Different partitioning behaviour of sulphonyl-containing compounds in reversed-phase high-performance liquid chromatography and octanol-water systems

Abstract The lipophilicities of 27 monosubstituted benzene derivatives bearing sulphonyl, carbonyl and other polar substituents were measured by two reversed-phase high-performance liquid chromatographic (RP-HPLC) methods, in the presence and absence of n-decylamine as a masking agent. The results were compared with literature n-octanol-water partition coefficients, showing that compounds with strong hydrogen-bond accepting groups have log kw values that are considerably higher than expected from their log Poct values. This deviant partitioning behaviour in RP-HPLC is attributed to strong adsorption on free silanol groups. A comparison with retention data on a silica gel stationary phase and with the hydrogen-bond acceptor basicity parameter (β) validated this hypothesis.

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