Process for obtaining enantiomers of chrysanthemic acid

A technology of enantiomers and isomer mixtures, applied in the field of obtaining chrysanthemic acid enantiomers, can solve problems such as cost and manufacturing time rebound, and hinder effective recovery of solvents

Active Publication Date: 2011-08-17
ENDURA AG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The need to use solvent mixtures of precise composition is an impediment to the efficient reconstitution of the solvents used, and their use in subsequent processes, and creates a strong rebound in cost and manufacturing time

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0101] d,l-trans-chrysanthemic acid was isolated from racemic chrysanthemic acid (trans:cis diastereomer ratio 65:35) using (1S,2S)-(+)-DMPP.

[0102] (1S,2S)-(+)-2-Dimethylamino-1-benzene-1,3-propanediol [(1S,2S)-(+)-DMPP], 41.0 g (0.21 moles), was added to 200 ml of isopropyl ether. The mixture was heated at reflux (65°C), and 100 ml of isopropyl ether dissolved with 50.5 g (0.30 moles) of racemic chrysanthemic acid (trans:cis achiral enantiomer ratio 65:35) was slowly added to the preceding mixture middle.

[0103] At the end of the addition, a corresponding salt precipitation was observed after a few minutes.

[0104] The mixture was maintained at 65°C for 45 minutes with stirring.

[0105] It was cooled to room temperature and then cooled down to 10 °C with stirring.

[0106] The salt was filtered and washed twice with 50 ml isopropyl ether.

[0107] 71.9 g of d-p were obtained after drying 1 , n 1 Salt dl-trans-ChA.1S,2S-(+)-DMPP. To the resulting salt was added ...

example 2

[0114] d,l-trans-chrysanthemic acid was isolated from racemic chrysanthemic acid (trans:cis diastereomer ratio 65:35) using (1R,2R)-(-)-DMPP.

[0115] The dl-trans isomer was separated from the dl-cis isomer of chrysanthemic acid using the method described in Example 1, but the base used was (1R,2R)-(-)-2-dimethylamino-1-benzene- 1,3-Propanediol, [(1R,2R)-(-)-DMPP]. l-p formed 1 , n 1 The salt is dl-trans-ChA 1R, 2R-(-)-DMPP:

[0116] mp=110-111.5°C;

[0117] [α] D = -26.4° (c 1.032, chloroform), d-p 1 , n 1 Enantiomers of salts.

example 3

[0119] (1S,2S)-(+)-DMPP was separated from racemic chrysanthemic acid (trans:cis diastereomer ratio 80:20) of d,l-trans-chrysanthemic acid.

[0120] Similar to that described in Example 1, dissolved with 46.9g (0.24moles) of (1S, 2S)-(+)-2-dimethylammonia-1-benzene-1,3-propanediol [(1S, 2S)-(+ )-DMPP] in 250 ml isopropyl ether was reacted with 50 g (0.30 moles) of racemic chrysanthemic acid (trans:cis diastereomer ratio 80:20) dissolved in 50 ml isopropyl ether.

[0121] Later on corresponding salt precipitation increases.

[0122] The mixture was maintained at 65°C for 1.5 hours with stirring.

[0123] Cool to room temperature and then to 10°C.

[0124] The salt was filtered and washed twice with 50 ml isopropyl ether.

[0125] 81.7 g of salt were obtained after drying.

[0126] Analysis (chiral column GC) of a salt sample after treatment with 1N HCl and extraction with ethyl ether showed that chrysanthemic acid had a trans:cis diastereomer ratio of 95:5, ee(l-trans)=0.6%...

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PUM

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Abstract

A new process is described, easy to perform on industrial scale, with high yield, for obtaining enantiomers of chrysanthemic acid starting from mixtures containing them. The process involves reacting said mixtures with enantiomers of 2- dimethylamino-1-phenyl-1 ,3-propanediol (DMPP) and 2-dimethylamino-1-[4- (methylthio)phenyl]propane-1 ,3-diol (MTDP) as chiral selectors. The invention includes salts of chrysanthemic acid with the aforesaid chiral selectors as process intermediates. The process allows operation in a single solvent rather than in solvent mixtures difficult to recover and reuse, and the final crystallization product does not incorporate molecules of solvent. The bases used are then recovered and reused in subsequent separations.

Description

Technical field: [0001] The invention relates to a pyrethroid insecticide and its preparation and purification process. A new method for obtaining the enantiomers of chrysanthemic acid is described. Background technique: [0002] The synthesis of 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid (chrysanthemic acid, hereinafter referred to as ChA) in the past 30 years. This compound is the starting material for the synthesis of different pyrethroid insecticides, which are widely used in agriculture and households to control ants, spiders, mosquitoes, flies and other nuisance insects; they are characterized by their low toxicity to mammals, while Has high insecticidal activity. [0003] Chrysanthemic acid is a chiral compound with an asymmetric center and is optically active: it exhibits four types, right-handed cis (d-cis), left-handed cis (l-cis), right-handed trans (d- trans), levorotatory trans (l-trans), differ by changing optical and geometric isomers, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C61/37C07C51/487C07C323/32
CPCC07C51/487C07C323/32C07C61/37
Inventor 瓦莱里奥·波扎塔高夫雷德·罗西尼克劳迪亚·阿尤伯保罗·雷奇伊利萨·卡帕雷拉
Owner ENDURA AG
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