CN113372286B - 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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- CN113372286B CN113372286B CN202110580938.5A CN202110580938A CN113372286B CN 113372286 B CN113372286 B CN 113372286B CN 202110580938 A CN202110580938 A CN 202110580938A CN 113372286 B CN113372286 B CN 113372286B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D257/04—Five-membered rings
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 CS 2 Then 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 use carbon disulfide and aniline as raw materials to prepare a target product 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 inevitable to generate by-products, and the purity of the 1-phenyl-5-mercaptotetrazole 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 CS 2 And then adding hydrochloric acid to prepare the target compound shown in the formula I, wherein the reaction route is as follows:
further preferably, the CS 2 And 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 to 3 hours, preferably 1 hour.
Further preferably, compounds II, P 2 S 5 、CS 2 The feeding molar ratio of (1): (0.25-4): (13 to 37), preferably 1:1:20.
further preferably, the molar concentration of the hydrochloric acid is 1-4mol/L, and is preferably 2mol/L.
Further preferably, the feeding molar ratio of the compound II to the hydrochloric acid is 1: (0.7 to 2.5), preferably 1.
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, CS 2 The adding mode is dropwise adding, so that the side reaction and the generation of side products caused by over violent reaction and rapid temperature rise can be avoided, and the 1-phenyl-5-mercapto tetrazole product prepared by the one-step method disclosed by the invention has high purity。
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 diphosphorus pentasulfide (0.01mol, 2.22g) were mixed, and 12mL of CS was added dropwise at room temperature 2 (0.2 mol), then 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 (21)
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 CS 2 And 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 CS 2 And dropwise adding the mixture into the reaction system at room temperature.
3. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 1, wherein: the reaction temperature is 35 to 55 ℃.
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 temperature was 45 ℃.
5. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 3 or 4, wherein: the reaction time is 0.8 to 3h.
6. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 5, wherein the method comprises the following steps: the reaction time was 1h.
7. 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, CS 2 The feeding molar ratio of (1): (0.25 to 4): (13 to 37).
8. 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, CS 2 The feeding molar ratio of (1): 1:20.
9. 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 to 2.5).
10. The one-step method for preparing 1-phenyl-5-mercapto tetrazole according to claim 9, wherein: the charging molar ratio of the compound II to the hydrochloric acid is 1.2.
11. 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.
12. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 1, wherein: the molar concentration of the hydrochloric acid is 2mol/L.
13. 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.
14. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 13, wherein the acidifying agent is hydrochloric acid or sulfuric acid.
15. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 14, wherein the acidifying agent is hydrochloric acid.
16. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 13, wherein the extraction reagent is ethyl acetate or dichloromethane.
17. The one-step method for preparing 1-phenyl-5-mercaptotetrazole of claim 16, wherein the extraction reagent is dichloromethane.
18. The one-step method for preparing 1-phenyl-5-mercaptotetrazole according to claim 13, wherein the cleaning reagent is hydrochloric acid, saturated sodium bicarbonate or sodium chloride aqueous solution.
19. The one-step method for preparing 1-phenyl-5-mercaptotetrazole of claim 18, wherein the cleaning reagent is sodium chloride aqueous solution.
20. The one-step method for preparing 1-phenyl-5-mercaptotetrazole of claim 13, wherein the drying agent is anhydrous magnesium sulfate, anhydrous copper sulfate, anhydrous magnesium perchlorate or anhydrous sodium sulfate.
21. The one-step method for preparing 1-phenyl-5-mercaptotetrazole of claim 20, wherein the drying agent is anhydrous sodium sulfate.
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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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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 |
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| 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;廖雅萍;《影像技术》;19991231(第2期);第13-17页 * |
| Clean Photodecomposition of 1-Methyl-4-phenyl-1H-tetrazole-5(4H)- thiones to Carbodiimides Proceeds via a Biradical;Olajide E.Alawode等;《J.Org.Chem.》;20101213;第76卷;第216-222页 * |
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