Abstract

The integrated intensity, <i>A,</i> of the free OH-stretching band of a large number of noncyclic and six-membered cyclic saturated monohydroxy compounds has been studied as a possible source of structural information. The intensity of primary alcohols proves to be constant, <i>viz.,</i> 16.8 ± 0.5 km/M. No factors have been found that influence this value. The standard <i>A</i>-value for secondary alcohols is 13.8 ± 0.4 km/M. OH-rotamers without trans-H-Oxygen-lone-pair interaction show a lower intensity; factors influencing the rotamer distribution might thus affect the overall <i>A</i>-value. A significant decrease is observed when a γ-methyl group is situated (very) close to and therefore strongly interacts with a lone pair of the oxygen atom. The standard <i>A</i>-value for tertiary alcohols is 11.2 ± 0.6 km/M. Initially all rotamers have the same <i>A</i>-value, but for the secondary ones a strongly interacting γ-methyl group may cause an appreciable intensity lowering. Besides, strong sterical interactions between the three alkyl substituents at the α-C-atom usually give rise to small changes in the intensity. The overall conclusion is that the integrated intensity proves to be a useful source of structural information.

Saturation-dip measurements for the ν₈ C-O stretching band of CH₃OH with a CO₂-laser-microwave-sideband spectrometer

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