The synthesis of undecylenic acid partial esters can be performed at mild temperature with a classical esterification reaction catalyzed by dodecylbenzene sulfonic acid (DBSA). A semi‐empirical molecular modeling on the different reaction intermediates indicates that DBSA can strongly decrease their heats of formation through hydrogen bonding. Diester formation seems to be thermodynamically favored with a selectivity for alpha, alpha, or alpha, beta forms that depend on the geometry of the catalyst‐intermediate configuration. Triesters are not favored but a high selectivity for monoesters requires a kinetic control. Experimental approach, considering different DBSA concentrations and temperature partially confirms the theoretical predictions but surfactant properties of DBSA and monoesters may induce nonpredicted geometries. Global apparent activation energies are calculated, corresponding to the formation and hydrolysis of mono and diesters. If water trapping allows the decrease of hydrolysis reaction constants, the presence of water and subsequent phase separation may explain differences between theoretical and experimental results and could help increasing monoester selectivity.

中文翻译：

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甘油对十一碳烯酸酯化的理论和动力学分析。

十一碳烯酸酯偏酯的合成可以在温和的温度下进行，并通过十二烷基苯磺酸（DBSA）催化经典的酯化反应。对不同反应中间体的半经验分子模型表明，DBSA可以通过氢键大大降低其形成热。热力学上有利于二酯的形成，对α，α或α，β形式的选择性取决于催化剂-中间构型的几何形状。三酯不受欢迎，但对单酯的高选择性需要动力学控制。考虑不同DBSA浓度和温度的实验方法部分证实了理论预测，但DBSA和单酯的表面活性剂性质可能会导致无法预测的几何形状。计算了整体表观活化能，其对应于单酯和二酯的形成和水解。如果捕水允许降低水解反应常数，则水的存在和随后的相分离可以解释理论和实验结果之间的差异，并有助于提高单酯的选择性。