Abstract
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-d 6-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 ln(k X k H) for the isomerization showed a good correlation with σ- values (ρ- = 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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Wehman, T.C. and Popov, I.A., J. Phys. Chem., 1966, vol. 70, p. 3688.
Duncia, J.V., Pierce, M.E., and Santella, J.B., J. Org. Chem., 1991, vol. 56, p. 2395.
El-Ahl, A.-A.S., Elmorsy, S.S., Elbeheery, A.H., and Amer, F.A., Tetrahedron Lett., 1997, vol. 38, p. 1257.
Zucchi, F., Trabanelli, G., and Fonsati, M., Corros. Sci., 1996, vol. 38, p. 2019.
Cubreo, E., Orozco, M., and Luque, F.J., J. Am. Chem. Soc., 1998, vol. 120, p. 4723.
Elguero, J., Marzin, C., and Roberts, J.D., J. Org. Chem., 1974, vol. 39, p. 357.
Wofford, D.S., Forkey, D.M., and Russell, J.G., J. Org. Chem., 1982, vol. 47, p. 5132.
Razynska, A., Tempczyk, A., Malinski, E., Szafranek, J., and Grzonka, Z., J. Chem. Soc., Perkin Trans. 2, 1983, p. 379.
Bauer, M., Harris, R.K., Rao, R.C., Apperley, D.C., and Rodger, C.A., J. Chem. Soc., Perkin Trans. 2, 1998, p. 475.
Katritzky, A.R., Jozwiak, A., Lue, P., Yannakopoulou, K., Palenik, G.S., and Zhang, Z.Y., Tetrahedron, 1990, vol. 46, p. 633.
Gall, J.H. and Purcell, W.L., Inorg. Chem., 1990, vol. 29, p. 3806.
Isaacs, N.S., Physical Organic Chemistry, Harlow, Essex, Enfland: Longman Scientific & Technical, 1987, p. 129.
Hansch, C. and Leo, A.J., Substituents Constants for Correlation Analysis in Chemistry and Biology, New York: Wiley, 1979, p. 3.
Dabbagh, H.A. and Lwowski, W., J. Org. Chem., 1989, vol. 54, p. 3952.
Dabbagh, H.A. and Ghaelee, S., J. Org. Chem., 1996, vol. 61, p. 3439.
Dabbagh, H.A. and Lwowski, W., J. Org. Chem., 2000, vol. 65, p. 7284.
Faure, R., Vincent, E.J., and Elguero, J., Heterocycles, 1983, vol. 20, p. 713.
Gassend, R., Maire, J.C., and Pommier, J.C., J. Organomet. Chem., 1977, vol. 132, p. 69.
Stone, W.E., Pharmacology, 1970, vol. 3, p. 367.
Butller, R.N., Adv. Heterocycl. Chem., 1977, vol. 21, p. 323.
Katritzky, A.R., Rachwal, S., and Rachwal, B., J. Chem. Soc., Perkin Trans. 1, 1987, p. 805.
Katritzky, A.R., Yannakopoulou, K., Lue, P., Rasala, D., and Urogdi, L., J. Chem. Soc., Perkin Trans. 1, 1989, p. 225.
Katritzky, A.R. and Drewniak, M., Tetrahedron Lett., 1988, vol. 29, p. 1755.
Katritzky, A.R., Gallos, J.K., and Yannakopoulou, K., Synthesis, 1989, p. 31.
Katritzky, A.R., Drewniak, M., and Lue, P., J. Org. Chem., 1988, vol. 53, p. 5854.
Katritzky, A.R., Urogdi, L., and Mayence, A., Synthesis, 1989, p. 323.
Dabbagh, H.A., Mansoori, Y., Jafari, M., and Rostami, M., J. Chem. Res., 2000, p. 442–445.
Dabbagh, H.A. and Davis, B.H., J. Org. Chem., 1990, vol. 55, p. 2011.
Dabbagh, H.A. and Mohammad Salehi, J., J. Org. Chem., 1998, vol. 63, p. 7619.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Dabbagh, H.A., Mansoori, Y. Kinetics and Mechanism of Izomerization of N-Alkoxycarbonyl-5-aroxytetrazoles. Russian Journal of Organic Chemistry 37, 1771–1781 (2001). https://doi.org/10.1023/A:1013947228772
Issue Date:
DOI: https://doi.org/10.1023/A:1013947228772