二[2-(甲基-3-氧杂亚戊基碳酸酯)]碳酸酯的合成
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摘要
以镁铝水滑石为催化剂,碳酸二甲酯与二甘醇为原料,控制合成了二[2-(甲基-3-氧杂亚戊基碳酸酯)]碳酸酯,优化反应工艺条件,在油浴温度100℃,碳酸二甲酯与二甘醇摩尔比15,催化剂用量1.2 wt%的条件下,采用两段工艺,目标产物收率达51%。提纯产物,通过核磁与高分辨质谱证实了其结构。以反应体系中产物分布变化为依据,提出了目标产物的两条生成路径。
The controlled synthesis of di-[2-(3-oxa-pentylidene methyl carbonate)]carbonate was achieved via transesterification of diethylene glycol with dimethyl carbonate on Mg-Al hydrotalcite.The highest yield of target product of 51% was obtained with two-stage process under the optimized reaction conditions of oil bath temperature of 100℃,molar ratio of dimethyl carbonate and diethylene glycol of 15 and catalyst dosage of 1.2 wt%.The desired product was purified and the structure was characterized by NMR and HRMS.The possible formation routes of target product were proposed based on the change rule of products distribution in the reaction system.
The controlled synthesis of di-[2-(3-oxa-pentylidene methyl carbonate)]carbonate was achieved via transesterification of diethylene glycol with dimethyl carbonate on Mg-Al hydrotalcite.The highest yield of target product of 51% was obtained with two-stage process under the optimized reaction conditions of oil bath temperature of 100℃,molar ratio of dimethyl carbonate and diethylene glycol of 15 and catalyst dosage of 1.2 wt%.The desired product was purified and the structure was characterized by NMR and HRMS.The possible formation routes of target product were proposed based on the change rule of products distribution in the reaction system.
引文
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[3]Sun J,Kuckling D.Synthesis of high-molecular-weight aliphatic polycarbonates by organo-catalysis[J].Polym Chem,2016;7(8):1642-49.
[4]Li Y,Chen X,Huang W,et al.Below the room temperature measurements of CO2 solubilities in six physical absorbents[J].J Chem Thermodyn,2018;122:133-41.
[5]石娅琴.二甲基-α,ω-亚烷基二碳酸酯的合成及用于CO2吸收的研究[D]:中国科学院成都有机化学研究所;2018.
[6]Wang S,Tang R,Zhang Y,et al.12-Molybdophosphoric acid supported on titania:A highly active and selective heterogeneous catalyst for the transesterification of dimethyl carbonate and phenol[J].Chem Eng Sci,2015;138:93-98.
[7]Kim JG,Jeon JY,Chun J,et al.Efficient synthesis of organic carbonates and poly(1,4-butylene carbonate-co-terephthalate)s[J].J Appl Polym Sci,2017;134(24).
[8]田杰.镁铝水滑石的共沉淀法制备[D].西安电子科技大学,2009.
[9]Liu Z,Wang J,Kang M,et al.Structure-activity correlations of LiNO3/Mg4AlO5.5 catalysts for glycerol carbonate synthesis from glycerol and dimethyl carbonate[J].J Ind Eng Chem,2015;21:394-99.
[10]Liu P,Derchi M,Hensen EJM.Promotional effect of transition metal doping on the basicity and activity of calcined hydrotalcite catalysts for glycerol carbonate synthesis[J].Appl Catal B-Environ,2014;144:135-43.