Preparation method for safely synthesizing dehydroabietic acid degraded amine

A dehydroabietic acid conversion technology, which is applied in the field of preparation of chiral compounds dehydroabietic acid degraded amines, can solve the problems of reduced yield, inability to prepare in large quantities, easy explosion and the like

Inactive Publication Date: 2011-05-11
INST OF MATERIA MEDICA CHINESE ACAD OF MEDICAL SCI
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  • Summary
  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

[0007] R.N.Seelye (Tetrahedron, 1969 (25); 447-451); Zhang Jingxia, Zhou Yongyan, Cai Qian (Synthetic Chemistry, 1997; 120-122) all need to drop the dehydroabietic acid chloride of preparation in the article published respectively In the mixed solvent of acetone and water of sodium azide, therefore there is the hydrolysis of part dehydroabietic acid acid chloride, which reduces the yield, and the obtained dehydroabietic acid acid azide needs to be extracted with an organic solvent, and then carried out The concentration process of the organic extractant is evaporated under reduced pressure. In this process, the high-concentration dehydroabietic acid acyl azide is easy to explode and is very dangerous. Therefore, it is not a safe and controllable preparation process, and it is impossible to prepare a large amount of this excellent chiral amine

Method used

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  • Preparation method for safely synthesizing dehydroabietic acid degraded amine
  • Preparation method for safely synthesizing dehydroabietic acid degraded amine
  • Preparation method for safely synthesizing dehydroabietic acid degraded amine

Examples

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Embodiment 1

[0053] In a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and a 500ml three-neck flask equipped with electromagnetic stirring, add 200ml of anhydrous toluene, start stirring, and dissolve 40g (0.133mol) of dehydroabietic acid in toluene Heating to 80°C, adding 40ml of freshly steamed thionyl chloride dropwise, and reacting for 5 hours, distilling off the solvent under reduced pressure, then adding 100ml of anhydrous toluene, removing the solvent under reduced pressure again to take away the residual thionyl chloride and Acid gas was obtained to obtain a yellow viscous liquid, which was dissolved in 100ml of anhydrous toluene and set aside.

[0054]In a 300ml three-neck flask equipped with a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and electromagnetic stirring, add 100ml of anhydrous toluene and 9.8g (0.15mol) of sodium azide, and heat to 70°C under stirring , stop heating, slowly add the above-m...

Embodiment 2

[0059] In a 500ml there-necked flask equipped with a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and electromagnetic stirring, add 200ml of anhydrous chloroform, start stirring, and dissolve 40g (0.133mol) of dehydroabietic acid In chloroform, heat to 60°C, add dropwise 40ml of freshly steamed thionyl chloride, react for 5 hours, evaporate the solvent under reduced pressure, and then add 100ml of anhydrous toluene, remove the solvent under reduced pressure again to take away the residual Thionyl chloride and acid gas were used to obtain a yellow viscous liquid, which was dissolved in 100ml of anhydrous chloroform and set aside.

[0060] In a 300ml three-neck flask equipped with a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and electromagnetic stirring, add 100ml of anhydrous chloroform, 9.8g (0.15mol) of sodium azide, and heat to 50°C, stop heating, slowly add the chloroform solution of the above...

Embodiment 3

[0065] In a 500ml there-necked flask equipped with a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and electromagnetic stirring, add 200ml of anhydrous xylene, start stirring, and dissolve 40g (0.133mol) of dehydroabietic acid in In xylene, heat to 80°C, add 40ml of freshly steamed thionyl chloride dropwise, react for 5 hours, evaporate the solvent under reduced pressure, and then add 100ml of anhydrous xylene, remove the solvent under reduced pressure again to take away the residual chlorine Dissolve sulfoxide and acid gas to obtain a yellow viscous liquid, which is dissolved in 100ml of anhydrous xylene and set aside.

[0066] In a 300ml three-neck flask equipped with a reflux condenser, a drying tube, a thermometer, a constant pressure dropping funnel, and electromagnetic stirring, add 100ml of anhydrous xylene and 9.8g (0.15mol) of sodium azide, and heat to 100 ℃, stop heating, slowly add the xylene solution of the above-mentioned deh...

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Abstract

The invention discloses a method for safely preparing dehydroabietic acid degraded amine. The method comprises the following steps of: mixing an azide with an inert organic solvent; adding dehydroabietic acid acyl halide or active ester under the condition of heating; immediately rearranging a generated dehydroabietic acid acyl azide in situ to generate corresponding isocyanate; and then hydrolyzing to generate the dehydroabietic acid degraded amine. By means of the method, a process of enriching dehydroabietic acid acyl nitrine easy to explode is avoided, the reaction process is safe and controllable, and all reactions and purification measures conform to the requirement of industrial production.

Description

technical field [0001] The invention relates to a preparation method of a chiral compound dehydroabietic acid degradation amine. Background technique [0002] Dehydroabietine degrades amines, as shown in formula 1 [0003] [0004] Formula 1 [0005] It is a right-handed chiral amine, which can be used to resolve many chiral acids and has important application value. For example, it can be used to resolve racemic trans chrysanthemic acid to obtain an optical purity of 99% (Lin Dongen, Cai Yubi, Cai Qian, Journal of South China University of Technology (Natural Science Edition), 1999; 100-105), so there is a high application value and needs. [0006] In the article published by Stockel (Canadian Journal of Chemistry 1963 (41); 834-836), the mixture of dehydroabietic acid and polyphosphoric acid and sodium azide needs to be heated to prepare dehydroabietic acid degradation amine. Producing explosive and highly toxic azide, the article also mentions the preparation of a ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/42C07C209/62
Inventor 吴松刘前杨庆云戚燕童元峰
Owner INST OF MATERIA MEDICA CHINESE ACAD OF MEDICAL SCI
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