α-ピネンの塩化クロミルによる酸化成績体について (第3報)

抄録

d-Pinocampheol, C₁₀H₁₈O, was obtained from d-pinocamphone by reduction with metallic sodium and alcohol. This reaction is reversible, pinocampheol yielding pinocamphone by oxidation with bichromate and sulfuric acid. The alcohol, when heated with potassium bisulfate, undergoes dehydration to give α-pinene which was confirmed by its nitrosochloride, m.p. 105-106°, and by pinic acid, m.p. 135-136°, obtained from the products of permanganate oxidation. Pinocampheol methylxanthate, m.p. 61-62°, also decomposes into α-pinene by pyrolysis. From physical and chemical grounds, this alcohol appears to be mixture of some of its stereoisomers, e.g. pino-, isopino-, neo-, or neoiso-pinocampheol. On oxidation of α-pinene with chromyl chloride, addition, hydration and dehydration seem to occur on the double bond and results in the formation of pinocamphone as the normal reaction product, and partial isomerization of α-pinene to camphene proceeds prior to the formation of camphenilanaldehyde.