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Method for synthesizing carbamate by ketone, amine and carbon dioxide

A carbamate and carbon dioxide technology, which is applied in the preparation of carbamic acid derivatives, chemical instruments and methods, and the preparation of organic compounds, can solve the problems of low substrate applicability, poor chemical selectivity, and low atom economy , to achieve the effects of reactive atom economy, simple operation and good compatibility

Active Publication Date: 2016-12-14
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Although great progress has been made in the synthesis of carbamates using carbon dioxide, there are still many shortcomings to be overcome in existing methods, such as low yield, poor chemoselectivity, low substrate applicability, low atom economy, etc.

Method used

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  • Method for synthesizing carbamate by ketone, amine and carbon dioxide
  • Method for synthesizing carbamate by ketone, amine and carbon dioxide
  • Method for synthesizing carbamate by ketone, amine and carbon dioxide

Examples

Experimental program
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Effect test

Embodiment 1

[0048] Add 1 mmol 1-phenyl-1-propanone, 0.2 mmol tetra-n-butylammonium iodide, 6 mmol tert-butanol peroxide, 3 ml dimethyl sulfoxide, 7 mmol Diethylamine, then slowly fill with carbon dioxide gas until its pressure reaches 3MPa, after stirring at 90°C for 12 hours, stop heating and stirring, cool to room temperature, and slowly release carbon dioxide to normal pressure. The reaction solution was washed with 20 mL of water, extracted three times with ethyl acetate (10 mL each time), the organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, 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 and ethyl acetate with a volume ratio of 20:1, and the yield was 60%.

Embodiment 2

[0050] Add 1 mmol of 1-phenyl-1-propanone, 0.2 mmol of tetra-n-butylammonium iodide, 8 mmol of tert-butanol peroxide, and 3 ml of N,N-dimethylformamide in the autoclave , 10 mmoles of diethylamine, and slowly filled with carbon dioxide gas until its pressure reached 3MPa, and stirred at 90°C for 6 hours, then stopped heating and stirring, cooled to room temperature, and slowly released carbon dioxide to normal pressure. The reaction solution was washed with 20 mL of water, extracted three times with ethyl acetate (10 mL each time), the organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, 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 and ethyl acetate with a volume ratio of 20:1, and the yield was 57%.

Embodiment 3

[0052] Add 1 mmol 1-phenyl-1-acetone, 0.2 mmol tetra-n-butylammonium iodide, 6 mmol tert-butanol peroxide, 3 milliliters of acetonitrile, and 7 mmoles of diethylamine in the autoclave, Slowly fill in carbon dioxide gas until its pressure reaches 3MPa, and after stirring at 90°C for 12 hours, stop heating and stirring, cool to room temperature, and slowly release carbon dioxide to normal pressure. The reaction solution was washed with 20 mL of water, extracted three times with ethyl acetate (10 mL each time), the organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, 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 and ethyl acetate with a volume ratio of 20:1, and the yield was 32%.

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Abstract

The invention relates to a method for synthesizing carbamate by ketone, amine and carbon dioxide. The method includes: adding the ketone, the amine and a solvent into a high-pressure reaction kettle, adding an iodine compound as a catalyst and peroxide as an oxidant, feeding carbon dioxide in a certain pressure, heating to 50-130 DEG C, stirring for 6-48h, cooling to the room temperature after reaction is finished, slowly discharging the carbon dioxide to the normal pressure, subjecting reaction liquid to water washing, ethyl acetate extraction, anhydrous sodium sulfate drying and vacuum distillation and concentration to obtain crude products, and performing column chromatography extraction to obtain a carbamate compound. The method for synthesizing the carbamate has advantages of simplicity in operation, low cost, easiness in acquisition and low toxicity or nontoxicity of raw materials, economy of reaction atoms, high compatibility of functional groups, environment friendliness and conduciveness to industrial production and has a potential application value in synthesis of medicines, agricultural chemicals and natural products.

Description

technical field [0001] The invention relates to the technical field of medicine, pesticide, natural product and organic chemical synthesis, in particular to a method for synthesizing carbamate by utilizing ketone, amine and carbon dioxide. Background technique [0002] Carbamate is an important class of organic compounds, and many natural products contain carbamate structural units, such as physostigmine. Because these compounds have important biological and pharmaceutical activities, they have many applications in agriculture and medicine (Wu, T.T.; Huang, J.; Arrington, N.D.; Dill, G.M.; J.Agric.Food Chem.1987,35,817; Divito , C.B.; Davies, S.; Masoudi, S.; Muhoro, C.N. Agric. Food Chem. 2007, 55, 5377; Sawatzky, E.; Wehle, S.; Kling, B.; Wendrich, J.; .; Sotriffer, C.A.; Heilmann, J.; Decker, M.J. Med. Chem. 2016, 59, 2067; Miller, K.; Neilan, B.; ,14). For example, the insecticides carbaryl and carbofuran, and the specific drug Exelon for the treatment of Alzheimer's ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C269/04C07C269/08C07C271/12C07D213/50C07D295/205
CPCC07C269/04C07C269/08C07D213/50C07D295/205C07C271/12Y02P20/141
Inventor 戚朝荣彭优斌袁高清刘娟江焕峰
Owner SOUTH CHINA UNIV OF TECH
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