title: Fragmentation of 3-hydroxyflavone; a computational and mass spectrometric study.
abstract: In a recent study of the collision-induced dissociation of protonated and deprotonated molecules of 3-, 5-, 6-, 7-, 2'-, 3'- and 4'-hydroxyflavone, it was observed that the ratio, gamma, of the propensities for cross-ring cleavage (CRC) to ring opening (RO) varied by a factor of 660, i.e., from 0.014:1 (for deprotonated 3-hydroxyflavone) to 9.27:1 (for deprotonated 5-hydroxyflavone). An explanation for the variation of gamma was presented in terms of experimental NMR (13)C and (1)H spectra modified by computation. Deprotonated 3-hydroxyflavone exhibited the highest ion signal intensity for fragmentation following RO relative to that for CRC in that gamma = 0.014:1. Because no chemical computations of the fragmentation of protonated and deprotonated monohydroxyflavone molecules have been carried out thus far, the basis on which fragmentation mechanisms for deprotonated 3-hydroxyflavone have been proposed is principally chemical intuition. The energy states of product ions formed in the fragmentation of deprotonated 3-hydroxyflavone molecules were computed by the CBS-4M method implemented in Gaussian 03. The overly demanding calculations needed to handle diradicals reliably and directly were circumvented by a process in which each of the bond-breaking reactions was approximated by a process that gave two monoradicals. Bond energies were calculated, with one exception, from the approximation reactions as the energy of products minus the energy of reactants.
authors.affiliation: Department of Chemistry, Trent University, 1600 West Bank Drive, Peterborough, ON K9J 7B8, Canada.
authors.forename: Errol G
authors.initials: EG
authors.lastname: Lewars
authors.forename: Raymond E
authors.initials: RE
authors.lastname: March
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005419:Flavonoids / Q000737:chemistry*; D008956:Models, Chemical; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry
chemical_list: D005419:Flavonoids; C062711:5-hydroxyflavone; C041477:3-hydroxyflavone