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解吸电喷雾电离质谱法用于监测 Baeyer-Villiger 固态有机反应的动力学。

Desorption electrospray ionization mass spectrometry for monitoring the kinetics of Baeyer-Villiger solid-state organic reactions.

机构信息

State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.

出版信息

J Am Soc Mass Spectrom. 2009 Nov;20(11):2087-92. doi: 10.1016/j.jasms.2009.07.010. Epub 2009 Jul 18.

DOI:10.1016/j.jasms.2009.07.010
PMID:19683938
Abstract

Desorption electrospray ionization mass spectrometry (DESI-MS) has been used for monitoring solid-state organic reaction in ambient air, specifically the Baeyer-Villiger (BV) type reaction involving the oxidation of ketones (benzophenone or deoxybenzoin) by m-chloroperbenzoic acid (m-CPBA) in solid-state. The DESI mass spectra obtained at regular intervals during the BV reaction processes are featured, with the amount of ester products increasing as those of ketone reactants decrease. Quantitative analyses of relative intensities of the product, made to quantify the reaction degree of typical solid-state organic reaction (SSOR), show a precision with RSDs of around 5% to 12%, though the RSDs for direct analysis of intensities of the reactant or the product in the solid-state are obviously larger. The kinetics of the Baeyer-Villiger type reactions in solid-state are shown to be dramatically different, in reaction rate, kinetic curve, as well as concentration dependence, from those of the same reactions taking place in solution.

摘要

解吸电喷雾电离质谱(DESI-MS)已被用于监测固态有机反应在环境空气中,特别是涉及氧化酮(苯甲酮或脱氧安息香)的 Baeyer-Villiger(BV)型反应通过间氯过苯甲酸(m-CPBA)在固态中。在 BV 反应过程中定期获得的 DESI 质谱图以特征方式显示,随着酮反应物的减少,酯产物的量增加。对产物相对强度的定量分析,用于定量典型固态有机反应(SSOR)的反应程度,显示出精度,RSD 在 5%到 12%左右,尽管直接分析固态中反应物或产物强度的 RSD 明显更大。固态中的 Baeyer-Villiger 型反应的动力学在反应速率、动力学曲线以及浓度依赖性方面与在溶液中进行的相同反应有很大的不同。

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