[(5-phenyl-1-heteroaryl-1H-pyrazol-3-yl)oxy] acetic acid derivatives as safeners for the protection of useful plants and crop plants

1 . A compound of general formula (I) or salt thereof

in which

R 1 is hydrogen, halogen, cyano, nitro, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 3 -C 8 )cycloalkyl, (C 3 -C 8 )cycloalkenyl, (C 1 -C 6 )alkoxy and (C 1 -C 6 )alkylS(O) p , where the latter seven radicals are unsubstituted or are substituted by one or more radicals from the group of halogen, cyano, (C 1 -C 6 )alkoxy and (C 1 -C 6 )alkylS(O) p ,

R 2 is heteroaryl, where the heteroaryl radical is unsubstituted or substituted by halogen, cyano, nitro, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 3 -C 8 )cycloalkyl, (C 3 -C 8 )cycloalkenyl, (C 1 -C 6 )alkoxy and (C 1 -C 6 )alkylS(O) p , where the latter seven radicals are unsubstituted or are substituted by one or more radicals from the group of halogen, cyano, (C 1 -C 6 )alkoxy and (C 1 -C 6 )alkylS(O) p ,

R 3 is hydrogen and (C 1 -C 6 )alkyl,

R 4 is hydrogen, (C 1 -C 18 )alkyl, (C 1 -C 18 )haloalkyl, (C 1 -C 18 )cyanoalkyl, (C 2 -C 18 )alkenyl, (C 2 -C 18 )alkynyl, (C 3 -C 12 )cycloalkyl, (C 3 -C 12 )cycloalkenyl, aryl, heteroaryl, (C 1 -C 18 )alkoxy-(C 1 -C 18 )alkyl, (C 1 -C 18 )haloalkoxy-(C 1 -C 18 )alkyl, (C 1 -C 18 )alkoxy-(C 1 -C 18 )haloalkyl, (C 1 -C 18 )alkylthio-(C 1 -C 18 )alkyl, (C 1 -C 18 )haloalkylthio-(C 1 -C 18 )alkyl, (C 2 -C 18 )haloalkenyl, (C 2 -C 18 )haloalkynyl, heterocyclyl-(C 1 -C 18 )alkyl, aryl-(C 1 -C 18 )alkyl, (C 3 -C 12 )cycloalkyl-(C 1 -C 18 )alkyl, (C 1 -C 18 )alkoxycarbonyl-(C 1 -C 18 )alkyl, and (C 1 -C 18 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 18 )alkyl,

a radical of the formula —NR a R b or —N═CR c R d ,

where, in the former 2 radicals, each of the R a , R b , R c and R d radicals is independently hydrogen, (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, benzyl, substituted benzyl, phenyl or substituted phenyl

or R a and R b together with the nitrogen atom may form a 3- to 8-membered heterocycle which may contain one or two further ring heteroatoms from the group of N, O and S and which is unsubstituted or substituted by one or more radicals from the group of (C 1 -C 4 )-alkyl and (C 1 -C 4 )-haloalkyl,

or R c and R d together with the carbon atom are a 3- to 8-membered carbocyclic or heterocyclic radical which may contain 1 to 3 ring heteroatoms from the group of N, O and S, where the carbocyclic or heterocyclic radical is unsubstituted or substituted by one or more radicals from the group of (C 1 -C 4 )-alkyl and (C 1 -C 4 )-haloalkyl,

n is a number from 0 to 5,

and

p is 0, 1 or 2.

2 . The compound of the general formula (I) of claim 1 or salt thereof,

in which

R 1 is hydrogen, halogen, cyano, nitro, (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, (C 3 -C 6 )cycloalkyl, (C 3 -C 6 )cycloalkenyl, (C 1 -C 4 )alkoxy and (C 1 -C 4 )alkylS(O) p , where the latter seven radicals are unsubstituted or are substituted by one or more radicals from the group of halogen, cyano, (C 1 -C 4 )alkoxy and (C 1 -C 4 )alkylS(O) p ,

R 2 is heteroaryl, where the heteroaryl radical is unsubstituted or substituted by halogen, cyano, nitro, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 4 )alkynyl, (C 3 -C 6 )cycloalkyl, (C 3 -C 6 )cycloalkenyl, (C 1 -C 4 )alkoxy and (C 1 -C 4 )alkylS(O) p , where the latter seven radicals are unsubstituted or are substituted by one or more radicals from the group of halogen, cyano, (C 1 -C 4 )alkoxy and (C 1 -C 4 )alkylS(O) p ,

