Mass spectrometric behaviour of cyclopentane-and cyclohexane-condensed pyrimidinediones under electron impact

Mass spectral fragmentations of four cyclopentane-condensed cis-pyrimidinediones and of six cyclohexane-condensed cis- or trans-pyrimidinediones were examined using metastable ion analyses and exact mass measurements. The fragmentation patterns of all of these compounds were clearly different and also cis- and trans-fused isomers were easy to distinguish from each other by their mass spectra. In spite of the differences in their mass spectral fragmentations, all compounds formed phenylisocyanates (m/z 119 and 153) and anilines (m/z 93 and m/z 127), the structures of which were verified by collision-induced dissociation experiments.     

Mass spectrometric behaviour of simple oxazolidines under electron impact and chemical ionization

The 70 eV electron impact mass spectra of 33 differently substituted oxazolidines were studied to determine the effect of substituents and the existence of the ring—chain tautomeric equilibrium on the decomposition of the molecular ions. Most of the fragmentations can be rationalized to start as the cleavage initiated by the radical site at nitrogen. Isomeric compounds showed different spectra and were easily differentiated. The position of the ring—chain equilibrium could be located only roughly. The chemical ionization mass spectra of the compounds were also recorded, with ammonia, isobutane, acetone or methane as reagent gas. Methane was the only reagent gas that promoted extensive fragmentation of the protonated molecules. However, no information about the position of ring-chain tautomerism was obtained under these conditions. Analogously to other related five-membered heterocycles, the oxazolidines reacted under acetone chemical ionization conditions to afford [M + CH₃CO]⁺ adduct ions. These adducts were stable, however, and unlike those of 1,3-dioxolanes and 1,3-oxathiolanes, they did not decompose and form stable oxonium ions.     

Mass spectrometric characterization of substituted 2-thiazolin-4-one derivatives

Electron ionization mass spectrometry was used for the structural characterization of substituted 2-thiazolin-4-one derivatives in the gas phase. The compounds follow common fragmentation pathways, producing ions whose abundances are dependent on the chemical nature of the substituent at position 2. Collision-induced dissociation tandem mass spectrometric experiments, carried out on both molecular ions and fragment ions produced in the source, allowed the elucidation of gas-phase decompositions. The presence of tautomeric forms is suggested for some ionic species. Rapid identification of a primary or secondary amine moiety at position 2 of the thiazoline ring can be achieved by the detection of characteristic fragmentations occurring both in the ion source and under the collision-induced dissociation regime.     

The behaviour of some ferrocene derivatives under electron impact

The behaviour of some mono- and di-substituted ferrocene compounds under electron impact has been investigated by means of low-resolution mass spectrometry. Some characteristic rearrangement processes have been observed and discussed.     

Mass spectrometric studies of 2-aryl-5-acetylthiazole derivatives

Electron ionisation mass spectrometry was usefully used to characterize structurally 2-aryl-5-acetylthiazole derivatives in the gas phase. The compounds show characteristic fragmentation pathways depending on the chemical nature of the substituent at position 2, consisting mainly in the cleavage of both the 1,2- and 3,4-bonds of the thiazole ring. Liquid secondary ion mass spectrometry was applied to study the effects of protonation on the gas-phase unimolecular reactions of this class of compound. Tandem mass spectrometric experiments, carried out on molecular and protonated molecular ions, and also on fragment ions produced in the source, allowed the elucidation of gas-phase decompositions of low-internal energy ions.     

The mass spectrometric behaviour of benzohydroxaraic and benzothiohydroxamic acids under electron impact

Primary fragmentation reactions in benzohydroxamic and benzothiohydroxamic acids have been studied and compared with those in benzamides and benzothioamides. Mass-analysed ion kinetic energy spectra, collisional activation spectra and spectral data from labelled compounds were used to elucidate fragment ion structures and reaction mechanisms. The mass spectra are shown to be dependent on ion source temperature. Losses of O and H₂O are proved to be thermal in origin. The formation of an S… HO bond, which is analogous to an intramolecular hydrogen bond in solution chemistry, directs many fragmentation pathways. This seems to be the major factor determining the differences between the mass spectra of benzothiohydroxamic acids and those of the corresponding carbonyl compounds.     

Mass spectrometric study of thiocarbamoyl-substituted 2-aminothiazoles and 2-iminothiazolines. 1. Aliphatic derivatives

Electron impact mass spectra of 10 thioureido derivatives of thiazole amino- and iminostructure are studied. The main difference between them appears in the ratio of peak heights of the 2-aminothiazolyl (2-iminothiazoline) and thiazolyl(thiazolinylidene)-2-isothiocyanate ions. A series of decay processes is revealed which occur through rearrangement in the thioureide chain and upon rupture of bonds in the heterocycle.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 547–552, April, 1989.     

Mass spectrometric study of kaurene derivatives III. (?)-Kaurene and methyl esters of kaurenoic acids

Summary For subsequent analytical use of the laws of fragmentation, the mass spectra of (–)-kaurene (I) and its derivatives (II)-(VI) have been studied.N. D. Zelinskii Institute of Organic Chemistry of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 281–286, May–June, 1971.     

