Chemistry: molecular biology and microbiology – Process of utilizing an enzyme or micro-organism to destroy... – Resolution of optical isomers or purification of organic...
Patent
1984-09-07
1986-08-19
Marantz, Sidney
Chemistry: molecular biology and microbiology
Process of utilizing an enzyme or micro-organism to destroy...
Resolution of optical isomers or purification of organic...
435149, C07P 4100, C12P 738
Patent
active
046070133
DESCRIPTION:
BRIEF SUMMARY
THE TECHNICAL FIELD
This invention relates to a biochemical process for optical resolution of (.+-.)-4-hydroxy-3-methyl-2-2'-propynyl-2-cyclopentenone represented by the following formula (I): ##STR1## More particularly, the invention relates to an industrially advantageous biochemical process for optical resolution of 4-hydroxy-3-methyl-2-2'-propynyl-2-cyclopentenone, which comprises asymmetrically hydrolyzing organic carboxylic acid (saturated or unsaturated carboxylic acids having 1 to 18 carbon atoms) esters of (.+-.)-4-hydroxy-3-methyl-2-2'-propynyl-2-cyclopentenone by the action of an esterase originated from a microorganism or an animal pancreas to give optically active 4-hydroxy-3-methyl-2-2'-propynyl-2-cyclopentenone and esters of its antipode with high optical purity.
BACKGROUND TECHNOLOGY
4-Hydroxy-3-methyl-2-2'-propynyl-2-cyclopentenone (hereinafter referred to as propynylcyclopentenolone) is known as one of the important alcohol components in a group of ester compounds called "synthetic pyrethroids" which have excellent insecticidal activities.
For example, a compound of the formula (II) as described below which is an ester of the propynylcyclopentenolone and 2,2,3,3-tetramethylcyclopropanecarboxylic acid is an excellent insecticide having quite strong knockdown and lethal effects (Japanese Published Examined Patent Application No. 50-15843). ##STR2##
There are two kinds of optical isomers in the propynylcyclopentenolone because it has an asymmetric carbon atom in the 4-position thereof, and usually, their activities as esters are greatly different. For example, in the ester represented by the foregoing formula (II), an ester of the (+)-propynylcyclopentenolone has an insecticidal activity several times higher than that of a corresponding ester of the (-)-propynylcyclopentenolone. Thus, there are demanded industrially advantageous technologies of optical resolution of the (.+-.)-propynylcyclopentenolone obtained by the conventional production processes.
As methods for producing optically active propynylcyclopentenolone, a following method has been known; which method comprises converting (.+-.)-propynylcyclopentenolone into a half ester of phthalic acid, reacting this ester with an optically active amine to form diastereomer salts of the optically active propynylcyclopentenolone, isolating and recovering a salt as the amine used and half ester, and then, hydrolyzing the resulting half ester (Japanese Published Unexamined Patent Application No. 56-2929). It is hard to say that this process is satisfactory, however, because it is low in overall yield and requires complicated procedures and expensive optically active reagents.
DISCLOSURE OF THE INVENTION
The present inventors have conducted extensive studies in order to establish a process for optical resolution of (.+-.)-propynylcyclopentenolone, which may overcome the foregoing problems and is more advantageous industrially. As a result, the present inventors have found that optically active propynylcyclopentenolone and esters of its antipode having high optical purity can be obtained by reacting the organic carboxylic acid (saturated or unsaturated organic carboxylic acids having 1 to 18 carbon atoms) esters of (.+-.)-propynylcyclopentenolone with an esterase originated from a microorganism or an animal pancreas. The present invention has been achieved by giving various considerations to such finding.
Hereunder, the present invention will be explained in detail. Organic carboxylic acid (saturated carboxylic acids having 1 to 18 carbon atoms) esters of (.+-.)-propynylcyclopentenolone used as the starting material in the process of the present invention can be easily prepared by conventional methods for the production of esters, e.g., a method for reacting (.+-.)-propynylcyclopentenolone with anhydrides of organic carboxylic acids, a method for reacting it with organic carboxylic acid chlorides in the presence of organic bases, or the like.
The microorganisms, which produce employable esterase in the invention, are those capable of asymme
REFERENCES:
patent: 4385186 (1983-05-01), Matsuo et al.
Oritani et al., Agr. Biol. Chem. 38(10), 1961-1964, (1974).
Chemical Abstracts I: 85: 61429y Mar. 25, 76.
Iriuchuima, S. et al., Agric. Biol. Chem., 45(6) pp. 1389-1392, 1981.
Hirohara Hideo
Mitsuda Satoshi
Krawczewicz L.
Marantz Sidney
Sumitomo Chemical Company Limited
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