Synthesis and heteroelectrocyclization of unsymmetrically substituted diazomalonamides / Morzherin Yu.Yu., Subbotina Yu.O., Nein Yu.I., Kolobov M.Yu., Bakulev V.A. // Russian Chemical Bulletin. - 2004. - V. 53, l. 6. - P. 1305-1310.

ISSN:
10665285
Type:
Article
Abstract:
A selective procedure was developed for the synthesis of 1,2,3-triazoles and unsymmetrically substituted diazomalonamides. Cyclization of unsymmetrically substituted diazomalonamides to 1,2,3-triazoles was studied by the method of intramolecular competitive reactions. The kinetic and thermodynamic characteristics of the process were determined. Quantum-chemical calculations for the monorotatory electrocyclic and nonrotatory heteroelectrocyclic mechanisms of cyclization were carried out. N-Aryldiazomalonamides undergo cyclization according to the heteroelectrocyclic mechanism, whereas cyclization of N-alkyldiazomalonamides proceeds by the monorotatory mechanism. The experimental constant of competition between these processes is (1.3 - 8.3)·10 3 (DMSO-d 6) and (45.2 - 72.4)·10 3 (CD 3OD).
Author keywords:
1,2,3-triazoles; cyclization; diazo compounds; method of intramolecular competitive reactions; quantum-chemical calculations; rate constant; thermodynamic stability
Index keywords:
malonic acid derivative; triazole derivative; article; chemical reaction kinetics; cyclization; drug synthesis; quantum chemistry; substitution reaction; thermodynamics
DOI:
10.1023/B:RUCB.0000042291.7028
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Affiliations Urals State Technical University, 19 Ul. Mira, 620002 Ekaterinburg, Russ. Fed., Russian Federation
Author Keywords 1,2,3-triazoles; cyclization; diazo compounds; method of intramolecular competitive reactions; quantum-chemical calculations; rate constant; thermodynamic stability
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Correspondence Address Urals State Technical University, 19 Ul. Mira, 620002 Ekaterinburg, Russ. Fed.Russian Federation; email: morjerine@htf.ustu.ru
Language of Original Document English
Abbreviated Source Title Russ. Chem. Bull.
Source Scopus