Conclusions
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1.
The influence of pressure and temperature on the isomeric composition of adducts of diene condensation of trans-piperylene with methyl acrylate was investigated. The cis-transition states possess lower values of the volume, entropy, and energy in comparison with the corresponding trans-states; the ortho-isomsrs are characterized by lower values of the entropy and energy of the transition states in comparison with the meta-isomers.
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2.
The differences in the volumes and entropies of the transition states were used to consider the structure of the latter; the results obtained agree with a cyclic structure of the transition states. It was concluded that the transition state apparently has a structure closer to the “plane parallel” model of the prereaction complex than to the structure of the adduct.
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3.
It was concluded that the determining influence on the structural and steric direction of the reaction is exerted by electronic, rather than steric factors.
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Literature cited
B. S. Él'yanov, B. A. Rudenko, M. G. Gonikberg, and V. F. Kucherov, Izv. Akad. Nauk SSSR, Ser. Khim., 1082 (1964).
D. Craig, J. Amer. Chem. Soc.,65, 1006 (1943).
V. M. Zhulin, M. G. Gonikberg, and V. N. Zagorbinina, Izv. AN SSSR. Otd. Khim. N, 716 (1962).
J. C. Bartlet and D. M. Smith, Canad. J. Chem.,38, 2057 (1960).
I. N. Nazarov, A. V. Kamernitskii, and A. A. Akhrem, Zh. Obshch. Khim.,28, 1458 (1958).
V. F. Kucherov, É. P. Serebryakov, and R. É. Valter, Dokl. Akad. Nauk SSSR,138, 1357 (1961).
Collection: Stereochemistry of Cyclohexane Derivatives [Russian translation], V. F. Kucherov (editor), IL (1958).
J. S. Meek and J. W. Rangsdale, J. Amer. Chem. Soc.,70, 2052 (1948).
I. N. Nazarov, Yu. A. Titov, and A. I. Kuznetsova, Izv. AN SSSR, Otd. Khim., N., 879 (1960).
J. E. Leffler, J. Organ. Chem.,20, 1202 (1955).
M. G. Gonikberg and A. I. Kitaigorodskii, Dokl. Akad. Nauk SSSR,122, 231 (1958).
G. S. Hammond, J. Amer. Chem. Soc.,77, 334 (1955).
C. Ingold, The Transition State, Chem. Soc. Spec. Publ., No. 16, 119 (1962).
I. N. Godnev, Calculation of Thermodynamic Functions according to Molecular Data [in Russian], Gostekhizdat (1956).
A. Wassermann, Diels-Alder Reactions, London (1965).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 565–572, March, 1969.
The authors would like to thank A. V. Kamernitskii for providing the cis-2-methyl-Δ3-cyclohexenecarboxylic acid.
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Él'yanov, B.S., Shakhova, S.K., Vitt, S.V. et al. Investigation of the transition state in the diene condensation of trans-piperylene with methyl acrylate. Russ Chem Bull 18, 504–509 (1969). https://doi.org/10.1007/BF00906966
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DOI: https://doi.org/10.1007/BF00906966