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US-12617760-B2 - [(5-phenyl-1-heteroaryl-1H-triazol-3-yl)oxy] acetic acid derivatives as safeners for the protection of useful plants and crop plants

US12617760B2US 12617760 B2US12617760 B2US 12617760B2US-12617760-B2

Abstract

The present invention relates to crop protection compounds and to compositions which comprise specific compounds as safeners for reducing phytotoxic effects of agrochemicals, especially herbicides. The invention relates more particularly to certain [5-(phenyl)-1-(heteroaryl)-1H-1,2,4-triazol-3-yl)oxy] acetic acid derivatives of the general formula (I) and their salts, to processes for preparing them and to their use as plant protection compounds (safeners).

Inventors

  • Thomas Müller
  • Anna Maria REINGRUBER
  • Jens Frackenpohl
  • Hendrik Helmke
  • Jan Dittgen

Assignees

  • BAYER AKTIENGESELLSCHAFT

Dates

Publication Date
20260505
Application Date
20211102
Priority Date
20201105

Claims (16)

  1. 1 . A compound of general formula (I) or salt thereof in which R 1 is selected from 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 )alkylS(O) p , wherein (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 are optionally 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 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 or (C 1 -C 6 )alkylS(O) p , wherein (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 are optionally 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 selected from 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 , wherein each of the R a , R b , R c and R d radicals is independently selected from 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 ring heteroatoms from the group of N, O and S, but not in the case of a 3- or 4-membered heterocycle, 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. 2 . The compound of the general formula (I) as claimed in claim 1 or salt thereof, in which R 1 is selected from 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 , wherein (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 )alkyl-S(O) p are optionally 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 2 is heteroaryl, where the heteroaryl radical is an 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 6 )alkoxy and (C 1 -C 4 )alkylS(O) p , wherein (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 are optionally 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 selected from 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. 3 . The compound of the general formula (I) as claimed in claim 1 or salt thereof, in which R 1 is selected from 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 or SCF 3 , R 3 is hydrogen, CH 2 CH 3 , or CH 3 , R 4 is selected from 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, or (C 1 -C 12 )alkoxycarbonyl-(C 3 -C 12 )cycloalkyl-(C 1 -C 12 )alkyl, and n is 0, 1, 2 or 3.
  4. 4 . The compound of the general formula (I) as claimed in claim 1 or salt thereof, in which R 1 is selected from 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-5-yl, 4H-1,2,4-triazol-3-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, or 1,2,3-thiadiazol-3-yl, which is an 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 or SCF 3 , R 3 is hydrogen or CH 3 , R 4 is selected from 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, and n is 0, 1, 2 or 3.
  5. 5 . The compound of the general formula (I) as claimed in claim 1 or salt thereof, in which R 1 is selected from 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-2.60 R 3 is hydrogen, R 4 is selected from 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-methyl-propanoate-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-methylcyclopropane-carboxylat-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-dichloro-cyclopropyl)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-di-chloro-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, I-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl and 1-ethyl-5-methyl-1H-pyrazole-4-methyl, n is 0, 1, 2 or 3.
  6. 6 . The compound of the general formula (I) as claimed in 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-2.60 R 3 is hydrogen, and R 4 is selected from 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-methyl-propanoate-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-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, cyclopropyl-methyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichlorocyclo-propyl)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, I-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl and 1-ethyl-5-methyl-1H-pyrazole-4-methyl.
  7. 7 . The compound of the general formula (I) as claimed in 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-2.60 R 3 is hydrogen, and R 4 is selected from 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-methyl-propanoate-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-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, cyclo-propylmethyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichloro-cyclopropyl)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, I-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl and 1-ethyl-5-methyl-1H-pyrazole-4-methyl.
  8. 8 . A plant-protecting composition, comprising: at least one compound of the general formula (I) or salts thereof as claimed in claim 1 ; and at least one agrochemical.
  9. 9 . The composition as claimed in claim 8 , comprising at least one herbicide.
  10. 10 . A method of reducing phytotoxic effects of pesticides on plants, the method comprising applying one or more compounds of claim 1 or of the composition as claimed in claim 8 to at least one plant or a habitat thereof.
  11. 11 . A method of reducing phytotoxic effects of pesticides on plants, the method comprising: applying one or more compounds of the general formula (I) as claimed in claim 1 to at least one plant or a habitat thereof; and deploying at least one pesticide simultaneously or sequentially to the at least one plant or habitat thereof.
  12. 12 . The method as claimed in claim 11 , wherein the pesticides are one or more herbicides.
  13. 13 . The method as claimed in claim 11 , characterized in that compounds of the formula (I) or salts thereof as claimed in claim 1 are applied to the plants, parts of the plants, or seeds or seed material thereof.
  14. 14 . The composition as claimed in claim 8 , further comprising at least one formulation auxiliary.
  15. 15 . The method of claim 10 , further comprising use of at least one herbicide.
  16. 16 . The method of claim 13 , further comprising use of at least one herbicide.

