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Synthesis method of m-dichlorobenzene

A synthesis method and technology of m-dichlorobenzene, which are applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve the problems of low selectivity, large equipment corrosion and high equipment requirements , to achieve the effect of mild reaction conditions, less three wastes, and low equipment requirements

Active Publication Date: 2019-12-20
JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The nitrification reaction in this process is dangerous to a certain extent, and a large amount of by-products such as waste sulfuric acid, nitroxyl chloride and nitrosyl chloride are produced during the production process, which not only corrodes the equipment greatly, but is also extremely unfriendly to the environment. Increasingly, the process will gradually be eliminated
[0005] 2. Dichlorobenzene transposition process: The isomers of m-dichlorobenzene are used to generate m-dichlorobenzene through catalytic isomerization reaction. According to different catalysts, it can be divided into the following three processes: 1. The catalyst is Lewis Acid aluminum trichloride, advantage is that yield (about 50%) and selectivity are higher (about 90%), and shortcoming is that reaction is homogeneous reaction, and processing catalyst can produce a large amount of waste acid water, and environment is not friendly; Two, catalyst It is a salt melt of aluminum trichloride and lithium chloride, which has the same advantages of high yield and selectivity, but the reaction requires a certain pressure to proceed, and the mechanical reaction requires the introduction of HCl gas, which requires high equipment and salt melting The number of times of solid reuse is limited, and it is more difficult to handle after becoming solid waste; three, the catalyst is ZSM-5 molecular sieve, the advantage of this catalyst is that it is environmentally friendly, and the disadvantage is that the yield is not high (about 40%) and the selectivity is low (80%) %), the reaction requires high temperature and high pressure, high requirements on equipment, and the catalyst activation conditions are also relatively harsh

Method used

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Examples

Experimental program
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Embodiment 1

[0025] (1) Preparation of Aluminum Trichloride-Chlorobutylmethylimidazolium Ionic Liquid

[0026] Put 20g (0.115mol) of 1-methyl-3-butylimidazole chloride in the flask, and slowly add 46g (0.345mol) of AlCl after raising the temperature to 50°C under the protection of nitrogen 3 , start stirring while adding, continue to keep warm and stir for 10 hours after the addition, and then put it into a vacuum drying oven to dry for later use.

[0027] (2) Preparation of m-dichlorobenzene

[0028] Put 50.7g (0.345mol) of pre-melted p-dichlorobenzene in the flask, start stirring and slowly add 7.5g of the catalyst prepared in step (1), react at 170°C for 4h under the protection of an inert gas, cool down to room temperature, and separate the liquids Separating the lower floor catalyst, the upper organic phase adopts gas chromatography analysis, and calculates the reaction product with the area normalization method to form: p-dichlorobenzene is 31.83%, m-dichlorobenzene is 65.02%, ortho...

Embodiment 2

[0036] (1) Preparation of ferric chloride-chlorobutylpyridine ionic liquid

[0037] Put 10g (0.059mol) chloro-N-butylpyridine in the flask, raise the temperature to 80°C under the protection of nitrogen, then slowly add 18.9g (0.117mol) FeCl 3 , start stirring while adding, continue to keep warm and stir for 12 hours after the addition, and then put it into a vacuum drying oven to dry for later use.

[0038] (2) Preparation of m-dichlorobenzene

[0039] Put 40g (0.272mol) of o-dichlorobenzene in a flask, start stirring and slowly add 4g of the catalyst prepared in step (1), react at 160°C for 6h under the protection of an inert gas, cool down to room temperature, and separate the catalyst from the lower layer. The upper organic phase is analyzed by gas chromatography, and the area normalization method is used to calculate the reaction product to form: o-dichlorobenzene is 32.23%, m-dichlorobenzene is 61.02%, p-dichlorobenzene is 6.75%, and the conversion rate is 67.77%. sex ...

Embodiment 3

[0041] (1) Preparation of zinc chloride-tetramethylammonium chloride ionic liquid

[0042] Put 15g (0.137mol) of tetramethylammonium chloride in the flask, and slowly add 46.6g (0.342mol) of ZnCl after heating up to 60°C under the protection of nitrogen 2 , start stirring while adding, continue to keep warm and stir for 8 hours after the addition, and then put it into a vacuum drying oven to dry for later use.

[0043] (2) Preparation of m-dichlorobenzene

[0044] Put 45g (0.306mol) of a mixture of o-dichlorobenzene and p-dichlorobenzene (p-dichlorobenzene accounts for 36%, o-dichlorobenzene accounts for 64%) in the flask, start stirring and slowly add 5g of the mixture prepared in step (1). The catalyst was reacted at 180°C for 3 hours under the protection of an inert gas, cooled to room temperature, and the lower catalyst was separated by liquid separation. The upper organic phase was analyzed by gas chromatography, and the composition of the reaction product was calculated...

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Abstract

The invention relates to a synthesis method of m-dichlorobenzene, which is obtained by translocation reaction with dichlorobenzene as a raw material under the action of a catalyst, wherein the catalyst is an ionic liquid including Lewis acid and onium salt chloride. The synthesis method of the present invention uses an ionic liquid composed of a Lewis acid and an onium salt chloride as a catalyst,the selectivity of the reaction is above 90%, the yield can be significantly increased to above 60%, no under-pressure reaction is required, the reaction conditions are mild, the requirements for equipment are low, the catalyst can be reused many times, the amount of the three wastes is small, the environment is friendly, and the industrial production is suitable.

Description

technical field [0001] The invention belongs to the field of fine chemicals, and in particular relates to a synthesis method of m-dichlorobenzene. Background technique [0002] As an important intermediate in organic synthesis, m-dichlorobenzene is widely used in medicine, pesticide and dyestuff industries. In medicine, m-dichlorobenzene is used to synthesize antifungal drugs (such as miconazole, ketoconazole, etc.) Agents (such as propiconazole, hexaconazole, etc.) and herbicides, such as oxaconazole; in terms of dyes, m-dichlorobenzene is mainly used for the synthesis of naphthol AS-ITR, etc. It can be seen that m-dichlorobenzene has a good application prospect. [0003] The existing preparation process of m-dichlorobenzene mainly contains the following: [0004] 1. Nitrification and chlorination process: benzene is first nitrated to generate m-dinitrobenzene, and m-dinitrobenzene is then chlorinated under high temperature conditions to generate m-dichlorobenzene. Due t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/358C07C25/08B01J31/02
CPCC07C17/358B01J31/0284B01J31/0279B01J31/0271C07C25/08
Inventor 徐秋龙陶伟曹楠楠包浩叶永胜
Owner JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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