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Method for preparing 7-chloroquinaldine by use of phase-transfer catalytic reaction

A phase transfer catalysis and reaction technology, applied in the direction of organic chemistry, etc., can solve the problems of harsh process conditions, product loss, high price of tetrachloro-p-benzoquinone, and achieve the effects of improving reaction efficiency, increasing emulsification, and simple post-treatment

Inactive Publication Date: 2014-01-22
LIANYUNGANG HUALUN CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

(US, 5126456) discloses a kind of use tetrachloro-p-benzoquinone as oxidant, reflux reaction in the isopropanol solution of hydrogen chloride, the yield of product 7-chloroquinaldine is 67%, but due to the separation of the 5-position isomer Need to use a lot of flammable tetrahydrofuran, and the price of the oxidant tetrachloro-p-benzoquinone is relatively high, the process conditions are harsh, and the time for adding crotonaldehyde is too long, which is restricted in industrial production
(CN 101638382) discloses a method for preparing 7-chloroquinaldine by phase transfer reaction, using m-chloroaniline and crotonaldehyde as raw materials, and using alkylphenol polyoxyethylene ether OP-10, OP-7, etc. as phase transfer Catalyst, tetrachloro-p-benzoquinone, etc. are used as catalysts to react in the prepared alkene acid solution at 98~103°C, and the yield is 70%. However, the post-treatment of this reaction is complicated and requires continuous vacuum distillation to collect the product, which makes the product loss serious , not suitable for industrial production

Method used

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  • Method for preparing 7-chloroquinaldine by use of phase-transfer catalytic reaction

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Effect test

Embodiment 1

[0024] First dissolve 12.7g m-chloroaniline in 50mL of organic solvent 2-butanol, add it to a three-necked flask and stir, add 14.4g of surfactant sodium lauryl sulfate and 18.25g of oxidant phosphomolybdic acid, add 100mL of aqueous solution and The mixed solvent of 2-butanol was stirred at 80 °C for 1 h; then 7 g of crotonaldehyde was added dropwise to the mixture, and the reaction was continued at 80 °C for 4 h; after the reaction, the mixture was layered, and 2-butanol was recovered from the organic phase , the aqueous phase was distilled under reduced pressure to remove acid, and the 3 The solution was washed and recrystallized from ethanol to obtain high-purity 7-chloroquinaldine with a yield of 85%.

Embodiment 2

[0026] First dissolve 12.7g m-chloroaniline in 50mL of organic solvent 2-butanol, add it to a three-necked flask and stir, add 28.8g of surfactant sodium lauryl sulfate and 36.5g of oxidant phosphomolybdic acid, add 100mL of aqueous solution and The mixed solvent of 2-butanol was stirred at 85°C for 2h; then 7g of crotonaldehyde was added dropwise to the mixture, and the reaction was continued at 85°C for 3h; after the reaction, the mixture was layered, and 2-butanol was recovered from the organic phase , the aqueous phase was distilled under reduced pressure to remove the acid, and the aqueous phase was distilled off with 8wt% 100mL NaHCO 3 The solution was washed and recrystallized with ethanol to obtain high-purity 7-chloroquinaldine with a yield of 83%.

Embodiment 3

[0028] First dissolve 12.7g m-chloroaniline in 50mL of organic solvent 2-butanol, add it to a three-necked flask and stir, add 20.4g of surfactant sodium lauryl sulfate and 30.5g of oxidant phosphomolybdic acid, add 100mL of aqueous solution and The mixed solvent of 2-butanol was stirred at 90°C for 2h; then 7g of crotonaldehyde was added dropwise to the mixture, and the reaction was continued at 90°C for 4h; after the reaction, the mixture was layered, and 2-butanol was recovered from the organic phase , the aqueous phase was distilled under reduced pressure to remove the acid, and the aqueous phase was distilled off with 8wt% 100mL NaHCO 3 The solution was washed and recrystallized with ethanol to obtain high-purity 7-chloroquinalidine with a yield of 89%.

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Abstract

The invention discloses a method for preparing 7-chloroquinaldine by use of a phase-transfer catalytic reaction. M-chloroaniline and crotonaldehyde are used as raw materials, lauryl sodium sulfate (serving as a surface active agent) and phosphomolybdic acid (serving as a oxidizing agent) are added in a water and 2-butanol reaction system for reaction to obtain the 7-chloroquinaldine with high yield. Compared with the prior art, the method has the remarkable advantages that (1) the lauryl sodium sulfate is added to enhance emulsibility of reaction liquid, the generation of byproducts (5-isomer) is inhibited, and the reaction efficiency is greatly improved; (2) the phosphomolybdic acid is also added, as the oxidizing agent has common gender of acid, the traditional acid solvent is avoided, and the property of the oxidizing agent can be realized; (3) the reaction can be performed in water, the aftertreatment is simple, and the reaction yield (up to 89%) is greatly improved.

Description

technical field [0001] The invention belongs to the field of pharmaceutical intermediates, and in particular relates to a method for preparing 7-chloroquinalidine by utilizing a phase transfer catalytic reaction. Background technique [0002] As an important pharmaceutical intermediate, 7-chloroquinalidine is mainly used to prepare the important intermediate of antiasthma drug motelast and leukotriene receptor antagonist MK-0679. The traditional method uses m-chloroaniline and crotonaldehyde as the main raw materials to prepare through the classic Skraup reaction and DeobnerMiller reaction. Since the reaction has 5-position isomers, ZnCl is required. 2 , tartaric acid or 4-nitrophthalic acid and isomers are mixed and complexed to separate and purify to obtain high-purity 7-chloroquinalidine, so the yield is low. (US, 5126456) discloses a kind of using tetrachloro-p-benzoquinone as an oxidant, and refluxing in the isopropanol solution of hydrogen chloride, the yield of the p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/18
CPCC07D215/18
Inventor 刘冰陆成洪席国华
Owner LIANYUNGANG HUALUN CHEM
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