Internal energy distribution of carboxylate negative-ions of the herbicide diclofop acid in the gas-phase

Abstract

Unimolecular dissociations of diclofop acid and three of its esters were studied using electron capture negative-ion mass spectrometry, to determine to what extent the gas-phase chemistry correlated with transformation products reported for the herbicide in soils and microbial biofilms. Electron capture of the trimethylsilyl (TMS) and pentafluorobenzyl (PFB) esters along with H + abstraction of diclofop acid were used to form the carboxylate ion at m / z 325. The degree of dissociation of this ion was strongly dependent on the relative distribution of internal energies, chemical nature and size of the ester group. For carboxylate ions formed with relatively low distribution of internal energies (PFB ester), elimination of HCl only was the preferred pathway. In contrast, m / z 325 from the TMS ester and diclofop acid, underwent loss of Cl, followed by loss of HCl to give m / z 254 with some direct loss of HCl for the TMS ester. For carboxylate ions formed with little or no internal energy under electrospray ionization, no unimolecular dissociations were observed. However, a wide range of product-ions were observed for the latter using collision-induced dissociations. For the methyl ester there was a preponderance for initial formation of a chlorodibenzofuran oxide ion ( m / z 217) instead of electron attachment on the carbonyl function. The ion ( m / z 217) was also prevalent for fragmentation of m / z 253 produced directly by electron capture of diclofop acid and the TMS ester. In general, the gas-phase ion chemistry correlated well with the distribution of some transformation products reported in the literature for the herbicide in soils and microbial biofilms.