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91.
W. Schramek F. Hempel Paul-August Koch W. W. Russell und N. T. Woodberry 《Fresenius' Journal of Analytical Chemistry》1943,125(3-4):145-148
Ohne Zusammenfassung 相似文献
92.
93.
Neuvonen H Neuvonen K Koch A Kleinpeter E 《The journal of physical chemistry. A》2005,109(28):6279-6289
Equilibria between the Z (tau1= 0 degrees) and E (tau1= 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, DeltaE(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mol(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between DeltaE of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (nO--> pi*C=O) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The nO --> pi*C=O electron donation has a minimum value with tau1= 90 degrees and a maximum value with tau1= 0 degrees (the Z conformer), the value with tau1= 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*C=O antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*C=O occupancies of the ester series 4 and 5. 相似文献
94.
Tobias S. Hermann Thomas M. Klapötke Burkhard Krumm Jörg Stierstorfer 《无机化学与普通化学杂志》2017,643(2):149-151
Two highly energetic nitric acid esters were synthesized from the dimer of dihydroxyacetone. 1,3‐Dinitratoacetone ( 1 ) and its dimer 2,5‐bis(nitratomethyl‐2,5‐nitrato)‐1,4‐dioxane ( 2 ) were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, and elemental analysis. The thermal behavior was investigated with DTA measurements. Although showing the same atomic stoichiometry, dimer 2 shows significantly higher sensitivities measured by BAM methods (drophammer and friction tester). Due to the high oxygen content of 62.2 %, 1 and 2 were evaluated as potential high energy dense oxidizers. 相似文献
95.
Andreas Uwe Meyer Karolína Straková Dr. Tomáš Slanina Prof. Dr. Burkhard König 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8694-8699
Alkyl‐ and aryl vinyl sulfones were obtained by eosin Y (EY)‐mediated visible‐light photooxidation of sulfinate salts and the reaction of the resulting S‐centered radicals with alkenes. Optimized reaction conditions, the sulfinate and alkene scope, and X‐ray structural analyses of several reaction products are provided. A detailed spectroscopic study explains the reaction mechanism, which proceeds through the EY radical cation as key intermediate oxidizing the sulfinate salts. 相似文献
96.
Rixt A. Wijma Bart C. H. van der Nagel Bram Dierckx Gwen C. Dieleman Daan J. Touw Teun van Gelder Birgit C. P. Koch 《Biomedical chromatography : BMC》2016,30(6):794-801
The antipsychotics risperidone, aripiprazole and pipamperone are frequently prescribed for the treatment in children with autism. The aim of this study was to validate an ultra‐high performance liquid chromatography–mass spectrometry method for the quantification of these antipsychotics in plasma. An ultra‐high performance liquid chromatography–mass spectrometry assay was developed for the determination of the drugs and metabolites. Gradient elution was performed on a reversed‐phase column with a mobile phase consisting of ammonium acetate, formic acid in methanol or in Milli‐Q ultrapure water at a flow rate of 0.5 mL/min. The method was validated according to the US Food and Drug Administration guidelines. The analytes were found to be stable enough after reconstitution and injection of only 5 μL improved the accuracy and precision in combination with the internal standard. Calibration curves of all five analytes were linear. All analytes were stable for at least 72 h in the autosampler and the high quality control of 9‐OH‐risperidone was stable for 48 h. The method allows quantification of all analytes. The advantage of this method is the combination of a minimal injection volume, a short run‐time, an easy sample preparation method and the ability to quantify all analytes in one run. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
97.
Dipl.‐Chem. Felix Koch Dr. Andreas Berkefeld Dr. Hartmut Schubert Claudius Grauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14640-14647
This work reports on the redox and acid–base properties of binuclear complexes of nickel from 1,4‐terphenyldithiophenol ligands. The results provide insight into the cooperative electronic interaction between a dinickel core and its ligand. Donor/acceptor contributions flexibly adjust to stabilize different redox states at the metals, which is relevant for redox reactions like proton reduction. Proton transfer to the [S2Ni2] core and Ni?H bond formation are kinetically favored over the thermodynamically favored yet unproductive proton transfer to ligand. 相似文献
98.
99.
100.
H. Endraß A. Fisher P. Klinger W. Koch G. Blaschczyk W. M. Murray Jr und S. E. Q. Ashley 《Fresenius' Journal of Analytical Chemistry》1943,126(3):118-126
Ohne Zusammenfassung 相似文献