Process for preparing pyrazoles

Patent metadata

Field	Value
Publication number	US-10414733-B2
Application number	US-201515329104-A
Country	US
Kind code	B2
Filing date	Jul 30, 2015
Priority date	Jul 31, 2014
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The present invention relates to a process for preparing a pyrazole compound of formula V, the process including cyclizing a hydrazone substituted α,β-unsaturated carbonyl compound of formula IV by reacting it with a suitable reagent, e.g. a reducing agent, an organometallic reagent or a nucleophilic reagent. The compounds of formula V are versatile reaction tools for the preparation of pyrazole derived fine chemicals. The present invention also relates to pyrazole compounds of formulae Va, Vb, Vc, and VI.

First claim

The invention claimed is:

1. A process for preparing a pyrazole compound of formula V, or a salt, stereoisomer, tautomer or N-oxide thereof

comprising the step of cyclizing a hydrazone substituted α,β-unsaturated carbonyl compound of formula IV

by reacting it with a reagent comprising a R 6 group,
wherein
R 1 is selected from H, halogen, CN, NO 2 , C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, wherein the C-atoms be unsubstituted, may be partially or fully halogenated or may be substituted by 1, 2 or 3 identical or different substituents R x ;
OR a , SR a , C(Y)OR c , S(O) m R d , S(O) m Y 1 R d , NR e R f , C(Y)NR g R h , heterocyclyl, hetaryl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl and aryl, wherein the cyclic moieties may be unsubstituted or may be substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the radicals R y and R x ;

R 2 is selected from H, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, wherein the C-atoms may be unsubstituted, may be partially or fully halogenated or may be substituted by 1, 2 or 3 identical or different substituents R x ;
C(Y)OR c , C(Y)NR g R h , heterocyclyl, hetaryl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl and aryl, wherein the cyclic moieties may be unsubstituted or may be substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the radicals R y and R x ; and

R 3 is selected from H, halogen, CN, NO 2 , C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, wherein the C-atoms may be unsubstituted, may be partially or fully halogenated or may be substituted by 1, 2 or 3 identical or different substituents R x ;
OR a , SR a , C(Y)OR c , S(O) m R d , S(O) m Y 1 R d , NR e R f , C(Y)NR g R h , heterocyclyl, hetaryl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl, and aryl, wherein the cyclic moieties may be unsubstituted or may be substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the radicals R y and R x ;

and wherein
R 4 and R 5 are independently of each other selected from H, NO 2 , C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, wherein the C-atoms may be unsubstituted, may be partially or fully halogenated or may be substituted by 1, 2 or 3 identical or different substituents R x ;
C 1 -C 10 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 10 -alkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by identical or different substituents R y ;
C(Y)OR c , C(Y)NR g R h , C(Y)NR i NR e R f , C 1 -C 5 -alkylen-OR a , C 1 -C 5 -alkylen-CN, C 1 -C 5 -alkylen-C(Y)OR c , C 1 -C 5 -alkylen-NR e R f , C 1 -C 5 -alkylen-C(Y)NR g R h , C 1 -C 5 -alkylen-S(O) m R d , C 1 -C 5 -alkylen-S(O) m NR e R f , C 1 -C 5 -alkylen-NR i NR e R f , heterocyclyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl, hetaryl, aryl, heterocyclyl-C 1 -C 5 -alkyl, C 3 -C 10 -cycloalkyl-C 1 -C 5 -alkyl, C 3 -C 10 -cycloalkenyl-C 1 -C 5 -alkyl, hetaryl-C 1 -C 5 -alkyl, aryl-C 1 -C 5 -alkyl, wherein the cyclic moieties may be unsubstituted or may be substituted by 1, 2, 3, 4, or 5 identical or different substituents R y ;

