Mass-spectrometric study of the cyclization of diazo compounds. 9. 2-Diazo-2-cyanoacetamides

An analysis of the electron impact mass-spectra of 2-diazo-2-cyanoacetamides and the 4-cyano-5-hydroxy-1,2,3-triazoles isomeric to them, showed that the molecular ions of these compounds do not isomerize one into another. The diazo compounds decompose, undergoing a Wolff rearrangement. To study the fragmentation of the diazoamides, one can use the crystalline adducts of these diazo compounds with triphenylphosphine, and to study the fragmentation of the triazoles, their salts with aliphatic amines.See [1] for No. 8 in the series.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1343–1349, October, 1986.     

Mass-spectrometric study of the cyclization of diazo ketones. 2. Cyclization of 1-diazo-4-sulfonylaminobutan-2-ones to N-sulfonylpyrrolidin-3-ones

A comparison of the mass spectra of 1-diazo-4-sulfonylamino-butan-2-ones and N-sulfonylpyrrolidin-3-ones makes it possible to conclude that under the conditions of electron impact and chemical ionization the molecular ions of the investigated diazo ketones lose a molecule of nitrogen and undergo partial cyclization to the corresponding pyrrolidinones without undergoing the Wolff rearrangement.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–925, July, 1982.     

Mass spectra of negative ions of aliphatic ω-oxocarboxylic acid derivatives

Conclusions Fragmentation of the molecules of methyl esters of aliphatic -oxocarboxylic acids upon dissociative capture of electrons includes processes of fragmentation that are characteristic for each functional group individually. It has been established that terminal functional groups separated by a saturated chain of four carbon atoms will interact, thus demonstrating that this molecule can exist in the folded conformation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2238–2246, October, 1984.     

Mass-spectrometric study of the cyclization of diazo ketones. 1. Cyclization of 1-diazo-3-sulfonylaminopropan-2-ones to N-sulfonylazetidin-3-ones

A comparison of the mass spectra of 1-diazo-3-sulfonylaminopropan-2-ones and N-sulfonylazetidin-3-ones makes it possible to conclude that under the conditions of electron impact and chemical ionization the molecular ions of diazo ketones lose a molecule of nitrogen and undergo partial cyclization to the corresponding azetidinones without undergoing the Wolff rearrangement.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 334–342, March, 1982.     

Mass spectra of the negative ions of some dioxanes

It was established by mass spectrometry of negative ions that fragmentation of some 1,3- and 1,4-dioxanes proceeds through intermediate [M-H]⁻ ions. The fragmentation pathway depends on the site of negative charge localization in these ions. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2199–2201, November, 1999.     

Mass spectra of the negative ions of some steroids

It has been shown that the main directions of the fragmentation of the molecular negative ions are connected with the formation of systems of conjugated bonds and the delocalization of the negative charge over a π-system of electrons. The mass spectrometry of the negative ions formed by the dissociative capture of electrons (DCE) is promising for the study of the molecules of steroid compounds.     

Mass spectra of negative ions of anabasine and esters of lupinine

Conclusions The mass spectra of negative ions of anabasine derivatives and lupinine esters have been studied. The resonance capture of slow electrons to form both fragmentary and molecular ions strongly depends on the donor-acceptor properties of the substituents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2249–2253, October, 1981.     

Mass spectra of negative ions of condensed aromatic hydrocarbons and biphenyl

Conclusions The positions of the maxima of the effective yield of the (M-H)^– ions on the energy scale of the electrons for condensed hydrocarbons and biphenyl coincide with the maximum yield of the (M-H)^– ions for benzene. The existence of a molecular ion M^–, with a life span with respect to autoionization of 21sec, was observed for anthracene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1885–1886, August, 1973.     

Mass-spectrometric study of the cyclization of diazo ketones. 3. Cyclization of o-(p-phenylsulfamoyl)-ω-diazoacetophenones to N-(p-phenylsulfonyl) indoxyls

A comparison of the mass spectra of o-(p-phenylsulfamoyl)--diazoacetophenones and N-(p-phenylsulfonyl)indoxyls makes it possible to conclude that under the conditions of electron impact and chemical ionization the molecular ions of the examined diazo ketones lose a molecule of nitrogen and under cyclization to the corresponding N-substituted derivatives of indoxyls without undergoing the Wolff rearrangement.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1056–1063, August, 1982.     

Mass spectra of negative ions from thiophane and its alkyl derivatives

The mass spectra of the negative ions from the dissociative capture of electrons were obtained for thiophane and its alkyl derivatives. With a few exceptions, all of these negative ions of the spectrum contain sulfur atoms: electron capture is not observed in cyclic compounds — cyclopentane and methylcyclopentane. The principle routes of dissociation during electron capture were isolated for thiophane and alkylthiophanes and explain the greater portion of the observed lines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1631–1632, December, 1971.     

Heterocyclization of compounds containing diazo and cyano groups. 3. Two pathways in the cyclization of 2-diazo-2-cyanoacetic acid derivatives under the influence of bases

1,2,3-Triazol-5-olates are formed in the reaction of diazomalonodiamide and 2-diazo-2-cyanoacetic acid amide and N-methylamide with sodium ethoxide, triethylamine, and ammonia. The products of the reaction of 2-diazo-2-cyanoacetamide with primary amines are mixtures of 4-cyano-1,2,3-triazol-5-olates and 5-amino-1-alkyl-1,2,3-triazole-4-carboxamides.See [1] for communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 926–931, July, 1986.     

Rhodium(II)-catalyzed cyclization of amido diazo carbonyl compounds

A series of acyclic diazo ketoamides were prepared from N-benzoyl-N-alkylaminopropanoic acids and were treated with a catalytic amount of rhodium(II) acetate. The resultant carbenoids underwent facile cyclization onto the neighboring amide carbonyl oxygen atom to generate seven-membered carbonyl ylide dipoles. Subsequent collapse of the dipoles with charge dissipation produce bicyclic epoxides which undergo further reorganization to give substituted 5-hydroxydihydropyridones in good yield. Depending on the nature of the substituent groups, it was possible to trap some of the initially formed carbonyl ylide dipoles with a reactive dipolarophile such as DMAD. In other cases, cyclization of the dipole to the epoxide is much faster than bimolecular trapping. A related cyclization/rearrangement sequence occurred when diazo ketoamides derived from the cyclic pyrrolidone and piperidone ring systems were subjected to catalytic quantities of Rh(II) acetate. With these systems, exclusive O-cyclization of the amido group onto the carbenoid center occurs to generate a seven-ring carbonyl ylide dipole. Starting materials are easily prepared, and the cascade sequence proceeds in good yield and does not require special precautions. The overall procedure represents an efficient one-pot approach toward the synthesis of various indolizidine and quinolizidine ring systems.