Automerisierung von 1,3,5,5‐Tetramethylcyclohexa‐1,3‐dien. Vorläufige Mitteilung

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Abstract
1,3,5,5‐Tetramethylcyclohexa‐1,3‐diene, specifically deuterated in all positions except the gem.‐dimethyl groups (11), was synthesized and found to undergo a rearrangement in the gas phase at 560°, which leads to a statistical distribution of the 6 hydrogen atoms to all 16 positions. This shows that the title compound (2) automerizes under these conditions and that the reaction proceeds via a series of ring openings (to 5) followed by degenerate [1,7]‐H‐shifts and rig closures (back to 2) rather than via [1,5]‐CH3‐shifts. It is suggested that the previously studied rearrangement of 5,5‐dimethylcyclohexa‐1,3‐diene (1) to 1,5‐dimethylcyclohexa‐1,3‐diene (3) takes its course by the same reaction pathway.