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51.
G. N. Merrill 《Journal of Physical Organic Chemistry》2007,20(1):19-29
Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
52.
N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods
in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization
of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly
accepted. Bridged TS are formed by both the substitution mechanism S
N
2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise
N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized
upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates
of N-acylalkylation, as was demonstrated by localization of the corresponding TS.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007. 相似文献
53.
In this paper, the notion of gap functions is extended from scalar case to vector one. Then, gap functions and generalized
functions for several kinds of vector equilibrium problems are shown. As an application, the dual problem of a class of optimization
problems with a system of vector equilibrium constraints (in short, OP) is established, the concavity of the dual function,
the weak duality of (OP) and the saddle point sufficient condition are derived by using generalized gap functions.
This work was supported by the National Natural Science Foundation of China (10671135) and the Applied Research Project of
Sichuan Province (05JY029-009-1). 相似文献
54.
By using the tools of statistical physics and recent investigations of the scaling properties of different complex networks,
the structural and evolving properties of the Chinese railway network (CRN) is studied. It has been verified that the CRN
has the same small-world properties of the Indian railway network (IRN). According to the class of small-world networks, we
believe the CRN is a single scale. In addition, a novel result is obtained. Measurements on the CRN indicate that the rate
at which nodes acquire links depends on the node’s degree and follows a power law.
相似文献
55.
56.
57.
Nash Equilibria,Variational Inequalities,and Dynamical Systems 总被引:2,自引:0,他引:2
Cavazzuti E. Pappalardo M. Passacantando M. 《Journal of Optimization Theory and Applications》2002,114(3):491-506
In this paper, we introduce some relationships between Nash equilibria, variational equilibria, and dynamical equilibria for noncooperative games. 相似文献
58.
59.
60.
采用从头算CCSD(T)/6-311 G(2d,2p)//B3LYP/6-311G(d,p)方法,研究了自由基-分子反应F CH2CHCH3的各种不同的反应通道.该反应主要是通过复合物形成机制进行,即F分别加到碳碳双键的两端形成自由基复合物1和2.这两种亚稳态自由基会解离成三种产物:H C3H5F、CH3 C2H3F和HF C3H5.理论计算结果表明,生成CH3 C2H3F是反应的主要通道,而生成H C3H5F和HF C3H5对产物也有一定的贡献.这一结果和实验符合得很好. 相似文献