Search

CN-120625076-B - Electrosynthesis method of 5-seleno tetrazole

CN120625076BCN 120625076 BCN120625076 BCN 120625076BCN-120625076-B

Abstract

The invention discloses an electrosynthesis method of 5-seleno tetrazole, which comprises the steps of taking a platinum sheet as a cathode and a carbon rod as an anode, taking tetrabutylammonium perchlorate or lithium perchlorate as an electrolyte under constant current catalysis, cyclizing diaryl diselenide, isonitrile compound and azido trimethylsilane by a one-pot method to prepare a 5-seleno tetrazole derivative, and obtaining a pure product of the 5-seleno tetrazole through column chromatography separation after post-treatment of an obtained reaction mixture. The 5-seleno tetrazole can be obtained by a one-step reaction, the operation steps are few, the use of an oxidant and an additive is avoided, the post-treatment process is simple, and the product is easy to separate.

Inventors

  • ZHANG CHONG
  • SONG BIN
  • HU BINGCHENG
  • GAO CHAO
  • CHEN LEI
  • PANG LIN

Assignees

  • 南京理工大学

Dates

Publication Date
20260512
Application Date
20250723

Claims (17)

  1. 1. The synthesis method of the 5-seleno tetrazole is characterized by comprising the step of synthesizing a target product by carrying out electrochemical reaction on diaryl diselenide, isonitrile compound and azido trimethylsilane in an electrolyte solution: ; wherein R 1 is any one of tert-butyl, tetramethylbutyl, cyclohexyl, ester group and benzyl, R 2 is any one of phenyl and thienyl; the solvent in the electrolyte solution is a mixed solvent of acetonitrile and hexafluoroisopropanol with the volume ratio of 5-10:1; the electrochemical reaction adopts constant current, and the current is 3-20 milliamperes.
  2. 2. The method of claim 1, wherein the electrolyte in the electrolyte solution is tetrabutylammonium perchlorate or lithium perchlorate.
  3. 3. The method of claim 1, wherein the solvent in the electrolyte solution is a 9:1 acetonitrile and hexafluoroisopropanol mixed solvent.
  4. 4. The method of claim 1, wherein the electrochemical reaction uses a carbon rod as the anode and a platinum sheet as the cathode.
  5. 5. The method of claim 1, wherein the electrochemical reaction uses a constant current of 10 milliamp to 15 milliamp.
  6. 6. The method of claim 1 or 5, wherein the current is 10 milliamps.
  7. 7. The method of claim 1, wherein the electrochemical reaction is performed at 0-50 ℃.
  8. 8. The method of claim 1 or 7, wherein the electrochemical reaction is performed at room temperature.
  9. 9. The method of claim 1, wherein the electrochemical reaction time is not less than 4 hours.
  10. 10. The method of claim 1 or 9, wherein the electrochemical reaction time is greater than 6 hours.
  11. 11. The method of claim 1 or 9, wherein the electrochemical reaction time is greater than 10 hours.
  12. 12. The method of claim 1, wherein the electrolyte is present in an amount of 0.2 to 1 times the amount of the isonitrile compound.
  13. 13. The method of claim 1 or 12, wherein the electrolyte is present in an amount of 0.8 times the amount of isonitrile.
  14. 14. The method of claim 1, wherein the amount of azido trimethylsilane is 3 to 6 times the amount of isonitrile.
  15. 15. The method of claim 1 or 14, wherein the amount of azido trimethylsilane is 4 times the molar amount of isonitrile.
  16. 16. The method of claim 1, wherein the amount of diaryl diselenide is from 0.5 to 2 times the amount of isonitrile compound.
  17. 17. The method of claim 1 or 16, wherein the amount of diaryl diselenide is 1.5 times the amount of isonitrile compound.

