鎖状テルペンアルコール類の合成に関する研究
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6-Methyl-6 (or 5)-hepten-2-one was synthesized from the addition compounds which were prepared from 4-methyl-1-penten-3-ol acetate or 2-methyl-4-penten-2-ol acetate and acetaldehyde by the Prins reaction. These addition compounds were at first hydrolyzed to sec- or tert-keto alcohols respectively and then dehydrated to methylheptenone under appropriate conditions in good yield. The dehydration of 6-methyl-5-hydroxy-2-heptanone was best carried out at 280〜370℃ by passing through a pyrex glass tube, packed with pumice catalyst containing phosphoric acid. 6-Methyl-6-hydroxy-2-heptanone was dehydrated to 6-methyl-5-hepten-2-one with a trace of iodine. On the other hand, 6-methyl-6-hydroxy-2-heptanone acetate was subjected to pyrolysis at 450℃ through a pyrex glass tube, filled with crushed glass in almost quantitative yield, giving 6-methyl-6-hepten-2-one. 6-Methyl-6-hydroxy-2-heptanone, reported by Verley in 1897, which was obtained by the hydration of methylheptenone with 40〜50% H_2SO_4, differed apparently from the hydrolyzate of 6-methyl-6-hydroxy-2-heptanone acetate. The substance which was obtained by Verley's method, was supposed to be 2,2-dimethyl-6-methyl-6-hydroxy-tetrahydropyran. When 6-methyl-5-hydroxy-2-heptanone acetate was hydrolyzed with alcoholic sodium hydroxide solution, 2-isopropyl-5-methyl-5-ethoxy-tetrahydrofuran and 6-methyl-5-hydroxy-2-heptanone were obtained, The furan ring of the former could be opened easily to the latter keto alcohol when it was boiled with dil HCl. By the same procedure, the auther prepared thujaketone by a series of reaction from methylisopropyl ketone, which is an intermediate of irone.
- 明治大学の論文
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