Hydrogenation process of oxime derivatives

Patent metadata

Field	Value
Publication number	US-12491503-B2
Application number	US-201917291122-A
Country	US
Kind code	B2
Filing date	Nov 1, 2019
Priority date	Nov 6, 2018
Publication date	Dec 9, 2025
Grant date	Dec 9, 2025

Abstract

The present invention relates to a novel process for the iridium-catalysed hydrogenation of oximes. The invention also relates to novel iridium catalysts for use in the iridium-catalysed hydrogenation of oximes and to processes of preparation of these catalysts. The invention further relates to the use of the novel iridium catalysts in ionic hydrogenation of other unsaturated substrates.

First claim

What is claimed is:

1 . A process for the hydrogenation of an oxime of formula (I) to produce a hydroxylamine salt of formula (II) by reacting oxime (I) with hydrogen in the presence of an iridium catalyst of formula (IIIa) or formula (IIIb) and an acid;

wherein R 1 , R 2 and R 3 are each independently hydrogen, C 1 -C 8 alkyl, C 1 -C 8 hydroxyalkyl, C 1 -C 8 cyanoalkyl, C 1 -C 6 alkoxyC 1 -C 8 alkyl, di(C 1 -C 6 alkoxy) C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 8 cycloalkyl, phenyl, phenylC 1 -C 8 alkyl or heteroaryl, and wherein the cycloalkyl and phenyl moieties are each optionally substituted with 1 to 5 groups selected from hydroxyl, halogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, phenyl, heteroaryl, C 1 -C 6 alkoxycarbonyl, acylamino, amido, cyano, nitro and C 2 -C 6 alkenyl; or
R 1 and R 2 together with the carbon atom to which they are attached may form a 4- to 8-membered saturated cycloalkyl or heterocyclyl ring, wherein the heterocyclic moiety is a non-aromatic monocyclic ring which comprises 1, 2 or 3 heteroatoms, wherein the heteroatoms are individually selected from N, O and S;
R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen or C 1 -C 3 alkyl;

represents a bidentate chelating ligand comprising at least one carbon atom which coordinates to iridium and at least one nitrogen atom which coordinates to iridium;
X represents an anionic group of the formula R 14 —SO 2 O— or R 15 —C(O)O—, wherein
R 14 is hydroxy, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl, or phenyl, wherein the phenyl moieties are optionally substituted by 1, 2, 3 or 4 substituents, which may be the same or different, selected from R 16 ;
R 16 is C 1-4 alkyl, C 1-4 haloalkyl, nitro, or halogen;
R 15 is C 1-6 haloalkyl or phenyl, wherein the phenyl moieties are optionally substituted by 1, 2, 3 or 4 substituents, which may be the same or different, selected from R 17 ,
R 17 is C 1-4 alkyl, C 1-4 haloalkyl, nitro or halogen;
Y represents a neutral ligand; and
Z represents an anionic group.

2 . The process according to claim 1 , wherein R 6 , R 7 , R 8 , R 9 and R 10 each represent hydrogen or methyl.

3 . The process according to claim 1 , wherein X represents a group of the formula R 14 —SO 2 O − .

4 . The process according to claim 1 , wherein the bidentate chelating ligand is selected from a compound of formula (IV-1), (IV-2), (IV-3), (IV-5), (IV-6), (IV-7), (IV-8), (IV-9), (IV-10), (IV-11) and (IV-12):

5 . The process according to claim 1 , wherein Z is R 14 —SO 2 O − , mesylate, sulfate, hydrogenosulfate, tetrafluoroborate, hexafluorophosphate, tetraphenylborate, or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

6 . The process according to claim 1 , wherein the acid is methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, sulfuric acid or triflic acid.

7 . The process according to claim 1 , wherein Y is H 2 O or MeCN.

8 . The process according to claim 1 , wherein the iridium catalyst is a compound of formula (III-1), (III-11), (III-17), (III-18), or (III-19):

9 . The process according to claim 1 , wherein the hydroxylamine of formula (II) is N-methoxy-1-(2,4,6-trichlorophenyl) propan-2-amine (II-1).

10 . The process according to claim 9 , wherein N-methoxy-1-(2,4,6-trichlorophenyl)propan-2-amine (II-1) is further reacted with 3-(difluoromethyl)-1-methyl-pyrazole-4-carbonyl chloride (XII) to provide 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide (XIII):

Assignees

• Syngenta Crop Protection Ag

Inventors

• Smejkal Tomas

Classifications

• C07F17/00

  Metallocenes · 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

• C07D211/18

  with substituted hydrocarbon radicals attached to ring carbon atoms · CPC title

• C07C239/20

  having oxygen atoms of hydroxylamino groups etherified · CPC title

• C07C239/12

  having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms · CPC title