Hydrogen Bonding Influences

Hydrogen bonding of hydroxyl and amino groups not only causes large variations in the chemical shift of the proton of the hydrogen bond, but also influences its coupling with adjacent C-H groups. As shown on the right, the 60 MHz proton nmr spectrum of pure (neat) methanol exhibits two signals, as expected. At 30° C these signals are sharp singlets located at δ 3.35 and 4.80 ppm, the higher-field methyl signal (magenta) being three times as strong as the OH signal (orange) at lower field. When cooled to -45 ° C, the larger higher-field signal changes to a doublet (J = 5.2 Hz) having the same chemical shift. The smaller signal moves downfield to δ 5.5 ppm and splits into a quartet (J = 5.2 Hz). The relative intensities of the two groups of signals remains unchanged. This interesting change in the nmr spectrum, which will be illustrated  in below, is due to increased stability of hydrogen bonded species at lower temperature. Since hydrogen bonding not only causes a resonance shift to lower field, but also decreases the rate of intermolecular proton exchange, the hydroxyl proton remains bonded to the alkoxy group for a sufficient time to exert its spin coupling influence.
Under routine conditions, rapid intermolecular exchange of the OH protons of alcohols often prevents their coupling with adjacent hydrogens from being observed. Intermediate rates of proton exchange lead to a broadening of the OH and coupled hydrogen signals, a characteristic that is useful in identifying these functions. Since traces of acid or base catalyze this hydrogen exchange, pure compounds and clean sample tubes must be used for experiments of the kind described here.

Another way of increasing the concentration of hydrogen bonded methanol species is to change the solvent from chloroform-d to a solvent that is a stronger hydrogen bond acceptor. Examples of such solvents are given in the following table. In contrast to the neat methanol experiment described above, very dilute solutions are used for this study. Since chloroform is a poor hydrogen bond acceptor and the dilute solution reduces the concentration of methanol clusters, the hydroxyl proton of methanol generates a resonance signal at a much higher field than that observed for the pure alcohol. Indeed, the OH resonance signal from simple alcohols in dilute chloroform solution is normally found near δ 1.0 ppm.
The exceptionally strong hydrogen bond acceptor quality of DMSO is demonstrated here by the large downfield shift of the methanol hydroxyl proton, compared with a slight upfield shift of the methyl signal. The expected spin coupling patterns shown above are also observed in this solvent. Although acetone and acetonitrile are better hydrogen-bond acceptors than chloroform, they are not as effective as DMSO.