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排序方式: 共有114条查询结果,搜索用时 21 毫秒
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2.
Synthesis of 2‐Unsubstituted 1,3‐Selenazoles by Cyclization of Selenoformamide with α‐Bromocarbonyl Compounds 下载免费PDF全文
Harald Below Wolf‐Diethard Pfeiffer Karlheinz Geisler Ashot S. Saghyan Christine Fischer Peter Langer 《Journal of heterocyclic chemistry》2015,52(2):592-596
2‐Unsubstituted 1,3‐selenazoles were prepared by cyclization of selenoformamide with α‐bromoacetophenones. Parent 1,3‐selenazole was prepared by cyclization of selenoformamide with α‐bromoacetaldehyde. 相似文献
3.
Voislav Blagojevic Sopeia N. Samad Laura Banu Michael C. Thomas Stephen J. Blanksby Diethard K. Bohme 《International journal of mass spectrometry》2011,299(2-3):125-130
Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and α-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also, Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly, Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion [Ag2(L–H)]+ where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I). 相似文献
4.
Cyclization of 4‐Phenylthiosemicarbazide with Phenacylbromide Revisited. Formation of 1,3,4‐Thiadiazines and of Isomeric 1,3‐Thiazoles 下载免费PDF全文
Wolf‐Diethard Pfeiffer Dieter Junghans Ashot S. Saghyan Peter Langer 《Journal of heterocyclic chemistry》2014,51(4):1063-1067
The cyclization of 4‐phenylthiosemicarbazide with phenacylbromide, carried out in refluxing ethanol, afforded 1,3,4‐thiadiazine 1 as the major product. In contrast to a previous report, 2‐phenylimino‐4‐phenyl‐2,3‐dihydro‐1,3‐thiazol‐3‐amine ( 2 ) and not 2‐hydrazono‐3,4‐diphenyl‐2,3‐dihydro‐1,3‐thiazole ( 8 ) was formed as a side‐product. This product is the main product when the reaction is carried out in concentrated hydrochloric acid. Our findings were independently confirmed by independent syntheses of the isomeric products and by a thorough study of their reactivity. It is important to note that the product distribution of the cyclization of thiosemicarbazides with haloketones strongly depends on the substitution pattern and on the reaction conditions. 相似文献
5.
Unexpected Ring Enlargement of 2‐Hydrazono‐2,3‐dihydro‐1,3‐thiazoles to 1,3,4‐Thiadiazines 下载免费PDF全文
Wolf‐Diethard Pfeiffer Klaus‐Dieter Ahlers Ashot S. Saghyan Alexander Villinger Peter Langer 《Helvetica chimica acta》2014,97(1):76-87
The cyclization of thiosemicarbazide with α‐bromoacetophenone can result in the formation of isomeric 1,3,4‐thiadiazines and two different thiazoles. We studied the use of 4‐methyl‐ and 4‐ethylthiosemicarbazide as dinucleophilic building blocks. In this context, we observed an unprecedented rearrangement of a 2‐hydrazono‐2,3‐dihydrothiazole to a 1,3,4‐thiadiazine. While ring contractions of 1,3,4‐thiadiazines to thiazoles are quite common, ring enlargements are new. The course of the reaction depends on the substitution pattern of the substrate. 相似文献
6.
