Sulfonyl hydrazide compounds and a regio-selective process to prepare 4-aroyl pyrazole derivatives

Patent metadata

Field	Value
Publication number	US-9926278-B2
Application number	US-201515305407-A
Country	US
Kind code	B2
Filing date	Apr 14, 2015
Priority date	May 23, 2014
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

Disclosed are compounds of Formula I, including all stereoisomers, (N-oxides), and salts thereof, wherein A and R are as defined in the disclosure.

Also disclosed is a method for preparing a compound of Formula I, comprising reacting a compound of Formula II with an aroyl enolate salt of Formula III in the presence of an acid in an aqueous solvent mixture, wherein A, R and M are as defined in the disclosure.
Also disclosed is a method for preparing a compound of Formula IV, comprising reacting a compound of Formula I with an aldehyde of Formula V in the presence of a secondary amine salt, wherein A, B and R are as defined in the disclosure

First claim

What is claimed is:

1. A compound selected from Formula I, N-oxides and salts thereof,

wherein
A is phenyl substituted with halogen, C 2 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy; or
A is a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy;R is C 1 -C 8 alkyl optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy; and
R is C 1 -C 8 alkyl optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy; or
R is phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy.

2. The compound of claim 1 wherein
A is phenyl substituted with halogen, C 2 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy or C 1 -C 4 haloalkylthio; and
R is C 1 -C 8 alkyl optionally substituted with halogen or C 1 -C 4 alkoxy; or phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy.

3. The compound of claim 2 wherein
A is phenyl substituted with halogen; and
R is C 1 -C 8 alkyl optionally substituted with halogen or C 1 -C 4 alkoxy; or phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.

4. The compound of claim 1 wherein
A is phenyl substituted with halogen, C 2 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy; and
R is C 1 -C 8 alkyl.

5. The compound of claim 4 wherein
A is phenyl substituted with halogen; and
R is CH 3 .

6. The compound of claim 3 wherein
A is phenyl substituted with halogen at 3- and 5-positions or 2- and 5-positions; and
R is phenyl optionally substituted with C 1 -C 4 alkyl.

7. The compound of claim 2 wherein
A is phenyl substituted with halogen, C 2 -C 4 alkyl and
R is 4-methylbenzene.

8. A method for preparing a compound of Formula I

wherein
A is phenyl, naphthalenyl, or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy; and
R is C 1 -C 8 alkyl optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy; or
R is phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy;

comprising the step of reacting a compound of Formula II

wherein
R is C 1 -C 8 alkyl optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy; or
R is phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, phenyl or phenoxy;
with an aroyl enolate salt of Formula III

wherein
M is an alkali metal or NH 4 ;
A is phenyl, naphthalenyl, or a 5- or 6- membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy;
in the presence of an acid in an aqueous solvent mixture.

9. The method of claim 8 wherein
A is phenyl, naphthalenyl, or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy or C 1 -C 4 haloalkylthio; and
R is C 1 -C 8 alkyl optionally substituted with halogen or C 1 -C 4 alkoxy; or phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy.

10. The method of claim 9 wherein
A is phenyl, naphthalenyl, or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen;
R is C 1 -C 8 alkyl optionally substituted with halogen or C 1 -C 4 alkoxy; or phenyl, naphthalenyl or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
M is an alkali metal or NH 4 ; and
the acid is a weak or moderate acid.

11. The method of claim 10 wherein
A is phenyl, 2-thienyl, 3-thienyl or 3-pyridyl, each optionally substituted with halogen or C 1 -C 4 alkyl;
R is methyl or phenyl optionally substituted with C 1 -C 4 alkyl;
M is Na or K; and
the acid is acetic acid.

12. A method for preparing a compound of Formula IV

wherein
A is phenyl, naphthalenyl, or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 2 -C 4 dialkylamino, cyano, nitro, C 1 -C 4 alkoxycarbonyl, phenyl or phenoxy;
B is phenyl, naphthalenyl, or a 5- or 6-membered heterocyclic ring, each ring or ring system optionally substituted with halogen, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalky

Assignees

• Du Pont

Inventors

• Patel Kanu Maganbhai

Classifications

• C07D231/16

  Halogen atoms or nitro radicals · CPC title

• C07D213/71

  to which a second hetero atom is attached · CPC title

• C07D261/10

  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

• C07D277/32

  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

• C07C303/36

  of amides of sulfonic acids · CPC title