Vibrational band intensities in substituted anilines

Abstract

The infra-red absorption bands associated with the stretching vibrations of the NH 2 group in a series of meta - and para -substituted anilines have been examined. The effect of the sub­stituet groups upon the frequencies and intensities of the bands has been correlated with their Hammett σ factors. The widths of the bands have also been found to depend upon the position and nature of substituent. The linear relation between log (intensity) and σ suggested previously on the basis of other data has been found to hold in this case too. Measurements in several solvents have been compared, and surprising variations of band intensity have been found. Analogous data have been obtained for the N—H bond stretching vibration band in substituted N -methyl anilines. The effect of ortho substituents has also been examined in a few cases.