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N-formylation synthesis method taking CO2 as carbon source under mild condition

A technology of chemical synthesis and conditions, applied in chemical instruments and methods, preparation of organic compounds, separation/purification of carboxylic acid amides, etc., can solve the problems of development restriction, low utilization rate, high price, etc. The effect of low cost and simple operation

Active Publication Date: 2018-10-09
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, silane as a reducing agent for formylation has also attracted widespread attention. However, its development is restricted by the high price and the low utilization rate of hydrogen, which requires the addition of excess silane.

Method used

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  • N-formylation synthesis method taking CO2 as carbon source under mild condition
  • N-formylation synthesis method taking CO2 as carbon source under mild condition
  • N-formylation synthesis method taking CO2 as carbon source under mild condition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] The preparation method of N,N-dibenzylformamide:

[0026] (1) Under the protection of nitrogen, sodium borohydride (0.019g, 0.5mmol) and ammonium sulfate (0.071g, 0.5mmol) were added to anhydrous THF (2mL), and stirred at 25°C for 1h. Then, nitrogen gas was replaced by carbon dioxide gas.

[0027] (2) Dibenzylamine (0.099g, 0.5mmol) was dissolved in anhydrous THF (3mL), and added dropwise to the reaction system under an atmosphere of carbon dioxide. After 0.75h, the dropwise addition was completed. GC monitors the reaction, and after the reaction of the raw material amine is complete, the reaction is terminated.

[0028] (3) Using ethyl acetate and petroleum ether (volume ratio 1:1) as developing solvents, the product was separated by plate chromatography. The silica gel was rinsed with a mixed solvent of dichloromethane and methanol (10:1 by volume). The eluate was collected, the solvent was removed by rotary evaporation, and vacuum-dried to obtain 0.087 g of the co...

Embodiment 2

[0030] The preparation method of N-methyl-N-phenyl formamide:

[0031] (1) Under nitrogen protection, sodium borohydride (0.076g, 2mmol) and ammonium sulfate (0.28g, 2mmol) were added to anhydrous THF (2mL), and stirred at 25°C for 1h. Then, nitrogen gas was replaced by carbon dioxide gas.

[0032] (2) N-Methylaniline (0.21g, 2mmol) was dissolved in anhydrous THF (3ml), and added dropwise to the reaction system under an atmosphere of carbon dioxide. After 0.5h, the dropwise addition was completed. GC monitors the reaction, and after the reaction of the raw material amine is complete, the reaction is terminated.

[0033] (3) Using ethyl acetate and petroleum ether (volume ratio 1:4) as the developing solvent, the product was separated by plate chromatography. Utilize the mixed solvent of dichloromethane and methanol (10:1 by volume) to rinse the silica gel, collect the eluate, remove the solvent by rotary evaporation, and dry in vacuo to obtain 0.127 g of the corresponding fo...

Embodiment 3

[0035] Under the condition of adding catalyst, the preparation method of N,N-dibenzylformamide:

[0036] (1) Under nitrogen protection, sodium borohydride (0.019g, 0.5mmol), ammonium sulfate (0.071g, 0.5mmol) and copper chloride dihydrate (0.002g, 0.012mmol) were added to anhydrous THF (2mL) , Stir the reaction at 25°C for 1h. Then, nitrogen gas was replaced by carbon dioxide gas.

[0037] (2) Dibenzylamine (0.099g, 0.5mmol) was dissolved in anhydrous THF (3mL), and added dropwise to the reaction system under an atmosphere of carbon dioxide. After 0.67h, the dropwise addition was completed. GC monitors the reaction, and after the reaction of the raw material amine is complete, the reaction is terminated.

[0038] (3) Using ethyl acetate and petroleum ether (volume ratio 1:1) as developing solvents, the product was separated by plate chromatography. The silica gel was rinsed with a mixed solvent of dichloromethane and methanol (10:1 by volume). The eluate was collected, the...

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Abstract

The invention provides an N-formylation synthesis method taking CO2 as a carbon source under a mild condition and belongs to the technical field of chemistry and chemical engineering. Under normal-temperature and normal-pressure conditions and in a solvent with a low boiling point, CO2 is used as a carbon source to realize N-formylation reaction of various amine type substrates. The N-formylationsynthesis method provided by the invention has the advantages that a reaction system takes sodium borohydride and ammonium sulfate as reaction reagents, and the CO2 is subjected to reduction under normal pressure to provide acyl, so that high-pressure hydrogen gas and toxic CO are not used and reaction conditions are mild; the sodium borohydride and the ammonium sulfate are cheap and easy to obtain and the economic applicability is high; a reagent is stable in the air and is convenient to operate; the organic solvent with the low boiling point is used and is easy to remove and a product is convenient to separate. A method for preparing formamide, provided by the invention, takes greenhouse gas, i.e., carbon dioxide, as a carbon source and has the advantages of relatively low cost, simplicity in operation and mild reaction conditions; the yield of the prepared formamide product is good and a green synthesis method is provided for N-acylation reaction.

Description

technical field [0001] The invention belongs to the technical field of energy and homogeneous catalysis, and relates to homogeneous catalysis, in particular to a method for realizing N-formylation of amines by using sodium borohydride, ammonium sulfate and carbon dioxide under normal temperature and pressure conditions. Background technique [0002] With the requirements of environmental protection and sustainable development, the utilization of carbon dioxide has received more and more attention in the past few decades. In particular, the conversion of CO2 as a green and renewable carbon source into other high value-added chemicals is of great significance and has been extensively studied. So far, many efforts have been made to realize CO under mild conditions 2 transformation. For example, ionic liquids, N-heterocyclic carbenes (NHCs) and some other efficient catalysts have been utilized to achieve CO 2 transformation. Catalyst-free systems have also been reported for ...

Claims

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Application Information

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IPC IPC(8): C07C233/03C07C231/10C07C231/24
CPCC07C231/10C07C231/24C07C233/03
Inventor 王万辉武锦渊包明
Owner DALIAN UNIV OF TECH
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