Cyclic unsaturated compounds
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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
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