Preparation method of 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride

A technology of benzenesulfonyl chloride and tetrazolyl, which is applied in the field of preparation of 3-benzenesulfonyl chloride, can solve the problem of increasing the difficulty of chlorination of sodium 3-(5-mercapto-1-tetrazolyl)benzenesulfonate and increasing the process Operation cost and sewage cost, influence of benzene ring sulfonylation activity, etc., to achieve the effect of improved yield, mild reaction conditions, and optimized reaction temperature

Active Publication Date: 2019-10-08
CHINA LUCKY FILM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 3-(5-mercapto-1-tetrazolyl) sodium benzenesulfonate, the sulfonylation activity of the benzene ring has been greatly affected by the presence of the tetrazole ring, increasing the 3-(5-mercapto- The difficulty of chloroacylation of 1-tetrazolyl) sodium benzenesulfonate, the preparation of 3-(5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is seldom reported in existing literature, Japanese Fuji Film Company in JPH08278585A And report in the US5667936A patent take 3-(5-mercapto-1-tetrazolyl) sodium benzenesulfonate as raw material to react with phenyl chloroformate in acetonitrile and triethylamine system, and then react with phosphorus oxychloride after discharging Carry out chlorination reaction and prepare 3-(5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, although this route can prepare target product, synthetic technique is two-step reaction and each step reaction all needs to discharge and use a large amount of Organic solvents virtually increase the operating cost and sewage discharge cost of the process
[0004] In addition, Fujifilm Corporation of Japan also reported in Japanese Patent JP1988147339 that 3-(5-mercapto-1-tetrazolyl) sodium benzenesulfonate was used as raw material, thionyl chloride was used as solvent and chlorinated reagent, N,N- Dimethylformamide is a catalyst for the synthesis of 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride, although the process is a one-step reaction, the yield of the product is very low and only 38%

Method used

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  • Preparation method of 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride
  • Preparation method of 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride
  • Preparation method of 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride

Examples

Experimental program
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Effect test

Embodiment 1

[0025] In a 100 mL three-necked flask, add 12 mL of chlorosulfonic acid, add 7.2 g of a mixture of sodium 3-(5-mercapto-1-tetrazolyl)benzenesulfonate (70%) and sodium chloride (30%) in batches and stir until solid Completely dissolve, add 3.9mL of thionyl chloride and catalytic amount of DMF dropwise at 45°C, drop it for 1h, raise the temperature to 70°C for 3hrs, add sulfuric acid with a mass concentration of 75% dropwise, and pour the reaction solution into the A white solid was precipitated in water, filtered and air-dried to obtain 4.51 g of 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride with a yield of 90.62%.

[0026] 1 HNMR (400MHz, (CD 3 )2CO)8.55(s,1H),8.42–8.44(d,1H)8.13(s,1H),8.13–8.17(t,1H)

Embodiment 2

[0028] In a 100 mL three-necked flask, add 25 mL of chlorosulfonic acid, add 12.4 g of a mixture of 3-(5-mercapto-1-tetrazolyl) benzenesulfonate sodium (65%) and sodium chloride (35%) in batches and stir until solid Completely dissolve, add 5.2mL of thionyl chloride and catalytic amount of DMF dropwise at 55°C, drop it for 1.5h, raise the temperature to 60°C and react for 4hrs, add sulfuric acid with a mass concentration of 70% dropwise, and pour the reaction solution until almost no bubbles are formed. A white solid was precipitated in water, filtered, and air-dried to obtain 7.30 g of 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride, with a yield of 91.74%.

Embodiment 3

[0030] In a 250 mL three-neck flask, add 53 mL of chlorosulfonic acid, add 21.4 g of a mixture of 3-(5-mercapto-1-tetrazolyl) benzenesulfonate sodium (70%) and sodium chloride (30%) in batches and stir until solid Completely dissolve, add 7.8mL of thionyl chloride and catalytic amount of DMF dropwise at 50°C, finish dropping for 2 hours, react at 50°C for 4hrs, add sulfuric acid with a mass concentration of 55% dropwise, and pour the reaction solution into water to precipitate after almost no bubbles are formed. The white solid was filtered and air-dried to obtain 13.49 g of 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride with a yield of 91.21%.

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Abstract

The invention provides a preparation method of 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride. The preparation method comprises the steps: a mixture of sodium 3-(5-mercapto-1-tetrazolyl)benzenesulfonate and sodium chloride is added into chlorosulfonic acid in batches, stirring is carried out till all solids are dissolved, then thionyl chloride and a catalyst DMF are slowly dropped into themixture at 40-60 DEG C, the dropwise adding time is controlled to be 1-3 h, after dropwise adding is completed, the temperature is increased to be 50-70 DEG C, a reaction is carried out for 2.5-4 h, after the complete reaction, sulfuric acid with the mass fraction being 60-80% is dropwise added to quench the reaction, materials are diluted, the sulfuric acid is dropwise added till no bubble is generated in reaction liquid basically, then the materials are dispersed into water to precipitate white solids, and the 3-(5-mercapto-1-tetrazolyl)benzene sulfonyl chloride is obtained through filtering. The synthesizing method has the characteristics of being high in yield, simple in process, free of organic solvent discharging and the like.

Description

Technical field: [0001] The invention relates to the technical field of chemical intermediate synthesis, in particular to a preparation method of 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride. Background technique: [0002] Aromatic sulfonyl chloride is an important intermediate for the synthesis of pesticides, dyes, and medicines. A series of compounds prepared from 3-(5-mercapto-1-tetrazolyl)benzenesulfonyl chloride as an intermediate are described in patent documents EP0283041A, EP0154293A2, and EP0736798A1 , GB2202341A and patent literature US5667936A and other patents have related reports, and are widely used in the fields of photographic photosensitive materials and photographic printing, and have good use value. [0003] At present, there are four main methods for the preparation of aromatic sulfonyl chlorides: a. preparation by direct chlorosulfonation; b. preparation of aromatic sulfonic acid or aromatic sulfonate by chlorination; c. preparation by chlorinatio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D257/04
CPCC07D257/04
Inventor 豆静杰康长瑞王玲玲
Owner CHINA LUCKY FILM CORP
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