
%0 Journal Article
%A Hambly, AN 
%A O'Grady, BV 
%T Hydrogen Bonding in Organic Compounds. VI. Interaction between Groups in <I>ortho</I>-Substituted Anilines
%J Australian Journal of Chemistry
%D 1962/12/01
%V 15
%N 4
%P 626-641
%K 
%R https://doi.org/10.1071/CH9620626
%U https://www.publish.csiro.au/paper/CH9620626 
%X The infrared spectra of anilines, with a single methyl group as ortho-substituent, conform to the modified Bellamy and Williams equation which was found to correlate the antisymmetric and symmetric stretching frequencies of the NH2 group when only meta- or para-substituents were present. Methyl substituents at both positions 2 and 6 to the amine produce a change that can be described as anti-hydrogen bonding. Substitution by alkoxy groups or halogen at the position ortho to the amine group causes deviations from the equation in the direction indicative of hydrogen bonding. Monodeuterated 2-bromo-, 2-iodo, and 2-cyanoaniline give evidence of extremely weak hydrogen bonds by a small difference in the NH and ND vibrations of two isomeric forms bonded through H and D respectively. The spectra of monodeuterated 2-alkoxy-, 2-fluoro-, and 2-phenylaniline did not show any resolution of the bands due to NH and ND vibrations, and hydrogen bonding between the ortho-substituents can be regarded as negligible in these compounds.   An o-trifluoromethyl substituent appears to exert a repulsive effect on the amine group with no formation of a hydrogen bond. Rotational isomers occur in carbon tetrachloride solutions of 2,6-dihalogeno-4-nitroanilines. 
