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41.
The acid catalysed dienone-phenol rearrangement of methyl substituted o-propargyl-cyclohexadienones (scheme 3) was investigated. The rearrangements were carried out in acetic anhydride containing about 10/00 sulfuric acid. Under these conditions acetoxy benzenium ions are formed as intermediates. These then undergo charge-controlled [3s, 4s]- and [1s, 2s]-sigmatropic rearrangements. Thus, the [3s, 4s]-process leads to the formation of the corresponding allenyl-phenol acetates ( 19 , 21 , 23 , 25 , 28 , 30 ) whereas the [1s, 2s]-process yields propargyl-phenol acetates ( 20 , 22 , 24 , 26 , 29 ), respectively (cf. scheme 4). 相似文献
42.
Christoph Kratky Heinz Falk Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1985,116(5):607-623
The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet. 相似文献
43.
Novel Inorganic Ring Systems. 34. Derivatives of the Cyclo-1-thiaIV- and of the Cyclo-1-thia VI-3,4-disila-2,5-diazane Variations of fivemembered “hetero” cyclosilazanes of the type Si2N2El could be enlarged to the systems with El = SO and SO2. They are obtained by the formation principles 4 + 1 and 2 + 3 respectively, according to the equation (1), (4) and (5). The prepared compound are described in their properties and confirmed in their structure (Tables 1–2). 相似文献
44.
Herbert Cadosch Ulrich Vgeli Peter Rüedi Conrad Hans Eugster 《Helvetica chimica acta》1978,61(2):783-794
On the Carotenoids Flavoxanthin and Chrysanthemaxanthin: 1H-NMR., 13C-NMR. and Mass Spectra, Absolute Configuration, Survey of Published Data Very pure flavoxanthin ( 1 ) and chrysanthemaxanthin ( 2 ) have been reisolated from flower heads of Taraxacum officinale. Both compounds were characterized by chromatographic, chemical and chiroptical data and extensive NMR. measurements. Examination of many published data on 1 and 2 led to the conclusion that flavoxanthin has often been mistaken for chrysanthemaxanthin and vice versa. Chemical degradation of 1 and 2 to (?)-loliolide ( 5 ) coupled with NMR. evidence (ASIS, spin-decoupling, NOE) allowed the assignment of the absolute configurations of 1 and 2 . Thus (+)-flavoxanthin is (3S,5R,8R, 3′R,6′R)-5, 8-epoxy-5, 8-dihydro-β, ε-carotene-3, 3′-diol and (+)-chrysanthemaxanthin its C(8)-epimer. 相似文献
45.
The radical yields and rate constants in the quenching reaction of thionine triplet with the complete series of monohalogen substituted anilines as electron donors were determined by flash spectroscopy. Whereas the quenching rate constants show little and unsystematic variation, the radical yields decrease with increasing spin—orbit coupling constant of the halogen substituent. This effect is very sensitive to the position of the halogen in the donor. The results are explained in terms of a heavy atom effect on the intersystem crossing rate constant in a triplet exciplex. 相似文献
46.
The applicability of the carbon paste electrode to the determination of trace quantities of mercury has been investigated in a base electrolyte of 0.1 N KSCN + 0.025 N HCl containing 25 ng/ml copper. The detection limit of the mercury determination has a value near 2.5 ng/ml (1.25×10?8 M), if pre-electrolysis is carried out 10 min at ?1.0 V and the current voltage curve is registered with a scan rate of 16.7 mV/sec between ?0.5 and +0.5 V. The peak height is directly proportional to the concentration in the range from 1.25×10?8 to 1.25×10?6 M. With appropriate preconditioning the carbon paste electrode can be used for several measurements without renewing the surface. 相似文献
47.
Mass-selected gas-phase UV spectra of laser-desorbed molecules at room temperature have been measured via resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass selection. The wavelength range of 260 to 320 nm is optimal for detection of polycyclic aromatic hydrocarbons (PAHs) using REMPI-mass spectrometry. A new laser desorption/laser ionisation source has been used which features a compact size and thermal equilibrium of the desorbed molecules. 16 PAHs have been investigated which have been selected by the US Environmental Protection Agency (EPA). These 16 EPA-PAHs are commonly used world-wide to characterise the PAH-load of environmental samples. 相似文献
48.
Ulrich Felgner 《Monatshefte für Mathematik》1984,98(3):185-191
Using Eisenstein's law of cubic reciprocity we investigate cases in whichx
3=y
2+k is unsolvable in the ring of rational integers In particular we show, that for all primesp ± 1 (mod 9),p3, the equationx
3=y
2+3p(p±9) has no solutions in . 相似文献
49.
B. T. Ulrich 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1978,29(2):359-361
A voltmeter of sensitivity
is based on direct conversion of the voltage to be measured into a frequency according to the Josephson voltage-frequency relation. Selfpumped parametric amplification in a d.c. biased loop containing two Josephson junctions and a measuring resistanceR
s=4.7×10–9 amplifies the femptovolt level voltages acrossR
s to microvolt levels that can be observed with a room temperature amplifier. The sensitivity of the femptovoltmeter is determined by Johnson-Nyquist noise voltages at 4.2 K in the 4.7×10–9 resistance. 相似文献
50.
Robert F. Kirchner Gilda H. Loew Ulrich T. Mueller-Westerhoff 《Theoretical chemistry accounts》1976,41(1):1-6
An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations. 相似文献