R 3 is hydrogen and (C 1 -C 4 )alkyl,

R 4 is hydrogen, (C 1 -C 16 )alkyl, (C 1 -C 16 )haloalkyl, (C 1 -C 16 )cyanoalkyl, (C 2 -C 16 )alkenyl, (C 2 -C 16 )alkynyl, (C 3 -C 12 )cycloalkyl, (C 3 -C 12 )cycloalkenyl, aryl, heteroaryl, (C 1 -C 16 )alkoxy-(C 1 -C 16 )alkyl, (C 1 -C 16 )haloalkoxy-(C 1 -C 16 )alkyl, (C 1 -C 16 )alkoxy-(C 1 -C 16 )haloalkyl, (C 1 -C 16 )alkylthio-(C 1 -C 16 )alkyl, (C 1 -C 16 )haloalkylthio-(C 1 -C 16 )alkyl, (C 2 -C 16 )haloalkenyl, (C 2 -C 16 )haloalkynyl, heterocyclyl-(C 1 -C 16 )alkyl, aryl-(C 1 -C 16 )alkyl, (C 3 -C 12 )cycloalkyl-(C 1 -C 16 )alkyl, (C 1 -C 16 )alkoxycarbonyl-(C 1 -C 16 )alkyl, and (C 1 -C 16 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 16 )alkyl,

n is a number from 0 to 4,

and

p is 0, 1 or 2.

3 . The compound of the general formula (I) of claim 1 or salt thereof,

in which

R 1 is hydrogen, halogen, cyano, methyl, ethyl, CF 3 , CF 2 Cl, CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 , SOCH 3 , SO 2 CH 3 and SCF 3 ,

R 2 is heteroaryl, where the heteroaryl radical is unsubstituted or mono- or polysubstituted by halogen, cyano, methyl, ethyl, CF 3 , CF 2 Cl, CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 , SOCH 3 , SO 2 CH 3 and SCF 3 ,

R 3 is hydrogen, CH 2 CH 3 and CH 3 ,

R 4 is hydrogen, (C 1 -C 12 )alkyl, (C 1 -C 12 )haloalkyl, (C 1 -C 12 )cyanoalkyl, (C 2 -C 12 )alkenyl, (C 2 -C 12 )alkynyl, (C 3 -C 12 )cycloalkyl, (C 3 -C 12 )cycloalkenyl, aryl, heteroaryl, (C 1 -C 12 )alkoxy-(C 1 -C 12 )alkyl, (C 1 -C 12 )haloalkoxy-(C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxy-(C 1 -C 12 )haloalkyl, (C 1 -C 12 )alkylthio-(C 1 -C 12 )alkyl, (C 1 -C 12 )haloalkylthio-(C 1 -C 12 )alkyl, (C 2 -C 12 )haloalkenyl, (C 2 -C 12 )haloalkynyl, heterocyclyl-(C 1 -C 12 )alkyl, aryl-(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl-(C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxycarbonyl-(C 1 -C 12 )alkyl, and (C 1 -C 12 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 12 )alkyl,

n is 0, 1, 2 or 3,

and

p is 0, 1 or 2.

4 . The compound of the general formula (I) of claim 1 or salt thereof,

in which

R 1 is hydrogen, fluorine, chlorine, bromine, iodine, CN, methyl, ethyl, CF 3 , CF 2 Cl, CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 , SOCH 3 , SO 2 CH 3 and SCF 3 ,

R 2 is pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrazin-2-yl, pyrazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-3-yl, pyridazin-4-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,2,3-triazin-4-yl, 1,2,3-triazin-5-yl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,3-oxazol-2-yl, 1,3-oxazol-4-yl, 1,3-oxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1,3-thiazol-2-yl, 1,3-thiazol-4-yl, 1,3-thiazol-5-yl, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1H-pyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, 1H-imidazol-1-yl; 1H-imidazol-2-yl; 1H-imidazol-4-yl; 1H-imidazol-5-yl; 1H-pyrazol-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1H-pyrazol-5-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H-1,2,3-triazol-2-yl, 2H-1,2,3-triazol-4-yl, 1H-1,2,4-triazol-1-yl, 1H-1,2,4-triazol-3-yl, 4H-1,2,4-triazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-thiadiazol-5-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,5-thiadiazol-3-yl, 1,2,5-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, which is unsubstituted or mono- or polysubstituted by halogen, cyano, methyl, CF 3 , CF 2 Cl, CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 , SOCH 3 , SO 2 CH 3 and SCF 3 ,