Description

Electrosynthesis method of 5-seleno tetrazole Technical Field The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing 5-seleno tetrazole. Background The 5-seleno tetrazole derivative is an organic molecule with various biological activities and has wide application in the fields of chemistry, materials and drug design. To date, the process for synthesizing 5-selenoetetrazole derivatives still requires a multistep reaction in which the starting materials are also presynthesized and the successive reactions require the use of various oxidants, metals and additives from the 5-thiotetrazole, after oxidative sulfonylation, to be replaced by a diaryl diselenide. Thus, it is necessary to prepare 5-selenoetetrazole derivatives from simple starting materials under mild green conditions. Electrochemical organic synthesis technology is becoming a powerful synthesis tool. Because the technology does not need an exogenous oxidant, the mild oxidation of the substrate can be completed only by virtue of the electrode, and in addition, most electrochemical reactions can be simply operated under mild conditions, and the starting and stopping of the experiment can be completed along with the control of the current. Therefore, the search for a green and efficient electrochemical method for synthesizing the 5-seleno tetrazole derivative is a significant research content. Disclosure of Invention The invention aims to provide a green and efficient simple method for preparing 5-seleno tetrazole from diaryl diselenide, isonitrile and azido trimethylsilane. The technical scheme for realizing the aim of the invention is as follows: In a first aspect, the invention provides a method for preparing 5-seleno tetrazole, comprising the steps of carrying out electrochemical reaction on diaryl diselenide, isonitrile compound and azido trimethylsilane in electrolyte solution to synthesize a target product: Wherein R 1 includes but is not limited to any one of tert-butyl, tetramethylbutyl, cyclohexyl, ester groups, and benzyl groups, and R 2 includes but is not limited to any one of phenyl groups, and thienyl groups. Further, the electrolyte in the electrolyte solution is tetrabutylammonium perchlorate or lithium perchlorate, and the solvent is a mixed solvent of acetonitrile and hexafluoroisopropanol with a volume ratio of 5-10:1, preferably 9:1. Further, the electrochemical reaction adopts a carbon rod as an anode, a platinum sheet as a cathode, and the current is constant current of 3-20 milliamperes, preferably constant current of 10-15 milliamperes, and more preferably constant current of 10 milliamperes. Further, the electrochemical reaction is carried out at 0-50 ℃, preferably at room temperature. Further, the electrochemical reaction time is not less than 4 hours, preferably 6 hours or more, more preferably 10 hours or more. Further, the electrolyte is used in an amount of 0.2 to 1 times, preferably 0.8 times the molar ratio of the amount of the isonitrile compound. Further, the amount of azido trimethylsilane is 3 to 6 times, preferably 4 times, the molar ratio of the amount of isonitrile compound. Further, the amount of the diaryl diselenide to be used is 0.5 to 2 times, preferably 1.5 times, the molar ratio of the amount of the isonitrile compound to be used. Compared with the prior art, the invention has the remarkable advantages that: (1) The synthesis method is simple and efficient, 5-seleno tetrazole can be obtained through one-step reaction, the operation steps are few, the use of an oxidant and an additive is avoided, the post-treatment process is simple, the product is easy to separate, and the operation requirement is greatly simplified; (2) The reaction condition of the invention is easy to realize, and the invention does not need harsh conditions such as low temperature, high temperature, illumination, pressure, strong acid and alkali, etc., thus avoiding special requirements of biocatalysis, noble metal catalysis, etc.; (3) The diaryl diselenide used in the invention shows excellent reactivity under electrochemical conditions, so that azido trimethyl silane and isonitrile are cyclized into 5-seleno tetrazole, and compared with exogenous oxidants, iodine reagents, metal catalysts and the like, the diaryl diselenide is difficult to realize efficient short-time conversion. Drawings FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 5- (phenylseleno) -1- (2, 4-trimethylpent-2-yl) -1H-tetrazole prepared in example 1 of the present invention. FIG. 2 is a nuclear magnetic resonance carbon spectrum of 5- (phenylseleno) -1- (2, 4-trimethylpent-2-yl) -1H-tetrazole prepared in example 1 of the present invention. FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 5- (phenylseleno) -1- (tolylmethyl) -1H-tetrazole prepared in example 2 of the present invention. FIG. 4 is a nuclear magnetic resonance carbon spectrum of 5- (phenylseleno) -1- (tolylmethyl) -1H-