Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1988-11-14
1990-03-13
Killos, Paul J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
562406, C07C 6976
Patent
active
049084739
DESCRIPTION:
BRIEF SUMMARY
DESCRIPTION
1. Technical Field
This invention relates to a process for selective hydroesterification. More particularly, the invention relates to a process for producing unsaturated acid or its ester by selectively hydroesterifying diolefin.
Furthermore, the invention relates to a process for selectively hydroesterifying only diolefin in a material which contains certain monoolefins.
2. Background Art
The methods of carbonylation of olefin by carbon monoxide are employed widely in industry, for example, in connection with monoolefins. Furthermore, for example, in U.S. Pat. No. 4,329,507, it is disclosed that ketoprofen (antiphlogistic agent, trade name) is obtained in a high yield by reacting 3-vinylbenzophenone with carbon monoxide in dilute hydrochloric acid in the presence of a catalyst of palladium.
However, with regard to diolefins, such instance is few. For example, in Japanese Laid-Open Patent Publication Nos. 58-210033 and 59-110643, 5-ethylidene bicyclo[2.2.1]heptene-2 is carbonated and its two unsaturated groups are carbonylated. In the same references, only one unsaturated group is carbonylated by regulating the feed quantities of hydrogen and carbon monoxide.
The inventors of the present application have found out that, with regard to diolefin having specific structure, when it is reacted with carbon monoxide and water or alcohol, only one unsaturated groups is carbonylated, thereby accomplishing the present invention.
DISCLOSURE OF INVENTION
That is, the present invention relates to a process for selective hydroesterification which is characterized in that (1-arylethenyl)vinylbenzene represented by the following formula (I) is reacted with carbon monoxide and water or an alcohol at a reaction temperature of 40.degree.-200.degree. C. and a carbon monoxide pressure of 20 to 700 kg/cm.sup.2 in the presence of a noble metal complex carbonylation catalyst to prepare .alpha.-((1-arylethenyl)phenyl)propionic acid or its alkyl ester represented by the following formula (II) ##STR1## wherein Ar is an aryl group which can have a substituent group except vinyl group and R is a hydrogen atom or a lower alkyl group.
The present invention is described in more detail in the following.
The aryl group Ar in the above (1-arylethenyl)vinylbenzene is exemplified by aryl groups such as phenyl, alkylphenyl, alkoxyphenyl, phenoxyphenyl and biphenyl groups as well as aryl groups in which various other substituent groups except vinyl group are introduced to phenyl groups. As such substituent groups for the aryl group, carboxyl group, hydroxyl group, alkoxy group, nitro group and alkoxycarbonyl group are exemplified.
More particularly, the above (1-arylethenyl)vinylbenzenes are exemplified those having aryl groups of phenyl, tolyl, xylyl or the like, such as (1-phenyletenyl)vinylbenzene, (1-tolylethenyl)vinylbenzene, (1-xylylethenyl)vinylbenzene, and (1-ethylphenylethenyl)vinylbenzene, having phenyl, tolyl or xylyl as the aryl group as well as (1-hydroxyphenylethenyl)vinylbenzene, (1-methoxyphenylethenyl)vinylbenzene, (1-dimethoxyphenylethenyl)vinylbenze ne, (1-ethoxyphenylethenyl)vinylbenzene, (1-carboxyphenylethenyl)vinylbenzene, (1-methoxycarbonylphenylethenyl)vinylbenzene, (1-di(methoxycarbonyl)phenylethenyl)vinylbenzene, (1-ethoxycarbonylphenylethenyl)vinylbenzene and (1-nitrophenylethenyl)vinylbenzene.
In the above compounds, all position isomers in view of the positions of substituent groups are included, however, m-isomers are preferable.
According to the method of the present invention, the compound of the formula (II) is produced by selectively hydroesterifying the vinyl group.
By the hydroesterification according to the present invention, only the vinyl group is carbonylated selectively in the compound of the foregoing formula (I) and the ethenyl group having the aryl groups does not react substantially under the foregoing reaction conditions of the present invention. Incidentally, in the case that the ethenyl group has an alkyl group in place of the aryl group, any of double bonds are hydroesterified.
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REFERENCES:
patent: 4172087 (1979-10-01), Knifton
patent: 4257973 (1981-03-01), Mrowca
patent: 4786443 (1988-11-01), Drent et al.
Arai Yutaka
Matsumura Yasuo
Shimizu Isoo
Killos Paul J.
Nippon Petrochemicals Company Limited
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