Mass spectrometry of aralkyl compounds with a functional group—VIII: Comparison of the breakdown of 3-phenylnitropropane with that of 3-phenylpropyl nitrite upon electron-impact

Mass spectra of 3-phenylnitropropane and of its analogues, specifically deuterated in the aliphatic chain and in the phenyl ring, show that the molecular ion loses a molecule of water in two different modes, viz. either with both α-hydrogen atoms or with a γ- and an ortho-hydrogen atom. Moreover, a molecule of nitric oxide is eliminated from the molecular ion and the resulting M - NO]⁺-ion appears to decompose further in many complicated ways. This loss of nitric oxide does not arise from an isomerization of the nitro group to a nitrite group, because the M - NO]⁺-ion of 3-phenylpropyl nitrite breaks down in an altogether different manner than that of 3-phenylnitropropane. This is demonstrated by the spectra of specifically deuterated analogues of 3-phenylpropyl nitrite.