Mass spectral studies of naphthoflavones

The electron impact induced fragmentations of the five possible naphthoflavones have been studied with the aid of low- and high-resolution measurements, metastable decompositions and isotope labelling using either deuterium or carbon-13 atoms. All compounds show both the direct expulsion of a CO residue from the carbonyl group and the retro Diels–Alder cleavage. The abundant [M–H]⁺ ion has been formulated as the substituted β-tropolone species, which, in the case of β-naphthoflavone, is in competition with a pentacyclic species arising from the elimination of H-5 as evidenced in the spectrum of 5-d-β-naphthoflavone. Other previously unsuspected ions are also in evidence.     

Mass spectral studies on tanshinones

The mass spectra of three groups of tanshinones have been examined and a number of characteristic features noted which might be helpful in the micro-identification of the natural products. The fragmentation patterns are similar to each other except for the relative intensity within the same group of tanshinones and are accounted for in terms of the general fragmentations of furans and quinones. Characteristic ions at m/e 178, 165 and 152 found in all kinds of tanshinones may be considered to be of highly aromatized hydrocarbon fragments and are of good for the structure elucidation of these compounds.     

Mass spectral fragmentation of functionalized lanostanes-I

Mass spectra of various functionalized lanostanes and their deuterated analogs are compared. It is proposed that the transfer of a hydrogen from the 18-methyl group to the 11-oxo group via a McLafferty rearrangement is made geometrically possible by prior ionization of the 13,14 bond which allows an optimum interatomic distance between the oxygen and hydrogen to be acquired; the 8,9 double bond is a requisite for electronic induction of this specific process. Transfer of the hydrogen from the 7β-hydroxy group to position 14 is implicated in the mass spectrum of 3β-acetoxy-7β-hydroxy-5α-lanostan-11-one.     

Mass spectral identification of isomeric fluoronitroanilines

The electron impact and methane chemical ionization mass spectra of 2-fluoro-5-nitroaniline and 4-fluoro-3-nitroaniline have been investigated. Similar fragment ions were observed for both compounds under electron impact conditions, but the difference in the relative ion intensities of two key fragment ions allowed the positive identification of these two isomers. The difference can be attributed to an ortho effect involving fluorine and the amino substituent. A fragmentation pathway consistent with this observation is suggested.     

Mass spectral aspects of 7-phenacylxanthopterins

7-Phenacylxanthopterin and its para-substituted derivatives, which exist in the chelate rign form initially lose CO from pyrazine rings followed by a hydrogen atom. This ion can also be formed in the reverse order, but not for the 4-amino analogues. Fragmentation of the intramolecularly hydrogen bonded sidechain also occurs involving loss of a benzoyl or phenyl radical. Linear plots at 40 eV for the loss of the benzoyl radical were obtained for log (Z/Z₀) against the Hammet σ constants not only for the fragmentation of the xanthopterins but also for that of the amino analogues.     

Studies on azaspiracid biotoxins. II. Mass spectral behavior and structural elucidation of azaspiracid analogs

In this report, the mass spectral analysis of azaspiracid biotoxins is described. Specifically, the collision-induced dissociation (CID) behavior and differences between CID spectra obtained on a triple-quadrupole, a quadrupole time-of-flight, and an ion-trap mass spectrometer are addressed here. The CID spectra obtained on the triple-quadrupole mass spectrometer allowed the classification of the major product ions of the five investigated compounds (AZA 1-5) into five distinct fragment ion groups, according to the backbone cleavage positions. Although the identification of unknown azaspiracids was difficult based on CID alone, the spectra provided sufficient structural information to allow confirmation of known azaspiracids in marine samples. Furthermore, we were able to detect two new azaspiracid analogs (AZA 1b and 6) in our samples and provide a preliminary structural analysis. The proposed dissociation pathways under tandem mass spectrometry (MS/MS) conditions were confirmed by a comparison with accurate mass data from electrospray quadrupole time-of-flight MS/MS experiments. Regular sequential MS(n) analysis on an ion-trap mass spectrometer was more restricted in comparison to the triple-quadrupole mass spectrometer, because the azaspiracids underwent multiple [M + H - nH(2)O](+) (n = 1-6) losses from the precursor ion under CID. Thus, the structural information obtained from MS(n) experiments was somewhat limited. To overcome this limitation, we developed a wide-range excitation technique using a 180-u window that provided results comparable to the triple-quadrupole instrument. To demonstrate the potential of the method, we applied it to the analysis of degraded azaspiracids from mussel tissue extracts.     

Mass spectral studies of N,N-dialkylaminoethanols

Some dialkylaminoethanols, precursors of chemical warfare agents such as V-agents and nitrogen mustards, were analyzed by electron impact (EI) and electrospray ionization (ESI) mass spectrometry. The fragmentation pathways in EI and ESI-MS/MS methods are rationalized. The collision-induced dissociation (CID) spectra of [M+H](+) ions of aminoethanols in ESI mode are clearly distinguishable from one another, including those of isomeric normal and branched chain dialkylaminoethanols. Structures can be proposed based on the general fragmentation pathways of these molecules.     

Mass spectral fragmentation of benzofurazan-1-oxide

Fragmentations in the mass spectrum of benzofurazan-1-oxide have been studied using linked scan, accelerating voltage scan and mass-analysed ion kinetic energy spectrometric techniques. Major pathways involve NO·+ NO· and NO·+CO loss, these double losses occurring in such rapid succession as to appear ‘concerted’ in some experiments. Minor pathways are loss of CO₂, C₂N₂O₂, or C₂HN₂O₂ from the molecular ion. The major fragment ion, m/z 76, in the conventional mass spectrum is not detected in a mass-analysed ion kinetic energy spectrometric experiment with the molecular ion until collision activation is provided. The conventional electron impact spectrum invariably includes ions from benzofurazan which is produced by thermal deoxygenation in the source.     

Mass spectrometry of nitrogen heterocycles. 4. Mass spectral behavior of triazolo[1,5-a]pyrido[2,3-d]pyrimidines

The electron impact mass spectra of substituted 9-imino- and 9-oxotriazolo[1,5-a]pyrido[2,3-d]pyrimidines were studied. The mass spectral data obtained permitted us to determine the order of the fusion of the triazole, pyrimidine, and pyridine rings as well as the position of the hydrogen atoms at the heteroatoms. Compounds labelled with ¹⁵N and ¹³C atoms were used to check the assignments made.For Communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 116–120, January, 1992.     

Mass spectral fragmentation of some phosphaaromatic compounds

The behaviour of 2-phosphanaphthalene, 3-methyl-phosphanaphthalene and 10-methyl-9-phosphaanthracene upon electron-impact has been compared with that of the carbon and nitrogen analogues. A close resemblance to the fragmentation pattern of the [M ? H]+ ions of 2-methyl-and 2-ethylbenzo[b]thiophene has been observed. It is concluded from the σ₄₀ intensities of the molecular ions, the relatively high intensities of the doubly charged molecular ions and the fragmentation patterns, that these phosphorin derivatives behave as aromatic compounds under electron-impact. From the molecular ion of 2-phosphanaphthalene a remarkable expulsion of a phosphours atom is observed.