Description

The present application is a 35 U.S.C. § 371 national phase entry of International Application No. PCT/EP2021/080352, filed on Nov. 2, 2021, which claims priority to European Patent Application No. 20206041.4, filed Nov. 5, 2020, the contents of each of which are hereby incorporated by reference in their entirety. 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 [(5-phenyl-1-(heteroaryl)-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives and salts thereof as safeners and to processes for preparation thereof. In the control of unwanted organisms in horticultural and sivicultural useful plant crops with pesticides, the useful plants are frequently also damaged to a greater or lesser degree by the pesticides used, such as herbicides, insecticides, fungicides inter alia. This unwanted phytotoxic side effect occurs to a particular degree when numerous herbicides are used—primarily in post-emergence application—in useful plant crops, for example maize, rice or cereal. The use of “safeners” or “antidotes” can in some cases protect the useful plants against the phytotoxic properties of the pesticides without reducing or significantly impairing the pesticidal action with respect to the harmful organisms. In some cases, in the presence of safeners, improved pesticidal action against harmful organisms such as weeds has even been observed. The compounds that have become known to date as safeners are among a large number of different chemical structure classes, the suitability of which for use as safeners generally also depends on the chemical structures of the pesticides and on the useful plant crops. Safener effects of compounds from the group of the derivatives of phenoxy- or heteroaryloxyalkanecarboxylic acids have long been known if these compounds are employed in combination with herbicides. Examples of such compounds are MCPA and similar compounds, which at the same time are still herbicidally active against harmful plants, or cloquintocet-mexyl. Also known are safeners from the group of the derivatives of N-phenyl-substituted heteroarylcarboxylic esters with multiple heteroatoms in the heteroaromatic system. Examples of such safeners are the mefenpyr-diethyl and isoxadifen-ethyl safeners that are used in commercial products. WO 2004/084631 discloses the use of hydroxy-substituted aromatic carboxylic acid derivatives. WO 2005/015994 describes specific derivatives of salicylic acid as safeners. These are particularly suitable for use as safener in maize and soya crops. In addition, WO 2005/112630 discloses 1,2-dihydroquinoxalin-2-one derivatives, and WO 2008/131860 discloses pyridonecarboxamides as safeners. Active ingredients from the chemical class of the [(5-phenyl-1-(heteroaryl)-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives with plant-active properties are not known from the literature. Various documents describe [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives having medical properties. Polish J. Chem. 2006, 80, 889-897 and Bioorganic & Medicinal Chemistry 2018, 26, 3321-3344 disclose [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy] acetic acid derivatives. When safeners are used for protection of crop plants from damage by pesticides, it has been found that the known safeners can have disadvantages in many cases. These include: the useful plant-protecting properties are inadequate,in combination with a particular herbicide, the spectrum of useful plants in which the safener/herbicide are to be used is insufficiently large,a particular safener is combinable with only a few herbicides,the use of safeners increases the application rate to be applied and amount of formulation auxiliaries, and can thus cause application-related problems. For the reasons mentioned, there is an increased need for the provision of alternative compounds having safener action. The invention provides novel useful plant-protecting compounds of the general formula (I) or salts thereof for reduction of phytotoxic effects of pesticides, especially of herbicides, on useful plants or crop plants, in whichR1 is hydrogen, halogen, cyano, nitro, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C8)cycloalkyl, (C3-C8)cycloalkenyl, (C1-C6)alkoxy and (C1-C6)alkylS(O)p, where the latter seven radicals are unsubstituted or are substituted by one or more radicals from the group of halogen, cyano, (C1-C6)alkoxy and (C1-C6)alkylS(O)p,R2 is heteroaryl, where the heteroaryl radical is an unsubstituted or substituted by halogen, cyano, nitro, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C8)cycloalkyl, (C3-C8)cycloalkenyl, (C1-C6)alkoxy and (C1-C6)alkylS(O)p, where the latter seven radicals are unsubstituted or are substituted by one already more radicals from the group of halogen, cyano, (C1-C6)alkoxy and (C1-C6)alkylS(O)p,R3 is h