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首页> 外文期刊>Journal of mass spectrometry: JMS >Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry
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Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry

机译：通过离子中性配合物的氢化物转移反应：质谱中质子化的N-苄基哌啶和质子化的N-苄基哌嗪的断裂

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摘要

An ion-neutral complex (INC)-mediated hydride transfer reaction was observed in the fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in electrospray ionization mass spectrometry. Upon protonation at the nitrogen atom, these compounds initially dissociated to an INC consisting of [RC6H4CH2](+) (R = substituent) and piperidine or piperazine. Although this INC was unstable, it did exist and was supported by both experiments and density functional theory (DFT) calculations. In the subsequent fragmentation, hydride transfer from the neutral partner to the cation species competed with the direct separation. The distribution of the two corresponding product ions was found to depend on the stabilization energy of this INC, and it was also approved by the study of substituent effects. For monosubstituted N-benzylpiperidines, strong electron-donating substituents favored the formation of [RC6H4CH2](+), whereas strong electron-withdrawing substituents favored the competing hydride transfer reaction leading to a loss of toluene. The logarithmic values of the abundance ratios of the two ions were well correlated with the nature of the substituents, or rather, the stabilization energy of this INC.
机译：在电喷雾电离质谱法中，质子化的N-苄基哌啶和质子化的N-苄基哌嗪的片段化过程中观察到离子中性络合物（INC）介导的氢化物转移反应。在氮原子上质子化后，这些化合物最初解离为由[RC6H4CH2]（+）（R =取代基）和哌啶或哌嗪组成的INC。尽管该INC是不稳定的，但它确实存在并且得到了实验和密度泛函理论（DFT）计算的支持。在随后的裂解过程中，氢化物从中性配偶体转移到阳离子物种中，与直接分离竞争。发现两种相应产物离子的分布取决于该INC的稳定能，并且也被取代基效应的研究所证实。对于单取代的N-苄基哌啶，强的供电子取代基有利于[RC6H4CH2]（+）的形成，而强的吸电子取代基有利于竞争的氢化物转移反应，从而导致甲苯的损失。两种离子的丰度比的对数值与取代基的性质或该INC的稳定能充分相关。

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