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Structural Effects on the Hydrogen-Bonding Descriptors of the Solvation Parameter Model

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Abstract

Optimized hydrogen-bond descriptors are provided for 21 primary and secondary alcohols, 16 phenols, 10 anilines and 4 amides derived from experimental chromatographic and liquid partition data analyzed using the solvation parameter model with the Solver method. Solver is an optimization package in Microsoft Excel that simultaneously adjusts the descriptor values to minimize the sum of the standard deviation of the residuals for the dependent experimental variable for a set of model equations using a Simplex algorithm. For the full data set the optimized hydrogen-bond acid descriptors are approximately 1.27 times larger than Abraham’s descriptors and the hydrogen-bond base descriptors roughly equivalent. For an isolated aliphatic primary hydroxyl group the hydrogen-bond acidity was estimated as A = 0.340 and hydrogen-bond basicity B = 0.539 and compared with a secondary hydroxyl group is a stronger hydrogen-bond acid and similar hydrogen-bond base, A = 0.26 and B = 0.54. For alcohols of the type C6H5(CH2)mOH the A and B descriptors are linearly related to m for at least m = 1 to 3. In unsubstituted phenols the hydroxyl group is more hydrogen-bond acidic, A = 0.740, and less hydrogen-bond basic, B = 0.158, than a primary aliphatic hydroxyl group. Ortho substituents reduce the hydrogen-bond acidity of a phenolic hydroxyl group in the order –CH3 < –Cl <  < –NO2 with 2-nitrophenol almost non-hydrogen-bond acidic, A = 0.062, due to favorable intramolecular hydrogen-bonding. For para-substituted phenols hydrogen-bond acidity increases in the order –CH3 < –Br < –C6H5 < –CN ≈ –Cl <  < –NO2 with a range for A from 0.673 to 0.975 and for hydrogen-bond basicity –Cl ≈ –Br < –NO2 < –CH3 < –CN < –C6H5 with a range for B from 0.775 to 1.267. The ranking order is not simply explained by consideration of inductive or mesomeric effects acting individually. The –NH2 group in aniline is a weaker hydrogen-bond acid, A = 0.238, and stronger hydrogen-bond base than phenol. A single methyl group in any ring position for anilines simultaneously increases the hydrogen-bond basicity and reduces the hydrogen-bond acidity of the –NH2 group. A single nitro group in any ring position has the opposite effect on the hydrogen-bonding properties of the –NH2 group. Primary amides are relatively strong hydrogen-bond acids and bases compared with primary alcohols and anilines and occupy the same descriptor space as phenols. An NMR correlation model is developed to estimate the optimized A descriptor using chemical shift differences for acidic protons in DMSO and CDCl3. The principle of additivity is not a good model for estimating the A and B descriptors for compounds with more than one hydrogen-bond acid/base site, although it provides acceptable results in some cases.

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All experimental data is in the public domain and can be retrieved from the cited sources without hinderance for free.

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  1. Department of Chemistry, Wayne State University, Rm 185 Chemistry, Detroit, MI, 48202, USA

    Colin F. Poole

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Poole, C.F. Structural Effects on the Hydrogen-Bonding Descriptors of the Solvation Parameter Model. J Solution Chem 51, 1056–1080 (2022). https://doi.org/10.1007/s10953-021-01133-z

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