The reaction of lead tetraacetate with alicyclic alcohols—I cycloalkanols

Abstract

Secondary cycloalkanols, containing 4- to 16-membered rings, have been treated with lead tetraacetate in refluxing benzene. It was found that the ease of oxidation to the corresponding ketones follows the reactivity order of reactions of alicyclic compounds involving an sp 3 → sp 2 ring carbon hybridization change, and that the amount of β-fragmentation resulting in opening of the ring is in accord with the total strain associated with carbocyclic rings. The yield of intramolecular ether formation appears to depend upon ring size and conformational factors in the transition state; it increases from cyclohexanol to cyclooctanol, drops sharply for cyclododecanol and reaches the highest value with cyclohexadecanol. The major ether obtained in the case of cyclodecanol was trans-1,2-epoxycyclodecane.