Electron impact mass spectrometry of substituted benzyl(1-allylcycloalkyl)amines and their cyclization products

Electron impact mass spectra have been measured for benzyl(1-allylcycloalkyl)amines and α-phenylethyl(1-allylcycloalkyl)amines and for the spiro(benzo-2-azepine-3,1′-cycloalkanes) produced by their cyclization.     

Electron impact mass spectrometry of some new macrocyclic tetraesters

The electron impact mass spectrometric behaviour of a new class of macrocyclic tetraesters is reported and discussed in detail with the aid of linked scans, exact mass measurements and collisionally activated decomposition mass analyzed ion kinetic energy spectra.     

Electron impact mass spectrometry of 2,5-bis(p-R-phenyl)thiophenes

The mass spectra of a series of 2,5-bis(p-R-phenyl)thiophenes are reported and discussed. The fragmentation patterns and mechanisms postulated have been confirmed by the determination of the metastable peaks. All the compounds possess the molecular ion as the base peak.     

Electron impact ionization mass spectrometry and tandem mass spectrometry of phenylalkylpyridazines

The mass spectrometric fragmentation behaviour of pyridazine and four monosubstituted derivatives containing a pbenylalkyl side-chain (3- and 4-benizylpyridazine, 3- and 4-(2-pbenylethyl)pyridazine) was investigated. In the electron impact ionization mess spectra of the 3-substituted compounds abundant [M – H]⁺ peaks are observed. This allows a clear distinction between 3- and 4-substituted pyridazines, as the spectra of the latter isomers show only very weak [M – H]⁺ signals. The stability of [M – H]⁺ ions derived from 3-alkylpyridazines (deduced from only the very low abundance of further fragment ions) gives strong evidence for a cyclic structure of these ions. One fragmentation pathway typical of the parent pyridazine, the [M - N₂] fragmentation, was not detectable with any of the phenylalkylpyridazines investigated. Instead, loss of HCN, H₃CN⁺ and N²H⁺ was observed. An interesting fragmentation, observed with 3-(2-phenylethyl)pyridazine, is the loss of ⁺CH₃ from the molecular ion and also from the [M – H]⁺ ion.     

Electron impact mass spectrometry of praziquantel derivatives

The electron impact mass spectra of a series of compounds related to the anthelmintic substance praziquantel are described in sufficient detail to permit their assay in biological samples by selected ion monitoring.     

Electron impact mass spectrometry of some naphthoxypolymethylenethiopyrimidines

The electron impact induced fragmentation of a large number of 2- and 4-S-(2-naphthoxy)-polymethyienethiouracils is discussed in detail, with the aid of exact mass measurements and observation of metastable decompositions. The 2- and 4-thiopyrimidine structures can be easily distinguished by their mass spectra.     

Electron impact mass spectrometry of some macrocyclic tetraesters

The electron impact mass spectrometric behaviour of five recently synthesized macrocyclic tetraesters is described and discussed in detail with the aid of exact mass measurements, linked scans and collisional activation experiments. The unusual primary loss of a dehydrogenated catecholic radical leads to a very stable cation which is the precursor of the most of the fragmentation products.     

Electron impact mass spectrometry of phenyl thiophosphoroorganic amides

The interpretation of the electron impact mass spectra of methyl phenyl phosphinomorpholinylamidothioate, O-methyl phenyl phosphonomorpholinylamidothioate, phenyl phosphonomorpholinylamidochloridothioate and O-ethyl phenyl phosphonomorpholinyhimidothioate is presented. Elucidation of the fragmentation pathways was aided by exact mass measurements and observation of peaks due to metastable transitions detected for the first and last of the above compounds.     

Electron impact mass spectrometry of some geminal bis-sulphones

The behaviour under electron impact of six 1,1-bis(benzenesulphonyl)cyclioalkanes and of 1-phenyl-1-(benzensesulphaonyl)cyclopropane has been studied in detail with the aid of exact mass measurements, linked scans for metastable ion analysis, collisional spectroscopy and kinetic energy release measurements. The molecular ions of these compounds undergo a sulphone-sulphinate rearrangement with alkyl group migration on oxygen, in analogy with what is found for simple monosulphones and, in general, their fragmentation resembles that of mono-sulphonyl compounds. Loss of SO₂ from the molecular ion is observed for all substrates, but only in the case of 1, 1-bis(benzenesulphonyl)cyclopropane is this followed by loss of the second SO₂ unit; the first loss of SO₂ is probably accompanied by rearrangement since the fragmentation pattern of [M ? SO₂]⁺˙ ions from this compound is different than that of the isobaric molecular ions of 1-phenyl-1-(benzenesulphonyl)cyclopropane.     

