1959 年 79 巻 10 号 p. 1288-1293
Reaction of phenylethynylmagnesium bromide with cinnamaldehyde and crotonaldehyde respectively forms 1, 5-diphenyl-1-penten-4-yn-3-ol (I) and 6-phenyl-2-hexen-5-yn-4-ol (II). Treatment of (I) with 16% sulfuric acid solution by shaking for 24 hours at room temperature results in recovery of the starting material and (I) does not undergo allyl rearrangement, while the heating of (I) in dioxane containing sulfuric acid for 7 hours results in normal Meyer-Schuster rearrangement and 1, 5-diphenyl-2, 4-pentadien-1-one is formed. (II) undergoes allyl rearrangement when shaken with 16% sulfuric acid solution for 24 hours at room temperature to form 6-phenyl-3-hexen-5-yn-2-ol which, when heated in dioxane with dil. sulfuric acid for 7 hours, changes into 6-phenyl-1, 3-hexadien-5-yne. Heating of (II) with dilute sulfuric acid in dioxane solution results in formation of 6-phenyl-1, 3-hexadien-5-yne and the product of normal Meyer-Schuster rearrangement, 1-phenyl-2, 4-hexadien-1-one. Oxidation of 6-phenyl-2-hexen-5-yn-4-ol and 6-phenyl-3-hexen-5-yn-2-ol with manganese dioxide affords the corresponding unsaturated ketones, 6-phenyl-3-hexen-5-yn-4-one and 6-phenyl-3-hexen-5-yn-2-one.