Partition Behavior of Anilines in Bulk‐Phase and High‐Performance Liquid Chromatographic Systems: Influence on Correlation with Biological Constants

Abstract The partition behavior of a mixed series of ring‐substituted anilines in reversed‐phase high‐performance liquid chromatographic systems is substantially different from that observed in a classical bulk‐phase partition system with n ‐heptane as the aprotic reference solvent. On the basis of the equivalence of each ring substituent in the p ‐straight‐chain methylene groups (ν value) as a function of the fraction of organic solvent (acetonitrile or methanol) in the mobile phase, the biased partition behavior for imperfect homologues and heterologues is verified relative to that of perfect homologues. This behavior was tentatively attributed, mainly, to differences in the hydrogen bond…