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Acid-Catalyzed Migration of the Methyl Substituent in the Dienone-Phenol Rearrangement of p-Quinol Ether

  • Published : 1989.04.20
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Abstract

4-Methoxy-4-methylcyclohexa-2,5-dienone 1 in aqueous sulfuric acid underwent the normal dienone-phenol rearrangement with methyl group migration. The fact that methyl is migrating group and methoxy is remaining group can be rationalized by the stabilization of positive charge at C-4 during the transition state. Methoxy methyl dienone 1 $((H_0)_{1/2} = - 4.6)$ is less basic than 4,4-dimethylcyclohexa-2,5-dienone whose half protonation acidity is reported as - 3.15 or - 3.66. This basicity difference comes from the unstabilization of the protonated methoxy methyl dienone 1 due to the electron withdrawing inductive effect of a methoxy group.

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  1. ChemInform Abstract: Acid‐Catalyzed Migration of the Methyl Substituent in the Dienone‐Phenol Rearrangement of p‐Quinol Ether. vol.20, pp.36, 1989, https://doi.org/10.1002/chin.198936173