Abstract
The thermodynamic stability of 1,2- and 1,3-azole molecules, as well as of cationic and bipolar (carbenoid) intermediates in the gas phase and in aqueous solution formed by electrophilic substitution (proton as a model electrophile) was compared based on the analysis of quantum chemical calculations performed at the DFT/B3LYP/6-31G(D) level of theory with zero-point energy corrections. The differences in the chemical behavior of the isomeric 1,2- and 1,3-azole pairs, viz., pyrazole—imidazole, isoxazole—oxazole, and isothiazole—thiazole, were considered.
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L. I. Belenkii, I. D. Nesterov, N. D. Chuvylkin, Chem.-Heterocycl. Compd. (Engl. Transl.), 2013, 49, 1611 [Khim.-Geterotsikl. Soedin., 2013, 1739].
L. I. Belen’kii, N. D. Chuvylkin, Chem. Heterocycl. Compd.-(Engl. Transl.), 1996, 32, 1319 [Khim. Geterotsikl. Soedin., 1996, 1535].
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrewski, J. A. Mont-gomery, Jr., R. E. Stratmann, J. C. Burrant, S. S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. S. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Menucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochters-ki, G. A. Peterson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malik, A. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomp-erts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe,. V. Gill, B. Johnson, W. Heng, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Revision A. 5, Gaussian Inc., Pittsburgh (PA), 1998.
L. I. Belen’kii, T. G. Kim, I. A. Suslov, N. D. Chuvylkin, Russ. Chem. Bull. (Ind. Ed.), 2005, 54, 853 [Izv. Akad. Nauk, Ser. Khim., 2005, 837].
L. I. Belen’kii, N. D. Chuvylkin, I. D. Nesterov, Chem. Heterocycl. Compd. (Engl. Transl.), 2012, 48, 241 [Khim. Geterotsikl. Soedin., 2012, 256].
N. D. Chuvylkin, I. D. Nesterov, L. I. Belenkii, Russ. Chem. Bull. (Engl. Transl.), 2007, 56, 1481 [Izv. Akad. Nauk, Ser. Khim., 2007, 1425].
F. Freeman, D. J. Lau, A. R. Patel, P. R. Pavia, J. D. Willey, J. Phys. Chem. A, 2008, 112, 8775.
A. J. Arduengo III, H. V. Rasina Dias, R. L. Harlow, M. Kline, J. Am. Chem. Soc., 1992, 114, 5530.
A. J. Arduengo III, H. V. Rasina Dias, D. A. Dixon, R. L. Harlow, T. F. Koetze, J. Am. Chem. Soc., 1994, 116, 6812.
A. J. Arduengo III, H. R. Goerlich, W. J. Marshall, J. Liebigs Ann. Chem., 1997, 365.
W. A. Herrmann, Angew. Chem., Int. Ed., 2002, 41, 1290.
F. E. Hah, M. C. Jahke, Angew. Chem., Int. Ed., 2008, 47, 3122.
N. I. Korotkikh, V. Sh. Saberov, N. V. Glinyanaya, K. A. Marichev, A. V. Kiselev, A. V. Knishevitskii, G. F. Raenko, O. P. Shvaika, Chem. Heterocycl. Compd. (Engl. Transl.), 2013, 49, 19 [Khim. Geterotsikl. Soedin., 2013, 25].
A. Schmidt, A. Dreger, Curr. Org. Chem., 2011, 15, 2897.
J. Wolf, W. Böhlmann, M. Findeisen, T. Gelbrch, H.-J. Hoff-mann, B. Schulze, Angew. Chem., Int. Ed., 2007, 46, 3118.
A. DeHope, V. Lavaleo, B. Donnadieu, W. W. Schneller, G. Bertrand, Angew. Chem., Int. Ed., 2007, 46, 6922.
J. Wolf, W. Bõhlmann, M. Findeisen, T. Gelbrch, H.-J. Hoff-mann, B. Schulze, Angew. Chem., Int. Ed., 2007, 46, 6926.
F. M. Stoyanovich, in Novye napravleniya khimii tiofena [New Directions in Chemistry of Thiophene], Ed. Ya. L. Goldfarb, Nauka, Moscow, 1976, p. 96 (in Russian).
Y. Wang, H. Li, S. Han, J. Chem. Phys., 2005, 174501.
M. Buehl, A. Chaumont, R. Schurhammer, G. Wipf, J. Phys. Chem. B, 2005, 109, 18591.
E. R. Talaty, S. Raja, V. J. Storhaug, A. Doelle, W. R. Carp-er, J. Phys. Chem. B, 2004, 108, 13177.
N. E. Heimer, R. E. Del Sesto, Z. Meng, J. S. Wilkes, W. R. Carper, J. Mol. Liq., 2006, 124, 84. Cited from Comprehen-sive Heterocyclic Chemistry III, Eds A. R. Katritzky, C. A. Ramsden, E. F. V. Scriven, R. J. K. Taylor, Elsevier, Oxford, 2008, v. 4, p. 149.
H. Chen, D. R. Justes, R. G. Cooks, Org. Lett., 2005, 7, 3949.
V. A. Ostrovskii, G. V. Erusalimskii, M. B. Shcherbina, Russ. J. Org. Chem. (Engl. Transl.), 1993, 29, 1073 [Zh. Org. Khim., 1993, 29, 1297].
R. B. Woodward, R. A. Olofson, J. Am. Chem. Soc.,1961, 83, 1007.
L. I. Belenkii, Chem. Heterocycl. Compd. (Engl. Transl.), 1986, 22, 587 [Khim. Geterotsikl. Soedin., 1986, 749].
A. Albert, Heterocyclic Chemistry. An Introduction, The Athlone Press, University of London, 1959, 424 pp.
M. W. Austin, J. R. Blackborow, J. H. Ridd, B. V. Smith, J. Chem. Soc., 1965, 1051.
I. I. Grandberg, S. V. Tabak, N. I. Bobrova, A. N. Kost, L. G. Vasina, Chem. Heterocycl. Compd. (Engl. Transl.), 1965, 1, 271 [Khim. Geterotsikl. Soedin., 1965, 407].
L. I. Belenkii, V. S. Bogdanov, I. A. Abronin, G. P. Gromova, M. A. Cheskis, R. Z. Zakharyan, Chem. Scripta, 1985, 25, 266.
L. I. Belenkii, M. A. Cheskis, Chem. Heterocycl. Compd. (Engl. Transl.), 1984, 20, 713 [Khim. Geterotsikl. Soedin., 1984, 881].
L. I. Belenkii, G. P. Gromova, M. A. Cheskis, Ya. L. Goldfarb, Chem. Scripta, 1985, 25, 295.
M. A. Khan, B. M. Lynch, Y.-Y. Hung, Canad. J. Chem., 1963, 41, 1540.
B. M. Lynch, Y.-Y. Hung, Canad. J. Chem., 1964, 42, 1605.
M. R. Grimmett, S. R. Hartshorn, K. Schofield, J. B. Weston, J. Chem. Soc., Perkin Trans. 2, 1972, 1654.
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For Part 1, see Ref. 1.
Dedicated to Academician of the Russian Academy of Sciences Yu. N. Bubnov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2236–2242, October, 2014.
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Belen´kii, L.I., Nesterov, I.D. & Chuvylkin, N.D. Quantum chemical studies of azoles 2. Thermodynamic stability of neutral molecules and intermediates formed during electrophilic substitution of 1,2- and 1,3-azoles. Russ Chem Bull 63, 2236–2242 (2014). https://doi.org/10.1007/s11172-014-0728-y
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DOI: https://doi.org/10.1007/s11172-014-0728-y