Method for producing carboxamides
View Patent ↗The present invention relates to a novel process for preparing known fungicidally active 1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamides from the corresponding acid fluoride and aniline derivatives in the absence of an acid acceptor.
1. A process for preparing a carboxamide of formula (I)
in which
R is C 3 -C 12 -cycloalkyl, C 3 -C 12 -cycloalkenyl, C 6 -C 12 -bicycloalkyl, C 2 -C 12 -oxacycloalkyl, C 4 -C 12 -oxacycloalkenyl, C 3 -C 12 -thiacycloalkyl, C 4 -C 12 -thiacycloalkenyl, C 2 -C 12 -azacycloalkyl, each of which may optionally be mono- or polysubstituted, identically or differently, by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen and/or cyano, or phenyl which is optionally mono- to pentasubstituted identically or differently, where the substituents are each selected from the list W 1 ,
or unsubstituted C 2 -C 20 -alkyl,
or C 1 -C 20 -alkyl which is mono- or polysubstituted, identically or differently, by halogen, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylamino, di(C 1 -C 6 -alkyl)amino, C 1 -C 6 -haloalkylthio, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -haloalkylsulfonyl, C 1 -C 6 -haloalkoxy, C 1 -C 6 -haloalkylamino, halodi(C 1 -C 6 -alkyl)amino, —SiR 1 R 2 R 3 and/or C 3 -C 6 -cycloalkyl, where the cycloalkyl moiety may in turn optionally be mono- to tetrasubstituted, identically or differently, by halogen, C 1 -C 4 -alkyl and/or C 1 -C 4 -haloalkyl,
W 1 is halogen, cyano, nitro, amino, hydroxyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 8 -alkylsulfinyl, C 1 -C 8 -alkylsulfonyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkenyloxy; C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkoxy, C 1 -C 6 -haloalkylthio, C 1 -C 6 -haloalkylsulfinyl or C 1 -C 6 -haloalkylsulfonyl having in each case from 1 to 13 identical or different halogen atoms; C 2 -C 6 -haloalkenyl or C 2 -C 6 -haloalkenyloxy having in each case from 1 to 11 identical or different halogen atoms; C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyloxy;
R 1 and R 2 are each independently hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl or C 1 -C 6 -haloalkyl,
R 3 is hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 4 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -haloalkynyl, C 3 -C 6 -cycloalkyl, or in each case optionally substituted phenyl or phenylalkyl,
said process comprising:
reacting 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl fluoride of formula (II)
with aniline derivatives of formula (III)
in which R is as defined above,
in the absence of an acid acceptor.
2. The process as claimed in claim 1 , wherein a temperature of from 120° C. to 150° C. is employed.
3. The process as claimed in claim 1 , wherein an aniline derivative of formula (III-1)
is used.
4. The process as claimed in claim 1 wherein 2-(1,3-dimethylbutyl)phenylamine is used as the aniline derivative of the formula (III).
5. The process as claimed in claim 2 , wherein a temperature of from 120° C. to 150° C. is employed.
6. The process as claimed in claim 2 , wherein 2-(1,3-dimethylbutyl)phenylamine is used as the aniline derivative of the formula (III).
7. The process as claimed in claim 3 , wherein 2-(1,3-dimethylbutyl)phenylamine is used as the aniline derivative of the formula (III).