CN113372286A - Method for preparing 1-phenyl-5-mercapto tetrazole by one-step method - Google Patents
Method for preparing 1-phenyl-5-mercapto tetrazole by one-step method Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
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Abstract
The invention relates to the field of chemistry, in particular to the field of organic synthesis, and more particularly relates to a preparation method of 1-phenyl-5-mercapto tetrazole, which takes a compound shown as a formula II as a raw material, mixes the compound shown as the formula II with phosphorus pentasulfide, and dropwise adds CS2Then hydrochloric acid is added to prepare the target compound shown in the formula I. The 1-phenyl-5-mercapto tetrazole is prepared by a one-step method, so that the preparation process is greatly simplified, special process conditions are not required, the operation is simple, the production cost is low, and the method is suitable for industrial production. The 1-phenyl-5-mercapto tetrazole product prepared by the one-step method disclosed by the invention has high purity.
Description
Technical Field
The invention relates to the field of chemistry, in particular to the field of organic synthesis, and more particularly relates to a preparation method of 1-phenyl-5-mercapto tetrazole.
Background
1-phenyl-5-mercapto tetrazole, also known as 5-mercapto-1-phenyl tetrazole, CAS number 86-93-1. The preparation methods described in the prior publications are mainly two types:
the first method is to prepare a target product by taking carbon disulfide and aniline as raw materials through addition, methylation and synthetic acidolysis, wherein the total yield is 90%. However, the preparation process has a long synthetic route and a complicated operation process. As shown in the scheme (1) (Acta Ciencia Indica, Chemistry, 34(4), 651-656, 2008; Chinese patent CN 104098522A).
The second method is to react phenyl thioisocyanate with sodium azide to prepare 1-phenyl-5-mercapto tetrazole. In the route, the reaction temperature is 90-95 ℃, the temperature is high, side reaction is difficult to avoid, and byproducts are generated, so that the purity of the 1-phenyl-5-mercapto tetrazole product is low. As shown in the scheme (2) (Chinese patent CN108947922B, PCT patent WO2020238369A 1).
Disclosure of Invention
The invention aims to solve the technical problem of how to realize the one-step preparation of the 1-phenyl-5-mercapto tetrazole on the premise of ensuring high purity of a target product, thereby simplifying the preparation process and reducing the industrial production cost.
In order to solve the technical problem, the invention discloses a one-step method for preparing 1-phenyl-5-mercapto tetrazole, which takes a compound shown as a formula II as a raw material, mixes the compound shown as the formula II with phosphorus pentasulfide, and adds CS2And then adding hydrochloric acid to prepare the target compound shown in the formula I, wherein the reaction route is as follows:
further preferably, the CS2And dropwise adding the mixture into the reaction system at room temperature. As used herein, room temperature means 25. + -. 5 ℃.
Further preferably, the reaction temperature is 35-55 ℃, and preferably 45 ℃; the reaction time is 0.8-3 h, preferably 1 h.
Further preferably, compounds II, P2S5、CS2The feeding molar ratio of (1): (0.25-4): (13-37), preferably 1: 1: 20.
further preferably, the molar concentration of the hydrochloric acid is 1-4mol/L, preferably 2 mol/L.
Further preferably, the feeding molar ratio of the compound II to the hydrochloric acid is 1: (0.7-2.5), preferably 1: 1.2.
As a preferable technical scheme, the method further comprises a refining step, wherein after the target compound shown in the formula I is obtained, the target compound is further diluted, and the target compound is sequentially acidified, extracted, cleaned, dried and distilled under reduced pressure to obtain the refined target compound 1-phenyl-5-mercaptotetrazole.
Preferably, the acidifying agent is hydrochloric acid or sulfuric acid, further preferably, the acidifying agent is hydrochloric acid.
Preferably, the extraction reagent is ethyl acetate or dichloromethane, further preferably, the extraction reagent is dichloromethane.
Preferably, the washing reagent is hydrochloric acid, saturated sodium bicarbonate or aqueous sodium chloride solution, preferably aqueous sodium chloride solution.
Preferably, the drying agent is anhydrous magnesium sulfate, anhydrous copper sulfate, anhydrous magnesium perchlorate or anhydrous sodium sulfate, preferably anhydrous sodium sulfate.
The 1-phenyl-5-mercapto tetrazole is prepared by a one-step method, so that the preparation process is greatly simplified, special process conditions are not required, the operation is simple, the production cost is low, and the method is suitable for industrial production. In the present invention, CS2The adding mode is dropwise adding, so that the side reaction and the generation of side products caused by violent reaction and rapid temperature rise can be avoided, and the purity of the 1-phenyl-5-mercapto tetrazole product prepared by the one-step method disclosed by the invention is high.
Detailed Description
In order that the invention may be better understood, we now provide further explanation of the invention with reference to specific examples.
