In proton NMR spectroscopy, primary amines and secondary amines showcase their N–H protons as a broad signal in the chemical shift range between δ 0.5 and 5 ppm. The exact position in this range depends on several factors, including sample concentration, hydrogen bonding, and the type of solvent used. Since amine protons undergo fast proton exchange in solution, the protons are labile and therefore do not participate in any splitting with adjacent protons. Thus, the observed peak is broad and does not provide any information about the adjacent proton environment. This problem is resolved, and N–H protons are made identifiable, by adding D₂O to the mixture. The addition causes the N–H protons to exchange with deuterons, leading to the disappearance of N–H proton peaks. This disappearance is indicative of the presence of labile protons in the sample.

In aliphatic amines, the α protons are deshielded by the electron-withdrawing nitrogen atom. Consequently, the α protons show higher chemical shifts (δ 2.2 to 2.9 ppm) than β protons (δ 1 to 1.7 ppm) that are less deshielded due to the increased distance from the nitrogen atom.

In the ¹³C NMR spectroscopy, the α carbons of aliphatic amines show the highest chemical shift values ranging from δ 30 to 60 ppm because of the deshielding effect of electronegative nitrogen.