Intramolecular Interaction between Hydroxyl Group and π-Eelctrons. V. Electronic Effect in Arylcarbinols and a Preliminary Note on the Interaction in Benzylaniline Derivatives

Absorption due to the O–H stretching vibration in the fundamental region was measured with fourteen benzyl alcohol derivatives to see the electronic effect of the substituent on the interaction between the hydroxyl group and the π-electrons and the following conclusions are deduced. 1) The nature of the interaction or the structure of the molecule which gives rise to the νO–H absorption at 3617 cm−1 is discussed and the interaction between the hydroxyl group and the π-electron on the carbon atom to which hydroxymethyl group is attached (structure III) is favored. 2) The consistency of the wave numbers at which two νO–H absorptions appear, gives further support to the idea that these absorptions originate in the existence of the two rotational isomers. 3) (Remark: Graphics omitted.) is in linear relation with Hammett’s σ values and the σ value of the m-benzyloxyl group is estimated as −0.204. A similar phenomenon is also observed in the substituted benzylanilines.