In this study, the gas‐phase fragmentations of protonated benzyl phenyl sulfones were investigated by electrospray ionization tandem mass spectrometry (ESI‐MSⁿ). Upon collisional activation, several characteristic fragment ions were observed, and the similar results occurred with different substituted benzyl phenyl sulfones. A mechanism involving an intramolecular benzyl cation transfer and the formation of intermediate ion was proposed and further identified by density functional theory (DFT) calculations. In addition, a reference compound, benzenesulfinic acid benzyl ester, has been synthesized, and its protonated ion has the same gas‐phase behavior as compared to the protonated benzyl phenyl sulfone. This work provides access to some insight into the intramolecular benzyl‐transfer reactions of benzyl phenyl sulfones in the gas phase and orients the characteristic peaks in collision‐induced dissociation spectrometry (CID‐MS).

中文翻译：

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质子化苄基苯基砜气相裂解中的分子内苄基阳离子转移

在这项研究中，通过电喷雾电离串联质谱（ESI-MS ⁿ）。碰撞活化后，观察到几个特征性碎片离子，不同的取代苄基苯基砜发生了相似的结果。提出了一种涉及分子内苄基阳离子转移和中间离子形成的机理，并通过密度泛函理论（DFT）计算进一步确定。此外，已经合成了参比化合物苯亚磺酸苄基酯，与质子化苄基苯基砜相比，其质子化离子具有相同的气相行为。这项工作提供了对气相中苄基苯砜的分子内苄基转移反应的一些见解，并确定了碰撞诱导解离光谱（CID-MS）中的特征峰的方向。