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51.
52.
PhI(OAc)2-mediated iminobromination was developed starting from alkenyl carbonitriles and Grignard reagents. The present transformation is carried out by a sequence of nucleophilic addition of Grignard reagents to alkenyl carbonitriles to form N-H imines and their iminohalogenation by subsequent treatment with PhI(OAc)2.  相似文献   
53.
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity.  相似文献   
54.
Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method. In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation (VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in which impurities were classified into several groups in terms of their abundance, availability of qualitative information and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS) to the International System of Units (SI).  相似文献   
55.
Zhang L  Ang GY  Chiba S 《Organic letters》2011,13(7):1622-1625
Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere was developed starting from carbonitriles and Grignard reagents via N-H imine intermediates. The present process is characterized by the following two-step sequence in a one-pot manner: (1) addition of Grignard reagents to carbonitriles to form N-H imines and (2) benzylic C-H oxygenation (C═O bond formation) triggered by 1,5-hydrogen atom transfer with transient iminyl copper species.  相似文献   
56.
Novel sesquiterpene alkaloids, halichonines A (1), B (2), and C (3), were identified from the marine sponge Halichondria okadai Kadota. By spectroscopic analyses and synthesis, their structures were revealed to include a 6,6-bicyclic ring system and two prenylated amine moieties. In addition, 2 induced apoptosis in HL60 human leukemia cells.  相似文献   
57.
The texture development mechanism during the extrusion of magnesium alloy is investigated by experimental observation and numerical analysis. First, we perform a finite element analysis of a full extrusion process using a phenomenological constitutive equation, and it is confirmed that the loading condition of the extrusion process near the central axis of the billet is approximated by an equi-biaxial compression mode. Then, the equi-biaxial compression problem is adopted as a simplified boundary value problem to be solved using a crystal plasticity model to clarify the detailed texture development mechanism during the extrusion process. The crystal plasticity analysis of equi-biaxial compression successfully reproduces the texture development from an initial random texture to the final experimentally observed texture. The effects of the deformation modes (i.e. slip and twinning systems) implemented in the calculation and the reference stress ratio of basal to nonbasal slip systems on texture development are studied in detail. Finally, the mechanism of texture development during the extrusion process is discussed in terms of the lattice rotation caused by the activated slip systems.  相似文献   
58.
Unexpected vibrations on a cylindrical filter made of nonwoven fabrics were clarified experimentally. Two types of filter with length L=1.8 m and 3.7 m, both 45 cm in diameter and 1.08 mm in thickness, were used. This is a new type of aeroelastic vibration phenomenon because the filter is a closed cylindrical vessel. In addition, the flow velocity of inner air was very slow and inner air flowed out slowly from the filter surface. The velocity distribution of air flow from a fan duct as well as the frequency and amplitude of the filter vibration were measured for two types of filter. By setting up a roll core panel at the outlet of the fan duct, we could rectify the outflow and suppressed the vibration of the shorter filter with L=1.8 m. However, this method was not adequate for the longer filter with L=3.7 m, and we could suppress the vibration by shielding the inner surface of the filter at the top region.  相似文献   
59.
Statistical Inference for Stochastic Processes - In this paper, we consider the problem of estimating the lead–lag parameter between two stochastic processes driven by fractional Brownian...  相似文献   
60.
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