乙氧羰基化-β-环糊精的合成工艺优化  

Optimization of Synthetic Process of Ethyl Carbonate Derivatives of β-Cyclodextrin

作　　者：张毅民[1] 王娜[1] 黄德超[1] 白家瑞[1] 

机构地区：[1]天津大学绿色合成与转化教育部重点实验室化工学院,天津300072

出　　处：《高校化学工程学报》2014年第2期416-420,共5页Journal of Chemical Engineering of Chinese Universities

摘　　要：选用环境友好的碳酸二乙酯为原料,研究了乙氧羰基化-β-环糊精的绿色合成新工艺。β-环糊精和碳酸二乙酯在无水碳酸钾的作用下经酯交换反应生成了乙氧羰基化-β-环糊精。研究了反应物的摩尔比、反应温度、反应时间和催化剂用量四个参数对反应的影响。利用响应曲面试验设计法进行试验设计,建立乙氧羰基化-β-环糊精的合成工艺模型。通过回归方程和响应曲面,得到乙氧羰基化-β-环糊精最佳合成工艺:10 gβ-环糊精溶于80 mLDMF中,反应温度126℃,催化剂用量(相对于β-环糊精的质量百分数)为12%,n(DEC):n(β-CD)=20.2:1,反应时间8.5 h。验证试验结果显示,在此条件下,乙氧羰基化β-环糊精的收率达到98%。通过高效液相色谱分析反应结果并利用半制备色谱分离获得纯产物,对其进行了FT-IR,MS,1H-NMR表征。A novel green synthesis process of ethyl carbonate derivatives of fl-cyclodextrin was investigatedby the selection of environmentally friendly diethyl carbonate （DEC） as a raw material. Ethyl carbonatederivatives offl-cyclodextrin were synthesized using fl-cyclodextrin and diethyl carbonate as raw materials andanhydrous potassium carbonate was used as a catalyst. Factors such as DEC to fl-CD mole ratio, temperature,reaction time and catalyst percentage on the yield were evaluated. Moreover, a mathematical model describingthe functional relationship between the yield and the four variables was set up based on a response surfacedesign method. The results show that the optimal conditions for the synthesis of ethyl carbonate derivatives offl-cyclodextrin are： 80 mL DMF as the solvent, reaction temperature 126℃, catalyst amount 12% by weight offl-eyclodextrin, n（DEC）：n（fl-CD）= 20.2：1 and reaction time 8.5 h. Verification experiments indicate that themaximum yield of ethyl carbonate derivatives of fl-cyclodextrin is 98% under the optimized condition. Themain compound was separated by semi-preparative chromatography and characterized by FT-IR, MS and1H-NMR spectroscopy.

关 键 词：Β-环糊精 碳酸二乙酯 乙氧羰基化 核磁共振 质谱 

分 类 号：TQ317[化学工程—高聚物工业]