Alpha-cyanidation method of mono-alkyl substituted aniline

A monoalkyl and benzyl aniline technology, applied in the field of organic chemical synthesis, can solve the problems of unfavorable industrial production, lack of investigation of other substrates, unsuitable for mass production, etc., achieve high yield, save industrial costs, and shorten the reaction cycle short effect

Inactive Publication Date: 2017-09-05
CHONGQING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] (1) Only the substrate of p-methoxyaniline was reported, and other substrates were not investigated
[0005] (2) The reaction time of this method is too long, thereby increases production cost, is unfavorable for suitability for industrialized production
[0006] (3) The reaction uses a vanadium complex as a catalyst, which is not suitable for industrial mass production due to the high cost of the catalyst

Method used

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  • Alpha-cyanidation method of mono-alkyl substituted aniline
  • Alpha-cyanidation method of mono-alkyl substituted aniline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] A kind of α-cyanation method of monoalkyl substituted aniline, its concrete steps are as follows:

[0023] (1) With N-benzylaniline as raw material, trimethylsilyl cyanide as cyanide reagent, ferrocene as catalyst, tert-butyl hydroperoxide as oxidant, according to N-benzylaniline mmol: trimethylsilyl Cyanogen mmol: ferrocene mmol: the ratio of tert-butyl hydroperoxide is 1: 2: 0.1: 2, and N-benzylaniline (91.6 mg, 0.5 mmol), ferrocene Iron (9.2 mg, 0.05 mmol), in the solvent dimethyl sulfoxide, under stirring, then add trimethylsilyl cyanide (125.1 μL, 1.0 mmol), tert-butyl hydroperoxide (148.0 μL, 1.0 mmol), After the addition, at 25°C, the catalytic oxidative cyanation reaction was carried out with continuous stirring for 4 hours.

[0024] (2) After the first (1) step is completed, the reaction solution of the α-aminonitrile compound prepared in the (1) step is quenched with saturated sodium bicarbonate and sodium thiosulfate solution, and dichloromethane is extracte...

Embodiment 2

[0027] A kind of α-cyanation method of monoalkyl substituted aniline, its concrete steps are with embodiment 1, wherein:

[0028] (1) With N-benzylaniline as raw material, trimethylsilyl cyanide as cyanide reagent, ferrocene as catalyst, tert-butyl hydroperoxide as oxidant, according to N-benzylaniline mmol: trimethylsilyl Cyanogen mmol: ferrocene mmol: the ratio of tert-butyl hydroperoxide is 1: 2: 0.1: 2, and N-benzylaniline (91.6 mg, 0.5 mmol), ferrocene Iron (9.2 mg, 0.05 mmol), in the solvent dimethyl sulfoxide, under stirring, then add trimethylsilyl cyanide (125.1 μL, 1.0 mmol), tert-butyl hydroperoxide (148.0 μL, 1.0 mmol), After the addition, at 80°C, the catalytic oxidative cyanation reaction was carried out with continuous stirring for 4 hours.

[0029] In step (2), the eluent was a mixture of ethyl acetate:petroleum ether at a ratio of 1:50 to obtain α-cyano-N-benzylaniline (33.3 mg, yield 32%) as a white solid.

Embodiment 3

[0031] A kind of α-cyanation method of monoalkyl substituted aniline, its concrete steps are with embodiment 1, wherein:

[0032] (1) With N-benzylaniline as raw material, trimethylsilyl cyanide as cyanide reagent, ferrocene as catalyst, tert-butyl hydroperoxide as oxidant, according to N-benzylaniline mmol: trimethylsilyl Cyanogen mmol: ferrocene mmol: the ratio of tert-butyl hydroperoxide is 1: 2: 0.1: 2, and N-benzylaniline (91.6 mg, 0.5 mmol), ferrocene Iron (9.2 mg, 0.05 mmol), in the solvent dimethyl sulfoxide, under stirring, then add trimethylsilyl cyanide (125.1 μL, 1.0 mmol), tert-butyl hydroperoxide (148.0 μL, 1.0 mmol), After the addition is complete, the catalytic oxidative cyanation reaction is carried out at 35° C. for 4 hours with continuous stirring.

[0033] In step (2), the eluent was a mixture of ethyl acetate:petroleum ether at a ratio of 1:50 to obtain a white solid α-cyano-N-benzylaniline (53.1 mg, yield 51%).

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Abstract

The invention discloses an alpha-cyanidation method of mono-alkyl substituted aniline. According to the method, various aromatic, aliphatic, and heterocycle substituted secondary amines of anilines are taken as the raw materials, trimethylsilyl cyanide is taken as the cyanidation agent, divalent iron is taken as the catalyst, tert-butyl hydroperoxide is taken as the oxidizing agent, raw materials carry out reactions in a solvent, and the reaction product is processed by a simple concentrating and purifying technology to obtain the finished product. The invention aims to solve the shortages of a conventional catalytic oxidation cyanidation method of secondary amines and provides a novel synthesis method. Cheap, low toxin, and easily available divalent iron is taken as the catalyst, tert-butyl hydroperoxide is taken as the oxidizing agent, and the catalytic oxidation cyanidation reactions between a secondary amine substrate of various aromatic, aliphatic, and heterocycle substituted anilines and trimethylsilyl cyanide are realized efficiently. The provided method has the advantages of simple technology, safe production reactions, easy operation, short reaction time, and easiness for industrialization.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a method for directly oxidizing and cyanating secondary amines to synthesize α-aminonitrile compounds. Background technique [0002] As an important synthon in organic synthesis, cyano group can be used as the precursor of many other functional groups. Cyano groups are widely used in chemical industry, pesticides, functional materials, pigments and spices and other fields. In particular, in the pharmaceutical industry, cyano groups are widely used in the structural modification of small molecule drugs, and the strategy of substituting cyano groups has become one of the important synthetic strategies for compound structure optimization. In addition, the cyano group is a biological electron emitter of functional groups such as halogen and carbonyl, which can enhance the interaction between small drug molecules and target proteins, so it is widely use...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/00C07C255/42C07D307/54C07D333/24C07D215/48
CPCC07C253/00C07D215/48C07D307/54C07D333/24
Inventor 熊燕王瑶黄明明
Owner CHONGQING UNIV
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