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Preparation method for aromatic nitrile compound

A compound, aromatic nitrile technology, applied in the field of preparation of aromatic nitrile compounds, can solve the problems of poor functional group compatibility, small range of reaction substrates, harsh reaction conditions, etc., to achieve wide substrate universality and easy purification of products , the effect of simple substrate

Inactive Publication Date: 2014-03-26
PEKING UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The disadvantage of method 1 is that high temperature and gas are required as raw materials, and the reaction conditions are relatively harsh; it is not friendly to the environment, and the operation is complicated; the compatibility of functional groups is not good, and the yield is generally not high.
The disadvantage of method 2 is that the reaction substrate must be a toluene derivative substituted with an electron-rich group at the para position, and there are few options for the reaction substrate

Method used

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  • Preparation method for aromatic nitrile compound
  • Preparation method for aromatic nitrile compound
  • Preparation method for aromatic nitrile compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Synthesis of p-methoxybenzonitrile

[0030] Under the protection of nitrogen, add 61mg (ie 0.5mmol) p-methoxytoluene, 103mg (ie 1.0mmol) nitroso tert-butyl ester, 25mg (0.15mmol) N-hydroxyphthaloyl to the microwave tube Amine and 5.6 mg of palladium acetate (ie 0.025 mmol) were heated to 70° C. in 0.5 mL of acetonitrile to react for 24 hours. After the reaction system was cooled to room temperature, 2 mL of dichloromethane was added for dilution. The mixture was filtered and concentrated. The reaction solution is purified by column chromatography with petroleum ether as an eluent to obtain p-methoxybenzonitrile, and its structure is shown in the following formula:

[0031]

[0032] The compound is a white solid with a yield of 84%, and its NMR data are as follows:

[0033] 1 HNMR(CDCl3,400MHz):δ=7.59(d,J=8.8Hz,2H),6.97(d,J=8.8Hz,2H),3.86(s,3H); 13 CNMR(CDCl3,100MHz):δ=162.8,133.9,119.2,114.7,103.9,55.5.

Embodiment 2

[0035] Synthesis of m-methoxybenzonitrile

[0036] Under the protection of nitrogen, add 61mg (ie 0.5mmol) m-methoxytoluene, 103mg (ie 1.0mmol) nitroso tert-butyl ester, 25mg (0.15mmol) N-hydroxyphthaloyl to the microwave tube Amine and 5.6 mg of palladium acetate (ie 0.025 mmol) were heated to 70° C. in 0.5 mL of acetonitrile to react for 24 hours. After the reaction system was cooled to room temperature, 2 mL of dichloromethane was added for dilution. The mixture was filtered and concentrated. The reaction solution is purified by column chromatography with sherwood oil as an eluent to obtain m-methoxybenzonitrile, and its structure is shown in the following formula:

[0037]

[0038] This compound is colorless oily liquid, and productive rate is 81%, and its data are as follows:

[0039] 1 H NMR (CDCl 3 ,400MHz):δ=7.39-7.35(m,1H),7.28-7.23(m,1H),7.14-7.13(m,2H),3.83(s,3H); 13 C NMR (CDCl 3,100MHz): δ=159.5,130.2,124.4,119.2,118.6,116.8,113.1,55.4.

Embodiment 3

[0041] Synthesis of o-methoxy tert-butyl ester

[0042] Under the protection of nitrogen, add 61mg (ie 0.5mmol) of o-methoxytoluene, 154mg (ie 1.5mmol) of nitroso tert-butyl ester, 25mg (0.15mmol) of N-hydroxyphthaloyl to the microwave tube Amine and 5.6 mg of palladium acetate (ie 0.025 mmol) were heated to 70° C. in 0.5 mL of acetonitrile to react for 24 hours. After the reaction system was cooled to room temperature, 2 mL of dichloromethane was added for dilution. The mixture was filtered and concentrated. The reaction solution is purified by column chromatography using petroleum ether as an eluent to obtain o-methoxybenzonitrile, and its structure is shown in the following formula:

[0043]

[0044] This compound is yellow liquid, and productive rate is 92%, and its data are as follows:

[0045] 1 H NMR (CDCl 3 ,400MHz):δ=7.57-7.53(m,2H),7.03-6.98(m,2H),3.93(s,3H); 13 C NMR (CDCl 3 ,100MHz): δ=161.0,134.3,133.5,120.6,116.4,111.2,101.5,55.8.

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Abstract

The invention provides a preparation method for an aromatic nitrile compound. The method comprises steps as follows: catalyzing the toluene or toluene derivative with a substituent or methyl substituted aromatic ring by a free radical initiating agent and a divalent palladium for reaction with an oxidizing nitrogen source in an organic solution to generate the substituent-reserved aromatic nitrile compound. According to the preparation method, the substrate related is simple and compatibility to various functional groups is realized, the method is relatively good in universality and can be conducted under highly mild environment; the application of toxic CN negative ion reagents is effectively avoided, and the problem of excessive waste and use of metal under the conventional condition is solved; the method is high in reaction rate, low in reaction cost and simple in post-reaction treatment, and the products can be easily purified, therefore the method can be widely used for preparation of various aromatic nitrile compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of aromatic nitrile compounds. Background technique [0002] The cyano group is a very important functional group in the field of organic synthesis. It can easily transform various functional groups, so it is often used in the synthesis of organic amines, amides, carboxylic acids, aldehydes and heterocyclic compounds middle. Aromatic nitrile compounds are widely used in the synthesis of various natural products, materials, medicines, agricultural supplies and dyes. However, for a long time, the synthetic method of introducing cyano group on the aromatic ring has been very limited. Traditional aromatic nitriles are produced by the Sandmeyer reaction and the Rosenmund-von Braun reaction. However, both reactions require the use of toxic CuCN reagents, which have great limitations. With people's further research, the method of forming aromatic nitrile compoun...

Claims

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Application Information

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IPC IPC(8): C07B43/08C07C253/00C07C255/54C07C255/50C07C269/06C07C271/28C07C255/55C07F5/02C07C255/57C07C255/51C07C255/52C07D209/42C07D209/08C07D213/84C07D215/54
Inventor 王剑波舒志斌叶宇轩邓亦范张艳
Owner PEKING UNIV
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