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61.
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
62.
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
63.
Satya Prakash 《Pramana》1989,33(1):109-131
This article summarizes the recent radiochemical investigations on mass, charge kinetic energy and fragment angular distributions
in low energy fission of actinides. 相似文献
64.
N. A. Gasviani M. Sh. Khutsishvili L. M. Abazadze 《Russian Journal of Electrochemistry》2006,42(9):931-937
Electrochemical reduction of sodium metavanadate in an equimolar KCl-NaCl melt and the effect of acid-base properties of environment on this process are studied by a voltammetry method on a stationary platinum electrode. It is established that the limiting current of the NaVO3 electroreduction process has a kinetic nature. The process proceeds via an autoinhibition scheme and its rate is limited by an acid-base reaction conjugated with an irreversible charge transfer reaction. A substantial role of cationic composition of the melt is revealed experimentally. Following acidification of the KCl-NaCl-NaVO3 melt by Mg2+ (from MgCl2), the process passes from an irreversible kinetic regime into a reversible diffusion (quasi-diffusion) process. Values of stability constants for vanadates produced with the aid of acid-base titration of vanadium pentoxide by oxygen ions in experimental conditions are presented. These values are taken into account when calculating kinetic parameters of the NaVO3 electroreduction. 相似文献
65.
小球与均质自由杆的碰撞 总被引:2,自引:2,他引:0
讨论了小球与自由杆碰撞过程中所遵从的物理规律,明确了完全非弹性碰撞过程的能量特征,指出完全非弹性碰撞后两物体不一定粘在一起共同运动的事实. 相似文献
66.
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
67.
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
68.
We have studied antimony and selenium atomization processes including a chemical matrix modifier (palladium-containing activated
carbon) during their determination by electrothermal atomic absorption spectrometry. We have developed and fine-tuned an experimental
setup for determining the kinetic characteristics (activation energy and frequency factor) for element atomization processes
from measurements in the initial section of the analytical signal. We provide a rationale for the most likely mechanism for
the interactions that occur. The results of the kinetic studies of the atomization processes showed that the modifier we developed
was highly effective, as a result of formation of a thermally stable condensed system C-Pd-A (where A is the analyte).
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 530–534, July–August, 2006. 相似文献
69.
本文在内生信息成本的基础上,通过引入投资银行的信息成本函数,考察了国际上主要股票发售机制的内在机理,并用一个统一的框架比较了各种发售机制的差异及演进趋势。本研究表明,在投资银行和投资者信息成本相同的情况下,由于固定价格发售机制须用额外的折价去解决投资者之间的信息问题,因而相对于累计投标询价制是一种处于劣势的机制选择。同时指出,具有信息成本优势的机构投资者的出现和发展,是固定价格发行向询价发行过渡的一个必要条件。 相似文献
70.
《科学通报(英文版)》1994,39(13):1074-1074