Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives from α,α-dihaloamines and ketimines

Patent metadata

Field	Value
Publication number	US-9701640-B2
Application number	US-201515127908-A
Country	US
Kind code	B2
Filing date	Mar 20, 2015
Priority date	Mar 24, 2014
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

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

First claim

The invention claimed is:

1. Process for preparing a 3,5-bis(haloalkyl)pyrazole of formula (Ia) and (Ib)

in which
R 1 and R 3 are each independently selected from C 1 -C 6 -haloalkyl;
R 2 is selected from H, halogen, COOH, (C═O)OR 5 , CN and (C═O)NR 6 R 7 ;
R 4 is selected from H, C 1 -C 8 -alkyl, CH 2 COOC 1 -C 8 -alkyl, aryl, pyridyl;
R 5 is selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 18 -aryl, C 7 -C 19 -arylalkyl and C 7 -C 19 -alkylaryl;
R 6 and R 7 are each independently selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 18 -aryl, C 7 -C 19 -arylalkyl and C 7 -C 19 -alkylaryl or where
R 6 and R 7 together with the nitrogen atom to which they are bonded may form a four-, five- or six-membered ring
wherein in one or more (A), α,α-dihaloamines of formula (II),

in which
R 1 is as defined above;
X is independently selected from F, Cl or Br,
R 10 and R 11 are each independently selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 18 -aryl, C 7 -C 19 -arylalkyl and C 7 -C 19 -alkylaryl or where
R 10 and R 11 together with the nitrogen atom to which they are bonded may form a five- or six-membered ring;
are reacted with one or more compounds of formula (III),

in which
R 8 is selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 18 -aryl, C 7 -C 19 -arylalkyl and C 7 -C 19 -alkylaryl, OR 9 ;
R 9 is selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 6 -C 18 -aryl, C 7 -C 19 -arylalkyl, C 7 -C 19 -alkylaryl;
R 2 and R 3 are as defined above;
to form the compound of formula (V): (V-1), (V-2), (V-3), (V-4) and (V-5)

and wherein in (B) in the presence of hydrazine H 2 N—NHR 4 (IV)—with R 4 being as defined above, —a cyclization of (V) takes place to form (Ia/Ib).

2. Process according to claim 1 , wherein
R 1 and R 3 are each independently 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(CF 3 CFH), pentafluoroethyl and 1,1,1-trifluoroprop-2-yl;
R 2 is selected from H, F, Cl, Br, COOCH 3 , COOC 2 H 5 , COOC 3 H 7 , CN and CON(CH 3 ) 2 , CON(C 2 H 5 ) 2 ;
R 4 is selected from H, C 1 -C 8 -alkyl, CH 2 COOC 1 -C 8 -alkyl, phenyl, pyridyl;
R 8 are each independently selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- and t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylethyl, C 7 -C 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;
R 10 and R 11 are each independently selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl, C 7 -C 19 -arylalkyl or
R 10 and R 11 together with the nitrogen atom to which they are bonded may form a five-membered ring.

3. Process according to claim 1 , wherein
R 1 and R 3 are each independently selected from trifluoromethyl, difluoromethyl, difluorochloromethyl, pentafluoroethyl;
R 2 is selected from H, Cl, CN, COOC 2 H 5 ;
R 4 is selected from H, methyl, ethyl, n-, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, phenyl, CH 2 COOCH 3 , CH 2 COOCH 2 CH 3 ;
R 8 is selected from methyl, ethyl, n-, iso-propyl, n-, iso-, sec- and t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, C 7 -C 19 -alkylaryl;
X is independently selected from F or Cl;
R 10 and R 11 are each independently selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl.

4. Process according to claim 1 , wherein,
R 1 and R 3 are each independently selected from CF 2 H and CF 3 ;
R 2 is selected from H or COOC 2 H 5 ;
R 4 is selected form H, methyl, ethyl, CH 2 COOCH 3 , CH 2 COOCH 2 CH 3 , phenyl;
R 8 is selected from ethyl, n-, iso-propyl, n-, cyclopentyl, cyclohexyl, benzyl;
X is F;
R 10 and R 11 are each independently selected from C 1 -C 12 -alkyl.

5. Process according to claim 1 , wherein,
R 1 and R 3 are CF 2 H;
R 2 is H;
R 4 is selected from H, methyl, CH 2 COOCH 2 CH 3 , phenyl;
R 8 is selected from iso-propyl and benzyl;
X is F;
R 10 and R 11 are each independently selected from methyl and ethyl.

6. Compound of formula (V-1)

in which
R 1 and R 3 are HCF 2 ;
R 2 is H;
R 8 is selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl and benzyl;
R 10 and R 11 are each independently selected from C 1 -C 5 alkyl;
A is BF 4 − .

7. Compound of formula (V-2)

in which
R 1 and R 3 are HCF 2 ;
R 2 is H;
R 8 is selected from C 1 -C 12 -alkyl, C 3 -C 8 -cycloalkyl and benzyl.

8. Compound of formula (V-3)

in which
R 1 and R 3 are HCF 2 ;
R 2 is H;
R 8 is selected from C 1-12 -alkyl, C 3-8 -cycloalkyl and benzyl;
R 10 and R 11 are each independently selected from C 1-5 alkyl.

9. Compound of formula (V-4)

in which
R 1 and R 3 are HCF 2 ;
R 2 is H;
R 8 is selected from C 1-12 -alkyl, C 3-8 -cycloalkyl and benzyl.

Assignees

• Bayer Cropscience Ag

Inventors

• Pazenok Sergii
• Lui Norbert
• Funke Christian
• Etzel Winfried
• Neeff Arnd

Classifications

• C07F5/022

  without C-boron linkages · CPC title

• C07D231/14

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms · CPC title

• C07C251/08

  being acyclic · CPC title

• C07D231/12 Primary

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title

• C07C225/14

  the carbon skeleton being unsaturated · CPC title