Multiple Hydrogen Shifts Leading to Ammonia Loss from the Molecular Ions of Cyanocyclohexanes

The loss of ammonia from the metastable molecular ions of cyclic cyano compounds has been examined with the use of deuterium labeling and tandem mass spectrometry. Loss of ammonia is significant for ionized cyanocyclohexane, 1-methyl-, 4-methyl-, 4-cyano-and 4-phenyl-cyanocyclohexanes, 4-cyanopiperidine, cyanocycloheptane and 2-cyanonorbornane. By contrast, loss of ammonia is of minor importance (or absent) for the molecular ions of cyanocyclopentane, 2-methyl-cyanocyclohexane, 1-phenyl-cyanocyclohexane, 1-cyanocyclohexene, 4-cyanotetrahydrothiopyran, 2-cyano-5-norbornene and isocyanocyclohexane. Deuterium labeling of cyanocyclohexane reveals the occurrence of an H-shift from the 4-position to the cyano function, followed by a 1,2-H shift from the 1-position to the C-atom of the newly-formed–CNH group. Subsequently, a series of H-shifts leads to a distonic ion that is formulated as an N-protonated methylamine attached to a cyclohexadienyl radical. Loss of ammonia ensues and leads to ionized toluene as indicated by collision-induced dissociation experiments. For 4-phenyl-cyanocyclohexane, the metastable ions of the cis- and trans-isomers display, essentially, the same unimolecular chemistry. Briefly, the labeling of 4-phenyl-cyanocyclohexane indicates the following: (i) the H atom at the 4-position of the cyclohexane ring is incorporated, to a minor extent, in the ammonia molecule, (ii) loss of NHD2 predominates in the reactions of the molecular ions of 2,2,6,6-d4-4-phenyl-cyanocyclohexane and (iii) the ionized 3,3,5-d3-labeled species expels mainly NH2D. In addition, the metastable molecular ions of the 4-[d5-phenyl]-cyanocyclohexane expel NH3 and NH2D in a ratio of 35:65. A mechanistic scheme is proposed that is consistent with the labeling results for 4-phenyl-cyanocyclohexane as well as the indicated formation of ionized 4-methylbiphenyl as the product ion of ammonia loss.