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)·103 (DMSO-d6) and (45.2—72.4)·103 (CD3OD).
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Morzherin, Y.Y., Subbotina, Y.O., Nein, Y.I. et al. Synthesis and heteroelectrocyclization of unsymmetrically substituted diazomalonamides. Russian Chemical Bulletin 53, 1305–1310 (2004). https://doi.org/10.1023/B:RUCB.0000042291.70287.2d
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DOI: https://doi.org/10.1023/B:RUCB.0000042291.70287.2d