Method for producing 3,5-bis(fluoroalkyl)-pyrazol-4-carboxylic acid derivatives and 3,5-bis(fluoroalkyl)-pyrazoles

Patent metadata

Field	Value
Publication number	US-10035773-B2
Application number	US-201615059759-A
Country	US
Kind code	B2
Filing date	Mar 3, 2016
Priority date	Feb 1, 2012
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

The present invention relates to novel 3,5-bis(fluoroalkyl)pyrazole-4-carboxylic acid derivatives and to a process for preparing 3,5-bis(fluoroalkyl)pyrazole-4-carboxylic acid derivatives and 3,5-bis(fluoroalkyl)pyrazoles.

First claim

The invention claimed is:

1. A 3,5-Bis(fluoroalkyl)pyrazole of formula (Ia) or (Ib)

in which
R 1 is selected from H, C 1-12 -alkyl, C 3-8 -cycloalkyl, C 6-18 -aryl, C 7-19 -arylalkyl, C 7-19 -alkylaryl, CH 2 CN, CH 2 CX 3 , CH 2 COOH, or CH 2 COO—(C 1-12 )-alkyl;
X is independently F, Cl, Br, or I;
R 2 is difluoromethyl
and R 3 is selected from C 1 -C 6 -haloalkyl groups,
R 4 is selected from the group of COOH, (C═O)OR 5 , CN or (C═O)NR 5 R 6 , where R 5 and R 6 are each independently selected from the group consisting of C 1-12 -alkyl, C 3-8 -cycloalkyl, C 6-18 -aryl, C 7-19 -arylalkyl and C 7-19 -alkylaryl, or where R 5 and R 6 together with the nitrogen atom to which they are bonded may form a five- or six-membered ring.

2. The compound of formula (Ia) or (Ib) according to claim 1 ,
wherein
R 1 is selected from H, methyl, CH 2 COOH, CH 2 COOR 5 , CH 2 CN, or CH 2 CX 3 :
X is independently F or Cl;
R 3 is selected from difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
R 4 is selected from the group consisting of COOCH 3 , COOEt, COOC 3 H 7 , CN, CONMe 2 , and CONEt 2 .

3. The compound of formula (Ia) or (Ib) according to claim 1 , wherein
R 1 is selected from H, CH 2 COOH, CH 2 COOMe, or CH 2 CN,
R 3 is selected from the group consisting of trifluoromethyl, difluoromethyl, difluorochloromethyl, and pentafluoroethyl;
R 4 is COOH.

4. The compound of formula (Ia) or (Ib) according to claim 1 , wherein R 1 =H; R 2 =CF 2 H and R 4 =COOH.

5. The compound of formula (Ia) or (Ib) according to claim 1 , wherein R 1 =tert-butyl, R 3 =CF 2 H and R 4 =CO 2 Et or COOH.

6. The compound of formula (Ia) or (Ib) according to claim 1 , wherein R 1 =H or tert-butyl, R 3 =CF 3 and R 4 =CO 2 Et or COOH.

7. A 3,5-Bis(fluoroalkyl)pyrazole of formula (Ia) or (Ib)

in which
R 1 is selected from H, C 1-12 -alkyl, C 3-8 -cycloalkyl, C 6-18 -aryl, C 7-19 -arylalkyl, C 7-19 -alkylaryl, CH 2 CN, or CH 2 CX 3 ;
X is independently F, Cl, Br, or I;

R 2 is difluoromethyl
and R 3 is selected from C 1 -C 6 -haloalkyl groups,
R 4 is selected from the group of COOH, (C═O)OR 5 , CN or (C═O)NR 5 R 6 , where R 5 and R 6 are each independently selected from the group consisting of C 1-12 -alkyl, C 3-8 -cycloalkyl, C 6-18 -aryl, C 7-19 -arylalkyl and C 7-19 -alkylaryl, or where R 5 and R 6 together with the nitrogen atom to which they are bonded may form a five- or six-membered ring.

8. The compound of formula (Ia) or (Ib) according to claim 7 , wherein R 4 is (C═O)OR 5 .

9. The compound of formula (Ia) or (Ib) according to claim 7 , wherein R 4 is COOH.

10. The compound of formula (Ia) or (Ib) according to claim 7 , wherein R 4 is CN.

11. The compound of formula (Ia) or (Ib) according to claim 7 , wherein R 4 is (C═O)NR 5 R 6 .

Assignees

• Bayer Cropscience Ag
• Centre Nat Rech Scient

Inventors

• Pazenok Sergii
• Lui Norbert
• Vors Jean-Pierre
• Leroux Frederic R
• Giornal Florence

Classifications

• A61P31/00

  Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics · CPC title

• A61P17/00

  Drugs for dermatological disorders · CPC title

• C07D231/14 Primary

  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

• C07C229/30

  the carbon skeleton being acyclic and unsaturated · CPC title