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Type: Artigo de periódico
Title: Transacetalization with acylium ions. A structurally diagnostic ion/molecule reaction for cyclic acetals and ketals in the gas phase
Author: Moraes, LAB
Gozzo, FC
Eberlin, MN
Vainiotalo, P
Abstract: Transacetalization takes place in high yields in gas phase ion/molecule reactions of acylium ions (RC+=O) with a variety of cyclic acetals and ketals, that is, five-, six-, and seven-membered 1,3-O,O-heterocycles and their mono-sulfur and nitrogen analogues. A general, structurally diagnostic method for the gas phase characterization of cyclic acetals and ketals is therefore available. Transacetalization occurs via initial O(or S)-acylation, followed by a ring-opening/ring-re-forming process in which a neutral carbonyl compound is eliminated and cyclic 'ionic ketals' (that is, cyclic 1,3-dioxonium ions and analogues) are formed. The nature of the substituents at the 2-position, which are eliminated in the course of the reaction, is found to affect considerably the extent of transacetalization. Substituents not at the 2-position remain in the ionic products; hence positional isomers produce different cyclic 'ionic ketals' and are easily differentiated. The triple-stage (MS3) mass spectra of the cyclic 'ionic ketals' show in all cases major dissociation to re-form the reactant acylium ion, a unique dissociation chemistry that is equivalent to the hydrolysis of neutral acetals and ketals and which is then determined to be a very general characteristic of cyclic 'ionic ketals'. Additionally, the O-18-labeled transacetalization product of 1,3-dioxolane shows dissociation to both CH3C+=O-18 and CH3C+=O to the same extent, which confirms its cyclic 'ionic ketal' structure and the 'oxygen-scrambling' mechanism of transacetalization. Ab initio MP2/6-31G(d,p)//6-31G-(d,p) + ZPE energy surface diagrams show that transacetalization is the most exothermic, thermodynamically favorable process in reactions of CH3C+=O with 1,3-dioxolane and 1,3-oxathiolane, whereas 1,3-dithiolane is unreactive due to the endothermicity of the initial acylation step.
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 62, n. 15, n. 5096, n. 5103, 1997.
Rights: fechado
Identifier DOI: 10.1021/jo970116m
Date Issue: 1997
Appears in Collections:Unicamp - Artigos e Outros Documentos

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