Abstract
A fact of a reversible thermal inversion of exo- and endo-isomers of methyl 1,3-diphenylbicyclo[1.1.0] butane-2-carboxylate was established experimentally. The equilibrium constant of the process at 126°C is 14.2 with endo-isomer prevailing. Using DFT/PBE/L22 method the geometry of the isomers was optimized and also the geometry of the previously studied related exo,exo- and endo,endo-isomers of dimethyl 1,3-diphenylbicyclo[1.1.0] butane-2,4-dicarboxylate. The energy barrier of these mutual conversions was estimated.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
D’yakonov, I.A., Razin, V.V., and Komendantov, M.I., Tetrahedron, Lett., 1966, p. 1135.
D’yakonov, I.A., Razin, V.V., and Komendantov, M.I., Zh. Org. Khim., 1969, vol. 5, p. 386.
Woodward, R.B., and Dalrymple, D.L., J. Am. Chem. Soc., 1969, vol. 91, p. 4612.
Hoz, S., The Chemistry of the Cyclopropyl Group, Patai, S. and Rappoport, S., Eds, Chichester: Wiley, 1987.
Nguyen, K.A., Gordon, M.S., and, Boatz, J.A., J. Am. Chem. Soc., 1994, vol. 116, 9241.
Frey, H.M. and Stevens, I.D.R., Trans. Faraday, Soc., 1969, vol. 61, p. 90.
Rauk, A., Sorensen, T.S., and Sun, F., J. Am. Chem. Soc., 1995, vol. 117, 4506.
Masamune, S., Tetrahedron Lett., 1965, p. 945.
Komendantov, M.I., Bekmukhametov, R.R., and Novinskii, V.G., Zh. Org. Khim., 1976, vol. 12, p. 801.
Barfield, M. and Chakrabarti, B., Chem. Rev., 1969, vol. 69, p. 757.
Jain, R., Sponsler, M.B., Coms, F.D., and Dougherty, D.A., J. Am. Chem. Soc., 1988, vol. 110, p. 1356.
MarvinBeans, 5.3.7, www,http://www.chemaxon.com/
Gassman, P.G., Greenlee, M.L., Dixon, D.A., Richtsmeier, S., and Gougoutas, J.Z., J. Am. Chem. Soc., 1983, vol. 105, p. 5865.
Newton, M.D. and Schulman, J.M., J. Am. Chem. Soc., 1972, vol. 94, p. 767.
Razin, V.V., Maevskaya, E.I., and Komendantov, M.I., Voprosy stereokhimii (Stereochemistry Problems), Kiev: Izd. Kiev. Univ. 1971, vol. 1, p. 22.
D’yakonov, I.A., Razin, V.V., and Komendantov, M.I., Zh. Org. Khim., 1972, vol. 8, p. 54.
D’yakonov, I.A., Razin, V.V., and Komendantov, M.I., Tetrahedron Lett., 1966, p. 1127.
Pranata, J. and Dougherty, D.A., J. Phys. Org. Chem., 1989, vol. 2, p. 161.
Stewart, J.J.P., MOPAC2009. Stewart Computational Chemistry, version 10.028W, www, http://www.openmopac.net/
Rocha, G.B., Freire, R.O., Simas, A.M., and Stewart, J.J.P., J. Comp. Chem., 2006, vol. 27, p. 1101.
Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996,, vol. 77, p. 3865.
Laikov, D.N., Chem. Phys. Lett., 2005, vol. 416, p. 116.
Laikov, D.N., Chem. Phys. Lett., 1997, vol. 281, p. 151; Laikov, D.N. and, Ustynyuk, Yu.A., Izv. Akad. Nauk, Ser. Khim., 2005, p. 804.
Varetto, U., MOLEKEL 5.4; Swiss National Supercomputing Centre: Manno (Switzerland).
Author information
Authors and Affiliations
Additional information
Original English Text © V.V. Razin, P.S. Petrov, V.A. Vasin, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 8, pp. 1045–1050.
Rights and permissions
About this article
Cite this article
Razin, V.V., Petrov, P.S. & Vasin, V.A. Methyl 1,3-Diphenylbicyclo[1.1.0]butane-2-exo-carboxylate. new example of the thermal inversion of bicyclobutane system. Russ J Org Chem 48, 1041–1046 (2012). https://doi.org/10.1134/S1070428012080027
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1070428012080027