Heterocyclization of compounds containing diazo and cyano groups. 6. Theoretical and experimental investigations of cyclization of 2-cyano-2-diazoacetamides to 5-hydroxy-1,2,3-triazole-4-carbonitriles |
| |
Authors: | Yu. Yu. Morzherin M. Yu. Kolobov V. S. Mokrushin M. Brauer E. Anders V. A. Bakulev |
| |
Affiliation: | (1) Ural State Technical University, Ekaterinburg, Russia;(2) Institut für Organische Chemie und Makromolekulare Chemie, Friedrich-Schiller-Universität, Jena, Germany |
| |
Abstract: | A series of N-alkyl- and N-aryl-2-cyano-2-diazoacetamides was synthesized by the reaction of 2-amino-2-cyanoacetamides with sodium nitrite in hydrochloric acid. The mechanism of their heteroclectrocyclization to 5-hydroxy-1,2,3-triazoles was investigated kinetically and theoretically by the B3LYP/6-31+G* method. The conclusion was made on the basis of the determined activation energy of the cyclization process. reaction parameters , and kinetic isotope effects, that there is a difference between the mechanisms of cyclization of the N-alkyl and N-aryl derivatives of 2-cyano-2-diazoacetamide; cyclization of the N-alkyl derivatives takes place by a monorotatory mechanism, while cyclization of the N-aryl derivatives takes place by a mechanism where one of the stages is heteroelectrocyclization of 2-diazoacetimidates.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 26–41, January, 2000. |
| |
Keywords: | diazo compounds 1,2,3-triazoles heteroelectrocyclization kinetic isotope effect quantumchemical calculations |
本文献已被 SpringerLink 等数据库收录! |
|