Analysis of the isobutane chemical ionization mass spectra of hexenols, cyclohexenols and various syn/anti pairs of bicyclic and tricyclic homoallylic alcohols shows that: (i) the spectra of the allylic alcohols are dominated by [M + H – H2O]+ and [M + C4H9–H2O]+ ions and contain traces of [M + H]+ ions; (ii) [M + H]+ ions are prominent in the spectra of acyclic and certain cyclic homoallylic alcohols; and (iii) [M + H]+ ions dominate the spectra of other acyclic unsaturated alcohols The [M + H]+ ions may result from either: (a) protonation of the hydroxyl group, followed by a very rapid intramolecular proton transfer from the protonated hydroxyl group to the carbon–carbon double bond or internal solvation of the protonated hydroxyl group by the carbon–carbon double bond; and/or (b) direct protonation of the carbon–carbon double bond with significant internal solvation of the resulting carbocation by the hydroxyl group, which may lead to carbon–oxygen bond formation to give a protonated cyclic ether The consequences of placing various geometric constraints on the possible intramolecular interactions between the hydroxyl group and the carbon–carbon double bond in unsaturated alcohols are explored

Isobutane chemical ionization mass spectra of unsaturated alcohols

Mass spectral study of geometrical (E)- and (Z)-isomers

Chemical ionization mass spectrometry (CI) of aliphatic and aromatic carbonyl compounds using water as the reagent gas provides intense pseudomolecular ions and class-specific fragmentation patterns that can be used to identify aliphatic aldehydes, ketones, carboxylic acids, and esters. The length of ester acyl and alkyl groups can easily be determined on the basis of loss of alcohols from the protonated parent. Water CI provides for an approximately 200:1 selectivity of carbonyl species over alkanes. No reagent ions are detected above 55 amu, allowing species as small as acetone, propanal, acetic acid, and methyl formate to be identified. When deuterated water was used as the reagent, only the carboxylic acids and β-diketones showed significant H/D exchange. The use of water CI to identify carbonyl compounds in a wastewater from the supercritical water extraction of lignite coal, in lemon oil, and in whiskey volatiles is discussed.

Water chemical ionization mass spectrometry of aldehydes, ketones, esters, and carboxylic acids

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

The chemical ionization mass spectra of different dicarboxylic acids, including saturated and unsaturated aliphatic, aromatic, hydroxyl and amino-substituted dicarboxylic acids, have been studied using pure methanol as the reagent gas. Biomolecular monoesterification and diesterification product ions [M+15]+ and [M+29]+, and adduct ion [M+33]+, were observed, in addition to the protonated molecule [MH]+ and unimolecular water elimination product ions. The formation of a protonated molecule with bridged intramolecular hydrogen bond, and its effect on the esterification of dicarboxylic acids is discussed. Geometric isomers, such as maleic and fumaric acid, and ortho and meta isomers of phthalic acids can be distinguished from each other by methanol chemical ionization mass spectra. When ethanol was used as the reagent gas, similar mass spectra of some dicarboxylic acids were obtained.

Bifunctional interaction and its effect on the esterification of dicarboxylic acids in chemical ionization mass spectrometry

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.

Chai Wen-Gang

Papers

Bifunctional interaction and its effect on the esterification of dicarboxylic acids in chemical ionization mass spectrometry

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