2-羧基环酮缩乙二醇的合成  

Synthesis of 2-Carboxy Cyclic Ketone Ethylene Ketal

作　　者：仝红娟 唐文强 张彦民 刘斌[1] Tong Hongjuan;Tang Wenqiang;Zhang Yanmin;Liu Bin(School of Pharmacy,Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province,Shaanxi Institute of International Trade&Commerce,Xi′an,Shaanxi 712046,China)

机构地区：[1]陕西国际商贸学院医药学院陕西省中药绿色制造技术协同创新中心

出　　处：《化学世界》2019年第11期799-803,共5页Chemical World

基　　金：陕西省自然科学基础研究计划(面上)(No.2018JM7046);陕西省教育厅2018年度专项科学研究计划(No.18JK0954);国家级大学生创新创业(No.201849002)资助项目

摘　　要：对甲苯磺酸为催化剂,2-甲氧羰基环酮(2-甲氧羰基环戊酮、2-甲氧羰基环己酮)和乙二醇为原料反应得到2-甲氧羰基环酮缩乙二醇,再经过碱性条件下酯水解得到目标化合物2-羧基环酮缩乙二醇,其结构经1H NMR、13C NMR和GC-MS表证。并以2-甲氧羰基环戊酮和乙二醇的反应为模型反应,考察了影响缩酮产物收率的因素。确定最佳缩酮合成条件为:n(乙二醇)∶n(2-甲氧羰基环戊酮)=2∶1;催化剂对甲苯磺酸用量n(TsOH)∶n(2-甲氧羰基环戊酮)=0.05∶1;溶剂为甲苯;反应时间为16 h;反应温度为110℃。在最佳反应条件下,化合物2-甲氧羰基环戊酮缩乙二醇收率为59.5%,化合物2-甲氧羰基环己酮缩乙二醇收率为73.1%。2-Carboxy cyclic ketone ethylene ketal was synthesized from 2-carbomethoxy cyclic ketone(2-carbomethoxy cyclopentanone or 2-carbomethoxy cyclohexanone) and ethylene glycol through a two step reaction, involving the ketal formation reaction catalyzed by 4-methylbenzenesulfonic acid and hydrolysis of ester under basic conditions. The structure of intermediates and products were confirmed by 1H NMR, 13C NMR and GC-MS. The influencing factor of ketal formation reaction was investigated by choosing the reaction of 2-carbomethoxy cyclopentanone and ethylene glycol as model reaction. The optimal reaction conditions are as follow: n(ethylene glycol)∶n(2-carbomethoxy cyclopentanone)=2∶1;n(TsOH)∶n(2-carbomethoxy cyclopentanone)=0.05∶1;the mixture was stirred in toluene at 110 ℃ for 16 h. Compounds methyl 1,4-dioxaspiro[4.4]nonane-6-carboxylate and methyl 1,4-dioxaspiro[4.5]decane-6-carboxylate were obtained in a yield of 59.5% and 73.1%, respectively, under the optimal reaction conditions.

关 键 词：2-甲氧羰基环酮缩乙二醇 乙二醇 缩酮 合成 

分 类 号：O62[理学—有机化学]