Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
1999-01-27
2001-07-31
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C560S124000, C562S506000
Reexamination Certificate
active
06268525
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Filed of the Invention
The present invention relates to a method for producing an optically active chrysanthemic acid (cyclopropanecarboxylic acid) derivative.
2. Description of the Related Art
Optically active cyclopropanecarboxylic acid derivatives are important intermediates for drugs and pesticides. For example, (+)-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid known as chrysanthemum mono-carboxylic acid constitutes an acid component of synthetic pyrethroid insecticide.
The insecticidal activity of a trans-pyrethroid ester is usually higher than that of a cis-isomer. Particularly, pyrethroid esters of (+)-trans-chrysanthemum mono-carboxylic acid(hereinafter referred to as “chrysanthemic acid”) or chrysanthemic acid enriched with the (+)-trans-chrysanthemic acid have exhibited excellent insecticidal activity. Accordingly, an industrially advantageous method to produce (+)-trans-chrysanthemic acid or chrysanthemic acid enriched with the (+)-trans-chrysanthemic acid has been desired.
As a method of producing an optically active chrysanthemic acid derivative by using a synthetic technique, there has been known a method of reacting a (±)-trans-chrysanthemum mono-carboxylic acid or trans rich (±)-chrysanthemum mono-carboxylic acid with an optical resolution agent, which are an optically active amine, to obtain an optically active chrysanthemic acid (JP46-20382B/1971, JP54-37130B/1979, JP49-109344A/1974 and JP51-23497B/1976). However, these optical resolution methods were not always satisfactory, because of low yield of the desired optically active chrysanthemic acid.
Therefore, the present inventors have intensively studied. As a result, they have found that, when chrysanthemic acid optically enriched with one isomer, e.g. (+)-trans-chrysanthemic acid can be purified by crystallization using an optical active amine in the production of an optically active chrysanthemic acid, whereby (+)-trans-chrysanthemic acid having excellent optical purity can be obtained with surprisingly good efficiency compared with the case of using racemic chrysanthemic acid, and trans isomer ratio of the chrysanthemic acid can also be improved efficiently when trans isomer having not less than 50% trans-isomer ratio are applied.
SUMMARY OF THE INVENTION
The present invention provides:
1. a method for producing an optically active chrysanthemic acid whose trans isomer ratio and optical purity are improved, which comprises:
reacting chrysanthemic acid having a trans isomer ratio of not less than 50% and an optical purity of not less than 10% e.e. with an optically active organic amine to optically resolve said chrysanthemic acid; and
2. a method for producing an optically active chrysanthemic acid whose trans isomer ratio and optical purity are improved, which comprises:
reacting 2,5-dimethyl-2,4-hexadiene with diazoacetates of the formula (1):
N
2
CHCO
2
R
7
(I)
wherein R
7
represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, in the presence of an asymmetric copper complex to produce an optically active chrysanthemic add ester (cyclopropanation step),
contacting chrysanthemic acid esters with an acid or base to form chrysanthemic acid (hydrolysis step); and
optically resolving chrysanthemic acid using at least one optically active organic amine selected from those of the formulas (A-1), (A-2), (A-3) and (A-4) shown below (optical resolution step).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
First, a description will be made to the method for producing an optically active chrysanthemic acid of which trans isomer ratio and optical purity are improved, which comprises:
reacting chrysanthemic acid having a trans isomer ratio of not less than 50% and an optical purity of not less than 10% e.e. with an optically active organic amine to optically resolve said chrysanthemic acid.
Chrysanthemic acid having a trans isomer ratio of not less than 50% and an optical purity of not less than 10% e.e. can be obtained by any method, for example, it can be produced in the following manner.
In the present invention, the “optical purity” or e.e. % of (+)-trans-chrysanthemic acid in the trans isomer is calculated based on the analysis using optically active column and is defined, for example, by the following equation: 100 ×{[(+-trans-chrysanthemic acid−(−)-trans-chrysanthemic acid]/[(+)-trans-chrysanthemic acid+(−)-trans-chrysanthemic acid]}.
