Active role of hydrogen bond and ambient water in Meyer-Schuster rearrangements in high-temperature water

作者：Wang, Zhizhong; Chang, Yongjuan; Gong, Xinxin; Dai, Liyi^*

来源：International Journal of Quantum Chemistry, 2012, 112(3): 647-652.

DOI：10.1002/qua.22956

• HTW
• Meyer-Schuster rearrangement
• hydrogen bond
• model

MeyerSchuster rearrangements of 2-phenyl-3-butyn-2-ol with H3O and (H2O)6 model in high-temperature water (HTW) have been investigated by the use of density functional theory calculations. In the substrate 2-phenyl-3-butyn-2-ol catalyzed by H3O and (H2O)6, the MeyerSchuster rearrangements were predicted by the frontier molecular orbital theory. The results show that the rearrangement does not involve the carbonium ion intermediates, but the first transition state is carboniumion like. Dehydration and hydration may occur via the intermolecular proton relay along the hydrogen-bond chains and the second step of reaction path is a total acidbase catalytic process. Based on the results, a model considered both HTW ambient and water molecules are proposed to represent mechanisms of other reactions in HTW.

• 出版日期2012-2-5
• 单位华东师范大学