论文部分内容阅读
本文报告2-羟甲基-顺-亚环己基乙酸(Ⅲ)及其内酯(Ⅱ)的合成及有关于Mannich-Braun化合物改正结构式的证实。 2-乙酰氧甲基环己酮(Ⅳ)经反应获得(Ⅱ)和Mannich-Braun化合物,我们根据后者紫外、红内吸收光谱的分析及高碘酸氧化的新结果证实了Mannich-Braun化合物的结构式为(Ⅴc). (Ⅱ)经皂化及酸化得其游离酸(Ⅲ)。(Ⅲ)经甲酯化得2-羟甲基-顺-亚环已基乙酸甲酯(Ⅺ),后者经乙酰化得2-乙酰氧甲基-顺-亚环已基乙酸甲酯(Ⅻ),经3,5-二硝基苯甲酰氯酰化得2-(3’,5’-二硝基苯甲酰氧甲基)-顺-亚环已基乙酸甲酯(ⅩⅢ)。(ⅩⅢ) 用浓硫酸水解得2-(3’,5’-二硝基苯甲酰氧甲基)-顺-亚环已基乙酸(ⅩⅣ),(ⅩⅣ)经重氮甲烷酯化又复得(ⅩⅢ)。
This paper reports the synthesis of 2-hydroxymethyl-cis-cyclohexylideneacetic acid (Ⅲ) and its lactone (Ⅱ) and the confirmation of the corrected formula of Mannich-Braun compound. (Ⅱ) and Mannich-Braun compounds were obtained through the reaction of 2-acetoxymethylcyclohexanone (Ⅳ). Based on the latter analysis of ultraviolet and red absorption spectra and new results of periodate oxidation, it was confirmed that Mannich-Braun compound The structural formula is (Vc). (II) Saponification and acidification of its free acid (Ⅲ). (III) Methyl 2-hydroxymethyl-cis-cyclohexylideneacetate (XI) is obtained by methyl esterification, which is acetylated to give methyl 2-acetoxymethyl-cis-cyclohexylideneacetate Ⅻ) and 3,5-dinitrobenzoyl chloride to give methyl 2- (3 ’, 5’-dinitrobenzoyloxymethyl) -cis-cyclohexylideneacetate (XIII). (XIII) Esterification of 2- (3 ’, 5’-dinitrobenzoyloxymethyl) -cis-cyclohexylideneacetic acid (XIV) with concentrated sulfuric acid, (XIV) Esterification with diazomethane Get (XIII).