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101.
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
102.
Arman Melkumyan 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》2007,58(2):330-349
The problem of electric and acoustic waves diffraction by a half-plane crack in a transversal isotropic piezoelectric medium
is investigated. The crack is assumed to be electric permeable and free of tractions. The so-called “quasi-hyperbolic approximation”
[15] is adopted. Applying Laplace transformations and Wiener–Hopf technique a closed form solution is obtained. By the means
of Cagniard–de Hoop method a detailed dynamic full electroacoustic wavefield’s investigation is conducted. Mode conversion
between electric and acoustic waves, effect of electroacoustic head wave, Bleustein–Gulyaev surface wave and the wavefield
structure depending on the type of the incident wave (acoustic or electric) and its angle of incidence are analyzed in details.
The dynamic field intensity factors at the crack tip depending on the angle of incidence and on time are derived explicitly.
Numerical analysis is presented. 相似文献
103.
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
104.
105.
在应变速率为5.56×10-5s-1—5.56×10-3s-1的范围内,在不同温度下(从223K至773K),对3004铝合金进行系列拉伸试验,探索其锯齿屈服规律;通过激活能的计算、内耗研究、微观组织观察和能谱分析,探讨锯齿屈服的机理与物理本质.结果表明,3004铝合金在形变过程中会出现动态应变时效现象;发现了一种“反常”的锯齿屈服现象:在出现锯齿屈服的温区内,存在锯齿屈服临界应变量转变温度Tt,
关键词:
动态应变时效
锯齿屈服
铝合金
内耗 相似文献
106.
Robert S. Maier 《Random Structures and Algorithms》1991,2(4):379-420
We analyze the performance of a prototypical scheme for shared storage allocation: two initially empty stacks evolving in a contiguous block of memory of size m. We treat the case in which the stacks are more likely to shrink than grow, but with the probabilities of insertion and deletion allowed to depend arbitrarily on stack height as a fraction of m. New results are obtained on the m → ∞ asymptotics of the stack collision time, and of the final stack heights. The results of Wentzell and Freidlin on the large deviations of Markov chains are used, and the relation of their formalism to the Hamiltonian formulation of classical mechanics is emphasized. Certain results on higher-order asymptotics follow from WKB expansions. 相似文献
107.
生物膜微观结构与形态特征直接影响废水生物处理效果。混合微生物可在适宜载体表面形成各种各样的生物膜,且其形成与发展是一个动态过程。采用差分-离散复合法动态模拟二维区域上的基质传递、生物膜形成与发展过程,并探讨生物质生长时间与初始接种数等对生物膜结构与形态造成的影响。与传统生物膜模型不同之处在于其结构特性包括孔隙率、厚度和密度等都是模型输出量。 相似文献
108.
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
109.
The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH3COO)2(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction. 相似文献
110.