Quantum-chemical investigation of certain physicochemical properties of C-nitro-1,2,3-triazole and N-alkyl-4(5)-nitro-1,2,3-triazoles
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Quantum-chemical calculations have been carried out on molecular electrostatic potentials, proton affinity in the gas phase, gas phase basicity, and pK BH+ values in aqueous solution for C-nitro- and N-alkyl-4(5)-nitro-1,2,3-triazoles, and the relative stability of the isomeric N-alkyl-4(5)-nitrotriazoles (alkyl = Me, Et, i-Pr, t-Bu) in the gas phase and in aqueous solution. For all the studied substances in the gas phase the 2H-tautomer and the N(2)-isomers were considerably more stable than the corresponding N(1) compounds, and the 3H-tautomer and N(3)-isomer were the least stable. In aqueous solution 1- and 3-isomers had close values of energies, but in the case of C-nitro-1,2,3-triazole the 1H form became even more stable than the 2H-form. It was established which ring nitrogen atoms of 1,2,3-triazoles are protonated in the gas phase and in solution. The obtained data correlate well with the results of experimental investigations on the alkylation of 1,2,3-triazoles in acidic and basic media and of the experimental investigation on the alkylation of C-nitro-1,2,3-triazoles with diethyl sulfate carried out in the present work.
Keywords4(5)-nitro-1,2,3-triazoles alkylation quantum-chemical calculations B3LYP method basicity
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- 1.V. P. Krivopalov and O. P. Shkurko, Usp. Khim., 74, 369 (2005).Google Scholar
- 2.L. I. Vereshchagin, N. I. Kuznetsova, L. P. Kirillova, G. T. Sukhanov, and V. V. Shcherbakov, Khim. Geterotsikl. Soedin., 932 (1986). [Chem. Heterocycl. Comp., 22, 745 (1986)].Google Scholar
- 6.J.-L. M. Abbound, C. Foces-Foces, R. Notario, R. E. Trifonov, A. P. Volovodenko, V. A. Ostrovskii, I. Alkorta, and J. Elguero, Eur. J. Org. Chem., 3013 (2001).Google Scholar
- 9.P. Ykman, G. L’abbe, and G. Smets, Tetrahedron Lett., 5225 (1970).Google Scholar
- 12.R. E. Trifonov, V. A. Ostrovskii, L. I. Vereshchagin, M. B. Shcherbinin, N. P. Shirokova, and A. O. Koren', Zh. Org. Khim., 31, 928 (1995).Google Scholar
- 13.R. E. Trifonov, M. B. Shcherbinin, and V. A. Ostrovskii, Zh. Org. Khim., 33, 1116 (1997).Google Scholar
- 14.Vad. E. Matulis, Thesis for Candidate of Chemical Sciences, Minsk (2005).Google Scholar
- 16.M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, J. T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Revision B.03, Gaussian Inc., Pittsburgh, PA (2003).Google Scholar
- 22.O. A. Ivashkevich, P. N. Gaponik, Vit. E. Matulis, and Vad. E. Matulis, Zh. Obshch. Khim., 73, 296 (2003).Google Scholar
- 25.L. V. Gurvich, G. A. Khachkuruzov, V. A. Medvedev, I. V. Veits, G. A. Bergman, V. S. Yungman, N. P. Rtishcheva, L. F. Kuratova, G. N. Yurkov, A. A. Kane, B. F. Yudin, B. I. Brounshtein, V. F. Baibuz, V. A. Kvlividze, E. A. Prozorovskii, and B. A. Vorob'ev, Thermodynamic Properties of Individual Substances [in Russian], Akad. Nauk SSSR, Moscow (1962).Google Scholar