TY - JOUR A1 - Shainyan, Bagrat A. A1 - Tolstikova, Ljudmila L. A1 - Schilde, Uwe T1 - Simple methods for the preparation of N-triflyl guanidines and the structure of compounds with the CF3SO2N=C-N fragment JF - Journal of fluorine chemistry N2 - Two novel and simple approaches to N-triflyl guanidines are elaborated. Owing to very strong conjugation the formally double C=N bond of TIN=C(NHR)(2) is longer than the formally single N-C bonds. Energetic effect of the triflylgroup on the conjugation in the N-C=N moiety is estimated to be >= 150 kcal/mol. KW - N-triflyl guanidines KW - Synthesis KW - Structure KW - X-ray KW - MP2 calculations Y1 - 2012 U6 - https://doi.org/10.1016/j.fluchem.2011.12.004 SN - 0022-1139 VL - 135 IS - 1 SP - 261 EP - 264 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Moskalik, Mikhail Yu A1 - Shainyan, Bagrat A. A1 - Astakhova, Vera V. A1 - Schilde, Uwe T1 - Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes JF - Tetrahedron N2 - In the oxidative system (t-BuOCl+NaI) trifluoromethanesulfonamide is regio- and stereoselectively added to only one double bond of cyclopentadiene and 1,3-cyclohexadiene giving rise to 1,1,1-trifluoro-N-(5-iodocyclopent-2-en-1-yl)methanesulfonamide 7 and trans-N,N'-cyclohex-3-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 8. The structure of 7 and 8 was determined by X-ray, NMR, and MS. With 1,4-cyclohexadiene, addition to both double bonds occurs with the formation of N,N'-(4-chloro-5-iodocyclohexan-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide) 9. Under the action of sodium iodide in acetone, the latter product undergoes halogenophilic attack with the reduction of the CHI group and elimination of HCl to give trans-N,N'-cyclohex-4-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 10, whose structure was also determined by X-ray analysis. 1,3,5-Cycloheptatriene under these conditions is oxidized to benzaldehyde and does not react with trifluoromethanesulfonamide. KW - Trifluoromethanesulfonamide KW - Cyclodienes KW - 1,2-Disulfonamides KW - Allylamides KW - X-ray Y1 - 2013 U6 - https://doi.org/10.1016/j.tet.2012.10.099 SN - 0040-4020 VL - 69 IS - 2 SP - 705 EP - 711 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Moskalik, Mikhail Yu. A1 - Astakhova, Vera V. A1 - Schilde, Uwe A1 - Sterkhova, Irina V. A1 - Shainyan, Bagrat A. T1 - Assembling of 3,6-diazabicyclo[3.1.0]hexane framework in oxidative triflamidation of substituted buta-1,3-dienes JF - Tetrahedron KW - Trifluoromethanesulfonamide KW - Arenesulfonamides KW - Cycloaddition KW - 1,3-Dienes KW - 3,6-Diazabicyclo[3.1.0]hexanes KW - X-ray Y1 - 2014 U6 - https://doi.org/10.1016/j.tet.2014.09.050 SN - 0040-4020 VL - 70 IS - 45 SP - 8636 EP - 8641 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Moskalik, Mikhail Yu A1 - Astakhova, Vera V. A1 - Schilde, Uwe T1 - Novel design of 3,8-diazabicyclo[3.2.1]octane framework in oxidative sulfonamidation of 1,5-hexadiene JF - Tetrahedron N2 - 1,5-Hexadiene reacts with trifluoromethanesulfonamide in the oxidative system (t-BuOCl+Nal) to give trans-2,5-bis(iodomethyl)-1-(trifluoromethylsulfonyl)pyrrolidine 5 and 3,8-bis(trifluoromethylsulfonyl)-3,8-diazabicyclo[3.2.1]octane 6. With arenesulfonamides ArSO2NH2 (Ar=Ph, Tol), the reaction stops at the formation of the trans and cis isomers of 2,5-bis(iodomethyl)-1-(arenesulfonyl)pyrrolidine 7 and 8 (1:1). The cis isomers of 7 and 8 do not undergo cyclization to the corresponding 3,8-disubstituted 3,8-diazabicyclo[3.2.1]octanes. The reaction with triflamide represents the first example of one-pot two-step route to 3,8-diazabicyclo[3.2.1]octane system. (C) 2014 Elsevier Ltd. All rights reserved. KW - Trifluoromethanesulfonamide KW - Arenesulfonamides KW - 1,5-Dienes KW - Cycloaddition KW - 3,8-Diazabicyclo[3.2.1]octane KW - X-ray Y1 - 2014 U6 - https://doi.org/10.1016/j.tet.2014.04.095 SN - 0040-4020 VL - 70 IS - 30 SP - 4547 EP - 4551 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Riebe, Daniel A1 - Eder, Alexander A1 - Ritschel, Thomas A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Beil, Andreas A1 - Blaschke, Michael A1 - Ludwig, Thomas T1 - Atmospheric pressure chemical ionization of explosives induced by soft X-radiation in ion mobility spectrometry: mass spectrometric investigation of the ionization reactions of drift gasses, dopants and alkyl nitrates JF - Journal of mass spectrometr N2 - A promising replacement for the radioactive sources commonly encountered in ion mobility spectrometers is a miniaturized, energy-efficient photoionization source that produce the reactant ions via soft X-radiation (2.8 keV). In order to successfully apply the photoionization source, it is imperative to know the spectrum of reactant ions and the subsequent ionization reactions leading to the detection of analytes. To that end, an ionization chamber based on the photoionization source that reproduces the ionization processes in the ion mobility spectrometer and facilitates efficient transfer of the product ions into a mass spectrometer was developed. Photoionization of pure gasses and gas mixtures containing air, N-2, CO2 and N2O and the dopant CH2Cl2 is discussed. The main product ions of photoionization are identified and compared with the spectrum of reactant ions formed by radioactive and corona discharge sources on the basis of literature data. The results suggest that photoionization by soft X-radiation in the negative mode is more selective than the other sources. In air, adduct ions of O-2 - with H2O and CO2 were exclusively detected. Traces of CO2 impact the formation of adduct ions of O-2 - and Cl -(upon addition of dopant) and are capable of suppressing them almost completely at high CO2 concentrations. Additionally, the ionization products of four alkyl nitrates (ethylene glycol dinitrate, nitroglycerin, erythritol tetranitrate and pentaerythritol tetranitrate) formed by atmospheric pressure chemical ionization induced by X-ray photoionization in different gasses (air, N-2 and N2O) and dopants (CH2Cl2, C2H5Br and CH3I) are investigated. The experimental studies are complemented by density functional theory calculations of the most important adduct ions of the alkyl nitrates (M) used for their spectrometric identification. In addition to the adduct ions [M + NO3](-) and [M + Cl](-), adduct ions such as [M + N2O2](-), [M + Br](-) and [M+ I](-) were detected, and their gas-phase structures and energetics are investigated by density functional theory calculations. Copyright (C) 2016 John Wiley & Sons, Ltd. KW - ion mobility spectrometry KW - mass spectrometry KW - explosives KW - X-ray KW - photoionization KW - alkyl nitrates Y1 - 2016 U6 - https://doi.org/10.1002/jms.3784 SN - 1076-5174 SN - 1096-9888 VL - 51 SP - 566 EP - 577 PB - Wiley-Blackwell CY - Hoboken ER -