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531.
Reaction conditions have been developed for palladium-catalyzed terminal (beta-) arylation of acyclic vinyl ethers with high regioselectivity using inexpensive aryl chlorides as starting materials and the P(t-Bu)3 releasing preligand [(t-Bu3)PH]BF4 as the key additive. This swift and straightforward protocol exploits non-inert conditions and controlled microwave heating to minimize handling and processing times and uses aqueous DMF or environmentally friendly PEG-200 as the reaction medium. The selectivity for linear beta-product in PEG-200 is slightly higher than in aqueous DMF. DFT calculations support a ligand-driven selectivity rationale, where the electronic and steric influence of bulky P(t-Bu)3 ligand provides improved beta-selectivity in the essential insertion step also with electron-rich aryl chlorides. A tentative computational rationalization of the improved selectivity in non-methylated PEG is discussed. Finally the synthetic methodology was used to provide efficient access to linear p-[2-(cyclopropylmethoxy)ethyl] phenol from p-nitrophenyl chloride, a key intermediate in the synthesis of the beta-adrenergic blocking agent Betaxolol. 相似文献
532.
This work addresses the issue of radiation chemical synthesis of MnO2 nanoparticles and also illustrates the ease of formation of nanorods and sheets by adroit manipulation of experimental conditions. The radiation chemical yield (G-value) for reduction of Mn (VII) by the hydrated electron was found to be 0.27 μmol J−1 and 0.17 μmol J−1 respectively, when tert. butanol and isopropanol were used as scavengers in nitrogen-saturated solutions. The colloids formed upon irradiation of air-saturated solution and N2-purged solution with tert. butanol as scavenger were found to be most stable. Irradiation of air-saturated solution containing 4×10−4 M KMnO4 at a dose of 1692 Gy resulted in the formation of nanorods of the dimension 100–150 nm and nanospheres in the range 10–20 nm. Irradiation of N2-purged solution containing tert. butanol as scavenger for OH-produced reticulated structure of nanorods with length varying from 50 to 100 nm at a dose of 1692 Gy. Elemental analysis was performed using scanning electron microscope on MnO2 formed by reduction and oxidation and the purity was found to be 98% of elemental Mn content. 相似文献
533.
The microstructure and rheological behaviour of inhomogeneous biopolymer gels was studied using a model system of β-lactoglobulin. It can form both fine-stranded and particulate gels which can be homogeneous or inhomogeneous depending on pH and heating rate. The dense and loose regions of the fine-stranded gels had different relaxation times which significantly influenced the mechanical spectrum. The particulate gels showed coarser inhomogeneities influencing the fracture properties of the gels. 相似文献
534.