Process for the production of biaryl compounds

Patent metadata

Field	Value
Publication number	US-10040732-B2
Application number	US-201515326860-A
Country	US
Kind code	B2
Filing date	Jul 15, 2015
Priority date	Jul 17, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Process for producing biaryl compounds by aerobic cross dehydrogenative coupling (CDC) of two arene groups comprising at least one aryl carbon-hydrogen bond, in the presence of a catalyst system comprising a palladium salt comprising at least one non-cyclopalladatable carboxylate anion and one or more non-beta-eliminatable, non-cyclopalladatable ligands comprising at least one N-donor atom, the one or more ligands having a 0.5/1-1.5/1 molar ratio of N-donor atoms relative to the Pd atoms.

First claim

The invention claimed is:

1. Process for producing biaryl compounds by aerobic cross dehydrogenative coupling (CDC) of two arene groups comprising at least one aryl carbon-hydrogen bond, in the presence of a catalyst system comprising a palladium salt comprising at least one non-cyclopalladatable carboxylate anion and one or more non-beta-eliminatable, non-cyclopalladatable ligands comprising at least one N-donor atom, the one or more ligands having a 0.5/1-1.5/1 molar ratio of N-donor atoms relative to the Pd atoms.

2. Process according to claim 1 , wherein the molar ratio of N-donor atoms relative to the Pd atoms is between 0.7/1 and 1.3/1.

3. Process according to claim 1 , wherein the molar ratio of N-donor atoms relative to the Pd atoms is between 0.8/1 and 1.2/1.

4. Process according to claim 1 , wherein aliphatic cyclic or non-cyclic primary, secondary or tertiary amines, aromatic N-heterocycles and/or benzofused derivatives thereof are used as the one or more ligands.

5. Process according to claim 4 , wherein pyridines, pyridazines, pyrimidines, pyrazines, triazines, imidazoles, triazoles, oxazoles, 4,5-dihydrooxazoles, isoxazoles, 4,5-dihydroisoxazoles, and 5,6-dihydro-4H-1,3-oxazines or quinolines, isoquinolines, cinnolines, phthalazines, quinazoline, quinoxalines, 1H-benzo[d]imidazoles, 1H-benzo[d][1,2,3]triazoles, benzo[d]oxazoles, benzo[d]isoxazoles and 4H-benzo[e][1,3]oxazines and/or benzofused derivatives thereof are used as the one or more ligands.

6. Process according to claim 4 , wherein pyridines, pyridazines, pyrimidines, pyrazines, triazines, quinolines, isoquinolines, cinnolines, phthalazine, quinazoline, and quinoxalines and/or benzofused derivatives thereof are used as the one or more ligands.

7. Process according to claim 1 , wherein the process is carried out under a (partial) pressure of oxygen of 0.2-2 bar, and wherein a catalyst system is used comprising a palladium salt comprising at least one non-cyclopalladatable carboxylate anion derived from a carboxylic acid that is triply substituted at the alpha-carbon atom relative to the carboxylate group, with the carboxylic acid also containing at least one beta-carbon atom.

8. Process according to claim 7 , wherein the carboxylate anion is derived from a 2,2-dialkylalkanoic acid, 2-fluoro-2-alkylalkanoic acid, 2,2-difluoroalkanoic acid, 2,2-difluoro-2-arylacetic acid, with the alkanoic acid containing at least one beta-carbon atom.

9. Process according to claim 7 , wherein the carboxylate anion is derived from pivalic acid, 3,3,3-trifluoro-2-methyl-2-(trifluoromethyl)propanoic acid, 3,3,3-trifluoro-2,2-bis(trifluoromethyl)propanoic acid, and 2,2-difluoro-2-phenylacetic acid.

10. Process according to claim 1 , wherein the process is carried out under a (partial) pressure of oxygen of 0.2-2 bar, and wherein a catalyst system is used comprising a palladium salt comprising at least one non-cyclopalladatable carboxylate anion derived from a carboxylic acid with an acidity constant in between that of acetic acid and 2,2,2-trifluoroacetic acid, with aforementioned acidity constant meaning the acidity constant average (pK a acid 1 +pK a acid 2 )/2 in case of two different carboxylate anions.

11. Process according to claim 10 , wherein the carboxylate anion is derived from 2,2-difluoroacetic acid, 2,2-difluoropropionic acid, 3,3,3-trifluoro-2-methyl-2-(trifluoromethyl)propanoic acid, 3,3,3-trifluoro-2,2-bis(trifluoromethyl)propanoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 2,2-difluoro-2-phenylacetic acid, 2-(2,3,4,5,6-pentafluorophenyl)acetic acid 2,4-dinitrobenzoic acid, 2,5-dinitrobenzoic acid, and 3,4-dinitrobenzoic acid.

12. Process according to claim 1 , wherein the process is carried out under a (partial) pressure of oxygen of 2-20 bar, and wherein a catalyst system is used comprising a palladium salt comprising at least one non-cyclopalladatable carboxylate anion derived from a strongly acidic carboxylic acid, i.e. with an acidity constant that is equal or less than the acidity constant average of acetic acid and 2,2,2-trifluoroacetic acid, with aforementioned acidity constant average being quantified as (pK a acetic acid +pK a trifluoroacetic acid )/2.

13. Process according to claim 12 , wherein the carboxylate anion is derived from trifluoroacetic acid, 3,3,3-trifluoro-2,2-bis(trifluoromethyl)propanoic acid, 3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid, and 2,2-difluoro-2-phenylacetic acid.

14. Process according to claim 1 , wherein at most 50 wt % of solvent is used, based on the total reaction mass.

15. Process according to claim 1 , wherein at most 10 wt % of solvent is used, based on the total reaction mass.

Assignees

• Dsm Ip Assets Bv

Inventors

• Alsters Paulus Lambertus

Classifications

• C07C2531/22

  Organic complexes · CPC title

• B01J2531/0213

  Complexes without C-metal linkages · CPC title

• C07C2/84 Primary

  catalytic · CPC title

• C07B37/04

  Substitution · CPC title

• B01J2531/824

  Palladium · CPC title