TY - JOUR
T1 - Atmospheric pressure Eberlin transacetalization reactions in the heterogeneous liquid/gas phase
AU - Augusti, Rodinei
AU - Chen, Hao
AU - Eberlin, Livia Schiavinato
AU - Nefliu, Marcela
AU - Cooks, R. Graham
N1 - Funding Information:
The authors acknowledge financial support from National Science Foundation, Grant CHE04-12782, the US Department of Energy and the Office of Basic Energy Sciences. R.A. and L.S.E. also acknowledge the Brazilian National Research Council (CNPq) for research fellowships.
PY - 2006/7/1
Y1 - 2006/7/1
N2 - The Eberlin reaction, the ionic transacetalization of cyclic acetals and analogues with acylium and related ions, is demonstrated in the course of ion/molecule reactions at atmospheric pressure. Selected gaseous acetals (1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane) react efficiently with the (CH3)2NCO+ acylium ion, generated by electrosonic spray ionization (ESSI) of an aqueous/methanol solution of tetramethylurea (TMU), to furnish the characteristic cyclic ionic acetals, the Eberlin products, in moderate to high yields. It is proposed that acylium ions on the surface of the ESSI-generated droplets interact with gaseous neutral reagents. The Eberlin products dissociate exclusively to re-form the reactant (CH3)2NCO+ acylium ion upon collision-induced dissociation (CID), confirming their structures. The intact adduct, i.e., acylium ion plus neutral reagent (the stable precursor of the Eberlin product), is observed in these experiments whereas it is not observed in studies of the same Eberlin reactions under conventional reduced pressure ion/molecule reaction conditions. It is suggested that under atmospheric pressure conditions these intact adducts are likely stabilized through deactivation via collision with buffer gas.
AB - The Eberlin reaction, the ionic transacetalization of cyclic acetals and analogues with acylium and related ions, is demonstrated in the course of ion/molecule reactions at atmospheric pressure. Selected gaseous acetals (1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane) react efficiently with the (CH3)2NCO+ acylium ion, generated by electrosonic spray ionization (ESSI) of an aqueous/methanol solution of tetramethylurea (TMU), to furnish the characteristic cyclic ionic acetals, the Eberlin products, in moderate to high yields. It is proposed that acylium ions on the surface of the ESSI-generated droplets interact with gaseous neutral reagents. The Eberlin products dissociate exclusively to re-form the reactant (CH3)2NCO+ acylium ion upon collision-induced dissociation (CID), confirming their structures. The intact adduct, i.e., acylium ion plus neutral reagent (the stable precursor of the Eberlin product), is observed in these experiments whereas it is not observed in studies of the same Eberlin reactions under conventional reduced pressure ion/molecule reaction conditions. It is suggested that under atmospheric pressure conditions these intact adducts are likely stabilized through deactivation via collision with buffer gas.
KW - Atmospheric pressure reaction
KW - Eberlin reaction
KW - Heterogeneous reaction
KW - Ion/molecule reaction
KW - Solvated ion
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U2 - 10.1016/j.ijms.2006.05.005
DO - 10.1016/j.ijms.2006.05.005
M3 - Article
AN - SCOPUS:33745268170
SN - 1387-3806
VL - 253
SP - 281
EP - 287
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
IS - 3
ER -