Example 1
Compound II (0.01mol, 1.62g) and phosphorus pentasulfide (0.01mol, 2.22g) were mixed and 12mL of CS was added dropwise at room temperature2(0.2mol), adding 6mL of 2mol/L hydrochloric acid, controlling the temperature to 45 ℃, and stirring for 1h to obtain a crude product of the product; diluting the reaction solution with 4mL of water, adding 2mol/L HCl to acidify the reaction solution, extracting with dichloromethane three times (5 mL each time) to remove organic by-products, washing with aqueous sodium chloride solution, drying with anhydrous sodium sulfate, and finally distilling under reduced pressure to obtain the target product compound I. The purity of the target product is 99.6%.
The dropping rate is not particularly limited in the present invention, and the dropping rate known to those skilled in the art is adopted for the dropping according to the production scale of the reagent, and the reaction internal temperature is not more than 30 ℃.
The acidifying agent hydrochloric acid of example 1 can be replaced by sulfuric acid; the extraction reagent dichloromethane can be replaced by ethyl acetate; the cleaning agent sodium chloride aqueous solution can be replaced by hydrochloric acid and saturated sodium bicarbonate; the anhydrous sodium sulfate of the drying agent can be replaced by anhydrous magnesium sulfate, anhydrous copper sulfate and anhydrous magnesium perchlorate.
Examples 2 to 13
Only the feed ratio or other conditions were changed, respectively, in the manner disclosed in example 1, detailed in table 1.
Note: the white portion in the table represents that the conditions are the same as in example 1.
Table 1 different reaction conditions and results
What has been described above is a specific embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (9)
1. The one-step method for preparing 1-phenyl-5-mercapto tetrazole is characterized by comprising the following steps: the method takes a compound shown as a formula II as a raw material, mixes the compound shown as the formula II with phosphorus pentasulfide, and adds CS2And then adding hydrochloric acid to prepare the target compound shown in the formula I, wherein the reaction route is as follows:
2. the one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: the CS2And dropwise adding the mixture into the reaction system at room temperature.
3. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: the reaction temperature is 35-55 ℃, and preferably 45 ℃.
4. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 3, wherein the method comprises the following steps: the reaction time is 0.8-3 h, preferably 1 h.
5. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: compound II, phosphorus pentasulfide, CS2The feeding molar ratio of (1): (0.25-4): (13-37), preferably 1: 1: 20.
6. the one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: the charging molar ratio of the compound II to the hydrochloric acid is 1: (0.7-2.5), preferably 1: 1.2.
7. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: the molar concentration of the hydrochloric acid is 1-4mol/L, and preferably 2 mol/L.
8. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 1, wherein the method comprises the following steps: the method also comprises a refining step, wherein after the target compound shown in the formula I is obtained, the target compound is further diluted, and the target compound is sequentially acidified, extracted, washed, dried and distilled under reduced pressure to obtain the refined target compound 1-phenyl-5-mercaptotetrazole.
9. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 8, wherein any one or more of the following conditions are selected from:
a. the acidifying agent is hydrochloric acid or sulfuric acid, and further preferably, the acidifying agent is hydrochloric acid;
b. the extraction reagent is ethyl acetate or dichloromethane, and further preferably, the extraction reagent is dichloromethane;
c. the cleaning reagent is hydrochloric acid, saturated sodium bicarbonate or sodium chloride aqueous solution, preferably sodium chloride aqueous solution;
d. the desiccant is anhydrous magnesium sulfate, anhydrous copper sulfate, anhydrous magnesium perchlorate or anhydrous sodium sulfate, preferably anhydrous sodium sulfate.
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| CN202110580938.5A CN113372286B (en) | 2021-05-26 | 2021-05-26 | Method for preparing 1-phenyl-5-mercapto tetrazole by one-step method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805164A (en) * | 2022-03-30 | 2022-07-29 | 法姆瑞斯医药科技(北京)有限公司 | Recycling method of 5-methyl-2-hydroxy-1, 3, 4-thiadiazole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098522A (en) * | 2014-07-25 | 2014-10-15 | 南通市华峰化工有限责任公司 | Preparation method for 5-sulfydryl-1-phenyl tetrazole |
| CN110627736A (en) * | 2019-09-26 | 2019-12-31 | 江苏阿尔法药业有限公司 | Method for recycling 1-phenyl-5-hydroxy tetrazole |
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2021
- 2021-05-26 CN CN202110580938.5A patent/CN113372286B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098522A (en) * | 2014-07-25 | 2014-10-15 | 南通市华峰化工有限责任公司 | Preparation method for 5-sulfydryl-1-phenyl tetrazole |
| CN110627736A (en) * | 2019-09-26 | 2019-12-31 | 江苏阿尔法药业有限公司 | Method for recycling 1-phenyl-5-hydroxy tetrazole |
Non-Patent Citations (2)
| Title |
|---|
| OLAJIDE E.ALAWODE等: "Clean Photodecomposition of 1-Methyl-4-phenyl-1H-tetrazole-5(4H)- thiones to Carbodiimides Proceeds via a Biradical", 《J.ORG.CHEM.》 * |
| 廖雅萍: "1-苯基-5-巯基-1,2,3,4-四氮唑的化学照相特性分析及合成方法的研究", 《影像技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805164A (en) * | 2022-03-30 | 2022-07-29 | 法姆瑞斯医药科技(北京)有限公司 | Recycling method of 5-methyl-2-hydroxy-1, 3, 4-thiadiazole |
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