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Abstract

The dienol-benzene rearrangement of syn and anti-4-allyl-4-methylcyclohexa-2,5-dien-1-ol (syn and anti 15) occurs by formation of a benzonium ion intermediate in p-toluene-sulphonic acid in ether below 0° and leads to a mixture of 2-, 3- and 4-allyltoluenes in the ratio 54:10:36. By the introduction of 14C-, D- and methyl labelled dienols it is shown that only the allyl group migrates and that this rearrangement is an intramolecular, one-step process. The formation of 2-allyltoluene occurs with retention, whereas the 3- and 4-allyltoluenes are formed by inversion of the carbon skeleton of the migrating allyl group. These rearrangements can be therefore classified as suprafacial, aromatic sigmatropic reactions of the order [1,2], [3,3] and [3,4]. The transition state can be postulated as representing a positively charged complex consisting of interacting allyl and tolyl radicals. The interaction of the two parts is controlled by the symmetry of the highest occupied π-orbitals (ψ3 for toluene and ψ2 for the allyl group) in agreement with the Woodward-Hoffmann rules. The better “distribution” of the charge in the transition state of these reactions in comparison to the ground state is chiefly responsible for the CoPE-like [3,3] sigmatropic reaction occurring at low temperatures. In general, sigmatropic reactions in charged systems are faster.

The rearrangement of syn and anti 2-allyl-2-methylcyclohexa-3,5-dien-1-ol (syn and anti 28) gives results similar to those obtained with the para-allyldienols.

The thermal rearrangement of 15 and 28 gives 3-allyltoluene by a [3,3] sigmatropic Cope rearrangement followed by elimination of water.