Abstract
The presence of two CD stretching bands for (CH3)2CDNH2 in dilute CCl4 solution is interpreted in terms of two conformations differing in enthalpy by 0.12 ± 0.02 kcal/mole. The low frequency component is assigned to the thermodynamically more stable conformer with the CD bond trans to the N lone pair. Similar rotational isomerism is observed in CH3CD2NH2 and CD3CH2NH2. Band contours for the NH stretching vibration in some N-alkyl anilines reported previously are also interpreted in terms of rotational isomerism and a change in hybridization of the N atom when the lone pair is trans to an α-CH bond, which results in an increase in vNH and a decrease in vCH.

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