The intramolecular ene reaction of some 1,2-diallylcyclohexanes Public Deposited

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  • The familiar equilibrium between 1, 7- octadiene and cyclooctene at temperatures exceeding 3000, indicates that an ene-retroene process could be used as a six atom ring expansion method. To test this possibility we prepared both cis and trans isomers of 1, 2- diallyl- 1, 2 -bis (trimethylsiloxy) cyclohexane and pyrolyzed this both in liquid and vapor phases. Reaction in either phase was clean leading essentially to a single product, 1,8-bis (trimethylsiloxy) bicyclo [6.4.0] dodec-2-ene, the ene product. This was not separated into cis and trans isomers either preparatively or analytically. This cis isomer of the reactant rearranges faster than the trans isomer. A minor by-product was identified as 7- spiro [6.5] dodecen-l-one, which apparently arises from 2-bicyclo [6.4.0] dodecen-1,8-diol through a pinacol rearrangement. This reaction must therefore result from the presence of traces of moisture, though it is possible to account for the rearrangement without hydrolysis. A sample of 1, 2-dially1-1-trimethylsiloxy cyclohexane was also prepared and rearranged. The product consisted of two isomers in a 9:1 ratio. The major isomer was 1-trimethylsiloxy-6-bicyclo [ 6. 4.0] dodecene and the mirror isomer was the 2-ene. These results show that the 2-ally1 group acts preferentially as the ene component, a result undoubtedly keyed by steric effects.
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