1H Chemical Shifts of Methanol in Selected Solvents

The solvent effect shown above suggests a useful diagnostic procedure for characterizing the OH resonance signals from alcohol samples. For example, a solution of ethanol in chloroform-d displays the spectrum shown on the left below, especially if traces of HCl are present (otherwise broadening of the OH and CH₂ signals occurs). Note that the chemical shift of the OH signal (red) is less than that of the methylene group (blue), and no coupling of the OH proton is apparent. The vicinal coupling (J = 7 Hz) of the methyl and methylene hydrogens is typical of ethyl groups. In DMSO-d₆ solution small changes of chemical shift are seen for the methyl and methylene group hydrogens, but a dramatic downfield shift of the hydroxyl signal takes place because of hydrogen bonding. Coupling of the OH proton to the adjacent methylene group is evident, and both the coupling constants can be measured. Because the coupling constants are different, the methylene signal pattern is an overlapping doublet of quartets (eight distinct lines) rather than a quintet. Note that residual hydrogens in the solvent give a small broad signal near δ 2.5 ppm.

For many alcohols in dilute chloroform-d solution, the hydroxyl resonance signal is often broad and obscured by other signals in the δ 1.5 to 3.0 region. The simple technique of using DMSO-d₆ as a solvent, not only shifts this signal to a lower field, but permits 1°-, 2 °- & 3 °-alcohols to be distinguished. Thus, the hydroxyl proton of 2-propanol generates a doublet at δ 4.35 ppm, and the corresponding signal from 2-methyl-2-propanol is a singlet at δ 4.2 ppm. The more acidic OH protons of phenols are similarly shifted – from δ 4 to 7 in chloroform-d to δ 8.5 to 9.5 in DMSO-d₆.