Pyridinylcarboxylic acid derivatives as fungicides
Pyridinylcarboxylic acid derivatives of the formula (I) in which the symbols A, X, Y 1 , Y 2 , Y 3 , L 1 , L 2 , R G , and R 1 are each as defined in the description, and also salts, metal complexes and N-oxides of the compounds of the formula (I), and the use thereof for controlling phytopathogenic harmful fungi and processes for preparing compounds of the formula (I).
1. A compound of formula (I), a salt, or an N-oxide thereof,
in which
A is
pyrazol-1-yl, pyrazol-3-yl, or pyrazol-4-yl, which optionally, contain up to two substituents, where the substituents are the same or different and are each independently
substituents on carbon:
fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl, chlorofluoromethyl, dichloromethyl, dichlorofluoromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, cyclopropyl, ethoxy, 1-methylethoxy, propoxy, methoxy, trifluoromethoxy, difluoromethoxy, 1-methylethylthio, methylthio, ethylthio, propylthio, difluoromethylthio, trifluoromethylthio or phenyl,
substituents on nitrogen:
methyl, ethyl, propyl, 1-methylethyl, 2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2-chloro-2-difluoroethyl or 2-chloro-2-fluoroethyl,
L 1 is (C(R L1 ) 2 ) p ,
p is 0, 1, 2 or 3,
R L1 are the same or different and are each independently hydrogen, halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy, C 3 -C 6 -cycloalkyl, C 1 -C 4 -haloalkyl or phenyl,
with the proviso that L 1 optionally contains not more than two R L1 other than hydrogen,
L 2 is NR L21 or C(R L22 ) 2 ,
R L21 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -haloalkynyl, C 2 -C 4 -alkoxyalkyl, C 2 -C 4 -alkylthioalkyl, C 2 -C 4 -alkylsulphinylalkyl, C 2 -C 4 -alkylsulphonylalkyl, C 2 -C 4 -alkylcarbonyl, C 2 -C 4 -haloalkylcarbonyl, C 2 -C 5 -alkoxycarbonyl, C 3 -C 5 -alkoxycarbonylalkyl, C 2 -C 5 -alkylaminocarbonyl, C 3 -C 5 -dialkylaminocarbonyl, C 1 -C 4 -alkylsulphonyl or C 1 -C 4 -haloalkylsulphonyl,
R L22 are the same or different and are each independently hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, cyclopropyl, or halogen,
or the two R L22 radicals, together with the carbon atom to which they are bonded, form a cyclopropyl ring,
Y 1 and Y 3 are the same or different and are each independently sulphur or oxygen,
Y 2 is sulphur or oxygen,
X is nitrogen,
R G is hydrogen, halogen or C 1 -C 3 -alkyl,
and
R 1 is hydrogen, 1,1-dimethylethyl, 3,3-dimethylbutyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl, pentyl, 1-ethylpropyl, butyl, 2-methylpropyl, 1-methylethyl, ethyl, propyl, 4-methylpentyl, hexyl, trifluoromethyl, methoxymethyl, ethoxymethyl, ethenyl, prop-2-en-1-yl or but-3-en-1-yl, or
R 1 is cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, each of which optionally contains up to two substituents, where the substituents are each independently
cyano, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl, ethenyl, 2-propenyl, 2-propynyloxy, phenyl, methoxy, ethoxy, propyloxy, trifluoromethoxy, ethynyl, methylthio, ethylthio or trifluoromethylthio, or
R 1 is cyclopentenyl, cyclohexenyl or cycloheptenyl, each of which optionally contains up to two substituents, where the substituents are each independently methyl, ethyl, methoxy, ethoxy, trifluoromethoxy, ethynyl, 2-propynyloxy, methylthio, ethylthio or trifluoromethylthio, or
R 1 is phenyl which optionally contains up to three substituents, where the substituents are each independently
fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, 1,2-dimethylethyl, ethenyl, ethynyl, trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, cyclopropyl, methoxy, ethoxy, propoxy, 1-methylethoxy, 1,1-dimethylethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, 1,1-dimethylethoxycarbonyl, 2-propynyloxy, methylthio, ethylthio, methylsulphinyl or methylsulphonyl or -L 3 Q, or
R 1 is naphthalen-1-yl naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl, 1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl, 5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl, dihydro-1H-inden-1-yl, 1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl, 1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl, indan-3-yl, indan-4-yl or indan-5-yl, which optionally contain up to three substituents, where the substituents are each independently methyl, methoxy, cyano, fluorine, chlorine, bromine, or iodine, or
R 1 is furan-2-yl, furan-3-yl, thiophen-2-yl, thiophen-3-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol 5-yl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl or pyrazin-2-yl, each of which optionally contains up to two substituents, where the substituents are each independently
substituents on carbon:
chlorine, fluorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, 1-methylethy, butyl, 1,1-dimethylethyl, ethenyl, ethynyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclopentyl, cyclohexyl, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methoxy, ethoxy, propoxy, 1-methylethoxy, 2-propynyloxy, trifluoromethoxy, methylcarbonyloxy, methylcarbonylthio, methylthio, ethylthio, trifluoromethylthio, methylsulphinyl, ethylsulphinyl, trifluoromethylsulphinyl, methylsulphonyl, ethylsulphonyl or trifluoromethylsulphonyl,
substituents on nitrogen: methyl, ethyl, propyl, cyclopropyl, cyclohexyl, phenyl or 2-propynyl, or
R 1 is indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl, 1,3-benzoxazol-7-yl, quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, Quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl; isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl or isoquinolin-8-yl, each of which optionally contains up to two substituents, where the substituents are each independently
substituents on carbon: fluorine, chlorine, bromine, iodine, methyl, methoxy, 2-propynyloxy, or 2-propenyloxy,
substituents on nitrogen: methyl, ethyl, propyl, cyclopropyl, cyclohexyl, phenyl or 2-propynyl, or
R 1 is piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, morpholin-1-yl, morpholin-2-yl, morpholin-3-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1,2,3,4-tetrahydroquinolin-1-yl, 1,2,3,4-tetrahydroisoquinolin-2-yl, 1,2,3,4-tetrahydroquinoxalin-1-yl, indolin-1-yl, isoindolin-2-yl, decahydroquinolin-1-yl or decahydroisoquinolin-2-yl, each of which optionally contains up to two substituents, where the substituents are each independently
substituents on carbon: fluorine, chlorine, bromine, iodine, methyl, methoxy, 2-propynyloxy, or 2-propenyloxy,
substituents on nitrogen: methyl, ethyl, propyl, cyclopropyl, cyclohexyl, phenyl or 2-propynyl,
L 3 is a direct bond, —O, —C(═O), —S(O) m , —CHR L31 or —NR L32 ,
m is 0, 1 or 2,
R L31 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl,
R L32 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 8 -cycloalkyl, C 2 -C 6 -alkylcarbonyl, C 2 -C 6 -haloalkylcarbonyl, C 2 -C 6 -alkoxycarbonyl or C 2 -C 6 -haloalkoxycarbonyl,
Q is a phenyl.
