneacetone)dipalladium(0) (0.12 g, 0.13 mmol) and 1 ,4-dioxane (13 ml) was heated at 140°C under microwave irradiation for 1 hour. The reaction mixture was allowed to cool, dilute hydrochloric acid added and the mixture extracted with ethyl acetate. The combined organic extracts
were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a residue that was purified by silica gel chromatography to provide ethyl 4- (trifluoromethylsulfonylamino)-thiazole-5-carboxylate (270 mg, 34%).
Characterising data for the compound are as follows: H NMR (400MHz, CDCI3) δ = 9.34 (br s, 1 H), 8.84 (s, 1 H), 4.41 (q, 2H) and 1.39 (t, 3H) ppm.
Example 6.3 Synthesis of 3-amino-1-(2-fluorophenyl)-propan-1-ol
A solution of 3-(2-fluorophenyl)-3-oxo-propanenitrile (5.5 g, 36.8 mmol) in tetrahydrofuran (120 ml) was added dropwise to a stirred solution of lithium aluminium hydride (1 M in tetrahydrofuran; 135 ml, 135 mmol) in tetrahydrofuran (120 ml) at 0°C. The reaction mixture was then allowed to warm to ambient temperature and stirred for 20 hours. It was cooled to 0°C, further lithium aluminium hydride (1 M in tetrahydrofuran; 40 ml, 40 mmol) added and the mixture allowed to warm to ambient temperature and stirred for 4 hours. Water (6.8 ml) was added, the resulting mixture stirred for 30 minutes, then sodium hydroxide (15% aqueous solution; 13.8 ml) and water (20.4 ml) added and stirring continued for a further 30 minutes. The mixture was filtered and the filtrate extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate, filtered and evaporated under reduced pressure to provide 3-amino-1-(2-fluorophenyl)-propan-1-ol (4.19 g, 73%) as a brown gum that was used without further purification.
Characterising data for the compound are as follows: H NMR (400MHz, CDCI3) δ = 7.49 (t, 1 H), 7.22 (m, 1 H), 7.16 (t, 1 H), 7.07 (dd, 1 H), 4.92 (t, 1 H), 2.63 (t, 2H) and 1 .62 (q, 2H) ppm.
Example 6.4 Synthesis of 1-[(3-chloro-4-pyridyl)-methyll-4-methyl-piperidin-2-one
A mixture of (3-chloro-4-pyridyl)-methanol (0.97 g, 6.8 mmol), 4-methylpiperidin-2-one (1.5 g, 14 mmol), 4-methylbenzenesulfonic acid hydrate (1.3 g, 6.8 mmol) and chlorobenzene (38 ml) were heated at reflux using a Dean Stark trap for 17 hours, then allowed to cool and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge
column, ammonium acetate buffer) to provide 1-[(3-chloro-4-pyridyl)-methyl]-4-methyl-piperidin-2-one (0.33 g, 20%) as a brown oil.
Characterising data for the compound are as follows: H NMR (400MHz, CDCI3) δ = 8.69 (s, 1 H), 8.53 (d, 1 H), 7.34 (d, 1 H), 4.77 (ABq, 2H), 3.46 - 3.27 (m, 2H), 2.71 - 2.62 (m, 1 H), 2.21 - 1.92 (m, 3H), 1.65-1.51 (m, 1 H), 1 .09 (d, 3H) ppm.
Example 7: Pre-emergence biological efficacy
Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE) and Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for one day under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 500 or 1000 g/ha of test compound.
The test plants were then grown under controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 12.
TABLE 12 Percentage damage caused to weed species by compounds of the invention when applied pre-emergence.
Species
Rate
Cpd No
(g/ha)
ZEAMX SETFA ALOMY ECHCG LOLPE SOLNI AMARE IPOHE ABUTH
9-59 1 ,000 80 70 90 60 60 70
15-55 1 ,000 0 30 10 20 30 10
15-64 1 ,000 0 0 0 0 0 0
16-68 1 ,000 0 0 0 0 0 0
24-64 1 ,000 0 0 0 0 0 0
37-68 1 ,000 0 0 0 0 0 0
53-536 500 0 0 0 0 0 0
54-68 900 20 70 20 50 60 20
55-59 1 ,000 80 50 90 40 40 20
55-536 1 ,000 50 20 20 30 0 0
59-64 1 ,000 0 0 0 0 0 0
60-64 1 ,000 0 0 0 0 0 0
60-65* 1 ,000 10 20 10 10 30 40
60-68 1 ,000 60 70 90 60 80 60
60-676 1 ,000 0 0 0 0 0 0
60-680 1 ,000 0 50 30 40 60 30
61-64 1 ,000 0 0 0 0 0 0
61-68 1 ,000 0 20 10 0 0 10
* Test evaluated 9 days after treatment
Example 8: Post-emergence biological efficacy
Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE) and Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for 8 days under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 500 or 1000 g/ha of test compound.
