Structural information from OH-stretching vibrations—XVI. On the intra- and intermolecular interactions of saturated tertiary alcohols in CCl 4 and CS 2

Abstract

The band parameters of the OH-stretching vibration of tertiary alcohols, including two cubylalcohols, dissolved in CCl 4 and CS 2 have been studied. The data of the strained cyclic cubylalcohols prove to be clearly different from the normal saturated tertiary alcohols. The different behaviour is related to an increased ionic character and a decreased shielding of the OH. Compared with the phenols the saturated tertiary alcohols are less sensitive to intermolecular interactions whereas the cubylalcohols behave more or less like the phenols. From the ΔHBW and the ν d parameters it is concluded that local and bulk solvent interactions contribute to all band parameters. Furthermore, it is demonstrated that for the tertiary alcohols and the phenols the intramolecular effects of ortho-alkyl substitution are similar.