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A kind of preparation method of thiabendazole intermediate

A technology for thiabendazole and intermediates, applied in the field of preparation of thiabendazole intermediates, can solve the problems of high price of pyruvic acid, difficult operation, unsafe process and the like, and achieves low cost of raw and auxiliary materials, low cost of raw materials, and low cost of raw materials. The effect of route novelty

Active Publication Date: 2022-03-25
PAPANNA BEIJING TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, domestic and foreign patents, reports such as CN102816120A, CN101712677A, CN106349235A, CN103204849A, etc., the route of synthesizing thiabendazole intermediate is mainly based on the condensation reaction of o-phenylenediamine and lactic acid under acidic conditions, and then under acidic conditions with a large amount of high Potassium manganate oxidation or direct condensation reaction with o-phenylenediamine and pyruvic acid under acidic conditions, and then halogenation reaction with halogenating reagents, the process yield is low, pyruvic acid is expensive, the process is unsafe, and the operation is difficult. The amount of three wastes is large, which has a great impact on the environment. Under the current environmental protection pressure, industrialization is difficult.

Method used

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  • A kind of preparation method of thiabendazole intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Under the condition of room temperature (10~35℃), add 110.3g (1mol, 98%, Bailingwei Technology Co., Ltd.) oxaloacetic acid 133.7g (1.1mol, 98%, Bailingwei Technology Co., Ltd.) Company) mixed in dilute hydrochloric acid, heated at 50-70°C for condensation reaction, reaction time 5-6h, after cooling, adjust pH between 7-8 with 30% aqueous sodium hydroxide solution, temperature controlled not higher than 35°C, continue Stir for 30min, separate out solid, cool below 15°C, filter, wash the filter residue with water, and dry 201.8g of crude product 1 at about 50°C, the effective content is 91%, and the yield is 90% in terms of o-phenylenediamine; the crude product 1-201.8 g into a 1000ml four-necked flask, add 500g of dichloroethane, heat at about 40°C, pass in chlorine gas to carry out chlorination reaction, the reaction time is 4-5h, the liquid phase detection of the crude product is 1<1%, the reaction is terminated, and the solvent is recovered at normal pressure Then, cr...

Embodiment 2

[0033] Under the condition of room temperature (10~35℃), add 110.3g (1mol, 98%, Bailingwei Technology Co., Ltd.) diethyl oxaloacetate 211.2g (1.1mol, 98%, o-phenylenediamine) into a 1000ml four-necked flask, Bailingwei Technology Co., Ltd.) mixed in dilute hydrochloric acid, heated at 50-70°C for condensation reaction, reaction time 5-6h, after cooling, adjust pH between 7-8 with 30% aqueous sodium hydroxide solution, and the temperature should not be higher than 35 ℃, continue to stir for 30min, separate out solid, cool below 15 ℃, filter, wash the filter residue with water, 201.8g of crude product 1 after drying at about 50 ℃, the effective content is 91%, and the yield is 90% in terms of o-phenylenediamine; Add 1-201.8g into a 1000ml four-necked flask, add 500g of dichloroethane, heat at about 40°C, pass in chlorine gas to carry out chlorination reaction, the reaction time is 4-5h, the liquid phase detection of crude product 1<1%, terminate the reaction, usually After the s...

Embodiment 3

[0037]Under the condition of room temperature (10~35℃), add 110.3g (1mol, 98%, Bailingwei Technology Co., Ltd.) oxaloacetic acid 133.7g (1.1mol, 98%, Bailingwei Technology Co., Ltd.) Company) mixed in dilute hydrochloric acid, heated at 50-70°C for condensation reaction, reaction time 5-6h, after cooling, adjust pH between 7-8 with 30% aqueous sodium hydroxide solution, temperature controlled not higher than 35°C, continue Stir for 30min, separate out solid, cool below 15°C, filter, wash the filter residue with water, and dry 201.8g of crude product 1 at about 50°C, the effective content is 91%, and the yield is 90% in terms of o-phenylenediamine; the crude product 1-201.8 g into a 1000ml four-necked flask, add 500g of dichloroethane, heat at about 40°C, pass in chlorine gas to carry out chlorination reaction, the reaction time is 4-5h, the liquid phase detection of the crude product is 1<1%, the reaction is terminated, and the solvent is recovered at normal pressure Then, cru...

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Abstract

The invention provides a preparation method of a thiabendazole intermediate. The preparation of the thiabendazole intermediate shown in formula (1) from a raw material containing o-phenylenediamine comprises the following steps: The amine raw material is subjected to condensation reaction to obtain crude product 1; the crude product 1 is subjected to halogenation reaction to obtain crude product 2; the crude product 2 is subjected to decarboxylation reaction and purified to obtain the thiabendazole intermediate. The method provided by the invention has low cost of raw materials, simple synthesis route, no catalyst, solvent recovery and mechanical application, almost zero discharge of three wastes, avoiding the impact on the environment, mild reaction conditions, simple operation, and a yield as high as 80%, which is suitable for modern Industrial production. R is Cl or Br.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of a thiabendazole intermediate. Background technique [0002] 2-(2-Chloroacetyl)benzimidazole, white solid, is an important intermediate of thiabendazole. At present, domestic and foreign patents, CN102816120A, CN101712677A, CN106349235A, CN103204849A and other reports, the route of synthesizing thiabendazole intermediates is mainly based on the condensation reaction of o-phenylenediamine and lactic acid under acidic conditions, and then using a large amount of high Potassium manganese is oxidized or directly carries out condensation reaction with o-phenylenediamine and pyruvic acid under acidic conditions, and then carries out halogenation reaction with halogenating reagent, the process yield is low, pyruvic acid is expensive, the process is unsafe, and the operation is difficult, The large amount of three wastes has a great impact on the environment. Unde...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D235/12
CPCC07D235/12
Inventor 焦体李星强
Owner PAPANNA BEIJING TECH
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