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Method for preparing aldehyde and ketone by catalyzing and oxidizing alcohol in air

A technology for oxidizing alcohol and air, applied in chemical instruments and methods, preparation of carbon-based compounds, preparation of organic compounds, etc., can solve the problems of unsafe, inconvenient use of bromine, etc.

Inactive Publication Date: 2007-02-14
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] 5) Bromine is inconvenient and unsafe to use

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] In a 300 mL Teflon-lined autoclave, add 1.08 g benzyl alcohol (10 mmol), 3.15 mg TEMPO (0.02 mmol), 114 mg 1,3-dibromo-5,5-dimethylhydantoin (0.4 mmol ), 27.6mg NaNO 2 (0.4mmol), 0.5mL water, 10mL dichloromethane. Seal the autoclave, fill it with air until the pressure gauge reaches 0.4 MPa, put the autoclave into an oil bath pre-heated to 100°C, and react for 1.2 hours. After lowering the temperature and carefully releasing the pressure, the organic phase was analyzed by gas chromatography (GC), the conversion rate was 100%, and the product selectivity was 100%. The isolated yield of benzaldehyde was 93%.

Embodiment 2

[0025] In a 300 mL Teflon-lined autoclave, add 1.22 g 4-methylbenzyl alcohol (10 mmol), 3.15 mg TEMPO (0.02 mmol), 114 mg 1,3-dibromo-5,5-dimethylsea Sodium (0.4mmol), 27.6mg NaNO 2 (0.4mmol), 0.5mL water, 10mL dichloromethane. Seal the autoclave, fill it with air until the pressure gauge is 0.4MPa, put the autoclave into an oil bath pre-heated to 100°C, and react for 1 hour. After lowering the temperature and carefully releasing the pressure, the organic phase was analyzed by gas chromatography (GC), the conversion rate was 100%, and the product selectivity was 100%. The isolated yield of p-tolualdehyde is 96%.

Embodiment 3

[0027] In a 300 mL Teflon-lined autoclave, add 1.22 g 3-methylbenzyl alcohol (10 mmol), 3.15 mg TEMPO (0.02 mmol), 114 mg 1,3-dibromo-5,5-dimethylseawater Sodium (0.4mmol), 27.6mg NaNO 2 (0.4mmol), 0.5mL water, 10mL dichloromethane. Seal the autoclave, fill it with air until the pressure gauge reaches 0.4 MPa, put the autoclave into an oil bath pre-heated to 100°C, and react for 1.5 hours. After lowering the temperature and carefully releasing the pressure, the organic phase was analyzed by gas chromatography (GC), the conversion rate was 100%, and the product selectivity was 99.8%. The isolated yield of m-tolualdehyde was 96%.

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PUM

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Abstract

This invention relates to a preparation method for aldehydes and ketones by catalytic airy oxidation of alcohols. Take 100mol alcohol substrate for example, 0.2mol% 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) or its derivatives, 4~10mol% active bromine and 4~10mol% nitrites as catalysts, 1~5mL water and 100mL dichloromethane are mixed together. The system is charged to a pressure of 0.4~0.9MPa and the reaction is kept at 100 deg.C for 1~10 hours. In this invention, benzylalcohols, heteroaromatic benzylalcohols (containing N, S and so on), aliphatic alcohols and alicyclic alcohols can be high selectively oxidized into corresponding aldehydes and ketones with TEMPO in catalytic amount (0.2mol%). Meanwhile, the employment of 1,3-dibromo-5,5-dimethylhydantoin as cocatalyst greatly improves the inconvenience and security factors caused by bromine.

Description

technical field [0001] The invention relates to a method for preparing aldehydes and ketones, in particular to a method for oxidizing alcohols into aldehydes and ketones without transition metal catalysts and using oxygen or air as an oxidant. Background technique [0002] In the previous research (Chinese Patent Application No. 200410003791.X), successfully developed a catalytic amount of 2,2,6,6-tetramethylpiperidine-oxyl radical (TEMPO), bromine (iodine) and Sodium nitrate is used as a catalyst, and oxygen below 0.5MPa or air below 1.0MPa is used as an oxidant to oxidize a series of alcohols into aldehydes and ketones with high selectivity at 60-100°C. However, it can be seen from several examples given in the above-mentioned patent application that the use of halogen bromine has certain toxicity and is inconvenient in technology. [0003] Chinese patent application 200410003791.X (TEMPO / Br 2 / NaNO 2 Alcohol Oxidation Process) [0004] Examples are as follows: [000...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C45/32
Inventor 刘仁华胡信全董春燕梁鑫淼
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI