CN110305069B - Preparation method of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride - Google Patents
Preparation method of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride Download PDFInfo
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Abstract
A preparation method of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride comprises the steps of adding a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride into chlorosulfonic acid in batches, stirring until all solids are dissolved, slowly dripping thionyl chloride and a catalyst DMF at 40-60 ℃, controlling the dripping time to be 1-3 h, heating to 50-70 ℃ after dripping is finished, reacting for 2.5-4 h, dripping sulfuric acid with the mass fraction of 60-80% after the reaction is completed to quench the reaction and dilute the material, dripping sulfuric acid until the reaction liquid basically has no bubble generation, dispersing the material into water, separating out a white solid, and filtering to obtain the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride. The synthesis method has the characteristics of high yield, simple process, no organic solvent emission and the like.
Description
The technical field is as follows:
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 art:
aromatic sulfonyl chloride is an important intermediate for synthesizing pesticides, dyes and medicines, a series of compounds prepared by taking 3- (5-mercapto-1-tetrazolyl) benzene sulfonyl chloride as an intermediate are reported in patents such as patent documents EP0283041A, EP0154293A2, EP0736798A1, GB2202341A, patent document US5667936A and the like, and the aromatic sulfonyl chloride is widely applied to the fields of photographic sensitive materials and photographic printing and has good use value.
At present, the preparation method of aromatic sulfonyl chloride mainly comprises the following four methods: a. preparing by a direct chlorosulfonation method; b. aromatic sulfonic acid or aromatic sulfonate is prepared by chlorination; c. the method comprises the following steps of (1) carrying out oxychlorination preparation on aromatic mercaptan and related derivatives; d. diazotizing arylamine to prepare. The aromatic sulfonic acid salt is usually treated with chlorine gas or some chlorinating agent such as phosphorus pentachloride, phosphorus oxychloride, sulfone dichloride and the like to obtain aromatic sulfonyl chloride by using an organic solvent as a solvent. In 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate, sulfonylation activity of benzene ring is greatly influenced due to existence of tetrazole ring, increasing chloracylation difficulty of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate, there are few reports in the existing literature on preparation of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, JPH08278585A and US5667936A patent report in japan fuji film company that 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate as raw material is first reacted with phenyl chloroformate in acetonitrile and triethylamine system, and then chlorinated with phosphorus oxychloride to prepare 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, although the route can prepare the target product, however, the synthesis process is a two-step reaction, and each step of reaction requires discharging and uses a large amount of organic solvent, thereby increasing the operation cost and the pollution discharge cost of the process virtually.
In addition, JP1988147339 also reports that 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is synthesized by using 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate as a raw material, thionyl chloride as a solvent and a chlorinated reagent, and N, N-dimethylformamide as a catalyst, and although the process is a one-step reaction, the yield of the product is very low and is only 38%.
The invention content is as follows:
the invention aims to provide a method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride by one-step reaction, which has the characteristics of high yield, simple process, stability, zero emission of organic solvent and the like.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a preparation method of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride comprises the following steps:
the preparation method comprises the following steps:
adding a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride into chlorosulfonic acid in batches, stirring until all solids are dissolved, slowly dripping thionyl chloride and a catalyst DMF at 40-60 ℃, controlling the dripping time to be 1-3 h, heating to 50-70 ℃ after the dripping is finished, reacting for 2.5-4 h, dripping 60-80% sulfuric acid after the reaction is completed to quench the reaction and dilute the material, dripping sulfuric acid until the reaction solution is substantially bubble-free, dispersing the material into water, separating out white solids, and filtering to obtain the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the mass fraction of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate in the mixture of the raw materials of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride is 60-75%.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the molar ratio of the used amount of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate to the used amount of chlorosulfonic acid is 1:10-1:15, preferably 1:11-1: 13.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the molar ratio of the used amount of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate to the used amount of thionyl chloride is 1:1-1:3, preferably 1:1.5-1: 2.5.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the dripping temperature of the thionyl chloride is 40-60 ℃, preferably 45-55 ℃; the dropwise addition is frequently carried out for from 1h to 3h, preferably from 1.5h to 2 h.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the chlorination reaction temperature is 50-70 ℃, preferably 55-65 ℃; the reaction time is 2.5h-4h, preferably 3h-4 h.
In the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the mass concentration of the sulfuric acid is 60-80%, and preferably 70-75%.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride provided by the invention can prepare a target product through one-step reaction, and reduces the operation cost.
2. The preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride provided by the invention does not use an organic solvent, does not discharge the organic solvent in the whole process, and reduces the environmental pollution.
3. According to the preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, the yield of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is greatly improved by adjusting the material composition of reaction raw materials, the types of a solvent and a chloracylation reagent, and optimizing the reaction temperature, the reaction time and the product discharge mode, and the yield can reach more than 90%.
4. The preparation method of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride provided by the invention has the advantages of mild and easily obtained reaction conditions, simple treatment after reaction, capability of obtaining a target product by pouring into water, no complex operations such as extraction, concentration and the like.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, but the embodiments of the present invention are not limited to the examples.
