8-氯辛酸乙酯系列化合物的合成

Synthesis of Ethyl 8-Chlorooctanoate Series Compounds

以端基取代的二氯代烃和丙二酸二乙酯为原料,经烃基化反应和脱羧反应合成了8-氯辛酸乙酯系列化合物,并利用1H NMR、13C NMR和GC-MS对目标产物的结构进行了确证。以8-氯辛酸乙酯的合成反应作为模板,考察了碱、相转移催化剂、物料配比、反应温度和反应时间对烃基化反应的影响,以及酸的种类和用量、反应温度、反应时间对脱羧反应的影响。结果表明,烃基化反应适宜的反应条件为:1,6-二氯己烷、丙二酸二乙酯、粉末状碳酸钾和相转移催化剂四甲基氯化铵的物质的量比为1∶1∶0.4∶0.03,反应温度60℃,反应时间1 h。脱羧反应适宜的反应条件为:浓硫酸与2-(6-氯己基)丙二酸二乙酯的物质的量比为0.1∶1,反应温度120℃,反应时间8.0 h。

Ethyl 8-chlorooctanoate series compounds were synthesized with end-substituted dichlorohydrocarbons and diethyl malonate as the materials in hydrocarbylation and decarboxylation processes, and the structures of target products were confirmed by 1H NMR, 13C NMR and GC-MS techniques. The effects of alkali, phase transfer catalyst, material ratio, reaction temperature, and reaction time on hydrocarbylation and that of the kind and amount of acid, reaction temperature, and reaction time on decarboxylation were studied with the synthesis reaction of ethyl 8-chlorooctanoate as the template. The test results have shown that the suitable conditions of hydrocarbylation reaction are: the molar ratio of 1,6-dichlorohexane, diethyl malonate, potassium carbonate powder, and tetramethylammonium chloride, i.e. the phase transfer catalyst, is 1 : 1 : 0.4 : 0.03, the reaction temperature is 60 ℃, and the reaction time is 1 h and that the suitable conditions of decarboxylation reaction are: the molar ratio of concentrated sulfuric acid to 2-(6-chlorohexyl) diethyl malonate is 0.1 : 1, the reaction temperature is 120 ℃, and the reaction time is 8.0 h.