A new reaction mechanism for the glycerol chlorination is proposed. This mechanism is based on theoretical calculations within density functional theory combined with polarizable continuum model . Two possibilities were investigated, the first is the S_N2 chlorination forming mono‐ and dichlorinated products and the second one is through an ester intermediate formed by glycerol esterification in the presence of acetic acid as catalyst. Our results indicate that the first chlorination reaction can occur in the absence of the catalyst and the main product is 3‐monochloropropane‐1,2‐diol (1‐MCP). The inhibitory role of water in the second chlorination is also revealed, that is, water formation suppresses the second chlorination when reaction is conducted in the absence of a carboxylic acid. In the presence of the catalyst, oxonium species are formed as reaction intermediates and the main products are 1‐MCP and 1,3‐dichloropropan‐2‐ol (1,3‐DCP). Our results are in agreement with the experimental data, which indicate that the 1,3‐DCP is the main product when an acid catalyst is employed and, also, there is no significant formation of 2‐monochloropropane‐1,2‐diol and 1,2‐dichloropropan‐3‐ol .

中文翻译：

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甘油氯化反应机理

提出了一种新的甘油氯化反应机理。该机制基于密度泛函理论中的理论计算并结合可极化连续体模型。研究了两种可能性，第一种是S _N2次氯化生成一氯化和一氯化产物，第二个是通过在乙酸作为催化剂存在下甘油酯化形成的酯中间体。我们的结果表明，第一次氯化反应可在没有催化剂的情况下发生，其主要产物是3-一氯丙烷-1,2-二醇（1-MCP）。还揭示了水在第二次氯化中的抑制作用，即，当在不存在羧酸的情况下进行反应时，水的形成抑制了第二次氯化。在催化剂的存在下，形成了氧鎓类物质作为反应中间体，主要产物为1-MCP和1,3-二氯丙烷-2-醇（1,3-DCP）。我们的结果与实验数据相吻合，实验数据表明当使用酸催化剂时，1,3-DCP是主要产物，此外，