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A kind of improved method of preparing 4-biphenylnitrile

A technology of biphenyl and biphenylcarboxamide, which is applied in the field of preparing 4-biphenylnitrile, can solve the problems of expensive catalyst, harsh reaction conditions, and low overall yield, and achieve the effect of easy control of the reaction process and reduced operating costs

Inactive Publication Date: 2016-08-10
河北允升精细化工有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The defect that this method exists is: the price of harsh reaction condition and used catalyst is expensive, so that this method does not have commercial value at present
The disadvantage of this method is: the preparation steps are tedious, although the yield of each step reaction is not low, the total yield is not high, so that the method has lost its economic value
But this method also has a shortcoming, that is, although the result of chloroform reaction has generated biphenylamide, chloroform has also been generated at the same time, because the medium used for carrying out this reaction is dichloroethane, chloroform just remains in dichloroethane like this. However, dichloroethane containing chloroform cannot be directly used in the Friedel-Crafts reaction between biphenyl and trichloroacetyl chloride, and the reaction medium after each batch of chloroform reaction must be separated and purified, which obviously increases the 4-linkage Production cost of benzonitrile

Method used

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  • A kind of improved method of preparing 4-biphenylnitrile

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Experimental program
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Effect test

Embodiment 1

[0027] Dichloromethane (150g) and anhydrous aluminum trichloride (19.1g, 0.145mol) were added to the reaction flask, and stirred for 1 hour to make the anhydrous aluminum trichloride evenly dispersed in the solvent, and biphenyl (14.6g, 0.145mol) was added. 85.7 mmol), after it was dissolved, N-methylcarbamoyl chloride (9.67 g, 103 mmol) was slowly added dropwise. During this period, the temperature of the reactant was kept at 0-5 °C with an ice-water bath. At this time, a large amount of gas escaped. After the gas no longer escapes, remove the ice-water bath, and after the temperature rises back to the ambient temperature, then heat to 40 °C, react for 5 hours, stop the reaction, slowly pour the reactant into ice water with pH=3, layer, and organically The phase was washed with water until neutral, the solvent was evaporated to dryness under reduced pressure, and the residue was recrystallized from ethanol to obtain 15.5 g of N-methyl-4-biphenylcarboxamide with a purity of 98....

Embodiment 2

[0030] Dichloroethane (150g) and anhydrous aluminum trichloride (25g, 189mmol) were added to the reaction flask, and stirred for 1 hour to make the anhydrous aluminum trichloride evenly dispersed in the solvent, and biphenyl (14.6g, 94.5g) was added. mmol), after it was dissolved, N-methylcarbamoyl chloride (9.67g, 104mmol) was slowly added dropwise. During this period, the temperature of the reactant should be kept at 0-5°C with an ice-water bath. At this time, a large amount of gas escaped. After the gas no longer escapes, remove the ice-water bath, and after the temperature rises back to the ambient temperature, then heat to 40 °C, react for 5 hours, stop the reaction, slowly pour the reactant into ice water with pH=3, layer, and organically The phase was washed with water until neutral, the solvent was evaporated to dryness under reduced pressure, and the residue was recrystallized from ethanol to obtain 15.95 g of N-methyl-4-biphenylcarboxamide with a purity of 98.4% (HPLC...

Embodiment 3

[0033] Dichloroethane (1000g) and anhydrous aluminum trichloride (252g, 1.89mol) were added to the reaction flask, and stirred for 1 hour to make the anhydrous aluminum trichloride evenly dispersed in the solvent, and biphenyl (146g, 0.945 g) was added. mol), after it dissolves, slowly add N-methylcarbamoyl chloride (103 g, 1.10 mol) dropwise. During this period, keep the temperature of the reactant at 0-5 °C with an ice-water bath. At this time, a large amount of gas escapes. After the gas no longer escapes, remove the ice-water bath, and after the temperature rises back to the ambient temperature, then heat to 40 °C, react for 5 hours, stop the reaction, slowly pour the reactant into ice water with pH=3, layer, and organically The phase was washed with water until neutral, the solvent was evaporated to dryness under reduced pressure, and the residue was recrystallized from ethanol to obtain 160 g of N-methyl-4-biphenylcarboxamide with a purity of 98.4% (HPLC) and a yield of 7...

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PUM

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Abstract

The present invention relates to a method for preparing 4-biphenylnitrile, comprising: (1) in the presence of a Lewis acid catalyst, reacting N-methylcarbamoyl chloride and biphenyl through Friedel-Craft to prepare N-methyl- The step of 4-biphenylcarboxamide; and (2) the step of obtaining the target object by removing methanol from N-methyl-4-biphenylcarboxamide in the presence of a catalyst. The present invention replaces trichloroacetyl chloride in the prior art with N-methylcarbamoyl chloride, and reacts with biphenyl. In this way, the step of separating and purifying the reaction medium after each batch of chloroform reaction in the prior art is avoided, and the operating cost is reduced. In addition, the raw materials used in the present invention are also cheap and easy to obtain, and the reaction process is easy to control, and the yield of the product after recrystallization can reach 70% or more, which can be directly used in the production of C.I. Pigment Red 264.

Description

technical field [0001] The present invention relates to a method for preparing 4-biphenylnitrile. Background technique [0002] 4-Biphenylnitrile is a key intermediate in the production of pigments (C.I. Pigment 264). About the synthesis of 4-biphenylnitrile, a variety of methods have been reported in the literature, which are briefly described as follows: [0003] 1) Biphenyl diazonium salt-cyanide method : Biphenyl is subjected to mixed acid nitration, reduction (to obtain 4-aminobiphenyl), diazotization (generated diazonium salt) and reaction with sodium cyanide to obtain 4-biphenyl nitrile (Mettler HP, patent No.: DE19833409 ( 1998-12-24)). In this method, two intermediate products (4-nitrobiphenyl and 4-aminobiphenyl) are generated, both of which are carcinogens, and the sodium cyanide used is a highly toxic substance, so during the production process, the operator's Poor physical and mental health. [0004] 2) Biphenyl bromination-cyanation method : Biphenyl is ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C255/50C07C253/00
Inventor 沈永嘉蒲帅天张毅吉李美菊陈丽媛左虎进施健美
Owner 河北允升精细化工有限公司
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