Ionic transacetalization with acylium ions: a class-selective and structurally diagnostic reaction for cyclic acetals...

Ionic transacetalization of cyclic acetals with the gaseous (CH3)2NCO+ acylium ion has been performed under unique in-source ion-molecule reaction (in-source IMR) conditions of electrospray (ESI) and atmospheric pressure chemical ionization (APCI). In-source IMR under ESI and APCI greatly expands the range of neutral molecules that can be brought to the gas phase to react by ionic transacetalization, a general, class-selective and structurally diagnostic reaction for cyclic acetals (Moraes, L. A. B.; Gozzo, F. C.; Vainiotalo, P.; Eberlin, M. N. J. Org. Chem. 1997, 62, 5096). Heavier, more polar, and less volatile cyclic acetals than those previously employed in quadrupole collision cells are shown to react efficiently by ionic transacetalization under the ESI and APCI in-source IMR conditions. Tetramethylurea (TMU) acts as an efficient dopant, being co-injected with the acetal in either benzene, toluene, methanol, or water/methanol solutions. Under APCI or ESI, the basic TMU dopant is protonated preferentially, and the labile protonated TMU then undergoes dissociation to (CH3)2NCO+, the least acidic and the most transacetalization-reactive acylium ion so far tested. Under the relatively high-pressure, low-energy collision conditions set to favor associative reactions, (CH3)2NCO+ reacts competitively both with TMU to form acylated TMU and with the acetal via ionic transacetalization to form the respective cyclic ionic acetals. Spectrum subtraction removes the ionic products of the dopant (TMU) self-reactions, thus providing clean ion-molecule reaction product ion mass spectra, which are used for the selective, structurally diagnostic detection of cyclic acetals. Information on ring substituents comes from characteristic mass shifts resulting from aldehyde/ketone by acylium ion replacement. Enhanced selectivity in structural characterization or chemical recognition for cyclic acetal monitoring is gained by performing on-line collision-induced dissociation via tandem mass spectrometric experiments. Most cyclic ionic acetals dissociate exclusively or nearly exclusively to re-form the reactant (CH3)2NCO+ acylium ion whereas the presence of additional functional groups with increased structural complexity tends to favor other specific but likewise selective dissociation channels.