The test plants were then grown on under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 13.
TABLE 13 Percentage damage caused to weed species by compounds of the invention when applied post-emergence
Species
Rate
Cpd No
(g/ha)
ZEAMX SETFA ALOMY ECHCG LOLPE SOLNI AMARE IPOHE ABUTH
9-59 1 ,000 70 70 80 70 50 80
15-55 1 ,000 0 0 0 0 0 0
15-64 1 ,000 0 0 0 0 0 0
16-68 1 ,000 20 0 0 0 0 20
24-64 1 ,000 0 0 0 0 0 0
37-68 1,000 20 0 0 0 0 10
53-536 500 0 0 10 10 0 20
54-68 900 20 50 50 30 10 40
55-59 1,000 70 40 70 40 20 80
55-536 1,000 10 10 40 50 0 50
59-64 1,000 20 10 0 10 10 10
60-65* 1,000 10 0 0 0 10 10
60-64 1,000 40 10 0 0 0 40
60-68 1,000 40 60 80 30 30 70
60-676 1,000 20 0 0 0 0 0
60-680 1,000 30 40 40 40 60 60
61-64 1,000 0 0 0 0 0 0
61-68 1,000 10 20 10 0 0 20
* Test evaluated 9 days after treatment
Claims
1 . A herbicidal compound of formula (I):
wherein:
A is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3, or 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not
R is H, Ci-4alkyl, C3.5alkenyl, propargyl,
d. 4haloalkoxyCi-2alkyl,
cyanoCi_2alkyl, d.
4alkoxycarbonylCi-2alkyl,
arylCi_2alkyl optionally substituted by 1 -3 groups R20, heteroarylCi_2alkyl optionally substituted by 1 -3 groups R20, arylthioCi_2alkyl optionally substituted by 1 -3 groups R20, arylCi-2alkoxyCi-2alkyl optionally substituted by 1 -3 groups R20, arylCi.2alkylthioCi-2alkyl optionally substituted by 1 -3 groups R20, arylcarbonylCi_2alkyl optionally substituted by 1 -3 groups R20, rylcarbonyloxyCi_2alkyl optionally substituted by 1 -3 groups R20,
aryloxycarbonyloxyCi_2alkyl optionally substituted by 1 -3 groups R20, Ci_8alkylcarbonyl, C2-5alkenylcarbonyl, Ci_
4haloalkylcarbonyl, Ci-4alkoxyCi-2alkylcarbonyl, C3.6cycloalkylcarbonyl, Ci.4alkoxycarbonylCi_ 2alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R20, aryloxyd-2alkylcarbonyl optionally substituted by 1-3 groups R20, Ci_i0alkoxycarbonyl, Ci_4haloalkoxycarbonyl, C3.