Example 1
Adding 12mL of chlorosulfonic acid into a 100mL three-neck flask, adding 7.2g of a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate (70%) and sodium chloride (30%) in batches, stirring until the solid is completely dissolved, dropwise adding 3.9mL of thionyl chloride and catalytic amount of DMF at 45 ℃, completing dropwise addition for 1h, heating to 70 ℃, reacting for 3h, dropwise adding 75% sulfuric acid with mass concentration, pouring the reaction solution into water after dropwise addition until basically no bubbles are generated, separating out white solid, filtering, and air-drying to obtain 4.51g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 90.62%.
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)
Example 2
Adding 25mL of chlorosulfonic acid into a 100mL three-neck flask, adding 12.4g of a mixture of 65% sodium 3- (5-mercapto-1-tetrazolyl) benzene sulfonate and 35% sodium chloride in batches, stirring until the solid is completely dissolved, dropwise adding 5.2mL of thionyl chloride and a catalytic amount of DMF at 55 ℃, completing dropwise addition for 1.5h, heating to 60 ℃, reacting for 4h, dropwise adding 70% sulfuric acid with mass concentration, dropwise adding until basically no bubbles are generated, pouring the reaction liquid into water to separate out white solid, filtering, and air-drying to obtain 7.30g of 3- (5-mercapto-1-tetrazolyl) benzene sulfonyl chloride, wherein the yield is 91.74%.
Example 3
Adding 53mL of chlorosulfonic acid into a 250mL three-neck flask, adding 21.4g of a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate (70%) and sodium chloride (30%) in batches, stirring until the solid is completely dissolved, dropwise adding 7.8mL of thionyl chloride and a catalytic amount of DMF at 50 ℃, reacting for 4hr at 50 ℃, dropwise adding 55% sulfuric acid until no bubbles are generated basically, pouring the reaction solution into water to separate out a white solid, filtering, and air-drying to obtain 13.49g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 91.21%.
Example 4
Adding 57mL of chlorosulfonic acid into a 250mL three-neck flask, adding 26.7g of a mixture of sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate (75%) and sodium chloride (25%) in batches, stirring until the solid is completely dissolved, dropwise adding 5.2mL of thionyl chloride and a catalytic amount of DMF at 55 ℃, finishing dropping for 2h, heating to 65 ℃, reacting for 2.5h, dropwise adding sulfuric acid with the mass concentration of 65%, dropwise adding until basically no bubbles are generated, pouring a reaction solution into water to precipitate a white solid, filtering, and air-drying to obtain 17.83g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 90.17%.
Example 5
Adding 78mL of chlorosulfonic acid into a 500mL three-neck flask, adding 46.1g of a mixture of 65% sodium 3- (5-mercapto-1-tetrazolyl) benzene sulfonate and 35% sodium chloride in batches, stirring until the solid is completely dissolved, dropwise adding 11.7mL of thionyl chloride and catalytic amount of DMF at 60 ℃, completing dropwise addition for 1h, heating to 70 ℃, reacting for 3h, dropwise adding 80% sulfuric acid with mass concentration, pouring the reaction solution into water after dropwise addition until basically no bubbles are generated, separating out white solid, filtering, and air-drying to obtain 26.76g of 3- (5-mercapto-1-tetrazolyl) benzene sulfonyl chloride, wherein the yield is 90.42%.
Example 6
Adding 153mL of chlorosulfonic acid into a 500mL three-neck flask, adding 71.4g of a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate (70%) and sodium chloride (30%) and stirring until the solid is completely dissolved, dropwise adding 32.5mL of thionyl chloride and a catalytic amount of DMF at 55 ℃, completing dropwise addition after 3h, heating to 60 ℃ for reaction for 3h, dropwise adding 65% sulfuric acid with mass concentration, pouring the reaction liquid into water after dropwise addition until basically no bubbles are generated to separate out white solid, filtering and air-drying to obtain 46.31g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 93.83%.
Example 7
245mL of chlorosulfonic acid is added into a 1L three-neck flask, 158.3g of a mixture of sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate (60%) and sodium chloride (40%) is added in batches and stirred until the solid is completely dissolved, 24.6mL of thionyl chloride and catalytic amount of DMF are added dropwise at 40 ℃, the mixture is dripped over for 1.5h, the temperature is increased to 65 for reaction for 3h, dilute sulfuric acid with the mass concentration of 50% is dripped, the reaction solution is poured into water after dropwise addition until basically no bubbles are generated, white solid is separated out, the mixture is filtered and air-dried, 85.09g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is obtained, and the yield is 90.72%.
Example 8
Adding 423mL of chlorosulfonic acid into a 1L three-neck flask, adding 160g of a mixture of sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate (75%) and sodium chloride (25%) in batches, stirring until the solid is completely dissolved, dropwise adding 93.4mL of thionyl chloride and a catalytic amount of DMF at 50 ℃, completing dropwise addition after 2h, heating to 65 for reaction for 4h, dropwise adding 70% sulfuric acid in mass concentration, pouring the reaction solution into water after dropwise addition until basically no bubbles are generated to separate out white solid, filtering, and air-drying to obtain 112.24g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 94.72%.
