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71.
72.
73.
Jacobson MA Keresztes I Williard PG 《Journal of the American Chemical Society》2005,127(13):4965-4975
N-Lithio-N-(trialkylsilyl)allylamines can be deprotonated in the presence of ethereal solvents exclusively at the cis-vinylic position to yield 3,N-dilithio-N-(trialkylsilyl)allylamines under mild conditions. Low temperature (1)H and (7)Li NMR ((1)H NOESY, TOCSY, (1)H/(7)Li HSQC, and DO-NMR) studies on the solution structure of 3,N-dilithio-N-(tert-butyldimethylsilyl)allylamine identified three major aggregates in THF (monomer, dimer and tetramer), but the aggregate structures failed to explain the solvent dependence and regiochemical outcome of the reaction. Low temperature (1)H NMR (NOESY, TOCSY, DO-NMR) studies on the solution structure of N-lithio-N-(tert-butyldimethylsilyl)allylamine in the presence of nBuLi identified amide/nBuLi mixed aggregates in both the ethereal solvent THF (1:1 dimer) and the hydrocarbon solvent toluene (1:3 tetramer). Addition of 2 equiv of THF to toluene solutions induces the formation of the same THF solvated 1:1 dimer as observed in neat THF. NMR evidence suggests that in THF the mixed aggregate has close contact between the olefin and the beta-CH(2) of nBuLi, while in the absence of THF, the allyl chain appears to be pointed away from the nearest nBuLi residues. 相似文献
74.
Wolfgang A. Herrmann Carl Krüger Richard Goddard Ivan Bernal 《Journal of organometallic chemistry》1977,140(1):73-89
μ-Carbonylbis(carbonyl-ν5-cycopentadienylrhodium)(Rh—Rh) reacts with N-methyl-and N-ethyl-N-nitrosourea in boiling benzene to yield the dinuclear, diamagnetic, neutral rhodium complexes μ-methylene- (A) and μ-ethylidenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh) (B), respectively. Deuterium labelled experiments prove the origin of the metal-stabilized methylene ligand to be the alkyl group of the organic precursor. This new method of preparation of transition metal—methylene complexes may be used as an alternative to the commonly used diazo method; the latter method was shown to work with diazodiethylmalonate and dicarbonyl-η5-cyclopentadienylrhodium, the reaction yielding μ-bis(ethoxycarbonyl)methylenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh).Compound A crystallizes in the triclinic system, P, and with cell constants of a 803.42(5), b 909.98(6), c 938.81(2) pm, α 74.402(3), β81.923(3), and γ 83.685(6)°. The unit cell volume and the calculated density are 651.6 Å3 and 2.069 g cm-3, for one molecule in the asymmetric unit. The molecular geometry of μ-CH2[η5-C5H5Rh(CO)]2 was established from 2718 unique reflections collected with a computer-controlled diffractometer and refined to a final R(F) = 0.0379. The molecular parameters derived from the single-crystal X-ray study conform to a remarkable degree with those found for μ-CO[η5-C5H5Rh(CO)]2. Thus, the bridging ligands CH2 and CO seem to be analogous in their effects on the structural characteristics of the molecular framework of the two molecules. 相似文献
75.
Ivan Ernest 《Helvetica chimica acta》1979,62(8):2681-2694
A synthesis of (6 R, 7 R)-7-acylamino-2-oxocephem-4-carboxylic acids from penicillins is reported based on the formation of the 2-oxocephem system in an intramolecular Wittig condensation. An interesting steric effect of the acylamino grouping on the course of this key step was used to advantage. Some physical and biological properties of this new type of Δ3-cephem are described. 相似文献
76.
Joachim GarricJean-Michel Léger Axelle GrelardMasakazu Ohkita Ivan Huc 《Tetrahedron letters》2003,44(7):1421-1424
X-Ray crystallography and NMR show a strong preference for trans conformers of N′-phenyl or N′-(2-pyridyl) 2-pyridinecarboxylic acid hydrazides, stabilized by an NHNpyr. intramolecular hydrogen bond both in the solid state and in solution. This allows us to extrapolate that oligomers of this unit should adopt extended linear conformations. 相似文献
77.
Silylstannanes can be regioselectively added across terminal alkynes in a quantitative fashion in the presence of a palladium(0) catalyst immobilised in the [bmim]PF6 ionic liquid which can be recycled without loss of activity. 相似文献
78.
S. Djurović N. Konjević M. S. Dimitrijević 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1990,16(4):255-260
We report results of a study of the Stark broadening of halogen atom lines from (1 D)n p levels. Wall stabilized arc is used as a plasma source. Electron densities 2.2–3.2×1022 m?3 are determined from the width ofH α line and electron temperature 9300–10000 K from plasma composition data. The agreement with the results of simple semiclassical calculations is within the limits of the estimated errors of both experiment and theory. An explanation for the large discrepancy between theory and experiment detected for three BrI lines is offered. 相似文献
79.
We report measured Stark shifts and widths of neutral flourine and chlorine lines. Wall stabilized arc is used as a plasma source. Electron densities 2–4×1022 m?3 are determined from the width of theH β line and electron temperatures 9500–10 000 K from plasma composition data. Experimental results for FI and ClI Stark widths and FI Stark shifts agree within 10% with semiclassical calculations. ClI Stark shifts are systematically smaller for about 20% than theoretical data with the only exception of the line from multiplet no. 15 where the discrepancy goes up to 49%. Results of investigation of similarities and regularities of Stark widths are in agreement with the study of Wiese and Konjevi?. Comparison of experimental Stark shifts shows certain types of regularities. 相似文献
80.
The subject of this report is the determination of lysophospholipids; lysophosphatidylcholine, lysophosphatidylethanolamine, lysophosphatidylserine and lysophosphatidic acid, by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS). The mean signal-to-noise ratio (S/N) was used for the first time as a measure of lysophospholipid concentration. Two different sample preparation procedures were applied, the 'standard' procedure and the 'premix' in order to check to what extent these methods influence the results of the lysophospholipid quantification. Results can be summarised as follows: (a) All classes of lysophospholipids can be easily and sensitively analysed by MALDI-TOF MS. The smallest detectable amount of lysophospholipids was 0.09 pmol on the sample plate. That is about two orders of magnitude lower than the amount detectable by standard chromatographic methods. (b) The mean S/N of all peaks detected in the positive ion mass spectra can be used as a measure of the lysophospholipid concentration. Whereas the S/N for neutral lysophospholipids correlated with the applied concentrations only when the samples were analysed as 'premix', the sample preparation and application procedure did not influence the quantification of acidic lysophospholipids. The standard deviations were not higher than 10% of the mean value. (c) All spectra were additionally analysed in the presence of CsCl. The addition of caesium ions makes the peak identification unambiguous in phospholipid mixtures, but the Cs adducts of lysophospholipids do not properly reflect their concentration and, therefore, they were not useful for quantification. (d) The applicability of the method was demonstrated on the organic extract of human neutrophils. 相似文献