320603-23-4Relevant articles and documents
Kinetics and mechanism of izomerization of N-alkoxycarbonyl-5-aroxytetrazoles
Dabbagh,Mansoori
, p. 1771 - 1781 (2007/10/03)
The kinetics and mechanism of the N2-N1-isomerization of 2-methoxycarbonyl-5-(p-X-phenoxy)-tetrazoles (X = H, CH3, NHCOCH3, Cl, Br, NO2) were studied by 1H NMR spectroscopy in a DMSO-d6-CDCl3 mixture (25: 75). The rate of isomerization of the N2-isomer into N1-isomer fit the first-order equation (after three half-conversion periods). The isomerization is accompanied by hydrolysis and decarboxylation. The Hammett plot of In(kXlkH) for the isomerization showed a good correlation with σ- values (p- = 1.33, r = 0.965). A poor correlation with σ values was obtained. The kinetic data, the effect of solvent polarity, the substituent effects, and the results of AM1 quantum-chemical calculations suggest an ionic mechanism of the isomerization in polar solvents and a concerted mechanism in nonpolar solvents.