Comparative example
Mixing and stirring 8.4g of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and 5mL of thionyl chloride, slowly dropwise adding 10mL of DMF in ice bath, stirring and reacting at room temperature for 2h after dropwise adding is finished, distilling off excessive thionyl chloride under reduced pressure after reaction is finished, pouring the obtained residual liquid into ice water, extracting with chloroform, drying an organic phase with anhydrous magnesium sulfate, and concentrating under reduced pressure to obtain 3.15g of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride, wherein the yield is 38%.
Note:
W 1 is the mass fraction of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate in the mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride;
W 2 is the mass fraction of sulfuric acid;
n 1 is the molar ratio of the dosage of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate to the dosage of chlorosulfonic acid;
n 2 is the dosage molar ratio of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate to the thionyl chloride;
T 1 the dropping temperature of thionyl chloride is used;
T 2 the chlorination reaction temperature;
t 1 the dripping time of the thionyl chloride is shown;
t 2 the chlorination reaction time.
The invention greatly improves the yield of the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride by adjusting the material composition of reaction raw materials, the types of solvents and chloracylation reagents and optimizing the reaction temperature, the reaction time and the discharge mode of products. The method is characterized in that a new method for preparing the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride by using a mixture of sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate and sodium chloride as reaction raw materials, chlorosulfonic acid and thionyl chloride as solvents and chloracylation reagents, DMF as a catalyst and sulfuric acid as a quencher and a diluent is provided, and the materials are subjected to water dispersion and filtration to obtain a product, and the method is used for preparing the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride by one-step reaction and can improve the yield to over 90%. Meanwhile, the method has the advantages of easily obtained reaction conditions, simple process, no organic solvent emission in the process and good practical value.
Claims (6)
1. A preparation method of 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is characterized in that a mixture of 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride is added into chlorosulfonic acid in batches, thionyl chloride and a catalyst DMF are slowly dropped at 40-60 ℃ after solids are completely dissolved by stirring, the temperature is raised to 50-70 ℃ after dropping is finished, the reaction is carried out for 2.5-4 h, sulfuric acid is dropped after the reaction is completely finished, the reaction is quenched and diluted, the sulfuric acid is dropped until the reaction liquid is basically free of bubble generation, the material is dispersed into water to separate out white solids, and the 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride is obtained by filtering;
the mass ratio of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate in the mixture of the 3- (5-mercapto-1-tetrazolyl) sodium benzenesulfonate and sodium chloride is 60% -75%.
2. The method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride as claimed in claim 1, wherein the molar ratio of the sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate to chlorosulfonic acid is 1:10-1: 15.
3. The method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride according to claim 1, wherein the molar ratio of sodium 3- (5-mercapto-1-tetrazolyl) benzenesulfonate to thionyl chloride is 1:1-1: 3.
4. The method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride according to claim 1, wherein the temperature of thionyl chloride is 40-60 ℃ and the time of addition is 1-3 h.
5. The method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride as claimed in claim 1, wherein said chlorination reaction is carried out at 50-70 ℃ for 2.5-4 h.
6. The method for preparing 3- (5-mercapto-1-tetrazolyl) benzenesulfonyl chloride as claimed in claim 1, wherein the mass concentration of sulfuric acid is 60-80%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH022541A (en) * | 1988-06-15 | 1990-01-08 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
| US4952483A (en) * | 1987-03-20 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photosensitive material and method for forming direct positive image |
| US5667936A (en) * | 1995-04-06 | 1997-09-16 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| JPH10171077A (en) * | 1996-12-16 | 1998-06-26 | Konica Corp | Method for processing silver halide photographic sensitive material |
| WO2005085218A1 (en) * | 2004-03-05 | 2005-09-15 | Chandiran Thakashinamoorthy | A novel process for preparing valdecoxib |
| CN104402782A (en) * | 2014-11-13 | 2015-03-11 | 江西仁明医药化工有限公司 | 2-[(4-dodecyloxy phenyl) sulfuryl] butyric acid synthetic method |
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- 2019-07-02 CN CN201910591587.0A patent/CN110305069B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952483A (en) * | 1987-03-20 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photosensitive material and method for forming direct positive image |
| JPH022541A (en) * | 1988-06-15 | 1990-01-08 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
| US5667936A (en) * | 1995-04-06 | 1997-09-16 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| JPH10171077A (en) * | 1996-12-16 | 1998-06-26 | Konica Corp | Method for processing silver halide photographic sensitive material |
| WO2005085218A1 (en) * | 2004-03-05 | 2005-09-15 | Chandiran Thakashinamoorthy | A novel process for preparing valdecoxib |
| CN104402782A (en) * | 2014-11-13 | 2015-03-11 | 江西仁明医药化工有限公司 | 2-[(4-dodecyloxy phenyl) sulfuryl] butyric acid synthetic method |
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