Mass spectrometric characterization of different norandrosterone derivatives by low-cost mass spectrometric detectors using electron ionization and chemical ionization

The abuse of nortestosterone in sport is an important problem in doping-control analysis. In order to detect the main urinary metabolite of nortestosterone, norandrosterone (NA), sensitive and specific methodology is necessary. In this context the use of a low-cost mass spectrometric detector such as the Finnigan MAT ion-trap detector (ITD) was studied. The electron ionization (EI) and positive-ion chemical ionization (PICI) mass spectra of the methoxime-trimethylsilyl, trimethylsilyl-enol trimethylsilyl ether and pentafluoropropionic ester derivatives of NA are described. The limits of detection of these derivatives are compared with those obtained by the Hewlett-Packard mass selective detector (MSD), another low-cost mass spectrometric detector and operating only in the EI mode. For the derivatives of the reference standard of NA the ITD has in the EI mode the same limit of detection, in the range of 0.5 to 1 ng injected on the column, as the MSD. However, under these conditions the ITD provides more spectrometric information, because it gives full scan data. Moreover, with the same or even improved limits of detection the ITD can operate in the PICI mode. On the other hand, for the analysis of NA isolated from urine samples, the performance of the MSD was better than that of the ITD. The ion trapping technique is probably limited when the chemical background is high.     

Mass spectrometric study of the dissolution behaviour of sanidine

Secondary ion mass spectrometry has been used to measure the silicon isotope ratio as a function of depth in feldspars after their interaction with dilute acid solutions. The reaction of feldspars with aqueous solutions implies the formation of relatively thick K, Na and Al depleted surface layers, especially when the dissolution experiments are conducted in the presence of silica powder. The latter is used to lower the silicon concentration gradient at the solid-solution interface. This generates an uncertainty in the interpretation of the results: the depleted surface layer may have been formed by leaching of the above-mentioned elements from the solid, or by precipitation of silica from the solution. Measurements using isotopically enriched silica powder (³⁰SiO₂) were therefore performed in the hope that they would solve the uncertainty. The measured silicon isotope ratio at the surface of the mineral appears to be different from its normal terrestrial value and from the enriched powder value, having a value somewhere in between which decreases towards its normal value as a function of depth. In addition the silicon isotope ratio of the solution, which was measured using thermal ionization mass spectrometry, shows an altered value compared with the enriched silica powder. The results of both analyses therefore indicate an exchange in silicon between solid and solution and suggest the combination of two or more mechanisms during dissolution.     

Regioselective syntheses, structural characterization, and electron ionization mass spectrometric behavior of regioisomeric 2,3-disubstituted 2-imino-1,3-thiazolidin-4-ones

The regioselective syntheses of 3-alkyl(aryl)-2-(anthracen-9'-ylimino)-1,3-thiazolidin-4-ones (2) and 2-alkyl(aryl)imino-3-(anthracen-9'-yl)-1,3-thiazolidin-4-ones (3) from N-(anthracen-9-yl)-N'-alkyl(aryl)thioureas were accomplished effectively using methyl bromoacetate and bromoacetyl bromide, respectively. Detailed structural characteristics were confirmed mainly by NMR techniques. The mass spectrometric behavior of the resulting sets of compounds of known structures was shown to be characteristic for each set. Some interesting fragmentation pathways involving the transfer and rearrangements of various moieties were also revealed, as well as regioisomerization for particular substituent-specific fragmentations.     

Mass spectrometric study of 2-keto(thio)tetrahydropyrimidine derivatives

The fragmentation pathways of 2-keto(thio)-6-methyl-5-carbethoxy(acetyl)-4-aryl-1,2,3,4-tetrahydropyrimidines were established using high resolution mass spectra and DADI spectra. An unusual rearrangement was observed, which involves cyclization of the aryl substituent in the 4 position with the oxygen of an ester group and elimination of a C₂H₅ radical.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 360–365, March, 1989.     

Mass spectrometric study of 2- and 4-silalactones

In contrast to the previously investigated 1-silalactones, ejection of a CO₂ molecule from the molecular ion is not characteristic in the disintegration of 2- and 4-silalactones under electron impact. Migration of the silicon atom to the oxygen atom during fragmentation of the 2- and 4-silalactones was observed. The dependence of the paths of disintegration of the silalactones on the ring size and the number of methylene links was established. The possibility of the identification of isomeric 2-silalactones on the basis of their mass spectra was observed.     

Mass spectrometric study of isatins III. Isatin and N-methylisatin ketals

In contrast to isatin and N-methylisatin, their ethylene-, propylene-, and 2,3-butyleneketals undergo fragmentation via several pathways. In addition to the principal fragmentation pathway — successive loss by the molecular ion (M⁺) of a CO group and a dioxolane ring or its fragment, the M⁺ ions of the ketals are also fragmented with elimination of a dioxolane fragment or the substituent attached to the nitrogen atom and, subsequently, a fragment of the dioxolane ring. The fragmentations of some of the fragment ions were investigated by means of the mass spectra of N-trideuteromethyl analogs.See [2] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 642–645, May, 1977.     

Synthesis of derivatives of 4-imino-2-amino-2-imidazoline. New example of a multicomponent condensation involving isonitriles

Isonitriles have been found to react with ketones and ammonium and methylammonium thiocyanates in methanol or ethyleneglycol at 20 °C to form derivatives of 4-imino-2-amino-2-imidazoline and 2,4-diaminoimidazolium salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 53–61, January, 1986.     

Design,synthesis and evaluation of PPAR gamma binding activity of 2-thioxo-4-thiazolidinone derivatives

We designed and synthesized a series of 2-thioxo-4-thiazolidinone derivatives and evaluated them on peroxisome proliferator activated receptor γ(PPARγ) binding activities.Through the biological assays,compounds 18 and 38 were highlighted with K_i values of 12.15 nmol/Land 14.46 nmol/L,respectively.Then structure-activity relationship(SAR) was analyzed to screen privileged structural modifications.Moreover,molecular fitting of these compounds onto the approved drug Rosightazone in the PPARγligand binding domain was performed to elucidate the SAR and explore potential receptor-ligand interactions.These results demonstrate that the 2-thioxo-4-thiazolidinones can be considered as new promising molecular probes with excellent binding activities to PPARγ.