5alkenyloxycarbonyl, propargyloxycarbonyl, Ci.4alkoxyCi.2alkoxycarbonyl, Ci_4alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, Ci.4alkylaminocarbonyl, di(Ci.4alkyl)aminocarbonyl, Ci_6alkylsulphonyl, Ci_6haloalkylsulphonyl or arylsulphonyl optionally substituted by 1-3 groups R20, and each R20 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_ 2alkoxyCi_2alkoxy, hydroxy, phenyl or phenoxy;
R2 is halogen, nitrile, C1_4alkyl, C-|.4haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4alkynyl, Ci_4alkoxy, Ci_ 4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, Ci_4alkylcarbonyl, Ci_4alkylsulphonyl, or phenyl or two R2 groups together form -OCH20- or -OCH2CH20-;
R3 and R4 are, independently, H, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxycarbonyl, or aryl optionally substituted by 1-3 groups R23 or R3 and R4 together form a C2.5alkylene chain or an oxo group or R3 together with one of R5, R8 or R forms a bond or R3 and R8 together form a C2.5alkylene chain and each R23 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_
2alkoxyCi_2alkoxy, hydroxy, phenyl or phenoxy;
R5 and R6 are, independently, H, Ci_5alkyl, Ci_4haloalkyl, C3.6cycloalkyl optionally substituted with 1- 3 groups selected from halogen, d_4alkyl or phenyl, Ci_4alkoxyCi_4alkyl, d- 4alkoxycarbonylaminoCi_4alkyl, Ci_4alkylcarbonyloxyCi_2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R2 , aryloxyCi_2alkyl optionally substituted by 1-3 groups R2 , arylCi_2alkoxyCi_2alkyl optionally substituted by 1-3 groups R2 , C2.4alkenyl, hydroxy, Ci_4alkoxy, Ci_4alkylthio, d- 4alkylcarbonyloxy, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1- 3 groups R2 or R5 and R6 together form an oxo group or a C2.6alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen or d- 2alkyl or R5 together with together with one of R3, R8 or R forms a bond or R5 and R together form a C2-salkylene chain and each R2 is, independently, halogen, cyano, d_4alkyl, d_4haloalkyl, Ci_4alkoxy, Ci.4haloalkoxy, Ci.2alkoxyCi.2alkoxy, hydroxy, phenyl or phenoxy or two R2 groups together form OCH20 or OCH2CH20;
R8 and R9 are, independently, H, halogen, cyano, d_4alkyl, d_4haloalkyl, d-salkenyl, d-salkynyl, Ci_4alkoxy, d_4alkylthio, Ci_4alkoxycarbonyl, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1-3 groups R24 or arylthio optionally substituted by 1-3 groups R24 or R8 and R9 together form a d-salkylene chain or an oxo group or R8 together with one of R3 or R5 forms a bond or R8 and R3 together form a d-salkylene chain and each R24 is, independently, halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci.4alkoxy, d_4haloalkoxy, Ci.2alkoxyCi.2alkoxy, hydroxy, phenyl or phenoxy;
R 0 is H, d_4alkyl, d-salkenyl, aryl optionally substituted by 1-3 groups R22, arylCi_2alkyl optionally substituted by 1-3 groups R22, heteroaryl optionally substituted by 1-3 groups R22, d_4alkylcarbonyl,
Ci-4alkoxycarbonyl, Ci_4haloalkoxycarbonyl, Ci-4alkoxyCi-2alkoxycarbonyl, C3.5alkenyloxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R22, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R22, aminocarbonyl, Ci.4alkylanriinocarbonyl, di(Ci.4alkyl)aminocarbonyl, Ci_6alkylsulphonyl or d-6haloalkylsulphonyl and each R22 is, independently, halogen, nitro, cyano, Ci-4alkyl, Ci_4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci-2alkoxyCi-2alkoxy, hydroxy, Ci_4alkylthio, Ci_
4haloalkylthio, Ci_4alkylsulphonyl, Ci_4alkoxycarbonyl, phenyl or phenoxy;
R and R 2 are, independently, H, halogen, hydroxy, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, carboxy, Ci_4alkoxycarbonyl or R and R 2 together form an oxo group or R together with one of R3 or R5 forms a bond or R and R5 together form a C2-5alkylene chain.
2. The compound of claim 1 , wherein A is a 5-membered heteroaromatic ring containing 1 to 4
heteroatoms selected from oxygen, sulphur and nitrogen.
3. The compound of claim 2, wherein A is a pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3-oxadiazole, 1 ,2,5-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,5-thiadiazole or tetrazole ring. 4. The compound of claim 3, wherein A is a thiophene, pyrazole, thiazole, 1 ,2,
4-triazole or tetrazole ring.
5. The compound of claim 1 , wherein A is a 6-membered heteroaromatic ring containing 1 to 3
nitrogen atoms.
6. The compound of claim 5, wherein A is a pyridine, pyridazine, pyrimidine, pyrazine, 1 ,2,3-triazine or 1 ,2,4-triazine ring.
7. The compound of claim 6, wherein A is a pyridazine, pyrimidine or pyrazine ring.
8. The compound of any one of the preceding claims, wherein W is oxygen.
9. The compound of any one of the preceding claims, wherein X is oxygen or CR3R4.
10. The compound of any one of the preceding claims, wherein Z is oxygen, CR8R9 or NR 0;
11. The compound of any one of the preceding claims, wherein m is 0 or 1.
12. The compound of claim 11 , wherein m is 0.
13. The compound of any one of the preceding claims, wherein n is 0, 1 or 2 and p is 0, 1 or 2 with the proviso that 1 < n + p < 2.
