Gas-Phase Alcoholysis of Benzylic Halides in the Atmospheric Pressure Ionization Source

文献类型： 外文期刊

第一作者： Shen, Shanshan

作者： Shen, Shanshan;Feng, Hongru;Pan, Yuanjiang;Shen, Shanshan;Chen, Yue;Chai, Yunfeng

作者机构： Zhejiang Univ, Dept Chem, Hangzhou 310027, Peoples R China;Zhejiang Inst Food & Drug Control, Key Lab Drug Contacting Mat Qual Control Zhejiang, Hangzhou 310052, Peoples R China;Chinese Acad Agr Sci, Tea Res Inst, Hangzhou 310008, Peoples R China

期刊名称：JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY （ 2022影响因子：3.2； 五年影响因子：3.2 ）

ISSN： 1044-0305

年卷期： 2024 年 35 卷 2 期

页码：

收录情况： SCI

摘要： The present study investigates the gas-phase alcoholysis reaction of benzylic halides under atmospheric pressure chemical ionization (APCI) conditions. The APCI corona discharge is used to initiate the novel reaction, which is monitored by ion trap mass spectrometry (IT-MS). The model compound alpha,alpha,alpha-trifluorotoluene is applied to observe the cascade methoxylation reaction during the +APCI-MS analysis, resulting in the formation of [PhC(OCH3)(2)](+). Based on the results of isotopic labeling and substrate expansion experiments, an addition-elimination mechanism is proposed: initially, the reaction was initiated by the dissociation of fluorine from PhCF3 under APCI condition, leading to the formation of [PhCF2](+); subsequently, two methanol molecules nucleophilicly attack [PhCF2](+) stepwisely, accompanied by the elimination of HF, yielding the product ion [PhC(OCH3)(2)](+). The proposed mechanism was further corroborated by theoretical calculations. The results of substrate scope expansion experiments suggest that this in-source reaction has the potential to differentiate the positional isomers of alcohols and phenols.

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