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71.
Contribution to the mass spectrometry of substituted α,ω-alkane diamines The main mass spectral fragmentation pattern of compounds of types 1 to 4 is discussed. After loss of C6H5 · CH2 · from the molecular ion the acid correspondin to the N,N-disubstituted residue is splitted off. The mechanism of this fragmentation reaction depends on the member of CH2-groups between the two nitrogen atoms (Schemes 1 and 3) and on the substitution pattern of both nitrogens (Scheme 2). 相似文献
72.
Winter B Weber R Hertel IV Faubel M Jungwirth P Brown EC Bradforth SE 《Journal of the American Chemical Society》2005,127(19):7203-7214
Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties. 相似文献
73.
74.
Guy Guelachvili K. Narahari Rao Richard H. Tipping Brenda P. Winnewisser Manfred Winnewisser 《Mikrochimica acta》1988,95(1-6):339-343
This paper reports the observation of the far infrared absorption spectrum of a single crystal of N2, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed. 相似文献
75.
Manfred Herrmann 《Fresenius' Journal of Analytical Chemistry》1961,181(1):122-125
Zusammenfassung Durch Anwendung der Röntgenfluorescenzanalyse an Stelle der bisher üblichen Methoden bei der quantitativen Bestimmung von Brom in organischen Substanzen läßt sich eine beträchtliche Zeitersparnis erzielen. Dies gilt besonders bei Anwesenheit anderer Halogenide wie Chlor oder Jod. Die Bestimmung wird unter Zugabe von Selen nach der Methode des inneren Standards durchgeführt, die Analysengenauigkeit deckt sich mit den Ergebnissen der bisher naßchemisch durchgeführten Bestimmungen.Herrn Dr. F. Ehrenberger und Dr. S. Gorbach danke ich für Anregungen und für ihre wertvolle Mitarbeit. 相似文献
76.
Thilo Berkenbusch Andy Ch. Laungani Reinhard Brückner Manfred Keller 《Tetrahedron letters》2004,45(52):9517-9520
4-tert-Butyl-2-cyclohexen-1-one dimerizes in THF solution via its kinetic enolate, leading to di-tert-butylditwistane 8 in up to 36% yield (−78 °C → room temp., protonolysis, flash chromatography). X-ray crystallography shows that 8 incorporates one R and one S enantiomer of the starting ketone; none of the diastereomeric ditwistanes epi-8, epi’-8 or iso-8 was isolated. This means that the formation of 8 proceeds with mutual kinetic resolution and 100% induced diastereoselectivity. 相似文献
77.
Rolf Kyburz Emanuel Schpp Manfred Hesse I. Ralph C. Bick 《Helvetica chimica acta》1979,62(8):2539-2546
Sorelline and Hobartine, Two New Indole Alkaloids from Aristotelia peduncularis (LABILL .) HOOK . F. From Aristotelia peduncularis (LABILL .) HOOK . F. two new indole alkaloids, sorelline ( 1 ) and hobartine ( 2 ), have been isolated. Their structures were elucidated on the basis of spectroscopic data (the formulae represent their relative configurations). The alkaloids 1 and 2 have closely related structures with a monosubstituted indole moiety and an unrearranged monoterpene unit in the aliphatic part. 相似文献
78.
79.
Kopsirachine, an Unusual Alkaloid from the Apocynaceae Kopsia dasyrachis Ridl. From the leaves of Kopsia dasyrachis Ridl. a new type of alkaloid, kopsirachine ( 1 ), built up from catechin ( 2 ) and skytanthine ( 3 ) has been isolated. The structure elucidationis based on spectral and chemical evidence. Oxidative cleavage of its derivative 4 with KMnO4 afforded veratric acid wich was identified as its methylester by comparison with an authentic sample. Pyrolysis of 1 yielded δ-skytanthine ( 3 ). The stereochemistry of the skytanthine substituents in 1 could not yet be established. 相似文献