Electron impact mass spectrometry of hemiterpenoid tricyclic quinoline alkaloids

The mass spectral behaviour of some quinoline-type alkaloids, 3,4-dihydro-2H,5H-pyrano[3,2-c]quinolin-5-ones, isomeric 3,4-dihydro-2H,5H-pyrano[2,3-b]quinolin-5-ones and 2H,5H-pyrano[3,2-c]quinolin-5-ones, was studied in detail with the aid of linked scans, exact mass measurements and collisional spectrometry. The occurrence of a partial isomerization of the differently annulated isomers to a common, open-chain structure is discussed.     

Electron impact mass spectrometry of some macrocyclic polyether lactones

Electron impact mass spectrometry has been used together with linked scans, exact mass measurements and mass-analysed ion kinetic energy spectrometry to study nine inacrocyclic polyether lactones in detail. The presence of abundant hydrogenated oxirane ions has been observed for all the compounds examined, and confirmed by kinetic energy release measurements.     

Electron impact mass spectrometry of alkanes in supersonic molecular beams

The electron impact mass spectrometry of straight chain alkanes C₈H₁₈-C₄₀H₈₂, squalane, methylstearate, 1-chlorohexadecane, 1-bromohexadecane, and dioctylphthalate was studied by sampling them with supersonic molecular beams. A fly-through Brink-type electron impact ion source was used, utilizing a vacuum background ion filtration technique based on differences between the kinetic energy of the supersonic beam species and that of thermal molecules. The 70-eV electron impact mass spectra of all the alkanes were characterized by a pronounced or dominant molecular weight peak together with all the fragment ions normally exhibited by the standard thermal 70-eV EI mass spectra. In contrast, the NIST library of most of these molecules did not show any molecular weight peak. By eliminating tile intramolecular thermal vibrational energy we gained control over the degree of molecular ion fragmentation by the electron energy. At an electron energy of 18 eV the molecular ion dissociation was further reduced considerably, with only a small absolute reduction in the peak height by less than a factor of 2. The effect of vibrational cooling increased with the molecular size and number of atoms. Pronounced differences were observed between the mass spectra of the straight chain triacontane and its branched isomer squalane. Similar mass spectra of octacosane (C₂₈H₅₈) achieved with 70-eV EI in a supersonic molecular beam were obtained with a magnetic sector mass spectrometer by using an electron energy of 14 eV and an ion source temperature of 150 °C. However, this ion source temperature precluded the gas chromatography-mass spectrometry (GC-MS) of octacosane. The GC-MS of alkanes was studied with an ion trap gas chromatograph-mass spectrometer at an ion source temperature of 230 °C. Thermal peak tailing was observed for C₂₀H₄₂ and heavier alkanes, whereas for C₂₈H₅₈ and heavier alkanes the severe peak tailing made quantitative GC-MS impractical. In contrast, no peak tailing existed even with C₄₀H₈₂ for GC-MS in supersonic molecular beams. The minimum detected amount of eicosane (C₂₀, H₄₂) was shown to be 60 fg. This was demonstrated by using single ion monitoring with the quadrupole mass analyzer tuned to the molecular weight peak of 282 u. The coupling of electron impact mass spectrometry in supersonic molecular beams with hyperthermal surface ionization and a fast GC-MS inlet is briefly discussed.     

Electron impact mass spectrometry of some macrocyclic and acyclic aldimines

The 70 eV electron impact mass spectra of some macrocyclic and acyclic aldimines, together with that of their synthon, are described and discussed with the aid of exact mass measurements, linked scans, deuterium labelling experiments and collisional experiments. The mass spectrometric behaviour of the acyclic compounds, not directly related to their structure, has been studied in detail with the aid of differential thermal analysis, which demonstrates the occurrence of pyrolysis.     

Electron impact mass spectra of some new macropolycycles

Mass spectra of some macropolycycles have been studied. Normal and metastable (B/E) mass spectra are presented. The fragmentation patterns and the structures of the main ions are discussed.     

Electron impact mass spectrometry of some 3-substituted 1,2,3,4-tetrahydroisoquinolines

The electron impact mass spectral fragmentation of a series of 3-substituted-l,2,3,4-tetrahydroisoquinolines are reported. The principal fragmentation modes of these compounds comply with the main generalizations reached earlier with simpler systems. Complete aromatizations to form the isoquinolinium ion are observed only for compounds 5 and 7 and no retro-Diels-Alder cleavage is observed when R¹ is a benzyl group.