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US 2018/0186749 A1Published application
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
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Abstract
The present invention relates to a novel process for preparing 3,5-bis substituted pyrazoles containing haloalkoxy- and haloalkylthio groups.
Claims10
1:
- A process for preparing a 3,5-bis(haloalkyl)pyrazole of the formula (Ia) or (Ib),
- in which
- R1 is selected from C1-C6-haloalkyl-ethers or C1-C6-haloalkyl-thioethers;
- R2 is selected from H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 are each independently selected from C1-C6-haloalkyl alkyl;
- R4 is selected from H, C1-C8 alkyl, aryl, pyridyl;
- R5 is selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- R6 and R7 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or where
- R6 and R7 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring
- characterized in that in step (A1), α,α-dihaloalkylamines of the formula (II),
- in which
- R1 is selected from C1-C6-haloalkyl-ethers or C1-C6-haloalkyl-thioethers;
- X is independently selected from F, Cl or Br,
- R10 and R11 are each independently selected from C1-6-alkyl, C3-8-cycloalkyl,
- are reacted in the presence of Lewis Acid with compounds of the formula (III),
- in which
- R8 is selected from C1-12-alkyl, C3-8-cycloalkyl, benzyl;
- R2 is selected from H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 are each independently selected from C1-C6-haloalkyl alkyl;
- R5 is selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- R6 and R7 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or where
- R6 and R7 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring
- to form the compound of formula (V-1),
- wherein A− is BF4, AlCl3F, AlF2Cl2, AlF3C1;
- R1 is selected from C1-C6-haloalkyl-ethers or C1-C6-haloalkyl-thioethers;
- R2 is selected from H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 are each independently selected from C1-C6-haloalkyl alkyl;
- R5 is selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- R6 and R7 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or where
- R6 and R7 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring
- R8 is selected from C1-12-alkyl, C3-8-cycloalkyl, benzyl;
- R10 and R11 are each independently selected from C1-6-alkyl, C3-8-cycloalkyl,
- and that in step (B) in the presence of hydrazine
- H2N—NHR4 (IV) wherein
- R4 is selected from H, C1-C8 alkyl, aryl or pyridyl
- a cyclization of (V-1) takes place to form (Ia/Ib).
33 more elements
2:
- The process according to claim 1, characterized in that in a step (A2) compound (V-1) is further reacted with water to compound of formula (V-2)
- in which
- R1 is selected from C1-C6-haloalkyl-ethers or C1-C6-haloalkyl-thioethers;
- R2 is selected from H, halogen, COOH, (C═O)OR5, CN and (C═O)NR6R7;
- R3 are each independently selected from C1-C6-haloalkyl alkyl;
- R5 is selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl;
- R6 and R7 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or where
- R6 and R7 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring
- R8 is selected from Cl_12-alkyl, C3-8-cycloalkyl, benzyl;
- and that in step (B) in the presence of hydrazine
- H2N—NHR4 (IV) wherein
- R4 is selected from H, C1-C8 alkyl, aryl or pyridyl
- a cyclization of (V-2) takes place to form (Ia/Ib).
10 more elements
3:
- The process according to claim 1, characterized in that the radicals in formula (Ia), (Ib), (II), (III), (IV), and (V-1) are
- R1 is selected from CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN and CON(CH3)2, CON(C2H5)2;
- R3 is selected from 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;
- R4 is selected from H, C1-C8 alkyl, aryl, pyridyl;
- R8 are each independently selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- und t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl;
- X is independently selected from F or Cl;
- R10 and R11 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C7-19-arylalkyl or
- R10 and R11 together with the nitrogen atom to which they are bonded may form a five-membered ring.
6 more elements
4:
- The process according to claim 1, characterized in that the radicals in formula (Ia), (Ib), (II), (III), (IV), and (V-1) are
- R1 is selected from fluoro(trifluoromethoxy)methyl, fluoro(pentafluoroethoxy)methyl;
- R2 is selected from H, Cl, CN, COOC2H5;
- R3 is selected from trifluoromethyl, difluoromethyl, difluorochloromethyl, pentafluoroethyl;
- R4 is selected from H, methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, aryl;
- R8 is selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- und t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, C7-C19-alkylaryl;
- X is independently selected from F or Cl;
- R10 and R11 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl.
5 more elements
5:
- A compound of formula (III-a)
- in which
- R2 is H,
- R3a is HCF2, or CF3;
- R8 is benzyl.
2 more elements
6:
- A compound of formula (V-1)
- in which
- R1 is CHFOCF3;
- R2 is H;
- R3 is CF2H, or CF3;
- R8 is selected from the group consisting of C1-C12-alkyl, C3-C8-cycloalkyl and benzyl;
- R10 and R11 are each independently C1-C5-alkyl;
- A− is selected from the group consisting of BF4, AlCl3F, AlF2Cl2, and AlF3Cl.
5 more elements
7:
- A compound of formula (V-2)
- in which
- R1 is CHFOCF3;
- R2 is H;
- R3 is CF2H, or CF3;
- R8 is selected from the group consisting of C1-C12-alkyl, C3-C8-cycloalkyl and benzyl.
3 more elements
8:
- A compound of formula (II-1):
- in which
- R1 is C1-C6-haloalkyl-ether or C1-C6-haloalkyl-thioether;
- X is F, Cl or Br,
- R10 and R11 are each independently selected from the group consisting of C1-6-alkyl, and C3-8-cycloalkyl;
- and
- A− is selected from the group consisting of BF4, AlCl3F, AlF2Cl2, and AlF3Cl.
4 more elements
9:
- The process according to claim 2, characterized in that the radicals in formula (Ia), (Ib), (II), (III), (IV), (V-1) and (V-2) are
- R1 is selected from CHF—OCF3 (fluoro(trifluoromethoxy)methyl), CHF—OC2F5 (fluoro(pentafluoroethoxy)methyl), CHF—SCF3 (fluoro(trifluorothiomethyl)methyl), CHF—SC2F5 fluoro(pentafluorothioethyl)methyl;
- R2 is selected from H, F, Cl, Br, COOCH3, COOC2H5, COOC3H7, CN and CON(CH3)2, CON(C2H5)2;
- R3 is selected from 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;
- R4 is selected from H, C1-C8 alkyl, aryl, pyridyl;
- R8 are each independently selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- und t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C7-19-alkylaryl, tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl;
- X is independently selected from F or Cl;
- R10 and R11 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C7-19-arylalkyl or
- R10 and R11 together with the nitrogen atom to which they are bonded may form a five-membered ring.
6 more elements
10:
- The process according to claim 2, characterized in that the radicals in formula (Ia), (Ib), (II), (III), (IV), (V-1) and (V-2) are
- R1 is selected from fluoro(trifluoromethoxy)methyl, fluoro(pentafluoroethoxy)methyl;
- R2 is selected from H, Cl, CN, COOC2H5;
- R3 is selected from trifluoromethyl, difluoromethyl, difluorochloromethyl, pentafluoroethyl;
- R4 is selected from H, methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, aryl;
- R8 is selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- und t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, C7-C19-alkylaryl;
- X is independently selected from F or Cl;
- R10 and R11 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl.
5 more elements