Preparation method of 2,4-disubstituted benzenesulfonyl chloride

A technology of benzenesulfonyl chloride and disubstituted, applied in the field of compound preparation, can solve the problems of complex post-processing, many by-products, and a large amount of waste acid by-products, simplifies the difficulty of separation and purification, and solves serious side reactions and waste acid. The effect of spawn reduction

Inactive Publication Date: 2018-05-29
TIANJIN RUILING CHEM CO LTD
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Problems solved by technology

However, during the preparation of 2,4-disubstituted benzenesulfonyl chloride, due to the activation or passivation of the other four vacancies on the benzene ring by the two substituents at the meta position, the main reaction of sulfonylation is related to the multiple vacancies on the benzene ring. A variety of side reactions such as sulfonation and intermolecular coupling are carried out simultaneously without selectivity, and the by-products are various and have a huge proportion, resulting in low yield, low purity, and difficulty in separation and purification of 2,4-disubstituted benzenesulfonyl chloride. Serious waste
Mykyta et al. and Savitha et al. have reported using chloroform as a solvent, using a large excess of chlorosulfonic acid to react with multiple substituted benzenes, and then through multi-step post-treatment operations to prepare the method for many substituted benzenesulfonyl chlorides, but there are many by-products in this method, resulting in The disadvantages are low efficiency, complex post-treatment and a large amount of waste acid by-product
[0004] The existing published patents for the preparation methods of similar compounds are as follows: Patents US 3686300 and CN1163264 only use chlorosulfonic acid for sulfonylation reaction, the reaction selectivity is poor, equipment corrosion is serious, and a large amount of waste acid is produced as a by-product; 6310140, EP 04039422, and CN 1436773 all use a large amount of highly toxic inorganic chlorides in the sulfonylation process, which seriously affects the environment and is not suitable for industrial production; patent CN 101195593 uses liquid paraffin and other high-boiling point mixed solvents in the reaction process, resulting in difficulties in solvent recovery , complex operation and other issues; patents CN 102633695, CN 102633687, CN102627589 and CN 102633696 used a one-pot continuous reaction in the preparation process to effectively improve the reaction efficiency, but this process is only applicable to the preparation of monosubstituted benzenesulfonyl chloride and cannot be effectively prepared 2,4-Disubstituted benzenesulfonyl chloride

Method used

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  • Preparation method of 2,4-disubstituted benzenesulfonyl chloride

Examples

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Effect test

Embodiment 1

[0030] The preparation method of 2,4-diethylbenzenesulfonyl chloride, the steps are as follows:

[0031] (1) In the reactor of 50L, add m-diethylbenzene 3.35kg, add anhydrous sodium sulfate 0.05kg under stirring, ice-water bath control reaction temperature is 10 ℃, slowly drips chlorosulfonic acid 3.25kg from dropping funnel, After the addition was completed, the reaction was incubated at 10°C for 0.5 hours;

[0032] (2) Control the reaction temperature to be 10°C, slowly add 6kg of chlorosulfonic acid dropwise from the dropping funnel, after the addition is complete, add 0.75kg of thionyl chloride, and incubate at 10°C for 5.0 hours to obtain the sulfonylated material;

[0033] (3) In a 100L glass storage tank, add 25kg of ice-water mixture, start stirring, slowly add the above-mentioned sulfonylated material into the ice-water mixture, keep it under 15°C for 0.5 hours, put the material in a separatory funnel After standing for 0.5 hours, the lower organic layer was separate...

Embodiment 2

[0035] The preparation method of 2,4-diethylbenzenesulfonyl chloride, the steps are as follows:

[0036] (1) In the reactor of 50L, add m-diethylbenzene 3.35kg, add anhydrous ammonium sulfate 0.07kg under stirring, ice-water bath control reaction temperature is 5 ℃, slowly drips chlorosulfonic acid 3.35kg from dropping funnel, After the addition was completed, the reaction was incubated at 10°C for 0.5 hours;

[0037] (2) Control the reaction temperature to 15°C, slowly add 6.5kg of chlorosulfonic acid dropwise from the dropping funnel, after the addition is complete, add 0.75kg of oxalyl chloride, and incubate at 15°C for 5.0 hours to obtain the sulfonylated material;

[0038] (3) In a 100L glass storage tank, add 24 kg of ice-water mixture, start stirring, slowly add the above-mentioned sulfonylated material into the ice-water mixture, keep it under 15°C for 1.0 hour, put the material in a separatory funnel After standing for 0.5 hours, the lower organic layer was separated...

Embodiment 3

[0040] The preparation method of 2,4-dimethylbenzenesulfonyl chloride, the steps are as follows:

[0041] (1) In a 50L reaction kettle, add 2.65kg of m-xylene, add 0.05kg of anhydrous potassium sulfate under stirring, control the reaction temperature in an ice-water bath to be 20°C, slowly drop 3.25kg of chlorosulfonic acid from the dropping funnel, add After finishing, heat preservation reaction at 20°C for 0.5 hours;

[0042] (2) Control the reaction temperature to be 20°C, slowly add 6kg of chlorosulfonic acid dropwise from the dropping funnel, after the addition is complete, add 0.5kg of phosphorus trichloride, and keep the temperature at 20°C for 5.0 hours to obtain the sulfonylated material;

[0043] (3) In a 100L glass storage tank, add 25 kg of ice-water mixture, start stirring, slowly add the above-mentioned sulfonylated material into the ice-water mixture, keep it under 15°C for 1.0 hour, put the material in a separatory funnel After standing for 1.0 hour, the lower o...

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Abstract

The invention provides a preparation method of 2,4-disubstituted benzenesulfonyl chloride. A solvent-free reaction is adopted, through accurate control of low-temperature stepwise reactions and introduction of a specific inorganic salt aid, the strong positioning effect, the steric hinerance effect and the like of superposition of two substituent groups in the meta-position are amplified to facilitate the positive effect of a main reaction, and production of byproducts such as various sulphone isomers, multiple sulfonated bodies, macromolecular conjugates and the like is significantly inhibited. Through combined use of small quantities of specific chlorination aids and chlorosulfonic acid, the conversion process of an acyl chloride structure is promoted, excessive use of inorganic chlorideis avoided, and the use amount of chlorosulfonic acid and the production of waste acid are both greatly reduced. With the adoption of the method, the total yields of various substrates are 85% or above, the product purity is 95% or above, the difficulty in separation and purification is reduced, the problems of severe side reactions, low product yield, poor quality and the like in existing methods and technologies are solved, and energy conservation and emission reduction are realized.

Description

technical field [0001] The invention relates to a preparation method of a compound, in particular to a preparation method of 2,4-disubstituted benzenesulfonyl chloride. Background technique [0002] As an important fine chemical intermediate, multi-substituted benzenesulfonyl chlorides are widely used in photosensitive materials, medicine, pesticides, dyes and other fields, among which 2,4-disubstituted benzenesulfonyl chloride is the key to the preparation of high-end photosensitive materials Intermediates, however, are limited by factors such as relatively high technical difficulty, and there are no mature and efficient preparation methods and process reports in the existing literature and patents. [0003] At present, in the conventional general preparation methods and processes of mono / multi-substituted benzenesulfonyl chlorides, mono / multi-substituted benzene is mostly used as raw material, and the product is obtained through sulfonylation reaction. However, during the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/08C07C309/86
CPCC07C303/08C07C309/86
Inventor 卢博为胡新龙谢志强
Owner TIANJIN RUILING CHEM CO LTD
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