Pyrazoylcarboxanilides as fungicides
View Patent ↗The present invention relates to novel pyrazolylcarboxanilides of the formula (I) in which R 1 , R 2 , G, R 3 and n are as defined in the disclosure, to a plurality of processes for preparing these substances and their use for controlling undesirable microorganisms and to novel intermediates and their preparation.
1. A pyrazolylcarboxanilide of formula (I)
in which
R 1 represents hydrogen, cyano, halogen, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl having 1 to 5 halogen atoms, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy having 1 to 5 halogen atoms, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio having 1 to 5 halogen atoms, or aminocarbonyl-C 1 -C 4 -alkyl,
R 2 represents hydrogen, C 1 -C 4 -alkyl, C 1 -C 6 -haloalkyl having 1 to 5 halogen atoms, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkylthio-C 1 -C 4 -alkyl having 1 to 5 halogen atoms, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl having 1 to 5 halogen atoms,
G represents halogen, C 1 -C 4 -alkyl, or C 5 -C 6 -alkyl,
R 3 represents unsubstituted C 5 -C 12 -alkyl; represents C 1 -C 20 -alkyl that is mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl; or represents C 2 -C 20 -alkenyl or C 2 -C 20 -alkynyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 1 -C 4 -alkyl, and
n represents 0, 1, or 2.
2. A pyrazolylcarboxanilide according to claim 1 in which
G represents halogen or C 1 -C 4 -alkyl, and
R 1 , R 2 , R 3 , and n are as defined in claim 1 .
3. A pyrazolylcarboxanilide according to claim 1 in which
R 1 represents hydrogen, cyano, halogen, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl having 1 to 5 fluorine, chlorine, and/or bromine atoms, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy having 1 to 5 fluorine, chlorine, and/or bromine atoms, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio having 1 to 5 fluorine, chlorine, and/or bromine atoms, or aminocarbonyl-C 1 -C 4 -alkyl,
R 2 represents hydrogen, C 1 -C 4 -alkyl, C 1 -C 6 -haloalkyl having 1 to 5 fluorine, chlorine, and/or bromine atoms, C 2 -C 6 -alkenyl, C 3 -C 6 cycloalkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkylthio-C 1 -C 4 -alkyl having 1 to 5 fluorine, chlorine, and/or bromine atoms, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl having 1 to 5 fluorine, chlorine, and/or bromine atoms,
G represents halogen, C 1 -C 4 -alkyl, or C 5 -C 6 -alkyl,
R 3 represents unsubstituted C 5 -C 12 -alkyl; represents C 2 -C 12 -alkyl that is mono- to tetrasubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, and C 3 -C 6 -cycloalkyl; or represents C 2 -C 12 -alkenyl or C 2 -C 12 -alkynyl, each of which is optionally mono- to tetrasubstituted by identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally mono- to tetrasubstituted by identical or different substituents selected from the group consisting of halogen and C 1 -C 4 -alkyl, and
n represents 0, 1, or 2.
4. A pyrazolylcarboxanilide according to claim 3 in which
G represents halogen or C 1 -C 4 -alkyl, and
R 1 , R 2 , R 3 , and n are as defined in claim 3 .
5. A pyrazolylcarboxanilide according to claim 1 in which
R 1 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl, or trifluoroethyl,
R 2 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl, or trifluoroethyl,
G represents fluorine, chlorine, methyl, ethyl, t-butyl, or 2,4-dimethylbutyl,
R 3 represents straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, or decynyl, each of which may be attached at any position and each of which is optionally mono- to tetrasubstituted by identical or different substituents selected from the group consisting of fluorine, cyclo-propyl, difluorocyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and
n represents 0, 1 or 2.
6. A pyrazolylcarboxanilide according to claim 5 in which
G represents fluorine, chlorine, or methyl, and
R 1 , R 2 , R 3 , and n are as defined in claim 5 .
7. A pyrazolylcarboxanilide according to claim 1 in which
R 1 represents methyl, and
R 2 represents methyl.
8. A pyrazolylcarboxanilide according to claim 1 in which
R 3 represents unsubstituted C 5 -C 6 -alkyl.
