Electrospray ionization tandem mass spectrometry of 4‐aryl‐3,4‐dihydrocoumarins

Abstract We have investigated the gas‐phase fragmentation reactions of 11 synthetic 4‐aryl‐3,4‐dihydrocoumarins by electrospray ionization tandem mass spectrometry (ESI‐MS/MS) on a quadrupole‐time‐of flight (Q‐TOF) hybrid mass spectrometer. We have also estimated thermochemical data for the protonated coumarins (precursor ion A ) and product ion structures by computational chemistry at a B3LYP level of theory to establish the ion structures and to rationalize the fragmentation pathways. The most abundant ions in the product ion spectra of coumarins 1–11 resulted from C 8 H 8 O 2 , CO 2 , C 4 H 4 O 3 , C 8 H 10 O 3 , C 8 H 8 O 2 , and CH 3 OH eliminations through retro‐Diels–Alder (RDA) reactions, remote hydrogen rearrangements (β‐eliminations), and β‐lactone ring contraction. Although the investigated coumarins shared most of the fragmentation pathways, formation of a benzylic product ion and its corresponding tropylium ion was diagnostic of the substituents at ring C. The thermochemical data revealed that the nature and position of the substituents at ring C played a key role in the formation of this product ion and determined its relative intensity in the product ion spectrum. The results of this study contribute to knowledge of the gas‐phase ion chemistry of this important class of organic compounds.