Mass spectrometric study of some protonated and lithiated 2,5-disubstituted-1,3,4-oxadiazoles

The mass spectrometric behavior of lithiated derivatives of 2,5-disubstituted-1,3,4-oxadiazoles has confirmed the skeletal rearrangement presented earlier for protonated derivatives. In the case of [M + H](+) ions the loss of isocyanic acid was observed and for [M + Li](+) ions the loss of lithium isocyanate occurred. On the other hand, benzoyl ions [RCO](+) were formed from [M + H](+) ions, but not from [M + Li](+) ions. Formation of benzoyl ions was in agreement with the differences between bond orders calculated for [M + H](+) ions and neutral molecules. From [M + Li](+) ions the [RCNLi](+) fragment ions were formed, but the formation of [RCNH](+) fragment ions from [M + H](+) ions was not observed. This result can be explained on the basis of theoretically calculated stabilities of these fragment ions, since the calculated heats of formation of [RCNLi](+) ions were found to be substantially lower than those of the respective [RCNH](+) ions.     

Mass spectrometric study of organocyclosiloxanes

Organocyclosiloxanes of various chemical structures were studied by mass spectrometry using different ionization methods. The electron ionization mass spectra contain no peaks of molecular ions, and the main fragment ions are formed due to complicated rearrangements in a molecular ion, which provides no comprehensive view about the molecular structure. The desorption spectra exhibit peaks of quasimolecular and fragment ions, which characterize both molecular weights and chemical structures of the compounds under study. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1746–1749, September, 2007.     

喜树碱及其类似物的质谱研究

本文对喜树碱及其类似物进行了质谱研究,阐明了它们在电子轰击下的裂解规律,对同类型新生物碱和药物代谢产物的结构鉴定提供依据。     

Mass spectrometric study of α-carbolines

A series of -carbolines were subjected to mass-spectrometric analysis. It is shown that these compounds are extremely stable with respect to electron impact. From 40 to 60% of the total ion current goes into the production of molecular ions during dissociative ionization. The mass spectra of these compounds are simple: the maximum peak corresponds to the molecular peak in the spectrum. The formation of the [M-1]⁺ ion and the detachment of a methyl group in monomethylcarbolines ([M-15]) are determined by the position of the methyl group. The mass-spectral fragmentation confirms the proposed scheme for the formation of -carbolines from arylhydrazones and 6-keto nitriles. A method for the synthesis of -carbolines on the basis of accessible arylsulfamidoindoles is proposed.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1227–1234, September, 1980.     

Mass spectrometric study of 4-azafluorenes

The dissociative ionization of 4-azafluorene and its methyl and phenyl derivatives was investigated. The relative intensity of the [M — CH₃]⁺ ion peak depends on the position of the CH₃ group in the 4-azafluorene ring. It was established that the loss of an RCN particle (R=H, CH₃, and C₆H₅) for unsubstituted 4-azafluorene takes place from the M⁺ and [M — H]⁺ ion, exclusively from the [M — H]⁺ ion for the methyl-substituted compounds, and from the [M — H]⁺ and [H — 2H]⁺ fragments for the phenyl-substituted derivatives. Randomization of the deuterium ions in the 9,9-d₂-4-azafluorene molecular ion was observed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–250, February, 1978.     

Mass spectrometric study of desoxyamino sugars

Conclusions The mass spectra of ten 3,4-didesoxy-3-amino sugars have been studied. A novel type of ring cleavage was detected in the molecular ions of these compounds, which had not been encountered in previously studied sugar derivatives.Translated from Izvestiya Akademii Nauk, SSSR Seriya Khimcheskaya, No. 2, pp.437–439, February, 1970.     

Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.     

Mass spectrometric study of 8-nitroisoxazolizidines

The mass spectra of dimethyl- and methylphenyl-8-nitroisoxazolizidines have been studied, and the possibility of establishing the position of the substituents on the basis of an analysis of these spectra has been shown. The main routes of the fragmentation of compounds of this class under the influence of electron impact are discussed.     

Mass spectrometric study of 2-azafluorenes

The fragmentation of 2-azafluorene and its methyl and phenyl-substituted derivatives was studied. It is shown that ejection of an RCN fragment (R=CH₃, C₆H₅) by the molecular ions leads to a more intense peak if R is in the 3 position of the azafluorene ring. It was established that, in contrast to the dissociative ionization of fluorene, all of the ions of which are formed from the (M-H)⁺ fragment, the fragmentation of 2-azafluorene and its derivative also takes place from the molecular ion. Randomization of the deuterium atoms attached to C₉ with the remaining hydrogen atoms was observed.Translated from Khimiya Geterotisiklicheskikh Soedinenii, No. 1, pp. 101–105, January, 1977.     

Porphyrins 34. Mass spectrometric study of ethane- and ethylene-bis-porphyrins

The mass spectral behavior of 1, 2-di (mesoetioporphyr inyl-1)- and 1, 2-di (mesooctaethylporphyrlnyl) ethanes and ethylenes, their Cu and Ni complexes, as well as Ni Schiff bases of 1, 2-di (mesooctaethylporphyrinyl)ethane complexes, under ionization by electron impact and bombardment by accelerated atoms, was studied. Peaks of molecular ions, for which the basic decomposition pathways were established on the basis of an analysis of the parent and daughter ions, were observed in the electron impact mass spectra of all these compounds.For Communication 29, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 24–29, January, 1994.     

Mass spectrometric study of derivatives of adamantane

Conclusions The mass spectra of adamantane derivatives, substituted at C-2, possess characteristic features distinguishing them from the mass spectra of adamantane derivatives substituted at C-1.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 337–342, February, 1972.     

Mass spectrometric fragmentation of the tautomers of 1,3-diketones. A gas chromatographic/mass spectrometric study

The diketo and ketoenol tautomers of aliphatic 1,3-diketones can be easily separated by gas chromatography. The mass spectra of tautomers of pentane-2,4-diones substituted at C(l) and C(3), separated in this way, have been obtained. The fragmentation mechanisms are discussed. The mass spectra of the tautomers are quite different, and the main fragmentation pathways can be easily linked to the structures of the (non-interconverting!) tautomeric molecular ions. Furthermore, isomers differing by the position of the substituent can also be identified by their mass spectra.     

Mass spectrometric study of fluorinated β-diketones

Mass spectrometry has been applied in an investigation of fluorinated -diketones and the decomposition of these compounds under electron impact. It has been shown that there is a possibility that intramolecular hydrogen bonds of the -H...O= and-H...F- types may exist in the fluorinated -diketones and the products of their decomposition in the gas phase, these bonds playing an important role in the mechanism of fragmentation. The formation of cyclic structures in this process is postulated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 2, pp. 182–187, March–April, 1985.