Christina Haberhauer-Troyer Marizela Delic Brigitte Gasser Diethard Mattanovich Stephan Hann Gunda Koellensperger 《Analytical and bioanalytical chemistry》2013,405(6):2031-2039
A novel method for the simultaneous quantification of both glutathione (GSH) and its oxidized form glutathione disulfide (GSSG) by hydrophilic interaction chromatography–MS/MS has been developed and is critically discussed. Internal standardization based on isotopically labeled standards for both analytes is an absolute prerequisite for accurate quantification of this redox pair. Hence, a highly efficient and selective miniaturized procedure for the synthesis of isotopically labeled GSSG from commercially available glutathione-(glycine-13C2,15N) was established using H2O2 as oxidant and NaI as catalyst. Moreover, a tool is presented to monitor and hence uncover artifactual GSSG formation due to oxidation of GSH during sample preparation, which is the main source of systematic error in GSSG analysis. For this purpose, we propose to monitor the oxidation product formed by reaction of naturally occurring GSH with the isotopically labeled GSH used as internal standard. For the determination of GSH/GSSG ratios in yeast, different extraction methods based on (1) hot extraction with aqueous, acidic, or organic solvents, (2) mechanical cell lysis, and (3) extraction at subambient temperature were investigated in terms of recovery, extraction efficiency, and artifactual formation of GSSG. Total combined uncertainties of as low as 25–30 % (coverage factor?=?2) for the determination of GSH/GSSG ratios without derivatization were made possible by the addition of the internal standards early in the analytical procedure (before extraction) and immediate analysis of the analytes. 相似文献
7.
8.
Zhao X Flaim E Huynh L Jarvis MJ Cheng P Lavrov VV Blagojevic V Koyanagi GK Bohme DK 《Inorganic chemistry》2006,45(24):9646-9653
Results are reported for experimental measurements of the room-temperature chemical reactions between ground-state Hg*+ ions and 16 important environmental and biological gases: SF6, CO, CO2, N2O, D2O, CH4, CH3F, O2, CH3Cl, OCS, CS2, NH3, C6F6, NO2, NO*, and C6H6. The inductively coupled plasma/selected-ion flow tube tandem mass spectrometer used for these measurements has provided both rate and equilibrium constants. Efficient electron transfer (>19%) is observed with CS2, NH3, C6F6, NO2, NO*, and C6H6, molecular addition occurs with D2O, CH4, CH3F, CH3Cl, and OCS, and SF6, CO, CO2, N2O, and O2 showed no measurable reactivity with Hg*+. Theory is used to explore the stabilities and structures of both the observed and unobserved molecular adducts of Hg*+, and reasonable agreement is obtained with experimental observations, given the uncertainties of the theory and experiments. A correlation is reported between the Hg*+ and proton affinities of the ligands investigated. Solvation of Hg*+ with formic acid was observed to increase the rate of electron transfer from NO* by more than 20%. 相似文献
9.
Shi T Orlova G Guo J Bohme DK Hopkinson AC Siu KW 《Journal of the American Chemical Society》2004,126(25):7975-7980
Despite reports to the contrary, doubly charged lead monohydrate is a stable species against both proton and charge transfers. [Pb(H(2)O)](2+) has been observed as a minor product in the ligand-exchange reaction of [Pb(CH(3)CN)](2+) with H(2)O after collisional activation. Density functional theory has been used to examine reaction profiles of [Pb(H(2)O)(n)](2+) where n = 1, 2, and 3. 相似文献
10.
Atomic cations (26), M+, have been shown to lie within a thermodynamic window for O-atom transport catalysis of the reduction of N2O by CO and have been checked for catalytic activity at room temperature with kinetic measurements using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Only 10 of these 26 atomic cations were seen to be catalytic: Ca+, Fe+, Ge+, Sr+, Ba+, Os+, Ir+, Pt+, Eu+, and Yb+. The remaining 16 cations that lie in the thermodynamic window (Cr+, Mn+, Co+, Ni+, Cu+, Se+, Mo+, Ru+, Rh+, Sn+, Te+, Re+, Pb+, Bi+, Tm+, and Lu+) react too slowly at room temperature either in the formation of MO+ or in its reduction by CO. Many of these reactions are known to be spin forbidden and a few actually may lie outside the thermodynamic window. A new measure of efficiency is introduced for catalytic cycles that allows the discrimination between catalytic cations on the basis of the efficiencies of the two legs of the catalytic cycle. Also, a potential-energy landscape is computed for the reduction of N2O by CO catalyzed by Fe+(6D) that vividly illustrates the operation of an ionic catalyst. 相似文献