14. The compound of any one of the preceding claims, wherein R is Ci-C6 alkyl.
The compound of any one of claims 1 to 13, wherein R is Ci_4haloalkyl.
16. The compound of claim 15, wherein R is trifluoromethyl.
17. The compound of any one of the preceding claims, wherein R is H, Ci.4alkoxyCi.2alkyl, d.
4alkoxyCi-2alkoxyCi-2alkyl, Ci-4haloalkoxyCi-2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R20, arylCi.2alkoxyCi-2alkyl optionally substituted by 1-3 groups R
arylcarbonyloxyCi-2alkyl optionally substituted by 1-3 groups R20,
Ci_8alkylcarbonyl, Ci_4haloalkylcarbonyl,
Ci_i0alkoxycarbonyl, Ci_ 4haloalkoxycarbonyl,
aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R20, Ci_6alkylsulphonyl or Ci-6haloalkylsulphonyl, and each R20 is, independently, halogen, C1_4alkyl, C-|.4haloalkyl, d-4alkoxy or Ci-4haloalkoxy
18. The compound of claim 17, wherein R is H, Ci_5alkylcarbonyl, Ci_4haloalkylcarbonyl, Ci_
5alkoxycarbonyl, Ci_4haloalkoxycarbonyl or Ci_4haloalkylsulphonyl.
19. The compound of claim 18, wherein R is H, Ci_5alkylcarbonyl or Ci_5alkoxycarbonyl.
20. The compound of any one of the preceding claims, wherein R2 is halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or Ci_4alkylsulphonyl.
21. The compound of claim 20, wherein R2 is halogen or methyl.
22. The compound of any one of the preceding claims,wherein R3 and R4 are, independently, H,
halogen or C1_4alkyl.
23. The compound of claim 22, wherein R3 and R4 are, independently, H or methyl.
24. The compound of any one of the preceding claims, wherein R5 and R6 are, independently, H, d.
5alkyl, Ci_4haloalkyl, C3.6cycloalkyl, Ci_4alkoxyCi_4alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R2 , C2-4alkenyl, Ci_4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1-3 groups R2 or R5 and R6 together form a C2-5alkylene chain optionally containing an oxygen atom, and each R2 is, independently, halogen, cyano, C1_4alkyl, Ci-4haloalkyl, Ci_4alkoxy or Ci_4haloalkoxy.
25. The compound of claim 24, wherein R5 and R6 are, independently, H, d_4alkyl, C-|.3haloalkyl, cyclopropyl, Ci_3alkoxy, Ci_3alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 , heteroaryl optionally substituted by 1-3 groups R2 or R5 and R6 together form a C3.5alkylene chain, and each R2 is, independently, halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy or Ci_4haloalkoxy.
26. The compound of claim 25, wherein R5 and R6 are, independently, H, Ci_3alkyl, trifluoromethyl, cyclopropyl, Ci_3alkoxy, aryl optionally substituted by 1-2 groups R2 or R5 and R6 together form a C3.5alkylene chain, and each R2 is, independently, halogen, methyl or methoxy.
27. The compound of any one of the preceding claims, wherein R8 and R9 are, independently, H, halogen, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1-3 groups R24 or arylthio optionally substituted by 1-3 groups
R24 and each R24 is, independently, halogen, cyano, C-^alkyl, Ci_4haloalkyl, Ci_4alkoxy or Ci_
4haloalkoxy.
28. The compound of claim 27,wherein R8 and R9 are, independently, H, halogen, C1_4alkyl, C-|.
4haloalkyl, Ci_4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-2 groups R24, and each R24 is, independently, halogen, methyl or methoxy.
29. The compound of claim 28, wherein R8 and R9 are, independently, H, halogen, d-3alkyl, Ci_3alkoxy or Ci-3alkylthio.
30. The compound of any one of the preceding claims, wherein R 0 is H, C1_4alkyl, aryl optionally
substituted by 1-3 groups R22, heteroaryl optionally substituted by 1-3 groups R22, Ci_4alkylcarbonyl, Ci-4alkoxycarbonyl, Ci_4alkylsulphonyl or Ci_4haloalkylsulphonyl and each R22 is, independently, halogen, cyano, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy or Ci_4alkylsulphonyl.
