Abstract
The thermolysis of β-pinene and the co-thermolysis of an equimolar mixture of β-and α-pinenes in supercritical ethanol were carried out. The reaction of β-pinene affords β-myrcene as the major product (>70%). Considerable differences in the temperature dependence of the reaction rate were revealed for the transformations of β-pinene into β-myrcene and of α-pinene into limonene. The pre-exponential factors and the activation energies were calculated. The enantiomeric ratios of the thermolysis products of β-and α-pinenes and limonene were estimated. The starting monoterpenes do not undergo racemization during thermolysis. The thermolysis of enantiomerically pure α-pinene affords racemic (±)-limonene, whereas (−)-β-pinene gives (−)-limonene. The enantiomeric ratio in the latter remains equal to the enantiomeric purity of the starting β-pinene.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. M. Chibiryaev, V. I. Anikeev, A. Yermakova, P. E. Mikenin, I. V. Kozhevnikov, and O. I. Sal’nikova, Izv. Akad. Nauk, Ser. Khim., 2006, 951 [Russ. Chem. Bull., Int. Ed., 2006, 55, 987].
A. V. Tkachev, Biblioteka khromato-mass-spektrometricheskikh dannykh letuchikh veshchestv rastitel’nogo proiskhozhdeniya [Library of GC/MS Data for Volatile Substances of Plant Origin], Novosibirskii Institut Organ. Khimii im. N. N. Vorozhtsova SO RAN, Novosibirsk, 2006 (in Russian).
H. G. Hunt and J. E. Hawkins, J. Am. Chem. Soc., 1950, 72, 5618.
L. A. Goldblatt and S. Palkin, J. Am. Chem. Soc., 1941, 63, 3517.
US Pat. 2420131; Chem. Abstrs, 1947, 41, 5550.
US Pat. 2507546; Chem. Abstrs, 1950, 44, 7341d.
J. E. Hawkins and J. W. Vogh, J. Phys. Chem., 1953, 57, 902.
T. Sasaki, S. Eguchi, and T. Ishii, J. Org. Chem., 1969, 34, 3749.
A. J. Johanson, F. L. McKennon, and L. A. Goldblatt, Ind. Eng. Chem., 1948, 40, 500.
W. J. Runckel and L. A. Goldblatt, Ind. Eng. Chem., 1946, 38, 749.
T. Nakagawa, H. Ozaki, T. Kamitanaka, H. Takagi, T. Matsuda, T. Kitamura, and T. Harada, J. Supercrit. Fluids, 2003, 27, 255.
R. L. Burwell, Jr, J. Am. Chem. Soc., 1951, 73, 4461.
D. V. Banthorpe and D. Whittaker, Chem. Rev., 1966, 66, 643.
W. R. Rocha, H. M. S. Milagre, and W. B. De Almeida, J. Mol. Struct. (Theochem.), 2001, 544, 213.
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1188–1192, June, 2007.
Rights and permissions
About this article
Cite this article
Chibiryaev, A.M., Yermakova, A., Kozhevnikov, I.V. et al. Comparative thermolysis of β-and α-pinenes in supercritical ethanol: the reaction characterization and enantiomeric ratios of products. Russ Chem Bull 56, 1234–1238 (2007). https://doi.org/10.1007/s11172-007-0186-x
Received:
Issue Date:
DOI: https://doi.org/10.1007/s11172-007-0186-x