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Specific cation effect in the reaction of nitroprusside with cysteine, acetophenone and sulfite (Legal and boedeker reaction)

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Abstract

The colour formation of cysteine (I), acetophenone (II) and sulfite (III) with the sodium and tetrabutylammonium (TBA) salt of nitroprusside (NP2−) in aqueous solution was studied. The intensity of colour formation depends strongly on the nature and concentration of the cations and increases in the order TBA<Li<Na<K<Rb<Cs (in case of cysteine TBA and Li are interchanged). This specific cation effect was known for the Boedeker reaction (III) and is now also demonstrated for the Legal reaction (I and II). The adduct formation between NP2− and I to III is based on an anion-anion interaction. The role of the cation is to reduce the Coulombic repulsion between the reactants by ion-pair formation. The efficiency of ion-pair formation corresponds with the order given before except for TBA, which behaves divergently.

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Authors and Affiliations

  1. Department of Pharmaceutical Analysis and Analytical Chemistry, Subfaculty of Pharmacy, Gorlaeus Laboratories, State University Leiden, P.O. Box 9502, 2300, RA Leiden, The Netherlands

    O. R. Leeuwenkamp, C. H. Vermaat & C. M. Plug

  2. Department of Chemical Pharmacy, Subfaculty of Pharmacy, Catharijnesingel 60, 3511, GH Utrecht, The Netherlands

    A. Bult

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  1. O. R. Leeuwenkamp
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  2. C. H. Vermaat
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  3. C. M. Plug
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  4. A. Bult
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Leeuwenkamp, O.R., Vermaat, C.H., Plug, C.M. et al. Specific cation effect in the reaction of nitroprusside with cysteine, acetophenone and sulfite (Legal and boedeker reaction). Pharmaceutisch Weekblad Scientific Edition 6, 195–202 (1984). https://doi.org/10.1007/BF01999942

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  • DOI: https://doi.org/10.1007/BF01999942

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