Synthesis of 5-phenyltetrazole and its N-methyl Derivatives in a Microreactor

Chemical and biochemical engineering quarterly

L. A. Lappalainen¹  S. D. Svetlov¹  T. V. Andreeva¹  R. E. Trifonov¹  R. S. Abiev¹  E. A. Popova¹  V. A. Ostrovskii¹ 

关键词: azidation of nitriles;    tetrazoles;    synthesis;    alkylation;    rate constants;    microreactor;   

DOI  :  10.15255/CABEQ.2013.1936

来源: Croatian Society of Chemical Engineers

【 摘 要 】

Abstract Azidation of benzonitrile with dimethylammonium azide yielding 5-phenyltetrazole dimethylammonium salt was performed under microreactor conditions. The kinetics of azidation of benzonitrile in DMF was investigated at the range 80–95 °С. The reaction rate constants were determined: kII·104 (L mol–1 s–1): 0.79, 0.97, 1.19, 1.51, at 80, 85, 90, and 95 °С, respectively. It was found that the reaction rate constants obtained in a microreactor are comparable to ones for a batch-type reactor. The thermodynamic parameters of azidation under the microreactor conditions correspond to the mechanism of the 1,3-dipolar cycloaddition of azides to nitriles. It was established that the excessive pressure in the microreactor notably accelerates the process. The alkylation of 5-phenyltetrazole with methyl iodide in microreactor was performed in dichloromethane-aqueous sodium hydroxide system. The accumulation of regioisomers of N1- and N2-methyl-5‑phenyltetrazole in the microreactor under the conditions of slug flow of the reaction mixture occurs considerably faster than in the batch-type reactor in the conditions of phase-transfer catalysis.

【 授权许可】

Unknown