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91.
The spontaneous reduction of TiIV to TiIII in soluble Ziegler—Natta catalysts of type Cp2RTiCl·R’AlCl2 (Cp = h5 -cyclopentadienyl, R and R’ = methyl or ethyl) was studied both spectrally and chromatographically. Varied were R, R’, Al/Ti ratio, total concentration, solvent, and added olefin. Kinetic order in [Ti] could be varied from zero to second order by changing solvent. This can be explained by a mechanism in which a Cp2 RTiCl—R’AlCl2—olefin complex forms in the rate determining step and ligand R is expelled as half alkane half olefin. The expelled olefin may either polymerize or catalyze reduction by forming the rate-determining complex. Different apparent kinetic orders arise from differences in the olefin competitive reactions. The reaction products appear to form in a rapid bimolecular reaction following the rate-determining step. Evidence is presented that neither free radicals nor Cp2RR’Ti are reduction intermediates. The intermediate is postulated to be a TiIV transient hydride formed by a reverse insertion step. 相似文献
92.
C. D. J. Waters 《The Journal of the Operational Research Society》1987,38(9):833-839
A solution routine, based on iterative improvement of an initial solution, has been developed for vehicle-scheduling problems. The improving routine combines a number of very simple procedures, each of which tries to reduce the overall distance travelled by moving customers in a systematic way. Tests were run using standard problems, and results obtained were of good quality. An application of the procedure is described briefly. 相似文献
93.
An example of a sequence of competing first-order reactions, leading to a common product, has been found for the sulfodeacylation of acetylpropionylmesitylene. The basic reaction scheme is Scheme l and a kinetic analysis of the component rate constants allows an estimate to be made of the concentrations of the reactant and products as a function of time. In the present system the total concentration of the intermediates B, C, and D never exceeds 0.26% at 25°C, and therefore the kinetics, which were followed spectrophotometrically, were essentially of the conversion of substrate A to the final product E. The kinetics of protiodeacylation have been measured, over a range of temperatures, of propionyl-, dipropionyl-, and acetylpropionylmesitylenes in 89.8% (w/w) sulfuric acid. 相似文献
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97.
Bio MM Xu F Waters M Williams JM Savary KA Cowden CJ Yang C Buck E Song ZJ Tschaen DM Volante RP Reamer RA Grabowski EJ 《The Journal of organic chemistry》2004,69(19):6257-6266
A practical, efficient synthesis of 1, a hepatitis C virus RNA replication inhibitor, is described. Starting with the inexpensive diacetone glucose, the 12-step synthesis features a novel stereoselective rearrangement to prepare the key crystalline furanose diol intermediate. This is followed by a highly selective glycosidation to couple the C-2 branched furanose epoxide with deazapurine. 相似文献
98.
To probe the selectivity possible in hydrophobic clusters, we have compared the cross-strand interactions of phenylalanine (Phe) and cyclohexylalanine (Cha) in a beta-hairpin peptide. We have found a preference for self-association among the aromatic residues, which provides 0.55 kcal/mol in stability relative to Cha-Cha cross-strand pair. NMR analysis of the Phe-Phe cross-strand pair indicates that it interacts in an edge-face interaction, despite the fact that it is highly solvent-exposed. The interaction geometry as well as the enthalpic and entropic values for the peptide containing the Phe-Phe cross-strand pair suggest that the preference for self-association arises from inherent differences in the nature of aromatic and aliphatic interactions in water. 相似文献
99.
Consideration is given to the flow of an inelastic ‘power-law’ liquid in a continuous flow squeeze film. This simulates the flow in a conventional squeeze film by continuously injecting fluid into the narrow gap between two plates through the lower plate (Oliver et al. [6]). To zero order in the usual lubrication approximation the results are identical with those for the conventional squeeze film. To first order, useful corrections to the normal force due to the effects of inertia are obtained. 相似文献
100.
M. F. Horstemeyer Ken Gall K. W. Dolan A. Waters J. J. Haskins D. E. Perkins A. M. Gokhale M. D. Dighe 《Theoretical and Applied Fracture Mechanics》2003,39(1):23-45
Void nucleation, growth, and coalescence in A356 aluminum notch specimens was determined from a combination of experiments, finite element analysis, nondestructive analysis, and image analysis. Notch Bridgman tension experiments were performed on specimens to failure and then other specimens were tested to 90%, 95%, and 98% of the failure load. The specimens were evaluated with nondestructive X-ray tomography and optical image analysis. Finite element simulations of the notch tests were performed with an elastic–plastic internal state variable material model that incorporated the pertinent microstructures (silicon particle volume fraction and size distribution and porosity volume fraction and size distribution). Parametric finite element simulations were performed to give insight into various initial conditions and responses of the notch tensile bars. The various methods all corroborated the same damage progression. 相似文献