Glycerol carbonate synthesis via Zn(OBu)2/AlCl2(OBu) initiated-glycerolysis of urea

Chemistry of Inorganic Materials Pub Date : 2024-01-30 DOI:10.1016/j.cinorg.2024.100040

Dita Dwi Andriyani , Laode Abdul Kadir , Nova Pratiwi Indriyani , Yessi Permana

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Abstract

Glycerol carbonate (4-hydroxymethyl-1,3-dioxolane-2-one) was efficiently synthesized from glycerolysis of urea initiated by Zn(OBu)₂/Al(OBu)Cl₂. The zinc-aluminum complex mixture was prepared from zinc chloride (ZnCl₂) and aluminum tri-sec-butylate (Al(OBu)₃. The complex successfully initiated the urea glycerolysis in 1 : 1 mol ratio of glycerol to urea to produce glycerol carbonate up to 85% and selectivity up to 97% at 150 °C and 1 atm of N₂ for 4 h in the absence of solvents. Isocyanate was observed as a key intermediate in this reaction. A kinetic study showed the reaction likely followed pseudo first-order kinetics with estimated activation energy (E_a) of 38 kJ/mol. Density-functional theory calculations with MN15-L functional described the formation of glycerol carbonate as spontaneous with the Gibbs free energy of −28.41 kJ mol⁻¹.

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通过 Zn(OBu)2/AlCl2(OBu)引发的尿素甘油分解合成碳酸甘油酯

由 Zn(OBu)2/Al(OBu)Cl2 引发的尿素甘油分解有效合成了碳酸甘油酯（4-羟甲基-1,3-二氧戊环-2-酮）。锌铝复合物混合物由氯化锌（ZnCl2）和三仲丁基铝（Al(OBu)3）制备而成。在 150 °C、1 个大气压的氮气环境中，在无溶剂条件下持续 4 小时，该复合物以 1 : 1 的甘油和尿素摩尔比成功引发了尿素的甘油分解，生成的碳酸甘油酯高达 85%，选择性高达 97%。据观察，异氰酸酯是该反应的关键中间体。动力学研究表明，该反应可能遵循假一阶动力学，估计活化能（Ea）为 38 kJ/mol。用 MN15-L 功能进行的密度功能理论计算表明，碳酸甘油酯的形成是自发的，其吉布斯自由能为 -28.41 kJ mol-1。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Chemistry of Inorganic Materials

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