31. The compound of claim 30, wherein R 0 is H, Ci_3alkyl or aryl optionally substituted by 1-3 groups R22, and each R22 is, independently, halogen, methyl or methoxy.
32. The compound of any one of the preceding claims, wherein R and R 2 are, independently, H, hydroxy, C1_4alkyl, C-|.4alkoxy, carboxy, Ci_4alkoxycarbonyl or R and R 2 together form an oxo group.
33. The compound of claim 32, wherein R and R 2 are each H.
34. A herbicidal composition comprising a compound of formula (I) as defined in any one of claims 1 to
33 together with at least one agriculturally acceptable adjuvant or diluent.
35. A composition according to claim 34 which comprises a further herbicide in addition to the
compound of formula (I).
36. A composition according to claim 34 or 35 which comprises a safener.
37. Use of a compound of formula (I) as defined in any one of claims 1 to 33 or a composition as
defined in any one of claims 34 to 36 as a herbicide.
38. A method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) as defined in any one of claims 1 to 33 or a composition as claimed in any one of claims
34 to 36.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB1312492.0A GB201312492D0 (en) | 2013-07-12 | 2013-07-12 | Herbicidal compounds |
| GB1312492.0 | 2013-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015004282A1 true WO2015004282A1 (en) | 2015-01-15 |
Family
ID=49081179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/064983 Ceased WO2015004282A1 (en) | 2013-07-12 | 2014-07-11 | Sulfonamide-heterocyclic herbicidal compounds |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB201312492D0 (en) |
| WO (1) | WO2015004282A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016207082A1 (en) * | 2015-06-23 | 2016-12-29 | Syngenta Participations Ag | Herbicidal haloalkylsulphonamide compounds |
| WO2016207081A1 (en) | 2015-06-23 | 2016-12-29 | Syngenta Participations Ag | Imine derivatives as herbicidal compounds |
| WO2017213252A1 (en) | 2016-06-10 | 2017-12-14 | Sumitomo Chemical Company, Limited | Oxadiazole compound and use as pesticide |
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| WO2020022350A1 (en) | 2018-07-24 | 2020-01-30 | 北興化学工業株式会社 | Isoxazolin-5-one derivative, and herbicide containing same as active ingredient |
| WO2023210623A1 (en) | 2022-04-28 | 2023-11-02 | 株式会社エス・ディー・エス バイオテック | Haloalkyl sulfone anilide compound and herbicide containing same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016207082A1 (en) * | 2015-06-23 | 2016-12-29 | Syngenta Participations Ag | Herbicidal haloalkylsulphonamide compounds |
| WO2016207081A1 (en) | 2015-06-23 | 2016-12-29 | Syngenta Participations Ag | Imine derivatives as herbicidal compounds |
| WO2017213252A1 (en) | 2016-06-10 | 2017-12-14 | Sumitomo Chemical Company, Limited | Oxadiazole compound and use as pesticide |
| WO2018135649A1 (en) | 2017-01-20 | 2018-07-26 | 北興化学工業株式会社 | Isoxazolin-5-one derivative and herbicide containing same as active ingredient |
| US11109593B2 (en) | 2017-01-20 | 2021-09-07 | Hokko Chemical Industry Co., Ltd. | Isoxazolin-5-one derivative and herbicide containing same as active ingredient |
| WO2020022350A1 (en) | 2018-07-24 | 2020-01-30 | 北興化学工業株式会社 | Isoxazolin-5-one derivative, and herbicide containing same as active ingredient |
| EP3828176A4 (en) * | 2018-07-24 | 2021-12-01 | Hokko Chemical Industry Co., Ltd. | ISOXAZOLIN-5-ONE DERIVATIVE, AND HERBICIDE CONTAINING IT AS ACTIVE SUBSTANCE |
| WO2023210623A1 (en) | 2022-04-28 | 2023-11-02 | 株式会社エス・ディー・エス バイオテック | Haloalkyl sulfone anilide compound and herbicide containing same |
| KR20250004702A (en) | 2022-04-28 | 2025-01-08 | 가부시키가이샤 에스디에스 바이오텍크 | Haloalkylsulfonanilide compounds and herbicides containing them |
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| Publication number | Publication date |
|---|---|
| GB201312492D0 (en) | 2013-08-28 |
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