R 3 is hydrogen and CH 3 ,

R 4 is hydrogen, (C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkyl, (C 1 -C 10 )cyanoalkyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, (C 3 -C 9 )cycloalkyl, (C 3 -C 9 )cycloalkenyl, aryl, heteroaryl, (C 1 -C 10 )alkoxy-(C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkoxy-(C 1 -C 10 )alkyl, (C 1 -C 10 )alkoxy-(C 1 -C 10 )haloalkyl, (C 1 -C 10 )alkylthio-(C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkylthio-(C 1 -C 10 )alkyl, (C 2 -C 18 )haloalkenyl, (C 2 -C 18 )haloalkynyl, heterocyclyl-(C 1 -C 10 )alkyl, aryl-(C 1 -C 10 )alkyl, (C 3 -C 9 )cycloalkyl-(C 1 -C 10 )alkyl, (C 1 -C 10 )alkoxycarbonyl-(C 1 -C 10 )alkyl and (C 1 -C 10 )alkoxycarbonyl-(C 3 -C 9 )cycloalkyl-(C 1 -C 10 )alkyl,

n is 0, 1, 2 or 3,

and

p is 0, 1 or 2.

5 . The compound of the general formula (I) of claim 1 or salt thereof,

in which

R 1 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, CF 3 , CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 , SOCH 3 , SO 2 CH 3 and SCF 3 ,

R 2 is selected from the group consisting of Q-2.1 to Q-2.61

R 3 is hydrogen,

R 4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl, CH 2 (4-Cl-Ph), CH 2 (4-F-Ph), CH 2 (4-MeO-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl, ethylacetate-2-yl, methylpivalate-2-yl, ethylpivalate-3-yl, methyl-2-methylpropanoate-3-yl, methyl-2,2-dimethylpropanoate-3-yl, ethyl-2-methylpropanoate-3-yl, methyl-2-propanoate-2-yl, ethyl-2-propanoate-2-yl, methylacet-2-yl, ethylacet-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylate-2-yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichlorocyclopropyl)methyl, (2,2-dimethylcyclopropyl)methyl, allyl, propargyl (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloro-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chlorobut-2-yn-1-yl, 3-methylbut-2-en-1-yl, 3-methylbut-1-en-1-yl, 1-(2E)-1-methylbut-2-en-1-yl, (E)-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl,

And

n is a number from 0, 1, 2 or 3.

6 . The compound of the general formula (I) of claim 1 or salt thereof,

in which

(R 1 ) n -phenyl is selected from the group consisting of Q-1.1 to Q-1.53

and

R 2 is selected from the group consisting of Q-2.1 to Q-2.61

R 3 is hydrogen,

and

R 4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl, CH 2 (4-Cl-Ph), CH 2 (4-F-Ph), CH 2 (4-MeO-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl, ethylacetate-2-yl, methylpivalate-2-yl, ethylpivalate-3-yl, methyl-2-methylpropanoate-3-yl, methyl-2,2-dimethylpropanoate-3-yl, ethyl-2-methylpropanoate-3-yl, methyl-2-propanoate-2-yl, ethyl-2-propanoate-2-yl, methylacet-2-yl, ethylacet-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylate-2-yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichlorocyclopropyl)methyl, (2,2-dimethylcyclopropyl)methyl, allyl, propargyl (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloro-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chlorobut-2-yn-1-yl, 3-methylbut-2-en-1-yl, 3-methylbut-1-en-1-yl, 1-(2E)-1-methylbut-2-en-1-yl, (E)-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl.

7 . A plant-protecting composition, comprising:

at least one compound of the general formula (I) or salts thereof of claim 1 ; and

at least one argrochemical.

8 . The composition of claim 7 , further comprising at least one herbicide.

9 . A method of reducing phytotoxic effects of pesticides on plants, the method comprising applying to the plants, parts of the plants, the seeds, or the seed material thereof one or more compounds of claim 1 or of the composition of claim 7 .

10 . A method of reducing phytotoxic effects of pesticides on plants, the method comprising applying to the plants, parts of the plants, the seeds, or the seed material thereof one or more compounds of the general formula (I) of claim 1 wherein the pesticides are deployed simultaneously or sequentially.

11 . The method of claim 10 , wherein the pesticides are one or more herbicides.

12 . The composition of claim 7 , further comprising at least one formulation auxiliary.

13 . The method of claim 9 , further comprising at least one herbicide.

14 . The method of claim 10 , further comprising at least one herbicide.