# US 9,518,025 B2 · Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives from a,a-dihaloamines

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- Number: US 9,518,025 B2
- Document ID: US9518025B2
- Status: Granted
- Kind: B2
- Application number: 15/034,512
- Filed: 2014-11-10
- Published: 2016-10-06
- Granted: 2016-12-13
- Earliest claimed: 2013-11-11
- Assignees: Bayer CropScience AG
- Applicants: Bayer Cropscience Aktiengesellschaft
- Inventors: Sergii Pazenok; Mark James Form; Arnd Neeff
- Web page: https://patentgrep.com/patent/US9518025B2

## CPC

- C07D 231/12: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07C 251/88: having also the other nitrogen atom doubly-bound to a carbon atom, e.g. azines
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention relates to a novel process for preparing 3,5-bis(haloalkyl)pyrazole derivatives.

## Claims

### Claim 1

A process for preparing a 3,5-bis(haloalkyl)pyrazole of formula (Ia) and (Ib)
in which
R1 and R3 are each independently selected from C1-C6-haloalkyl;
R2 is selected from H, Hal, COOH, (C═O)OR4, CN and (C═O)NR4R5;
R4 and R5 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or
R4 and R5 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring;
comprising in (A), reacting one or more α,α-dihaloamines of the formula (II),
in which
X is independently selected from F, Cl or Br;
R5 and R6 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl,
C7-19-arylalkyl and C7-19-alkylaryl or where
R5 and R6 together with the nitrogen atom to which they are bonded may form a five- or six-membered ring;
R1 is as defined above;
with one or more compounds of formula (III),
in which
R2 and R3 are as defined above;
to form the compound of formula (IV) or (V)
and in (B) in the presence of an acid and hydrazine cyclization of (IV) or (V) takes place to form (la/Ib).

### Claim 2 (depends on 1)

A process according to claim 1, wherein
R1 and R3 are each independently selected from trifluoromethyl, difluoromethyl, difluorochloromethyl, pentafluoroethyl;
R2 is selected from H, Cl, CN, COOC2H5;
X is independently F or Cl.

### Claim 3 (depends on 1)

A process according to claim 1, wherein
R1 and R3 are each independently selected from trifluoromethyl, difluoromethyl, difluorochloromethyl, pentafluoroethyl;
R2 is selected from H, Cl, CN, COOC2H5;
X is independently F or Cl;
R5 and R6 are each independently selected from methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-nonyl.

### Claim 4 (depends on 1)

A process according to claim 1, wherein
R1 and R3 are CF2H;
R2 is selected from H;
X is F.

### Claim 5 (depends on 1)

A process according to claim 1, wherein
R1 and R3 are CF2H;
R2 is selected from H;
X is F;
R5 and R6 are methyl.

### Claim 6 (depends on 1)

A process according to claim 1 wherein the compound of formula (II) is 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA), 1,1,2,2-tetrafluoroethyl-N,N-diethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-dimethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)-ethyl-N,N-diethylamine, 1,1,2-trifluoro-2-chloroethyl-N,N-dimethylamine or 1,1,2-trifluoro-2-chloroethyl-N,N-diethylamine.

### Claim 7

A compound of formula (III-1): Bis(1,1-difluoropropan-2-ylidene) hydrazine

### Claim 8

A process for preparing Bis(1,1-difluoropropan-2-ylidene) hydrazine of formula (III-1)
wherein one or more ketones of formula (VI),
in which
R3 is selected from C1-C6-haloalkyl;
R2 is selected from H, Hal, COOH, (C═O)OR4, CN and (C═O)NR4R5;
R4 and R5 are each independently selected from C1-12-alkyl, C3-8-cycloalkyl, C6-18-aryl, C7-19-arylalkyl and C7-19-alkylaryl, or
R4 and R5 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring;
are reacted with hydrazine hydrate in the presence of a Lewis Acid and a solvent.

### Claim 9 (depends on 8)

The process for preparing Bis(1,1-difluoropropan-2-ylidene) hydrazine of formula (III-1) according to claim 8, wherein the Lewis Acid comprises BF3 or AlCl13.