The optically active chrysanthemic acid can be obtained by reacting 2,5-dimethyl-2,4-hexadiene with diazoacetate of the formula (I):
N
2
CHCO
2
R
7
(I)
wherein R
7
represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, in the presence of an asymmetric copper complex to produce optically active chrysanthemic acid esters (cyclopropanation step); and decomposing chrysanthemic acid esters with an alkali or acid (hydrolysis step).
In this method trans isomer ratio of not less than 50% and optical purity of not less than 20% e.e. is preferably employed, more preferably, chrysanthemic acid having trans isomer ratio of from 60% e.e. to 95% e.e. and optical purity of from 30% e.e. to 90% e.e. is employed.
The optically active organic amine for optically resolving the optically active chrysanthemic acid includes, for example, an optically active organic amine of the formula (A-1):
wherein R
1
and R
2
respectively represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
X and Y respectively represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group; and
* represents an asymmetric carbon atom; or
an optically active organic amine of the formula (A-2):
wherein R
1
and R
2
respectively represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
R
3
represents an alkyl group having 1 to 6 carbon atoms, and
* represents an asymmetric carbon atom; or
an optically active organic amine of the formula (A-3):
wherein R
4
represents a naphthyl group, a cyclohexyl group, or a phenyl group which may be substituted with halogen, nitro, lower alkyl or lower alkoxy;
R
5
represents a lower alkyl group, or a benzyl group which may be substituted with a lower alkyl group;
R
6
represents a p-hydroxyphenyl group or a 2-hydroxy-3-lower alkoxyphenyl group when R
5
is a lower alkyl group, and
R
6
represents a p-hydroxyphenyl group when R
5
is a benzyl group which may be substituted with a lower alkyl group, and
* represents an asymmetric carbon atom, or an optically active organic amine of the formula (A-4):
wherein R
1
and R
2
respectively represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and
* represents an asymmetric carbon atom.
The optically active amine includes, for example, optically active compounds such as 1-phenyl-2-(p-tolyl)ethylamine, &agr;-(1-naphthyl)-ethylamine,
&agr;-(2-naphthyl)-ethylamine, 1-phenylethylamine,
erythro-&agr;,&bgr;-diphenyl-&bgr;-hydroxyethylamine, N-methylephedrine,
N-(2,2,2-trichloro-1-formamideethyl)piperidine, 2-benzylamino-1-butanol,
ephedrine, cis-N-benzyl-2-(hydroxymethyl)cyclohexylamine,
N-(p-hydroxybenzyl)-1-phenylethylamine,
N-(p-hydroxybenzyl)-1-(p-tolyl)ethylamine,
N-(p-hydroxybenzyl)-1-(p-isopropylphenyl)ethylamine,
N-(p-hydroxybenzyl)-1-(p-nitrophenyl)ethylamine,
N-(p-hydroxybenzyl)-1-(p-bromophenyl)ethylamine,
N-(p-hydroxybenzyl)-1-(1-naphthyl)ethylamine,
N-(p-hydroxybenzyl)-1-cyclohexylethylamine,
N-(p-hydroxybenzyl)-1-(p-methoxyphenyl)ethylamine,
N-(p-hydroxybenzyl)-1-phenylpropylamine,
N-(p-hydroxybenzyl2-methyl-1-phenylpropylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-phenylethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-(p-tolyl)ethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-(p-isopropylphenyl)ethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-(p-nitrophenyl)ethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-(p-bromophenyl)ethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-(1-naphthyl)ethylamine,
N-(2-hydroxy-3-methoxybenzyl)-1-cylohexylethylamine,
N
Fujita Kunihiko
Itagaki Makoto
Sasaki Kazuaki
Suzukamo Goufu
Killos Paul J.
Sughrue Mion Zinn Macpeak & Seas, PLLC
Sumitomo Chemical Company Limited
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