Abstract-Biologically active primary amines (phenethylamines, amphetamines and tryptamines) form thermally stable isothiocyanate derivatives by reacting with carbon disulfide. Phenolic hydroxyl and indole (NH) nitrogens are further converted to their trimethylsilyl derivatives. The gas chromatographic and mass spectrometric properties of several amines are presented. It is shown that the combined use of gas chromatography and mass spectrometry of these derivatives is well suited for the differentiation of several structural isomers. Fragmentation mechanisms leading to the formation of structurally significant ions are discussed.