Mass-spectrometric study of benzopyridosilaazepines and -azepinones

The influence of various structural factors on the dissociative ionization of benzopyridosilaazepines and -azepinones has been investigated. It has been shown that the mass spectra can be used to identify isomeric benzopyridosilaazepinones with respect to the position of the amide fragment in the central heterocycle. The anomalously high intensity of the ion [M-H]⁺ in the mass spectra of these compounds is attributed to fragmentation of the molecular ions from the open form.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 704–707, May, 1986.     

Secondary ion mass spectra of organic cationic dyestuffs

Rules for the behavior under fast atom bombardment (FAB) have been established for 15 cationic dyes — quaternary ammonium salts of heterocyclic amines and heterocycles containing quaternary nitrogen atoms with aliphatic substituents. Intense peaks corresponding to the molecular mass of the cationic part of the dyes [M-Hal]⁺ are observed in the spectra of all the derivatives. Fragmentation of the azodyes is determined by the azo group and the heterocyle. The base peaks in the case of compounds containing a quaternary nitrogen atom with aliphatic substituents correspond to the ammonium ion and a fragment of amine type. The results obtained can be used to identify dyes of unknown structure from their secondary ion mass spectra (SIMS).DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1411–1417, October, 1992     

Electron-ionization-induced fragmentation of N-monosubstituted 2-phenylacetamides

Electron-ionization-induced mass spectra of N-monosubstituted 2-phenylacetamides were recorded and their fragmentation patterns were studied by metastable-ion analyses. Representative deuterated analogues of these compounds have also been synthesized and their mass spectra compared with those of the unlabelled parent compounds. The most typical fragmentation for N-alkyl-, N-isoalkyl- and N-cycloalkyl-2-phenylacetamides is cleavage of the bond alpha to the carbonyl function, resulting in an ion fragment of m/z 92, following the transfer of hydrogen and elimination of a corresponding ketene. The primary fragmentation process for N-aryl substituted 2-phenylacetamides is the loss of an aromatic hydrogen atom from the molecular ion. The other principal fragmentation processes observed with these compounds are discussed.     

Alkaloids of a new type fromSophora alopecuroides L.

Summary The structures of aloperine and allylaloperine (fromSophora alopecuroides L.) — alkaloids of a new structural type for the genusSophora — have been established by chemical and spectral methods. A number of parameters, NMR spectra, and mass spectra characterizing this class of compounds has been obtained. The partial synthesis of allylaloperine has been performed.All-Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 30–37, January–February, 1975.     

Mass-spectrometric study of 2- and 4-azafluorenones

A mass-spectrometric study of 2- and 4-azafluorenones and their mono- and polymethyl derivatives showed that the presence of a methyl group in the benzene ring leads to a sharp increase in the relative intensity of the [M — H]⁺ ion peak. In contrast to the fragmentation of 2- and 4-azafluorenes, the mass spectra of monomethyl-substituted compounds do not contain an [M — CH₃]⁺ fragment; this is probably associated with expansion of the pyridine or benzene ring to a seven-membered ring in the step involving the formation of the molecular ion due to inclusion of the methyl group. The intensity of the [M — CO]⁺ ion peak in the mass spectra of the 4-azafluorenones is higher by a factor of two with respect to the 2-azafluorenone isomers, and the [M — HCN]⁺ and [M — H, -HCN]⁺ ion peaks observed in the mass spectra of 2-azafluorenones are absent in them.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 89–95, January, 1979.     

Software improvements for gas chromatography-mass spectrometry-calculator system used in the analysis of trace organic compounds from environmenta samples

Computer programs are described which have significantly increased the capabilities of a low-cost gas chromatogaphy-mass spectrometry (GC-MS)-calculator system. These programs allow storage on floppy disk of ion abundance and retention time data for the total ion current and as many as six mass chromatograms in addition to mass spectra taken at the top of eluting GC peaks. Manufacturer-supplied software was only capable of storing the mass spectra. Ion abundance data may be displayed by means of a flexible, interactive program which uses an x–y plotter. Both qualitative and quantitative analyses may be performed for selected compounds in a single GC-MS run. Examples of the use of this software in the analysis of benzene extracts of incinerator fly-ash samples are presented.     

Doubly charged ion mass spectra of organophosphorus compounds

Doubly charged ion mass spectra have been obtained for 11 organophosphorus compounds. Methane has been used as a target gas to increase the probability of single electron transfer collisions in the first field-free region of an Hitachi RMU-7L mass spectrometer. In general, the spectra of organophosphorus compounds do not exhibit molecular ions but are dominated by fragment ions, many of which must be formed by rearrangement processes. A geometry-optimized self-consistent field molecular orbital method has been employed to compute energies and structural parameters for prominent ions. In addition, a diabatic curve crossing model has been used to examine the single electron transfer reactions responsible for intense ions in the doubly charged ion mass spectra. Appearance energies measured for ions prominent in the 2E spectra of organophosphorus compounds have ranged from 23 to 38 eV.     

