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On the role of solvent in complexation equilibria. I. The acid-base chemistry of some α,ω-diaminocarboxylic acids in water-dioxane mixed solvents

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Abstract

The macroscopic and microscopic acid-base chemistry of a series of α,ω-diaminocarboxylic acids, H2N(CH2)nCH(NH2)COOH [n=4, lysine (LYS);n=3, ornithine (ORN);n=2, 2,4-diaminobutyric acid (DAB);n=1, 2,3-diaminopropionic acid (DAP)], was determined in water and its binary mixtures with dioxane (20.5, 40.7, 60.7, and 80.5 mass % dioxane) using carbon-13 nuclear magnetic resonance spectroscopy. The macroscopic acid dissociation constants for the titration of the two ammonium groups decrease uniformly with increasing dioxane composition. The microscopic constants, however, which characterize the relative concentrations of the two tautomers of singly protonated amino acid (I and II)

$$\begin{gathered} H_3 \mathop N\limits^ + (CH_2 )_n CHCOO^ - H_2 N(CH_2 )_n CHCOO^ - \hfill \\ || \hfill \\ NH_2 \mathop N\limits_ + H_3 \hfill \\ III \hfill \\ \end{gathered}$$

reveal that while tautomer I is favored in aqueous solution, tautomer II becomes more important with increasing dioxane composition for LYS and ORN. The relative concentrations of I and II remain unchanged with solvent composition for DAP. These results are explained in terms solute-solvent and solvent-solvent interactions.

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Authors and Affiliations

  1. Department of Chemistry, Kent State University, 44242, Kent, Ohio

    Mark S. Greenberg

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  1. Robert Griffith Jr.
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  2. Lakshmikumar Pillai
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  3. Mark S. Greenberg
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Griffith, R., Pillai, L. & Greenberg, M.S. On the role of solvent in complexation equilibria. I. The acid-base chemistry of some α,ω-diaminocarboxylic acids in water-dioxane mixed solvents. J Solution Chem 8, 601–613 (1979). https://doi.org/10.1007/BF00716000

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  • DOI: https://doi.org/10.1007/BF00716000

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