SULFENAMIDES AND SULFINAMIDES VIII) THE CHROMATOGRAPHY OF ARYL SULFENAMIDES

Abstract

Substituent effects with respect to position and extent of substitution in a series of N-aryl benzenesul fenamides (ArSNHAr') have been examined over several chromatographic systems. In normal phase TLC, although methyl substitution in either ring leads to higher Rφ values (Rf relative to that of the parent compound, N-(phenyl)benzenesulfenamide, 1) a dominant influence is shown by substitution at the 2-position on the amine side–Rφ value greater than that of the isomeric 4-methyl derivative. In contrast, substitution at the 4-position on the sulfenyl side gives a higher Rφ value.

The respective contributions to Rφ values are maintained in di-substituted derivatives so that the highest is fiven byu the mixed dervative-2-position on the amine side plus 4-position on the sulfenyl side. Similar relative effects, but with a greater spread of Rφ values, are given by chloro and methocyl dervatives.

In reversed phase TLC (on parffined slicia gel) all the methly and clhoro dervatives have Rφ values >1 but values for the chloro derivatives were lower than expected on the basis fo polarity. Smilarly, in reversed phase HPLC (on μBondpak C₁₈ porasil) all methly and chloro derivatives ahd tr values ont he basis of polarity. GC on non-polar methly silicone, OC-1, and on mildly polar methly phenyl dimethly < monochloro < dichloro. Solutility and polar features are discussed.

Key Words:

• Sulfenamides
• chromatography.