Mass spectrometric study of isomeric coordination compounds of nickel(II) with octaazamacrocyclic ligands based on SR-isothiocarbohydrazide and unsymmetrical α-dicarbonyl compounds

A study has been made of isomeric complexes of nickel(II) with octaazamacrocyclic ligands based on SR-isothiocarbohydrazide and unsymmetrical -dicarbonyl compounds, and also their deuterio analogs. It has been found that the mass spectra of such compounds become more characteristic with increasing energy of the ionizing electrons. Overall paths of fragmentation have been proposed, as well as a scheme for interconversion of structural isomers due to delocalization and migration of the metal-ligand bond in the gas phase under electron impact. Feasibility has been demonstrated for identification of isomers of the basis of the character of fragmentation.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 311–316, May–June, 1989.     

Field desorption mass spectra of flavonoid acylglycosides. I. Natural acetyl derivatives

The field desorption mass spectra (FD spectra) of 17 natural flavonoid acetylglycosides have been studied. In the spectra of each of the 0-monoglycosides the molecular ion (M or M + H) appears as the main peak and it is accompanied by the ions of the aglycone (A or A + H) and of the acylated anhydrosugar (S). The intensity of the latter peak is largely connected with the structure of the substance. In the FD spectra of flavone 0-biosides, fragment S is absent but its mass can be calculated from the difference (M – A). Useful information for establishing the position of the acetyl group is given by the fragments S₁ and (M – S₁) corresponding to the detachment of the terminal sugar residue. The FD spectra of flavone C-glycosides differ greatly from the spectra of the 0-glycosides: In them the main peak is that of the ion (M), but peaks (A) and (S) are absent and the ions present resemble the fragmentation of the C-glycosides under the action of electron impact.All-Union Scientific-Institute of Medicinal Plants, Moscow. L. Ya. Karpov Scientific-Research Institute of Physical Chemistry, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 573–582, September–October, 1984.     

Characteristic and spectroscopic properties of the Schiff-base model compounds

Two series of conjugated aromatic imines (Schiff-base model compounds) with different central groups and various side-group substitutions have been synthesized and characterized by elemental analysis, differential scanning calorimetry (DSC) technique, hydrogen nuclear magnetic resonance (¹H NMR), Fourier transform infrared (FTIR) and ultra-violet and visible light (UV–vis) spectroscopy measurements. The UV–vis absorption of solutions of these compounds in dimethylacetamid (DMA), chloroform and methanol was investigated in the optical range from 240 to 450 nm, where two distinct absorption bands: at 250–280 and 315–360 nm with the different level of absorption have been observed. The influence of compound molecular structure and polarity of solvent on the absorption spectra and the possible optical transitions have been discussed. Structure of diamines in the azomethine models fundamentally affected their spectroscopic properties and conjugation of π-electrons.     

Doubly charged ion mass spectra 8—alkenes

Doubly charged ion mass spectra of 23 alkenes have been measured using a double focusing Hitachi RMU-7L mass spectrometer. Ion mass spectra were obtained using 100 eV electron energy and 3.2 kV ion accelerating voltage. Each 2E spectrum was determined using the olefinic compound under investigation as the target gas. In general, spectra are dominated by fragment ions which result from extensive hydrogen loss from the doubly charged molecular ion. Appearnce energies have been measured for intense fragment ions in each spectrum.     

Chimera Spectrum Diagnostics for Peptides Using Two-Dimensional Partial Covariance Mass Spectrometry

The rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra’, which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines. This calls for a diagnostic method able to identify chimera spectra to single out the cases where this assumption is not valid. Here, we demonstrate that, within the recently developed two-dimensional partial covariance mass spectrometry (2D-PC-MS), it is possible to reliably identify chimera spectra directly from the two-dimensional fragment ion spectrum, irrespective of whether the co-isolated peptide ions are isobaric up to a finite mass accuracy or isomeric. We introduce ‘3-57 chimera tag’ technique for chimera spectrum diagnostics based on 2D-PC-MS and perform numerical simulations to examine its efficiency. We experimentally demonstrate the detection of a mixture of two isomeric parent ions, even under conditions when one isomeric peptide is at one five-hundredth of the molar concentration of the second isomer.     

Electron-impact mass spectra of natural phenylethanoids

The electron-impact mass spectra of a number of phenylpropanoids and iridoid glycosides containing a phenylethanoid fragment in their structure have been studied. This has revealed features of the formation of fragments of 4-hydroxyphenylethyl and 3,4-dihydroxyphenylethyl alcohols and also of fragments of phenylethylamine and indolylethylamine derivatives present in the structures of the compounds investigated.Samara State Medical Institute. All-Russian Scientific Research Institute of Medicinal and Aromatic Plants Scientific Production Combine, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 506–509, July–August, 1994.     

