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Process for preparing optical active chrysanthemic acid

An optically active and chrysanthemic acid technology is applied in the field of preparation of optically active chrysanthemic acid and can solve the problems of low yield of optically active chrysanthemic acid and the like

Inactive Publication Date: 2002-10-09
SUMITOMO CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these optically resolved methods are not always satisfactory due to the low yield of the desired optically active chrysanthemic acid

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0157] To 30 g of chrysanthemic acid having an optical purity of 7.9% e.e. about the trans isomer and 26.8% about the optical purity of the cis isomer, and a trans / cis ratio of 80 / 20, add 120 g of toluene and Dissolve with stirring. Then, 14.8 g of (S)-1-phenyl-2-(p-tolyl)ethanamine (an optically active organic amine) was added thereto and dissolved under heating. After cooling to room temperature, deposited crystals were collected by filtration, washed with toluene and then dissolved in 5% aqueous sodium hydroxide solution. After extraction of the optically active organic amine with toluene, the aqueous phase was acidified with 5% aqueous sulfuric acid and extracted with toluene. Then, toluene was distilled off to obtain 10.3 g trans / cis with a ratio of 82 / 18 and an optical purity of 95% e.e. with respect to the (+)-trans isomer and an optical purity with respect to the (+)-cis isomer. Chrysanthemic acid with a purity of 98% e.e. (yield: 37.6%).

Embodiment 2

[0159] To 30 g of chrysanthemum with an optical purity of 3.7% e.e. for the (+)-trans isomer and 21.4% for the (+)-cis isomer, and a trans / cis ratio of 79 / 21 acid, add 180 g of toluene and dissolve under stirring. Then, 21.2 g of (S)-1-phenyl-2-(p-tolyl)ethanamine (an optically active organic amine) was added thereto and dissolved under heating. After cooling to room temperature, deposited crystals were collected by filtration, washed with toluene and then dissolved in 5% aqueous sodium hydroxide solution. After extraction of the optically active organic amine with toluene, the aqueous phase was acidified with 5% aqueous sulfuric acid and extracted with toluene. Then, toluene was distilled off to obtain 10.3 g trans / cis with a ratio of 82 / 18 and an optical purity of 95% e.e. with respect to the (+)-trans isomer and an optical purity with respect to the (+)-cis isomer. Chrysanthemic acid with a purity of 98% e.e. (yield: 34.3%).

Embodiment 3

[0161] 3.62 mg from 1.6 mg (0.008 mmol) of copper acetate monohydrate and 3.44 mg of (R)-N-salicylidene-2-amino-1,1-bis(2-methoxyphenyl)propanol Prepared copper complex, and 6.0g (55mmol) 2,5-dimethyl-2,4-hexadiene were added to a 50ml Schlenk tube, wherein the atmosphere was replaced with nitrogen, followed by adding 0.86mg of phenylhydrazine, and at 80 At °C, 1.14 g (10 mmol) of ethyl diazoacetate was added dropwise within 2 hours. After the dropwise addition of ethyl diazoacetate was completed, the mixture was further stirred at 80° C. for 1 hour. The amount of ethyl chrysanthemum acid formed was found to be 1.76 g by gas chromatography in a yield of 90.0%, based on ethyl diazoacetate and a trans / cis ratio of 59 / 41. After distilling off 2,5-dimethyl-2,4-hexadiene (boiling point: 51° C. / 30 mmHg) from the reaction mixture, 1 g of the concentrated solution was withdrawn and mixed with 10 ml of 1N aqueous sodium hydroxide solution and 5 ml of ethanol, In the alkaline solution...

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PUM

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Abstract

The invention discloses a preparation method of optically active chrysanthemum acid, which is characterized in that the ratio of the trans isomer is not less than 70% and the optical purity is 2%e.e.-less than 10%e.e. through the optical analysis of an optically active organic amine acid.

Description

technical field [0001] The invention relates to a preparation method of optically active chrysanthemic acid. Background technique [0002] (+)-2,2-Dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, known as Chrysanthemum monocarboxylic acid, constitutes the acid component of synthetic pyrethroid insecticides. [0003] The insecticidal activity of the trans-pyrethroids is generally higher than that of the cis-isomer. In particular, pyrethroids of (+)-trans-chrysanthemum monocarboxylic acid or chrysanthemic acid enriched in (+)-trans-chrysanthemum acid exhibit excellent insecticidal activity. Therefore, there has been a need for an industrially advantageous preparation of (+)-trans-chrysanthemic acid or enriched (+)-trans-chrysanthemic acid. [0004] As a method for producing an optically active chrysanthemic acid derivative by using a synthetic technique, there is known a method in which (±)-trans-chrysanthemum monocarboxylic acid or trans-rich (±)-chrysanthmonoca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B65H5/02C07C61/37
Inventor 铃鸭刚夫佐佐木和明
Owner SUMITOMO CHEM CO LTD
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