Abstract First step of formose or Butlerov reaction involves C–C bond formation between two formaldehyde molecules resulting in glycolaldehyde. This reaction happens under basic conditions in solution. A tandem mass spectrometry investigation of dissociation of deprotonated glycolaldehyde in the gas phase, to study the formose reaction in a retro-synthetic point of view, has been reported. In the present work, we have carried out electronic structure theory calculations and quasi-classical direct chemical dynamics simulations to model the gas phase dissociation of the conjugate base of glycolaldehyde. The dynamics simulations were performed on-the-fly using the hybrid density functional B3LYP theory with the 6-31+G* basis set under collision induced dissociation (CID) conditions. Trajectories were launched with two different deprotonated forms of glycolaldehyde for a range of collision energies mimicking experiments. Reverse formose reaction was observed primarily from the slightly higher energy isomer via a non-statistical pathway. Intramolecular hydrogen transfer was ubiquitous in the trajectories. Simulation results were compared with experiments and detailed atomic level dissociation mechanisms are presented.

中文翻译：

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碰撞诱导去质子化乙醇解离的化学动力学模拟

摘要甲糖或 Butlerov 反应的第一步是在两个甲醛分子之间形成 C-C 键，从而生成乙醇醛。该反应在溶液中的碱性条件下发生。已经报道了在气相中去质子化乙醇醛解离的串联质谱研究，以从逆合成的角度研究甲糖反应。在目前的工作中，我们进行了电子结构理论计算和准经典直接化学动力学模拟，以模拟乙醇醛共轭碱的气相离解。动力学模拟是在碰撞诱导解离 (CID) 条件下使用混合密度泛函 B3LYP 理论和 6-31+G* 基组即时进行的。使用两种不同的去质子化形式的乙醇醛发射轨迹，用于模拟实验的一系列碰撞能量。通过非统计途径主要从稍高能量的异构体观察到逆甲糖反应。分子内氢转移在轨迹中无处不在。将模拟结果与实验进行比较，并展示了详细的原子级解离机制。