Mass spectra of 1- and 2a-substituted 1,3,5,7-tetramethyl-2,4,6,8-tetrathiaadamantanes

A comparative analysis was made of the mass spectra of monosubstituted 1,3,5,7-tetramethyl-2,4,6,8-tetrathiaadamantanes (TMITA). It is shown that the pathways of monomolecular fragmentation depend on the character of the substituent and the isomeric form of the TMTTA. The principal lines in the mass spectra of the investigated compounds indicate the occurrence of competitive processes of fragmentation of the molecular ions (M⁺) with detachment of the substituent from the M⁺ ion or with cleavage of the cellular structure. The first process makes it possible to form a judgement regarding the mechanism of the fragmentation of the molecular ion and the site of primary localization of the charge on the fragment ions as a function of the donor—acceptor properties of the substituents, and the second process enables one to form a judgement regarding the character of the fragmentation of the cellular structures of the various isomeric forms.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 748–752, June, 1978.     

Complexes with metal-nitroxyl group coordination

This review covers research on coordination compounds of transition metals with stable nitroxyl radicals, in which the nitroxyl fragment is coordinated by the metal ion. Greatest attention is given to generalized aspects of the synthesis of compounds containing a metal-nitroxyl group bond and their magnetic properties in the solid state. Recent developments in the theoretical understanding of the magnetic properties of polycrystalline compounds of this class are discussed. The structure of these complexes and the nature of exchange interactions in them between unpaired electrons of various paramagnetic sites are examined. The review covers studies published in the period from 1980 to 1987. Earlier investigations were reviewed by Larionov [6].Institute of Inorganic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 142–165, September–October, 1989.     

二烷氧基膦酰乙酸酯的电子轰击正离子和化学电离负离子质谱研究

本文报道一系列二烷氧基膦酰乙酸酯的电子轰击(EI)正离子和甲烷化学电离负离子(NCI)质谱.在EI谱上出现特征的[M+H]^+离子,进一步发生氢重排,然后失去烯烃,再失水和脱CH2CO.而在NCI谱中则生成[M-H]^-离子(基峰),易失去烷基,再失烷氧基和CH2CO,或氢重排后脱烯烃.正、负离子的断裂机理不同,但数据可以互相补充,以利于类似未知物的结构分析.     

Mass-spectrometric identification of isomeric 1-benzoyl-2-azetidinones and 2-phenyl-4,5-dihydro-1,3-oxazin-6-ones

The mass spectra of isomeric 1-benzoyl-2-azetidinones and 2-phenyl-4,5-dihydro-1,3-oxazin-6-ones were analyzed. A more stable molecular ion and high intensities of the peaks of the ions formed from the molecular ion with the loss of ketene or a substituted ketene are characteristic for the former compounds, while low stability of the molecular ion and a higher probability of the loss of one of the groupings in the 4 position are characteristic for the latter compounds. Fragmentation schemes that are confirmed by the high-resolution mass spectra are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1627–1631, December, 1980.We sincerely thank E. Simova and C. Drey for providing us with samples of a number of the compounds.     

Resonance capture of electrons and photoelectron spectroscopy of the molecules of substituted anisoles and thioanisoles

In the electron resonance capture mass spectra of phenol, anisole, thioanisole, and their fluorinated analogs the resonances above 3.8 eV are electronically excited Fischbach resonances due to the excitation of the electron from several occupied MOs to one unoccupied MO. The mechanisms of the formation of the negative ions for these compounds are identical and do not depend on the nature of the heteroatoms. The low-energy resonances in the second energy region for PhR compounds (R=OH, OMe, SMe) correlate with the positions of the second singlet transitions. With thermal electron energies fluorinated anisoles are characterized by the formation of long-lived rearrangement ions. The absence of the rearrangement ion in fluorinated thioanisole can be explained by the energetically less favorable removal of the neutral CHF=S fragment compared with the CHF=0 fragment for fluorinated anisole.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1990.     

A program for generating empirical spectrum classification schemes

Programs are described which derive a set of compound classification tests from data specifying a required classification hierarchy and example low resolution mass spectra. The generated tests are expressed in terms of conventional operations such as searching for a molecular ion and checking for fragment ions. These tests can be used in a laboratory computer to give real-time classification of spectra collected by gas chromatography mass spectrometry.     

Mass-spectrometric study of ring-chain tautomerism in a series of substituted 4-hydroxyhexahydropyrimidine-2-thiones

In order to investigate the ring-chain tautomerism of substituted 4-hydroxyhexahydropyrimidine-2-thiones the mass spectra of a series of compounds of this group were studied. It is shown that equilibrium exists between the cyclic hydroxy form and the acyclic oxo form, which belongs to the oxoalkylthiourea class, in a series of 3-alkyl(aryl)-4,6,6-trimethyl derivatives in the gas phase. The mass spectra of these compounds contain intense peaks of [M-18]⁺ and [M-33]⁺ ions, which are formed as a result of the successive elimination of a water molecule and a methyl radical by the molecular ions. The fragmentation of 3-alkyl-4,5-dimethyl derivatives takes place from the open oxo form of the molecular ion with detachment of the terminal groups.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1273–1278, September, 1983.