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US 10,273,215 B2Granted
Process for preparing substituted pyrazoles containing haloalkoxy- and haloalkylthio groups from alpha,alpha -dihaloalkylamines and ketimines
AssigneesBayer CropScience AG, Centre National De La Recherche Scientifique
InventorsSergii Pazenok, Jean-Pierre Vors, Frédéric R. Leroux, Etienne Schmitt
Life of this patent
Estimating the term…
Abstract
The present invention relates to a novel process for preparing 3,5-bis substituted pyrazoles containing haloalkoxy- and haloalkylthio groups.
Claims6
A process for preparing a 3,5-bis(haloalkyl)pyrazole of formula (Ia) or (Ib)
- wherein:
- R1 is selected from the group consisting of C1-C6-haloalkyl-ether and C1-C6-haloalkyl-thioether;
- R2 is selected from the group consisting of H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 is C1-C6-haloalkyl;
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl;
- R5 is selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- and
- R6 and R7 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl,
- or
- R6 and R7 are taken together with the nitrogen atom to which they are attached to form a four-, five- or six-membered ring,
- comprising:
- step (A1), reacting an α,α-dihaloalkylamine of formula (II)
- wherein:
- R1 is selected from the group consisting of C1-C6-haloalkyl-ether and C1-C6-haloalkyl-thioether;
- each X is independently selected from the group consisting of F, Cl and Br;
- and
- R10 and R11 are independently selected from the group consisting of C1-6-alkyl and C3-8-cycloalkyl,
- in the presence of a Lewis Acid with a compound of formula (III)
- wherein:
- R8 is selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl and benzyl;
- R2 is selected from the group consisting of H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 is C1-C6-haloalkyl;
- R5 is selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- and
- R6 and R7 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl,
- or
- R6 and R7 are taken together with the nitrogen atom to which they are attached to form a four-, five- or six-membered ring,
- to form a compound of formula (V-1)
- wherein:
- A− is BF4, AlCl3F, AlF2Cl2 or AlF3Cl;
- R1 is selected from the group consisting of C1-C6-haloalkyl-ether and C1-C6-haloalkyl-thioether;
- R2 is selected from the group consisting of H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 is C1-C6-haloalkyl;
- R5 is selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- R6 and R7 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl,
- or
- R6 and R7 are taken together with the nitrogen atom to which they are attached to form a four-, five- or six-membered ring;
- R8 is selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl and benzyl;
- and
- R10 and R11 are independently selected from the group consisting of C1-6-alkyl and C3-8-cycloalkyl,
- and step (B), cyclizing the compound of formula (V-1) in the presence of a hydrazine of formula (IV)
- H2N—NHR4 (IV)
- wherein:
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl, to form the compound of formula (Ia) or (Ib).
41 more elements
A process for preparing a 3,5-bis(haloalkyl)pyrazole of formula (Ia) or (Ib)
- wherein:
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl;
- and
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl,
- comprising:
- step (A1), reacting an α,α-dihaloalkylamine of formula (II)
- wherein:
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- each X is independently selected from the group consisting of F and Cl;
- and
- R10 and R11 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, and C7-19-arylalkyl,
- or
- R10 and R11 are taken together with the nitrogen atom to which they are attached to form a five-membered ring,
- in the presence of a Lewis Acid with a compound of formula (III)
- wherein:
- R8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- and
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl,
- to form a compound of formula (V-1)
- wherein:
- A− is BF4, AlCl3F, AlF2Cl2 or AlF3Cl;
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl;
- R8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl;
- and
- R10 and R11 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, and C7-19-arylalkyl,
- or
- R10 and R11 are taken together with the nitrogen atom to which they are attached to form a five-membered ring,
- and step (B), cyclizing the compound of formula (V-1) in the presence of a hydrazine of formula (IV)
- H2N—NHR4 (IV)
- wherein:
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl,
- to form the compound of formula (Ia) or (Ib).
34 more elements
A process for preparing a 3,5-bis(haloalkyl)pyrazole of formula (Ia) or (Ib)
- wherein:
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl;
- and
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl,
- comprising:
- step (A1), reacting an α,α-dihaloalkylamine of formula (II)
- wherein:
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- each X is independently selected from the group consisting of F and Cl;
- and
- R10 and R11 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, and C7-19-arylalkyl,
- or
- R10 and R11 are taken together with the nitrogen atom to which they are attached to form a five-membered ring,
- in the presence of a Lewis Acid with a compound of formula (III)
- wherein:
- R8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- and
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl,
- to form a compound of formula (V-1)
- wherein:
- A− is BF4, AlCl3F, AlF2Cl2 or AlF3Cl;
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl;
- R8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl;
- and
- R10 and R11 are independently selected from the group consisting of C1-12-alkyl, C3-8-cycloalkyl, and C7-19-arylalkyl,
- or
- R10 and R11 are taken together with the nitrogen atom to which they are attached to form a five-membered ring,
- step (A2), reacting the compound of formula (V-1) with water to form a compound of formula (V-2)
- wherein:
- R1 is selected from the group consisting of CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), and CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from the group consisting of H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN, CON(CH3)2 and CON(C2H5)2;
- R3 is selected from the group consisting of difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, tetrafluoroethyl (CF3CFH), pentafluoroethyl, and 1,1,1-trifluoroprop-2-yl;
- and
- R8 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl,
- and step (B), cyclizing the compound of formula (V-2) in the presence of a hydrazine of formula (IV)
- H2N—NHR4 (IV)
- wherein:
- R4 is selected from the group consisting of H, C1-C8 alkyl, aryl and pyridyl, to form the compound of formula (Ia) or (Ib).
40 more elements
Dependencies are inferred from the claim text.