US4439618A
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Process for the preparation of methyl esters of arylpropionic acids optically active
Assignee: Montedison SpA
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Filing: 1982-08-05
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Granted: 1984-03-27
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Expires: 2002-08-05
Abstract
Abstract Optically active methyl esters of arylpropionic acids are prepared by reaction of the corresponding vinylaromatic compounds with carbon monoxide and methyl alcohol in the presence of a palladium catalyst system consisting of a palladium compound associated with optically active diphenyl-neomenthylphosphine and with trifluoroacetic acid, at substantially atmospheric pressure and at a temperature comprised between 20° and 80° C. There is dealt with particular regioselective and enantioselective catalysis conditions. The products obtained consist of esters of arylpropionic acids or of the corresponding acids obtainable from them, and are useful intermediates in the synthesis of organic compounds, particularly of pharmaceutical products.
Inventors
- 👤 Giuseppe Cometti
- 👤 Gian P. Chiusoli
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 01:59
CPC Classifications
C; C07; C07C; C07C59/00; C07C59/40; C07C59/58; C07C59/64; C07C69/00; C07C69/612
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
111 words
A process for the regioselective and enantioselective preparation of methyl esters of arylpropionic acids, by carbonylation of the corresponding vinylaromatic compound, in the presence of palladium catalysts, characterized in that a compound having the formula (II): R--CH═CH.sub.2 (II) wherein R is selected from the group consisting of aryl radicals and aryl radicals substituted with groups that are inert under the reaction conditions, is made to react with carbon monoxide and with methyl alcohol in the presence of a palladium catalyst associated with the optically active diphenylneomenthylphosphine and in the further presence of trifluoroacetic acid, under a substantially atmospheric pressure and at a temperature comprised between 20° C. and 80° C. about.
Claim 2
Dependent Claim
111 words
A process for the regioselective and enantioselective preparation of methyl esters of arylpropionic acids, by carbonylation of the corresponding vinylaromatic compound, in the presence of palladium catalysts, characterized in that a compound having the formula (II): R--CH═CH.sub.2 (II) wherein R is selected from the group consisting of aryl radicals and aryl radicals substituted with groups that are inert under the reaction conditions, is made to react with carbon monoxide and with methyl alcohol in the presence of a palladium catalyst associated with the optically active diphenylneomenthylphosphine and in the further presence of trifluoroacetic acid, under a substantially atmospheric pressure and at a temperature comprised between 20° C. and 80° C. about.
Claim 3
Dependent Claim
25 words
A process according to claim 1, characterized in that the aryl group R is selected from the group consisting of phenyl-, diphenyl and naphthyl groups.
Claim 4
Dependent Claim
40 words
A process according to claim 1, characterized in that the aryl group is substituted by inert groups selected from the group consisting of alkyl-, alkoxyl-, ketonic, ester groups having from 1 to 4 carbon atoms, nitrilic, halogenhydric and nitric groups.
Claim 5
Dependent Claim
97 words
A process according to claim 1, characterized in that the palladium catalyst is selected from the group consisting of complex compounds of Pd(O) with the diphenylneomenthylphosphine, having formula (III): PdL.sub.n L'.sub.m (III) wherein: L represents the optically active diphenylneomenthylphosphine; L' represents an olefinic ligand of the conjugated type containing electron-attracting groups; n is an integer comprised between 1 and 3; m is an integer comprised between 0 and 2, such that n+m=3, associated with trifluoroacetic acid, and a Pd(II) salt of carboxylic acids and/or palladium acetylacetonate, associated with the optically active diphenylneomenthylphosphine and with the trifluoroacetic acid.
Claim 6
Dependent Claim
24 words
A process according to claim 4, characterized in that the olefinic ligand L' is selected from the group consisting of dibenzylidenacetone, benzylidenacetone and methylmaleate.
Claim 7
Dependent Claim
36 words
A process according to claim 1, characterized in that said process is conducted in a reaction medium selected from the group consisting of an excess of methyl alcohol and mixtures of methyl alcohol with organic solvents.
Claim 8
Dependent Claim
30 words
A process according to claim 6, characterized in that the solvent consists of methyl alcohol in admixture with a solvent selected from the group consisting of butyl alcohol and anisol.
Claim 9
Dependent Claim
30 words
A process according to claim 4, characterized in that the molar ratio between the Pd(O) complex of formula (III) and trifluoroacetic acid is comprised between about 1:10 and about 1:100.
Claim 10
Dependent Claim
29 words
A process according to claim 4, characterized in that the molar ratios between Pd(II) salt, the diphenylneomethylphosphine and the trifluoroacetic acid are comprised between about 1:3:10 and about 1:3:100.
Claim 11
Dependent Claim
15 words
A process according to claim 4, characterized in that the Pd salt is palladium acetylacetonate.
Claim 12
Dependent Claim
26 words
A process according to claim 1, characterized in that there are used from 1 to 100 mols of palladium catalyst per 1 mol of compound (II).
Claim 13
Dependent Claim
24 words
A process according to claim 1, characterized in that said process is conducted at a temperature comprised between about 40° C. and 50° C.
Claim 14
Dependent Claim
24 words
A process according to claim 1, characterized in that said process is conducted under a pressure comprised between atmospheric pressure and about 2 atmospheres.
Claim 15
Dependent Claim
20 words
A process according to claim 1, characterized in that said process is conducted in the presence of an inert gas.
Claim 16
Dependent Claim
26 words
A process according to claim 1, characterized in that said process is conducted in a reaction medium selected from the group consisting of alcohols and ethers.
Claim 17
Dependent Claim
29 words
A process according to claim 1, characterized in that said process is conducted in the presence of an inert gas selected from the group consisting of nitrogen and argon.
Claim 18
Dependent Claim
40 words
A process according to claim 2, characterized in that the aryl group is substituted by inert groups selected from the group consisting of alkyl, alkoxy, ketonic, ester groups having from 1 to 4 carbon atoms, nitrilic, halogenhydric and nitric groups.
References Cited (Backward Citations)
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