he appearance of the 1H NMR signals of protic samples in aprotic solvents depends critically on the concentration of the sample. The -OH, -NH2 or -COOH signals can have chemical shift values and line widths over a wide range due to varying extents of hydrogen bonding and chemical exchange. The concentration can also determine whether or not one is able to observe J coupling between and -OH proton and other protons in the sample. An example of this is illustrated below. The figure shows the spectrum of methanol in deuterated acetone. The spectrum on the top is that of concentrated methanol and it consists of two singlets. In this case the methanol molecules are hydrogen bonded to one another and the -OH protons are undergoing fast exhange with one another. The spectrum on the bottom is that of very dilute methanol. It is a second order spectrum with two signals approximating a doublet and a quartet due the J coupling between the methyl protons and -OH proton, respectively. Note that the chemical shift of the -OH proton is much lower for the dilute methanol compared to the concentrated methanol. In this case the methanol molecules are not hydrogen bonded to one another and there is no (or very slow) exchange among the -OH protons between molecules allowing for the observation of the J coupling.
