Electron impact induced fragmentations of 2‐(2‐nitroanilino)thiophens and Di(2‐nitrophenyl)sulphides

Abstract

A prominent orfho interaction occurs during the maSs spectrai fragmentation of di(2-nitrophenyl)sulphides. No such effects are observed for the corresponding ethers or 2-(2-nitroaniiino)thiophens. Variation of aromatic substituents can dramatically alter the effect. Examination of anaiogous suiphone, sulphoxide, and disuiphide moledes, Snplicates the involvement of the ortho Níro substituent and the sulphw atom i0 this rearrangement.

Studies in organic mass spectrometry. Part 24† Electron ionization mass spectra of some aryl(2-nitrobenzo[b]thiophen-3-yl)amines

“…The loss of OH Á is a classic example of an ortho effect, observed in the mass spectra of o-nitrodiarylamines, 9,12,13 onitroanilines, [13][14][15] and o-nitroaminopyridines. 16 By using Ndeuterated 2-nitrodiphenylamine it has been demonstrated that the OH Á ejected contains either the aminic or an aryl hydrogen atom.…”

Tandem mass spectrometry of some nitropyridylaryl sulfides

“…Different mechanistic pathways have been reported to account for the fragmentation processes in mass spectrometric studies of o ‐dinitrodiaryl amines5,, 6 and of ether,7 sulfide,8,, 9 sulfoxide10 and sulfone10 derivatives of nitroaryl compounds. All of these proposed mechanisms involve either skeletal rearrangment, i.e.…”

Sequential ortho effects: characterization of novel [M - 35]+ fragment ions in the mass spectra of 2-alkyl-4, 6-dinitrophenols

“…In particular, aromatic compounds containing a nitro group show pronounced ortho effects [4][5][6][7][8][9][10][11][12]. Some of the reported nitroaromatic ortho effects include hydrogen transfer to a n itro oxygen [6,8), simple oxygen migration [4,6,[8][9][10] , nitro oxygen insertion into the ortho substituent [8], ring closure between the nitro group and the ortho substituent [4, U), and other ma jor skeletal rearrangements (11).…”