Chemistry: molecular biology and microbiology – Micro-organism – tissue cell culture or enzyme using process... – Preparing oxygen-containing organic compound
Reexamination Certificate
1999-05-13
2001-03-27
Lilling, Herbert J. (Department: 1651)
Chemistry: molecular biology and microbiology
Micro-organism, tissue cell culture or enzyme using process...
Preparing oxygen-containing organic compound
19
Reexamination Certificate
active
06207429
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for producing (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid.
2. Description of the Related Art
2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acids, which are represented by the general formula (1):
(wherein X is a hydrogen atom or a chlorine atom; and Y is a methyl group when X is a hydrogen atom, whereas Y is a methyl group or a fluorine atom when X is a chlorine atom) constitute the acid components of esters collectively called a synthetic pyrethroid having a highly effective insecticidal activity.
Since these cyclopropanecarboxylic acids have asymmetric carbon atoms in C
1
and C
3
positions thereof, there are 4 stereoisomers of cyclopropanecarboxylic acid. And, the pesticidal activity of the pyrethroid, whose acid component is one of these stereoisomers, varies according to target noxious insects, kinds of formulation, and the like. Accordingly, there is a demand for a method by which a desired specific stereoisomer of the cyclopropanecarboxylic acid is produced in an industrially advantageous way.
Under these circumstance, after intense studies for the establishment of an industrially advantageous method for producing (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid, the present inventors have achieved the invention based on finding that an esterase derived from a microorganism belonging to Genus Arthrobacter can act on 2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid esters represented by the general formula (2):
(wherein X is a hydrogen atom or a chlorine atom; Y is a methyl group when X is a hydrogen atom, whereas Y is a methyl group or a fluorine atom when X is a chlorine atom; and R is a C
1
-C
4
alkyl group) so that the ester is asymmetrically hydrolyzed.
SUMMARY OF THE INVENTION
The present invention provides:
1. a method for producing (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid, comprising reacting with 2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid esters represented by the general formula (2) an esterase capable of acting on and asymmetrically hydrolyzing said esters to (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof so that said esters are made resoluble into (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof; and isolating and recovering the (1R)-trans-2,2-dimethyl-3-(substituted vinyl)cyclopropane-1-carboxylic acid;
2. a method for producing (1R)-trans-2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid, comprising reacting with 2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid esters represented by the general formula (3):
(wherein R is a C
1
-C
4
alkyl group) an esterase capable of acting on and asymmetrically hydrolyzing said esters to (1R)-trans-2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof so that said esters are made resoluble into (1R)-trans-2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof; and isolating and recovering the (1R)-trans-2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid;
3. a method for producing (1R)-trans-2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid, comprising reacting with 2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid esters represented by the general formula (4):
(wherein R is a C
1
-C
4
alkyl group) an esterase capable of acting on and asymmetrically hydrolyzing said esters to (1R)-trans-2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof so that said esters are made resoluble into (1R)-trans-2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof; and isolating and recovering the (1R)-trans-2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid;
4. a method for producing (1R)-trans-2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxylic acid, comprising reacting with 2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxylic acid esters represented by the general formula (5):
(wherein R is a C
1
-C
4
alkyl group) an esterase capable of acting on and asymmetrically hydrolyzing said esters to (1R)-trans-2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof so that said esters are made resoluble into (1R)-trans-2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxylic acid and esters of diastereomers thereof; and isolating and recovering the (1R)-trans-2,2-dimethyl-3-(2-chloro-2-fluorovinyl) cyclopropane-1-carboxylic acid;
5. the method according to the above 1 to 4, wherein the esterase is an esterase derived from a microorganism belonging to Genus Arthrobacter; and
6. the method according to the above 1 to 4, wherein the esterase is an esterase derived from Arthrobacter SC-6-98-28 strain (FERM BP-3658).
There are geometrical isomers on a basis of the double bond of substituted vinyl group at a 3-position of cyclopropane ring which is comprised in the ester compounds represented by the general formulas 3 to 5 as described in the above 1 to 4, i.e. E-isomer and Z-isomer. Those geometrical isomer and a mixture thereof at any ratio may be used as a raw material in the present invention (2,2-dimethyl-3-(substituted vinyl) cyclopropane-1-carboxylic acid ester), and thus an end product corresponding to the raw material ((1R)-trans-2,2-dimethyl-3-(substituted vinyl) cyclopropane-1-carboxylic acid) can be obtained.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
In an addition, throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The 2,2-dimethyl-3-(1-propenyl)cyclopropane-1-carboxylic acid esters represented by the general formula (3) for use as a raw material in the present invention may be produced by, for example, the method described in J. Chem. Soc. 1076 (1970). The carboxylic acid esters may be a methyl ester, an ethyl ester, a propyl ester, a butyl ester, and the like. In these esters, a methyl ester and an ethyl ester are preferable.
Further, the 2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropane-1-carboxylic acid esters represented by the general formula (4) for use as a raw material in the present invention may be produced by, for example, the method described in Chemical Listy 52, 688 (1958). The carboxylic acid esters may be a methyl ester, an ethyl ester, a propyl ester, a butyl ester, and the like. In these esters, a methyl ester and an ethyl ester are preferable.
Still further, the 2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxylic acid esters represented by the general formula (5) for use as a raw material in the present invention may be produced by, for example, the method described in Chemical Listy 52, 688 (1958). The carboxylic acid esters may be a methyl ester, an ethyl ester, a propyl ester, a butyl ester, and the like. In these esters, a methyl ester and an ethyl ester are preferable.
The esterase used in the present invention is one capable of acting on and asymmetrically hydrolyzing the 2,2-dimethyl-3-(1-propenyl)cyclopropane-1-ca
Asako Hiroyuki
Fukita Yoshikazu
Ishii Takeshi
Birch & Stewart Kolasch & Birch, LLP
Lilling Herbert J.
Sumitomo Chemical Company Limited
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