Trends in alkyl substituent effects on nucleophilic reactions of carbonyl compounds: Gas phase reactions between ammonia and R1R2COCH3+ oxonium ions

Literature Information

Publication Date 2003-01-30
DOI 10.1039/B209955C
Impact Factor 3.876
Authors

Lihn Bache-Andreassen, Einar Uggerud


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Abstract

The reactivity of carbonyl substituted methyl oxonium ions (R1R2COCH3+) towards ammonia has been investigated using an FT-ICR mass spectrometer and ab initio calculations. The monosubstituted ions (R1=H; R2= H, CH3, C2H5 and i-C3H7) show different reaction patterns with variable degree of: (1) nucleophilic substitution, (2) addition–elimination and (3) proton transfer, when reacted with ammonia. In all cases addition–elimination dominates over nucleophilic substitution, and the observed reactions are slow. The trends in reactivity are consistent with the alkyl group's electronic properties, as expressed by a single parameter linear or slightly non-linear model.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
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Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

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