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Intermolecular Alkyl Transfer Reactions in the Fast Atom Bombardment Mass Spectrometry of Esters
Author(s) -
Yao Zhongping,
Wen Hanhui,
Zha Qingmin,
Zhao Shankai
Publication year - 1996
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199609)31:9<955::aid-jms364>3.0.co;2-k
Subject(s) - chemistry , moiety , alkyl , fast atom bombardment , transalkylation , medicinal chemistry , molecule , adduct , dissociation (chemistry) , photochemistry , mass spectrometry , nucleophile , methyllithium , carboxylate , stereochemistry , organic chemistry , ion , alkylation , catalysis , chromatography
Fast atom bombardment mass spectrometry (FABMS) of five neat phthalates (dimethyl, diethyl, diallyl, dibutyl and dinonyl) were investigated and intermolecular alkyl transfer reactions were observed in the mass spectra. FABMS of some related compounds was also studied and the results indicate that intermolecular alkyl transfers can occur in the FABMS of esters, the transferred alkyl group being associated with the carboxylate group in the adduct ion [M+R] + . A possible mechanism is proposed which suggests that the transalkylation reactions in these non‐ionic compounds arise from two routes: (i) nucleophilic attack by the electron‐rich moiety of one energized desorbed molecule on to the electron‐poor moiety of another and (ii) dissociation of the internally excited desorbed molecules. The study also demonstrated that the transalkylation reaction could be effectively controlled by addition of a suitable matrix, such as 3‐nitrobenzyl alcohol.