Instituto de Quimica-Fisica Rocasolano, CSIC, Serrano 119, 28006, Madrid, Spain.
J Org Chem. 2010 Apr 16;75(8):2564-71. doi: 10.1021/jo100085b.
We have carried out a study of the energetics, structural, and physical properties of o-, m-, and p-hydroxybenzophenone neutral molecules, C(13)H(10)O(2), and their corresponding anions. In particular, the standard enthalpies of formation in the gas phase at 298.15 K for all of these species were determined. A reliable experimental estimation of the enthalpy associated with intramolecular hydrogen bonding in chelated species was experimentally obtained. The gas-phase acidities (GA) of benzophenones, substituted phenols, and several aliphatic alcohols are compared with the corresponding aqueous acidities (pK(a)), covering a range of 278 kJ.mol(-1) in GA and 11.4 in pK(a). A computational study of the various species shed light on structural effects and further confirmed the self-consistency of the experimental results.
我们已经研究了邻羟基二苯甲酮、间羟基二苯甲酮和对羟基二苯甲酮中性分子（C13H10O2）及其相应阴离子的能量学、结构和物理性质。特别是，我们确定了这些物质在 298.15 K 气相下的标准生成焓。我们通过实验获得了螯合物种中分子内氢键相关焓的可靠实验估计。我们比较了二苯甲酮、取代苯酚和几种脂肪醇的气相酸度（GA）与相应的水酸度（pK(a)），GA 的范围为 278 kJ·mol(-1)，pK(a)的范围为 11.4。对各种物质的计算研究揭示了结构效应，并进一步证实了实验结果的一致性。