2. The compound of the formula (I) according to claim 1 , in which
L 2 is CH 2
Y 1 is oxygen,
and
R G is hydrogen.
3. A method for controlling phytopathogenic harmful fungi, comprising applying at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , to the phytopathogenic harmful fungi, their habitat, or a combination thereof.
4. A composition, comprising at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , and an extender, a surfactant, or a combination thereof.
5. A method of controlling phytopathogenic harmful fungi, comprising applying the composition according to claim 4 , to the phytopathogenic harmful fungi, their habitat, or a combination thereof.
6. A process for making a composition, comprising mixing at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , with an extender, a surfactant, or a combination thereof.
7. A method of treating a seed for controlling phytopathogenic harmful fungi, comprising applying at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , to the seed.
8. A method of treating a transgenic plant for controlling phytopathogenic harmful fungi, comprising applying at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , to the transgenic plant.
9. A method of treating a transgenic seed for controlling phytopathogenic harmful fungi, comprising applying at least one compound of formula (I), a salt, or an N-oxide thereof, according to claim 1 or 2 , to the transgenic seed.
10. The compound of the formula (I) according to claim 1 , in which A is 3,5-bis-(difluoromethyl)-1H-pyrazol-1-yl.
11. The compound of the formula (I) according to claim 1 , in which Y 2 is oxygen.
12. The compound of the formula (I) according to claim 1 , in which Y 2 is sulphur.
13. The compound of the formula (I) according to claim 1 , in which
R 1 is hydrogen, 1,1-dimethylethyl, 3,3-dimethylbutyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl, pentyl, 1-ethylpropyl, butyl, 2-methylpropyl, 1-methylethyl, ethyl, propyl, 4-methylpentyl, hexyl, trifluoromethyl, methoxymethyl, ethoxymethyl, ethenyl, prop-2-en-1-yl or but-3-en-1-yl, or
R 1 is cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, each of which optionally contains up to two substituents, where the substituents are each independently cyano, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl, ethenyl, 2-propenyl, 2-propynyloxy, phenyl, methoxy, ethoxy, propyloxy, trifluoromethoxy, ethynyl, methylthio, ethylthio or trifluoromethylthio, or
R 1 is cyclopentenyl, cyclohexenyl or cycloheptenyl, each of which optionally contains up to two substituents, where the substituents are each independently methyl, ethyl, methoxy, ethoxy, trifluoromethoxy, ethynyl, 2-propynyloxy, methylthio, ethylthio or trifluoromethylthio, or
R 1 is phenyl which optionally contains up to three substituents, where the substituents are each independently
fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, 1,2-dimethylethyl, ethenyl, ethynyl, trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, cyclopropyl, methoxy, ethoxy, propoxy, 1-methylethoxy, 1,1-dimethylethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, 1,1-dimethylethoxycarbonyl, 2-propynyloxy, methylthio, ethylthio, methylsulphinyl or methylsulphonyl or -L 3 Q, or
R 1 is naphthalen-1-yl, naphthalen-2-yl, 1,2,3,4-tetrahydronaphthalen-1-yl, 1,2,3,4-tetrahydronaphthalen-2-yl, 5,6,7,8-tetrahydronaphthalen-1-yl, 5,6,7,8-tetrahydronaphthalen-2-yl, decalin-1-yl, decalin-2-yl, dihydro-1H-inden-1-yl, 1H-inden-1-yl, 1H-inden-2-yl, 1H-inden-3-yl, 1H-inden-4-yl, 1H-inden-5-yl, 1H-inden-6-yl, 1H-inden-7-yl, indan-1-yl, indan-2-yl, indan-3-yl, indan-4-yl or indan-5-yl, which optionally contain up to three substituents, where the substituents are each independently methyl, methoxy, cyano, fluorine, chlorine, bromine, or iodine,
L 3 is a direct bond, —O, —C(═O), —S(O) m , —CHR L31 or —NR L32 ,
m is 0, 1 or 2,
R L31 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl,
R L32 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 8 -cycloalkyl, C 2 -C 6 -alkylcarbonyl, C 2 -C 6 -haloalkylcarbonyl, C 2 -C 6 -alkoxycarbonyl or C 2 -C 6 -haloalkoxycarbonyl,
and
Q is a phenyl.