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Quantitative Scale for the Extent of Conjugation of Carbonyl Groups: “Carbonylicity” Percentage as a Chemical Driving Force

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journal contribution
posted on 25.09.2008, 00:00 by Zoltán Mucsi, Gregory A. Chass, Béla Viskolcz, Imre G. Csizmadia
Despite the carbonyl group being one of the most pervasive chemical building blocks in natural, synthetic, and industrial processes, its exact description in terms of precise quantification of the degree of carbonyl conjugation has yet to be determined. The present work suggests a novel yet simple method for quantifying the conjugation in general carbonyl groups (such as ketones, aldehydes, carboxylic acids and their respective halogenides, amides, etc.) on a linear scale, defined as the “carbonylicity scale”. This was achieved by use of the computed enthalpy of hydrogenation (ΔHH2) of the >CO group in the compounds examined. In the present conceptual work, the ΔHH2 value for formate ion is used to define complete conjugated character (carbonylicity = +100%), while formaldehyde represents complete absence of conjugation (carbonylicity = 0%). The component ΔHH2 values were computed at differing levels of theory, providing a nearly “method-independent” measure of carbonylicity computationally. A total of 49 common carbonyl compounds were used as accuracy scoring criteria of the methodology. For the compounds examined, correlations have been made between the computed carbonylicity percentage and the >CO proton affinities, IR frequencies, and their reactivity values in a nucleophilic addition reaction. Selected chemical reactions were also studied to illustrate the utility of carbonylicity scale. Examples herein include demonstrating that change in the carbonylicity value represents a thermodynamic driving force in acylation reactions. The definition was extended to substituted thiocarbonyl and imino compounds.