Abstract
The geometric structures of the conformers of 2,3,4-trimethyl-7-methylidene-1,5-di-(thiophen-2-yl)-6,8-dioxabicyclo[3.2.1]octane were studied by the MP2/6-311++G**// B3LYP/6-31G* method. The average deviations of the calculated bond lengths from those determined by X-ray diffraction are no larger than 0.02 Å, and the deviations of the bond angles and dihedral angles are 0.7 and 3.5°, respectively. In the gas phase, the chair conformation is thermodynamically ∼7.3 kcal mol−1 more favorable than the boat conformation, and, taking into account the solvent effect of DMSO, the chair conformation is ∼9.4 kcal mol−1 more favorable. For formaldehyde and a series of ketones, including alkyl hetaryl ketones, the enthalpies of competitive formation of acetylenic alcohols and 7-methylidene-6,8-dioxabicyclo[3.2.1]octanes were calculated. The formation of the latter compounds is characterized by a considerable decrease in the enthalpy (to −91 kcal mol−1).
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
B. A. Trofimov, Sovremennye problemy organicheskoi khimii [Modern Problems of Organic Chemistry] 2010, 15, 23 (in Russian).
A. I. Mikhaleva, A. M. Vasil’tsov, L. N. Sobenina, V. K. Stankevich, B. A. Trofimov, Nauka proizvodstvu [Science for Industry], 2003, 6, 28 (in Russian).
B. A. Trofimov, E. Yu. Schmidt, I. A. Ushakov, A. I. Mikha- leva, N. V. Zorina, N. I. Protsuk, E. Yu. Senotrusova, E. V. Skital’tseva, O. N. Kazheva, G. G. Alexandrov, O. A. Dyachenko, Eur. J. Org. Chem., 2009, 30, 5142.
A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
C. Lee, W. Yang, R. G. Parr, Phys. Rev. B, 1988, 37, 785.
M. J. Frisch, J. A. Pople, J. S. Binkley, J. Chem. Phys., 1984, 80, 3265.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupius, J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
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, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, 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 A.1, Gaussian, Inc., Wallingford (CT), 2009.
C. Gonzales, H. B. Schlegel, J. Chem. Phys., 1989, 90, 2154.
T. Clark, J. Chandrasekhar, G. W. Spitznagel, P. von R. Schleyer, J. Comput. Chem., 1983, 4, 294.
C. Möller, M. S. Plesset, Phys. Rev., 1934, 46, 618.
M. Head-Gordon, J. A. Pople, M. J. Frisch, Chem. Phys. Lett., 1988, 153, 503.
J. Tomasi, B. Mennucci, E. Cancès, J. Mol. Struct. (THEOCHEM), 1999, 464, 211.
G. I. Almerindo, D. W. Tondo, J. R. Pliego, Jr., J. Phys. Chem. A, 2004, 108, 166.
E. Yu. Larionova, N. M. Vitkovskaya, N. V. Kempf, V. B. Kobychev, B. A. Trofimov, Dokl. AN, 2011, 439, 62 [Dokl. Chem. (Engl. Transl.), 2011, 439].
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2306–2310, Novemer, 2013.
Rights and permissions
About this article
Cite this article
Vitkovskaya, N.M., Larionova, E.Y., Shmidt, E.Y. et al. Quantum chemical study of the formation of acetylenic alcohols and 7-methylidene-6,8-dioxabicyclo[3.2.1]octanes from acetylene and carbonyl compounds. Russ Chem Bull 62, 2306–2310 (2013). https://doi.org/10.1007/s11172-013-0334-4
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-013-0334-4