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Method for synthesizing carbamate by using olefin, amine, carbon dioxide and Togni reagent

A carbamate, carbon dioxide technology, applied in the fields of medicine, chemical industry, and organic synthesis, can solve problems such as threats to human life and health, industrial application restrictions, environmental pollution, etc., achieves good application prospects, is beneficial to industrial production, and is compatible with Good results

Active Publication Date: 2017-09-22
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Traditionally, carbamate is obtained by aminolysis of chloroformate and alcoholysis of isocyanate, but these methods require the use of highly toxic phosgene or isocyanate as raw materials, which are likely to cause environmental pollution during the production process, threatening human life and health, so its industrial application is greatly limited
However, there is no report on the direct synthesis of carbamates using olefins and carbon dioxide as raw materials.

Method used

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  • Method for synthesizing carbamate by using olefin, amine, carbon dioxide and Togni reagent
  • Method for synthesizing carbamate by using olefin, amine, carbon dioxide and Togni reagent
  • Method for synthesizing carbamate by using olefin, amine, carbon dioxide and Togni reagent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Add 1.5 ml of dimethyl sulfoxide, 0.20 mmol of styrene, 1.0 mmol of diethylamine, and 0.24 mmol of 1-trifluoromethyl-1,2-phenyliodyl-3(1H) to the autoclave successively. - Ketone, add 0.02 mmol copper acetate, then fill with 4MPa carbon dioxide, stir and react at 60°C for 8 hours, stop heating and stirring, cool to room temperature, slowly release carbon dioxide to normal pressure. The reaction solution was washed with 10 mL of water, extracted three times with ethyl acetate (15 mL each time), the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated by distillation under reduced pressure to obtain a crude product, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was a mixed solvent of petroleum ether:ethyl acetate with a volume ratio of 2:1, and the yield was 90%.

Embodiment 2

[0051] Add 1.5 ml of dimethyl sulfoxide, 0.20 mmol of styrene, 1.0 mmol of diethylamine, and 0.24 mmol of 1-trifluoromethyl-1,2-phenyliodyl-3(1H) to the autoclave successively. -ketone, then add 0.02 mmol cuprous iodide, then fill with 4MPa carbon dioxide, stir and react at 60°C for 8 hours, stop heating and stirring, cool to room temperature, slowly release carbon dioxide to normal pressure. The reaction solution was washed with 10 mL of water, extracted three times with ethyl acetate (15 mL each time), the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated by distillation under reduced pressure to obtain a crude product, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was petroleum ether:ethyl acetate mixed solvent with a volume ratio of 2:1, and the yield was 51%.

Embodiment 3

[0053] Add 1.5 ml of dimethyl sulfoxide, 0.20 mmol of styrene, 1.0 mmol of diethylamine, and 0.24 mmol of 1-trifluoromethyl-1,2-phenyliodyl-3(1H) to the autoclave successively. - Ketone, then add 0.02 mmol copper trifluoromethanesulfonate, then fill with 4MPa carbon dioxide, stir and react at 60°C for 8 hours, stop heating and stirring, cool to room temperature, slowly release carbon dioxide to normal pressure. The reaction solution was washed with 10 mL of water, extracted three times with ethyl acetate (15 mL each time), the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated by distillation under reduced pressure to obtain a crude product, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was petroleum ether:ethyl acetate mixed solvent with a volume ratio of 2:1, and the yield was 88%.

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Abstract

The present invention relates to a method for synthesizing carbamate by using an olefin, an amine, carbon dioxide and a Togni reagent. The method comprises: in a high pressure reaction kettle, sequentially adding an organic solvent, an olefin, an amine and a Togni reagent, adding a copper salt as a catalyst, introducing carbon dioxide, carrying out a stirring reaction for 5-24 h at a temperature of 40-100 DEG C, cooling to a room temperature after completing the reaction, slowly releasing carbon dioxide to achieve an atmospheric pressure, carrying out water washing on the reaction solution, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, carrying out pressure reducing distillation concentration to obtain a crude product, and carrying out column chromatography purification to obtain the carbamate compound. According to the present invention, the synthesis method avoids the use of toxic raw materials such as phosgene or isocyanate, and the like, has characteristics of safe and simple operation, mild reaction condition, good functional group compatibility, wide substrate applicability and high yield, is suitable for industrial production, and has good application prospects in synthesis of pesticides, medicine, and natural products.

Description

technical field [0001] The invention relates to the technical fields of organic synthesis, medicine and chemical industry, in particular to a method for synthesizing carbamate by using olefin, amine, carbon dioxide and Togni reagent under the catalysis of copper salt. Background technique [0002] Carbamates are a very important class of organic compounds, which are widely used in agriculture, medical and health and other fields. In agriculture, carbamates can be used as insecticides, acaricides, herbicides and fungicides, such as carbofuran, fenzazolin, methomyl, hexacarb and other pesticides. In medicine, many important drugs such as the drug Exelon for the treatment of Alzheimer's disease and the drug Xeloda for the treatment of colorectal, breast and stomach cancers are carbamates Esters (B.Shen and T.F.Jamison, Org.Lett., 2012, 14, 3348; E.Sawatzky, S.Wehle, B.Kling, J.Wendrich, G.Bringmann, C.A.Sotri er, J.Heilmann, and M. Decker, J. Med. Chem., 2016, 59, 2067). Car...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C271/12C07C269/04C07C269/08C07D295/20
CPCC07C269/04C07C269/08C07D295/20C07C271/12
Inventor 戚朝荣郭天佐江焕峰
Owner SOUTH CHINA UNIV OF TECH
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