[(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives and salts thereof, crop protection compositions comprising them, methods for producing them and use thereof as safeners
The present invention relates to useful plant-protecting compounds and compositions comprising specific compounds as safeners for reduction of phytotoxic effects of agrochemicals, especially of herbicides. More particularly, the invention relates to particular [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives of the general formula (I) and salts thereof, to processes for preparation thereof and to their use as useful plant-protecting compounds (safeners).
1 . A compound of formula (I) or salt thereof
in which
R 1 and R 2 are independently 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 or (C 1 -C 6 )alkyIS(O) p , where the latter seven radicals are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, (C 1 -C 6 )alkoxy and (C 1 -C 6 )alkylS(O) p ,
R 3 is hydrogen or (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, or
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 form a 3- to 8-membered heterocycle which, in addition to the nitrogen atom, 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 form 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 and m are independently a number from 0 to 5,
and
p is 0, 1 or 2,
excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate (CAS [931426-67-4]).
2 . The compound of formula (I) as claimed in claim 1 or salt thereof, in which
R 1 and R 2 are independently 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 or (C 1 -C 4 )alkylS(O) p , where the latter seven radicals are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, (C 1 -C 4 )alkoxy and (C 1 -C 4 )alkylS(O) p ,
R 3 is hydrogen or (C 1 -C 4 )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, or (C 1 -C 18 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 18 )alkyl,
n and m are independently a number from 0 to 4,
and
p is 0, 1 or 2, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.
3 . The compound of formula (I) as claimed in claim 1 or salt thereof, in which
R 1 and R 2 are independently hydrogen, halogen, cyano, methyl, CF 3 , CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 or SCF 3 ,
R 3 is hydrogen, CH 2 CH 3 or CH 3 ,
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, or (C 1 -C 18 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 18 )alkyl,
n and m are independently a number 0, 1, 2 or 3,
excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.
4 . The compound of formula (I) as claimed in claim 1 or salt thereof,
in which
R 1 and R 2 are independently hydrogen, fluorine, chlorine, bromine, iodine, CN, methyl, CF 3 , CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 or SCF 3 ,
R 3 is hydrogen or 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 or (C 1 -C 10 )alkoxycarbonyl-(C 3 -C 9 )cycloalkyl-(C 1 -C 10 )alkyl,
n and m are independently a number 0, 1, 2 or 3,
excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.
5 . The compound of formula (I) as claimed in claim 1 or salt thereof,
in which
R 1 and R 2 are independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, CF 3 , CH 2 F, CHF 2 , OCH 3 , OCF 3 , SCH 3 or SCF 3 ,
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-OMe-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, methylacetate-2-yl, ethylacetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylat-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,
n and m are independently a number 0, 1, 2 or 3,
excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.
6 . The compound of formula (I) as claimed in claim 1 or salt thereof, in which
(R 1 ) n -phenyl is one of groups Q-1.1 to Q-1.53
Q-1.1
Q-1.2
Q-1.3
Q-1.4
Q-1.5
Q-1.6
Q-1.7
Q-1.8
Q-1.9
Q-1.10
Q-1.11
Q-1.12
Q-1.13
Q-1.14
Q-1.15
Q-1.16
Q-1.17
Q-1.18
Q-1.19
Q-1.20
Q-1.21
Q-1.22
Q-1.23
Q-1.24
Q-1.25
Q-1.26
Q-1.27
Q-1.28
Q-1.29
Q-1.30
Q-1.31
Q-1.32
Q-1.33
Q-1.34
Q-1.35
Q-1.36
Q-1.37
Q-1.38
Q-1.39
Q-1.40
Q-1.41
Q-1.42
Q-1.43
Q-1.44
Q-1.45
Q-1.46
Q-1.47
Q-1.48
Q-1.49
Q-1.50
Q-1.51
Q-1.52
Q-1.53
(R 2 ) m -phenyl is one of groups Q-2.1 to Q-2.53
Q-2.1
Q-2.2
Q-2.3
Q-2.4
Q-2.5
Q-2.6
Q-2.7
Q-2.8
Q-2.9
Q-2.10
Q-2.11
Q-2.12
Q-2.13
Q-2.14
Q-2.15
Q-2.16
Q-2.17
Q-2.18
Q-2.19
Q-2.20
Q-2.21
Q-2.22
Q-2.23
Q-2.24
Q-2.25
Q-2.26
Q-2.27
Q-2.28
Q-2.29
Q-2.30
Q-2.31
Q-2.32
Q-2.33
Q-2.34
Q-2.35
Q-2.36
Q-2.37
Q-2.38
Q-2.39
Q-2.40
Q-2.41
Q-2.42
Q-2.43
Q-2.44
Q-2.45
Q-2.46
Q-2.47
Q-2.48
Q-2.49
Q-2.50
Q-2.51
Q-2.52
Q-2.53
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-OMe-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, methylacetate-2-yl, ethylacetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylat-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,
excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.
7 . A plant- or crop plant-protecting composition, comprising a content of at least one compound of formula (I) or salt thereof as claimed in claim 1 in combination with one or more further agrochemicals and optionally one or more formulation auxiliaries.
8 . The composition as claimed in claim 7 , further comprising at least one herbicide.
9 . A method of reducing phytotoxic effects of one or more pesticides on one or more plants or crop plants comprising using one or more compounds of claim 1 or a composition thereof.
10 . A method of reducing phytotoxic effects of one or more pesticides on one or more plants or crop plants, comprising employing one or more compounds of formula (I) as claimed in claim 1 for joint use with one or more pesticides deployed simultaneously or in any sequence with the one or more pesticides.
11 . The method as claimed in claim 10 , wherein the pesticides are one or more herbicides.
12 . The method as claimed in of claim 10 , wherein the one or more compounds of formula (I) or salts thereof are applied to one or more plants, one or more parts of the plants, and/or seeds or seed material thereof.