Abstract
Thermodynamic characteristics of electrophilic substitution reactions of 2-methyltetrazole and 2H-tetrazole proceeding according to the elimination–addition pathway (with the HO– anion and hydroxonium ion as model agents) were compared on the basis of analysis of the results obtained by quantum chemical calculation performed using the DFT/B3LYP/6-31G(d,p) method and taking account of the specific solvation effects. Comparison with previous results for 1-methyltetrazole obtained by the same authors using the same method revealed probable reasons for the known lack of ability of 2-methyltetrazole to undergo electrophilic substitution reactions, particularly, the substantially lower polarity and HOMO and LUMO energies, that is, higher Mulliken electronegativity of 2-methyltetrazole compared with the 1-isomer.
Similar content being viewed by others
References
N. D. Chuvylkin, A. N. Subbotin, L. I. Belen’kii, Russ. Chem. Bull. (Int. Ed.), 2016, 65, 1716 [Izv. Akad. Nauk, Ser. Khim., 2016, 1716].
P. N. Gaponik, O. A. Ivashkevich, in Vybranyya navukovyya pratsy Belaruskaga dzyarzha-naga universiteta [Selected Scientific Publications of Belarusian State University], vol. V, Khimiya, Minsk, BDU, 2001, p. 353.
V. P. Ananikov, E. A. Khokhlova, M. P. Egorov, A. M. Sakharov, S. G. Zlotin, A. V. Kucherov, L. M. Kustov, M. L. Gening, N. E. Nifantiev, Mendeleev Commun., 2015, 75.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery,, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2013.
N. D. Chuvylkin, I. D. Nesterov, L. I. Belen’kii, Russ. Chem. Bull. (Int. Ed.), 2007, 56, 1425 [Izv. Akad. Nauk, Ser. Khim., 2007, 1425].
L. I. Belen’kii, A. N. Subbotin, N. D. Chuvylkin, Russ. Chem. Bull. (Int. Ed.), 2015, 64, 2610 [Izv. Akad. Nauk, Ser. Khim., 2015, 2610].
N. D. Chuvylkin, A. N. Subbotin, L. I. Belen’kii, Russ. Chem. Bull. (Int. Ed.), 2016, 63, 939 [2016, Izv. Akad. Nauk, Ser. Khim., 939].
A. Szabo, N. S. Ostlund, Modern Quantum Chemistry, Mac Million Publishing Co., Inc., New York, Collier Macmillan Publishers, London, 1982, p. 123.
Author information
Authors and Affiliations
Corresponding author
Additional information
For Part 7, see Ref. 1.
Based on the materials of the International Congress on the Heterocyclic Chemistry “KOST-2015” (October 18–23, 2015, Moscow, Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1722–1726, July, 2016.
Rights and permissions
About this article
Cite this article
Belen’kii, L.I., Subbotin, A.N. & Chuvylkin, N.D. Quantum chemical studies of azoles 8. Effect of N(2)-methyl substituent on the calculated thermodynamic parameters of electrophilic substitution in tetrazole according to the elimination–addition scheme without preceding formation of N-protonated azolium salts. Russ Chem Bull 65, 1722–1726 (2016). https://doi.org/10.1007/s11172-016-1501-1
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-016-1501-1