Electron ionization mass spectra of a series of 2,4-disubstituted dihydro- and tetrahydro-1,5-benzodiazepines are discussed. The fragmentation of these compounds is dominated by ring contractions of diazepine, which give both five- and six-membered rings, benzimidazoles and quinoxalines. Tetrahydro compounds showed a tendency to eliminate one nitrogen from the ring system and give quinoline rings through NH2 and NH4 eliminations. The electron ionization spectra of cis and trans isomers of tetrahydro compounds are identical.

Ring contractions of dihydro- and tetrahydro-1,5-benzodiazepines in electron ionization mass spectrometry

Fast-atom bombardment mass spectrometric studies of trisubstituted 3a,4,5,11-tetrahydro- 6H-1,2,4-oxadiazolo[4,5-a][1,5]benzodiazepines

Separation of positional and cis-trans-isomers of tetrahydro-1,5-benzothiazepines and tetrahydro-1,5-benzodiazepines was studied using reversed-phase chromatography and liquid-solid chromatography. The selection of solvent was based on the selective triangle for solvents. Systems of separation consisted of C18 columns and methanol, THF or acetonitrile in water for the reversedphase method; it was suitable for the separation of positional isomers only but the liquid-solid method was suitable for separation of cis-trans-isomers as well as positional isomers using a silica column and ethyl ether, chloroform or ethyl acetate as the mobile phase respectively.

HPLC separation of isomers of tetrahydro-1,5-benzothiazepines and tetrahydro-1,5-benzodiazepines

The mass spectrometric behaviour of three 1a,3-diaryl-1,1,4, 4-tetrachloro-1a,2,3,4-tetrahydro-1H-azirino-[2,1-e][1, 6]benzothiazocines has been studied with the aid of mass-analyzed ion kinetic energy spectro--metry and exact mass measurements under electron impact ionization. All compounds show a tendency-to eliminate a neutral substituted/unsubstituted 1,1-dichlorostyrene from the eight-membered thiazocine ring to yield azirino[2,1-c][1, 4]benzothiazine ions, which can then lose a chlorine radical and a sulfur-atom to form azirino[2,1-c][1,4]benzothiazine ions and dihydroquinoline ions. All compounds could also eliminate a chlorine radical plus hydrogen chloride, stepwise or consecutively, to undergo a ring enlargement rearrangement to produce nine-membered 1, 7-benzothiazonine ions. The [M(+) - Cl] ions could undergo a four-membered ring rearrangement to yield 1,5-benzothiazepine ions by loss of 1,1-dichlorostyrene or styrene ions and HCl, and undergo alpha, alpha-cleavage to form benzothiazine ions by loss of arylchlorocyclopropane. The [M(+) - Cl - HCl] ions could further eliminate some atoms, small molecules or molecular fragments to form some abundant fragment ions. Copyright 1999 John Wiley & Sons, Ltd.

Mass spectral fragmentation patterns of 1a,3-diaryl-1,1,4,4-tetrachloro-1a,2,3,4-tetrahydro-1H-azirino[2,1-e]­[1,6]benzothiazocines

The mass spectrometric behavior of seven 2a,4-disubstituted 2,2a,3,4-tetrahydro-2-phenyl-1H-azeto[2,1-d][1,5]benzothiazepin-1-ones has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization. All compounds show a tendency to eliminate a phenylketene molecule, an ethyl or benzyl radical, or a phenylketene molecule plus an SH radical. The mass spectrometric behavior of the title compounds was compared to those of 2-heteroatom-substituted analogues.

Mass Spectrometric Fragmentation of 2a,4-Disubstituted 2,2a,3,4-Tetrahydro-2-phenyl-1H-azeto[2,1-d]- [1,5]benzothiazepin-1-ones Under Electron Impact Ionization Conditions and Comparison with their 2-Heteroatom Substituted Analogues

The fragmentation mechanisms of dihydro- and tetrahydro-1,5-benzothiazepines under electron impact have been studied in detail using high resolution mass spectrometry, metastable decompositions and deuterium labelling techniques. Both kinds of the benzothiazepines possess high stability. The [MSH]+ and the cyclic benzothiazole ions derived from the fragmentation and severe skeletal rearrangement of the molecular ion comprised the main features of the spectra. Some doubly charged ions were noticed in the low resolution electron impact mass spectra.

Jin Heng-Liang

Papers

Fragmentation of dihydro- and tetrahydro-1,5-benzothiazepines under electron impact