Electron impact mass spectral studies of hydrazine monoamine oxidase inhibitor drugs

Identification of hydrazine monoamine oxidase inhibitor drugs such as isoniazid, iproniazid, nialamide, isocarboxazid and iproclozide is made by electron impact mass spectrometry using the direct insertion technique. The molecular ion itself, although of low relative abundance, is found in the mass spectra of all compounds studied. Relative intensities of the major fragments and data on metastable ions useful in the identification of these compounds are reported. With the aid of synthesized structurally related products, deuterium labelling of exchangeable hydrazidic and hydrazinic protons and by the use of hexadeuterated isopropylic analogues, detailed information about fragmentation patterns is obtained. Splitting processes are chiefly governed by the nature of the aromatic substituent at the hydrazidic end and the alkyl sidechain located at the second hydrazinic nitrogen. The major fragmentations occurring are loss of small neutral molecules, double rearrangement, cleavage of the NN bond, amide bond rupture, β‐cleavage to the hydrazinic nitrogen atom and McLafferty rearrangements.