9. A pyrazolylcarboxanilide according to claim 1 in which
n represents 0.
10. A pyrazolylcarboxanilide according to claim 1 in which
R 1 represents methyl,
R 2 represents methyl,
R 3 represents unsubstituted C 5 -C 12 -alkyl, and
n represents 0.
11. A pyrazolylcarboxanilide according to claim 10 in which
R 3 represents unsubstituted C 5 -C 6 -alkyl.
12. A pyrazolylcarboxanhlide according to claim 10 in which
R 3 represents 1,3-dimethylbutyl.
13. A process for preparing a compound of formula (I) according to claim 1 comprising
(a) reacting a carboxylic acid derivative of formula (II)
in which
R 1 and R 2 are as defined for formula (I) in claim 1 , and
X represents halogen,
with an aniline derivative of formula (III)
in which G, R 3 , and n are as defined for formula (I) in claim 1 , optionally in the presence of an acid binder and optionally in the presence of a diluent, or
(b) hydrogenating a pyrazolylcarboxanilide of formula (Ia)
in which
R 1 , R 2 , G, and n are as defined for formula (I) in claim 1 , and
R 4 represents C 2 -C 20 -alkenyl or C 2 -C 20 -alkynyl, each of which is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by halogen and/or C 1 -C 4 -alkyl,
optionally in the presence of a diluent and optionally in the presence of a catalyst, or
(c) dehydrating a hydroxyalkylpyrazolylcarboxanilide of formula (IV)
in which
R 1 , R 2 , G and n are as defined for formula (I) in claim 1 , and
R 5 represents C 5 -C 12 -hydroxyalkyl that is optionally additionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by halogen and/or C 1 -C 4 -alkyl,
optionally in the presence of a diluent and optionally in the presence of an acid, or
(d) reacting a halopyrazolylcarboxanilide of formula (V)
in which
R 1 , R 2 , G, and n are as defined for formula (I) in claim 1 , and
Y represents bromine or iodine,
with an alkyne of formula (VI)
HC≡—R 6 (VI),
in which R 6 represents C 2 -C 18 -alkyl that is optionally mono- or polysubstituted by identical or different substituents selected from the roup consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by h alogen and/or C 1 -C 4 -alkyl, or
with an alkene of formula (VII)
in which R 7 , R 8 , and R 9 independently of one another each represent hydrogen or alkyl that is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by halogen and/or C 1 -C 4 -alkyl and where the total number of carbon atoms of the open-chain moiety does not exceed the number 20,
optionally in the presence of a diluent, optionally in the presence of an acid binder, and in the presence of one or more catalysts, or
(e) reacting a ketone of formula (VIII)
in which
R 1 , R 2 , G, and n are as defined for formula (I) in claim 1 ,
R 10 represents hydrogen or C 1 -C 18 -alkyl that is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by halogen and/or C 1 -C 4 -alkyl,
with a phosphorus compound of formula (IX)
R 11 —Px (IX),
in which
R 11 represents hydrogen or C 1 -C 18 -alkyl that is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen and C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety is optionally substituted by halogen and/or C 1 -C 4 -alkyl, and
Px represents a group —P + (C 6 H 5 ) 3 Cl − , —P + (C 6 H 5 ) 3 Br − , —P + (C 6 H 5 ) 3 I − , —P(═O)(OCH 3 ) 3 , or —P(═O)(OC 2 H 5 ) 3 ,
with the proviso that when R 10 and R 11 are both unsubstituted alkyl, the total number of alkyl carbon atoms in R 10 and R 11 together is from 5 to 12, optionally in the presence of a diluent.
14. A composition for controlling phytopathogenic fungi, bacteria, and viruses comprising one or more pyrazolylcarboxanilides of formula (I) according to claim l and one or more extenders and/or surfactants.
15. A method for controlling phytopathogenic fungi, bacteria, and viruses comprising applying an effective amount of a pyrazolylcarboxanilide of formula (I) according to claim 1 to a microorganism and/or its habitat.
16. A process for preparing a composition for controlling phytopathogenic fungi, bacteria, and viruses comprising mixing a pyrazolylcarboxanilide of formula (I) according to claim 1 with one or more extenders and/or surfactants.