groups -D-E, wherein
D is a direct bond, C 1 -C 6 -alkylene, C 2 -C 6 -alkenylene, or C 2 -C 6 -alkynylene, which carbon chains can be partially or fully substituted by R n , and
E is a non-aromatic 3- to 12-membered carbo- or heterocycle, which may contain 1, 2, 3, or 4 heteroatoms selected from N—R 1 , O, and S, wherein S may be oxidized, which carbo- or heterocycle may be partially or fully substituted by R n ;
and
groups -A-SO m -G, wherein
A is C 1 -C 6 -alkylene, C 2 -C 6 -alkenylene and C 2 -C 6 -alkynylene, wherein the C-atoms may be unsubstituted, or partially or fully substituted by R p , and
G is C 1 -C 4 -haloalkyl or C 3 -C 6 -cycloalkyl which may be halogenated;
or
R 4 and R 5 together with the carbon atom to which they are attached form a 3- to 12-membered non-aromatic carbo- or heterocycle, which heterocycle may contain 1, 2, 3, 4, or 5 heteroatoms selected from N—R 1 , O, and S, wherein S may be oxidized, and which carbo- or heterocycle may be partially or fully substituted by RR;
and wherein
the reagent comprising the R 6 group is selected from the groups consisting of:
(i) a reducing agent, wherein R 6 is H,
(ii) an organometallic reagent, wherein R 6 is selected from C 1 -C 6 -fluoroalkyl, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -cycloalkenyl-C 1 -C 2 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 2 -alkyl, aryl, aryl-C 1 -C 2 -alkyl, hetaryl, hetaryl-C 1 -C 2 -alkyl, wherein the carbon chains or cyclic moieties may be unsubstituted, partially or fully substituted by identical or different substituents R x , and
(iii) a nucleophilic reagent of formula H—R 6 , M a + R 6− or ½M ea 2+ R 6− , wherein M a is an alkaline metal and M ae is an alkaline earth metal, and wherein R 6 is selected from the groups consisting of CN, OR a , SR a , NR e R f , and groups of the general formula (i)

and wherein
R a , R b are independently of each other selected from H, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkylmethyl, C 3 -C 6 -halocycloalkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -cycloalkenylmethyl, C 3 -C 6 -halocycloalkenyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 4 -alkyl, aryl, hetaryl, aryl-C 1 -C 4 -alkyl and hetaryl-C 1 -C 4 -alkyl, wherein the cyclic moieties may be unsubstituted or may be substituted by 1, 2, 3, 4 or 5 substituents which, independently of each other, are selected from halogen, CN, C(O)NH 2 , NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
R c is selected from H, C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cyclo-alkylmethyl, C 3 -C 10 -halocycloalkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -cycloalkenylmethyl, C 3 -C 6 -halocycloalkenyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 4 -alkyl, aryl, hetaryl, aryl-C 1 -C 4 -alkyl and hetaryl-C 1 -C 4 -alkyl, wherein the ring in the six last mentioned radicals may be unsubstituted or may be substituted by 1, 2, 3, 4 or 5 substituents which, independently of each other, are selected from halogen, CN, C(O)NH 2 , NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy; or
R c together with the C(Y)O group forms a salt [C(Y)O] − NR 4 + , [C(Y)O] − M a + or [C(Y)O] − ½M ea 2+ , wherein M a is an alkali metal and M ea is an alkaline earth metal, and wherein the substituents R at the nitrogen atom are independently of each other selected from H, C 1 -C 10 -alkyl, phenyl and phenyl-C 1 -C 4 -alkyl;
R d is selected from C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkylmethyl, C 3 -C 6 -halocycloalkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -cycloalkenylmethyl, C 3 -C 6 -halocycloalkenyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, heterocyclyl, heterocyclyl-C 1 -C 4 -alkyl, aryl, hetaryl, aryl-C 1 -C 4 -alkyl and hetaryl-C 1 -C 4 -alkyl, wherein the cyclic moieties may be unsubstituted or may be substituted b

Assignees

• Basf Se

Inventors

• Gockel Birgit
• Saelinger Daniel
• Soergel Sebastian
• Rack Michael

Classifications

• C07D405/06

  linked by a carbon chain containing only aliphatic carbon atoms · CPC title

• C07D403/12

  linked by a chain containing hetero atoms as chain links · CPC title

• C07D401/12

  linked by a chain containing hetero atoms as chain links · 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

• A01N43/56

  1,2-Diazoles; Hydrogenated 1,2-diazoles · CPC title