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本文报告2,2-双羟亚环己基乙酸内酯(Ⅳ)的合成作为纯化学法合成维生素丁类型的3,4-顺-共轭三烯化合物的原料. 2-氧代环己基羟基丙二酸二乙酯(Ⅵ)经乙酰氯脱水未得V,而仅得α-乙氧羰基-2-羟基亚环己烯-[2]-基乙酸内酯(Ⅷ).Ⅷ的结构是根据其水解物α-羧基-2-羟基亚环己烯-[2]-基乙酸内酯(Ⅸ)的脱羧与臭氧化结果而证明. Ⅵ经皂化为2-氧化环己基羟基丙二酸(Ⅷ),再以溴化氢的冰醋酸鲍和溶液处理,反应复杂.产生2-氧代环己烯-[6]-基乙酸(XV)、邻羟基苯乙酸(ⅩⅦ)及其内酯(ⅩⅥ)、2-羟基亚环己烯-[2]-基乙酸内酯(Ⅻ)及其他二种产物. Ⅷ经焦化法脱水脱羧终于获得Ⅳ和其反式异构体2-氧代-反-亚环己基乙酸(XXI).Ⅳ与XXI的结构已由其衍生物制备及臭氧降解结果而加以证明.
This paper reports the synthesis of 2,2-bishydroxycyclohexaneacetolactone (Ⅳ) as a pure chemical method for synthesis of vitamin D type 3,4-cis-conjugated triene compounds. 2-oxocyclohexylhydroxypropyl Diethyl diacetate (VI) is devoid of V by acetyl chloride to give only α-ethoxycarbonyl-2-hydroxycyclohexene- [2] -ylacetolactone (VIII). The structure of VIII is based on The result of the decarboxylation and ozonation of its hydrolyzate α-carboxy-2-hydroxycyclohexene- [2] -acetolactone (Ⅸ) proved that Ⅵ was saponified to 2-oxydicyclohexylmalonic acid (Ⅷ ), Which is then treated with glacial acetic acid in a mixture of hydrogen bromide and glacial acetic acid in a solution of 2-oxocyclohexene- [6] -ylacetic acid (XV), orthohydroxyphenylacetic acid (XVII) and its lactone ), 2-hydroxycyclohexene- [2] -acetolactone (Ⅻ), and other two products. Ⅷ Dehydration decarboxylation by coking finally yields IV and its trans isomer 2-oxo-trans- Cyclohexyl acetic acid (XXI). The structures of IV and XXI have been demonstrated by the preparation of their derivatives and the results of ozone degradation.