Cyclic unsaturated compounds
A study was made of the thermal transformations of spiro[4,4]-1,3-nonadiene (I).
Diene (I) is isomerized to bicyclo[4,3,0]nonadiene (IV) in the temperature range 250–320°. Diene (IV) can be obtained in up to 90% yield in preparative experiments. Consequently, the thermal isomerization of (I) is a new and convenient method for the synthesis of compounds of the hydrindene series.
We consider the intramolecular 1,2-shift of a substituent from the 5 position of the cyclopentadiene ring to be the mechanism of the isomerization (I)→(IV).
Bicyclo[4,3,0]nonadiene represents an equilibrium mixture of isomers with a different position of the double bonds in the cyclopentadiene ring, in which bicyclo[4,3,0]-1(5),2-nonadiene (IV) predominates (not less than 80%).
In the temperature range 350–400° there occurs thermal isomerization of diene (IV) to bicyclo[4, 3,0]-1,5-nonadiene (VI). The indicated transformation is the first example of the isomerization of a substituted cyclopentadiene to a diene with a fixed transoid system of double bonds.
The thermal dehydrogenation of dienes (IV) and (VI) to indan (VII) takes place at 450–500°. Diene (VI) is an intermediate product in the reaction (IV)→(VII). The transformation (VI)→ (VII) occurs as the result of the direct cleavage of hydrogen, and not by its redistribution between the molecules, since monoolefins and perhydrindan are absent in the reaction products.
A study was made of the thermal transformations of spiro[4,2]-1,3-heptadiene (II). In contrast to diene (I), diene (II) exhibits a much greater thermal stability, and at 400–500° is converted to a complex mixture of hydrocarbons.
KeywordsHydrocarbon Double Bond Diene Dehydrogenation Spiro
Unable to display preview. Download preview PDF.
- 1.V. A. Mironov, B. D. Polkovnikov, É. P. Mikos, T. M. Fadeeva, and A. A. Akhrem, Izv. Akad. Nauk SSSR, Ser. Khim., 129 (1970).Google Scholar
- 2.V. A. Mironov, E. V. Sobolev, and A. N. Elizarova, Tetrahedron,19, 1939 (1963).Google Scholar
- 3.K. Alder and R. Muders, Chem. Ber.,91, 1083 (1958).Google Scholar
- 4.J. W. de Haan and H. Kloosterziel, Rec. Trav. Chim.,84, 1594 (1965).Google Scholar
- 5.J. W. de Haan and H. Kloosterziel, Rec. Trav. Chim.,87, 298 (1968).Google Scholar
- 6.V. A. Mironov, V. S. Pashegorova, T. M. Fadeeva, and A. A. Akhrem, Izv. Akad. Nauk SSSR, Ser. Khim., 182 (1968).Google Scholar
- 7.V. A. Mironov, V. S. Pashegorova, T. M. Fadeeva, and A. A. Akhrem, Tetrahedron Letters, 3997 (1968).Google Scholar
- 8.B. F. Hallam and P. L. Pauson, J. Chem. Soc., 646 (1958).Google Scholar
- 9.B. A. Kazanskii, E. V. Sobolev, V. T. Aleksanyan, L. A. Nakhapetyan, and M. Yu. Lukina, Dokl. Akad. Nauk SSSR,159, 839 (1964).Google Scholar
- 10.R. Ya. Levina and T. I. Tantsyreva, Dokl. Akad. Nauk SSSR,89, 697 (1953).Google Scholar
- 11.C. F. Wilcox and R. R. Craig, J. Am. Chem. Soc.,83, 3866 (1961).Google Scholar
- 12.R. Ya. Levina, N. N. Mezentsova, and O. V. Lebedev, Zh. Obshch. Khim.,25, 1097 (1955).Google Scholar
- 13.C. L. Wilson, J. Chem. Soc., 48 (1945).Google Scholar
- 14.W. Borche and M. Pommer, Chem. Ber.,54, 102 (1921).Google Scholar
- 15.W. M. Kutz, J. E. Nickels, J. J. McGovern, and B. B. Corson, J. Am. Chem. Soc.,70, 4026 (1948).Google Scholar
- 16.B. A. Kazanskii, A. F. Plate, and B. M. Terent'eva, Organic Syntheses [in Russian], Vol. 2 (1952), p. 70.Google Scholar
- 17.S. I. Khromov, E. S. Balenkova, O. E. Lishenok, and B. A. Kazanskii, Dokl. Akad. Nauk SSSR,135, 627 (1960).Google Scholar
- 18.A. L. Liberman, O. V. Bragin, and B. A. Kazanskii, Dokl. Akad. Nauk SSSR,111, 1039 (1956).Google Scholar
- 19.R. Mecke and F. Langenbucker, Infrared Spectra of Selected Chemical Compounds, No. 945.Google Scholar
- 20.V. A. Mironov, S. N. Kostina, and A. N. Elizarova, Izv. Akad. Nauk SSSR, Ser. Khim., 875 (1964).Google Scholar
- 21.A. N. Elizarova and V. A. Mironov, “Problems in Organic Synthesis,” Zh. Obshch. Khim., 68 (1965).Google Scholar
- 22.V. A. Mironov and A. A. Akhrem, Izv. Akad. Nauk SSSR, Ser. Khim., 698 (1967).Google Scholar