102 resultados para CONJUGATE ADDITION

em Chinese Academy of Sciences Institutional Repositories Grid Portal


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A new series of fine-tunable phosphite-pyridine (P,N) ligands derived from (S)-2-amino-T-hydroxy-6,6'-dimethyl-1,1'-biphenyl and (S)-2-amino-2'-hydroxy-4,4',6,6'-tetramethyl-1,1'-biphenyl was employed in Cu(I)-catalyzed conjugate addition of diethylzinc to acyclic enones. Excellent enantioselectivities (up to 98% ee) and highly catalytic activities were achieved for a variety of acyclic enones.

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The asymmetric Michael addition of aldehydes to nitroolefins was investigated using L-prolinamide derivatives of 2-(2'-piperidinyl)pyridine as catalyst and a variety of phenols as co-catalyst. Extensive screening toward the effect of prolinamides, phenols, and solvents on this transformation revealed that a combination of (S)-2-(2'-piperidinyl)pyridine-derived trans-4-hydroxy-L-prolinamide 2c, (S)-1,1'-bi-2-naphthol, and dichloromethane was a promising system. This system was shown to be amenable to a rich variety of aldehydes and nitroolefins and afforded the nitroaldehyde products with excellent yield, enantiomeric excess (up to 99%) and diastereoselectivity ratio (up to 99/1), even in the case of 1 mol % catalyst loading and 1.5 equiv of aldehydes.

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3-[Bis(ethylthio)methylene]pentane-2,4-dione (1a) and 3-[bis(benzylthio)methylene]pentane-2,4-dione (1b) have been investigated as non-thiolic and odorless thiol equivalents in thia-Michael addition reactions. In the presence of aqueous p-dodecyl benzenesulfonic acid (DBSA), compound (1) was cleaved and the generated thiols underwent facile conjugate addition to alpha,beta-unsaturated ketones 2 in-situ, affording the corresponding beta-keto sulfides (3) in good yields.

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A facile and convenient synthesis of dihydropyranones has been developed by a formal [4+2] annulation of readily available alpha-acetyl ketene S,S-acetals with various aldehydes, involving a tandem aldol reaction and conjugate addition-elimination reaction, in the presence of NaOH in water.

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在应用激光技术加工复杂曲面时,通常以采样点集为插值点来建立曲面函数,然后实现曲面上任意坐标点的精确定位。人工神经网络的BP算法能实现函数插值,但计算精度偏低,往往达不到插值精确要求,造成较大的加工误差。提出人工神经网络的共轭梯度最优化插值新算法,并通过实例仿真,证明了这种曲面精确定位方法的可行性,从而为激光加工的三维精确定位提供了一种良好解决方案。这种方法已经应用在实际中。

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Minor yttrium addition can improve the glass-forming ability of Cu-Zr-Al ternary alloys via suppression of the growth of eutectic clusters. Yttrium addition also makes the room temperature ductility of the alloys decrease, and both the compressive strength and elastic strain limits increase slightly.

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Heat and mass transfer of a porous permeable wall in a high temperature gas dynamical flow is considered. Numerical simulation is conducted on the ground of the conjugate mathematical model which includes filtration and heat transfer equations in a porous body and boundary layer equations on its surface. Such an approach enables one to take into account complex interaction between heat and mass transfer in the gasdynamical flow and in the structure subjected to this flow. The main attention is given to the impact of the intraporous heat transfer intensity on the transpiration cooling efficiency.

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A new phenomenological deformation theory with strain gradient effects is proposed. This theory, which belongs to nonlinear elasticity, fits within the framework of general couple stress theory and involves a single material length scale l. In the present theory three rotational degrees of freedom omega(i) are introduced in addition to the conventional three translational degrees of freedom u(i). omega(i) has no direct dependence upon ui and is called the micro-rotation, i.e. the material rotation theta(i) plus the particle relative rotation. The strain energy density is assumed to only be a function of the strain tensor and the overall curvature tensor, which results in symmetric Cauchy stresses. Minimum potential principle is developed for the strain gradient deformation theory version. In the limit of vanishing 1, it reduces to the conventional counterparts: J(2) deformation theory. Equilibrium equations, constitutive relations and boundary conditions are given in details. Comparisons between the present theory and the theory proposed by Shizawa and Zbib (Shizawa, K., Zbib, H.M., 1999. A thermodynamical theory gradient elastoplasticity with dislocation density Censor: fundamentals. Int. J. Plast. 15, 899) are given. With the same hardening law as Fleck et al. (Fleck, N.A., Muller, G.H., Ashby, M.F., Hutchinson, JW., 1994 Strain gradient plasticity: theory and experiment. Acta Metall. Mater 42, 475), the new strain gradient deformation theory is used to investigate two typical examples, i.e. thin metallic wire torsion and ultra-thin metallic beam bend. The results are compared with those given by Fleck et al, 1994 and Stolken and Evans (Stolken, J.S., Evans, A.G., 1998. A microbend test method for measuring the plasticity length scale. Acta Mater. 46, 5109). In addition, it is explained for a unit cell that the overall curvature tensor produced by the overall rotation vector is the work conjugate of the overall couple stress tensor. (C) 2002 Elsevier Science Ltd. All rights reserved.

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A kind of novel Ti-based composites was developed by introducing different amounts of carbon element to the Ti-50 Cu-23 Ni-20 Sn-7 bulk metallic glass forming alloys. The thermal stability and microstructural evolution of the composites were investigated. Room temperature compression tests reveal that the composite samples with 1% and 3% (mass fraction) carbon additions have higher fracture strength and obvious plastic strain of 2 195 MPa, 3.1% and 1 913 MPa, 1.3% respectively, compared with those of the corresponding carbon-free Ti-50 Ni-20 Cu-23 Sn-7 alloys. The deformation mechanisms of the composites with improved mechanical properties were also discussed.

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The influence of the momentum addition, which may be associated with the average or fluctuation transverse component of the magnetic field or others, on the acceleration the solar wind or stellar wind is studied in a local streamtube. The results show that the larger the momentum addition the stronger the acceleration of the wind. For example, if the typical transverse magnetic field is about 0.1 of the longitudinal field, the velocity of the solar wind at 1 AU may be increased by 40%. The coronal hole may be considered as a streamtube, the presence of a high stream from the coronal hole may be explained by the existence of an average or fluctuation transverse magnetic field in the streamtube. A similar conclusion may be applied to the polar region, where the velocity of the solar wind will be larger than elsewhere as if there is a transverse component of magnetic field, as well as to the stellar wind. The influence of other parameters on the acceleration of the solar wind is also discussed. From the viewpoint of the solar wind mechanism, the present paper shows that the momentum addition in the subsonic flow region can increase the velocity of the solar wind at 1 AU.

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This paper is concerned with some mathematical aspects of the Van Dyke method inperturbation theory, i.e. the singularity criteria of perturbation series. The author suggestsa sign criterion and a Domb-syke plot for the cases with complex conjugate singularities, thussucceeding in extending the conclusions of Van Dyke's. Subsequently. effects of singularitiesof the lower order upon the criteria are taken into account. In addition, a method of locat-ing singular points is developed by analysing the new perturbation series derived by the Eulertransformation.