Synthesis of Novel Nucleoside Analog （3R）-2,3-Dideoxy-3-（N-hydroxy-N-methylamino）-L-arabinofuranosyl Uracil

The synthesis of novel nucleoside analog (3R)-2,3-dideoxy-3-(N-hydroxy-N-methylamino)-L-arabinofuranosyl uracil was studied. A twelve-step synthetic route, started from L-ascorbic acid, was designed, and the final product was obtained in 20.8% yield.     

Action of HCl on 3-hydroxypyrazolo(iso)quinolines to give 1-chloropyrazoles: evidence for an addition–elimination mechanism by ab initio calculations in gas phase and water

 Addition–elimination reactions involving a nucleophile and a remote leaving group [S^H _N(AE)^tele] are well-known under basic conditions, especially amongst electron-poor six-membered heterocycles, but are less commonly encountered for five-membered heterocycles and are rare under acidic conditions. Concentrated HCl converts 1-hydroxy-1H-pyrazolo[3,4-c] isoquinoline and 1-hydroxy-1H-pyrazolo[3,4-c]quinoline into 3-chloro-1H-pyrazolo[3,4-c]isoquinoline and 3-chloro-1H-pyrazolo[3,4-c]quinoline, respectively. However, apparently neither the isomeric 1-hydroxy-1H-pyrazolo[4,3-c](iso)-quinolines nor the parent 1-hydroxypyrazole undergo this reaction. Additionally, all these systems are refractory under basic conditions. We present a plausible mechanism for the reaction, involving the 3-addition of Cl^- to the diprotonated heterocycle, followed by the elimination of water. Calculations of the initial transition states and intermediates, using optimisation at B3LYP/6-311+G(d,p), including thermochemistry [HF/6-31+G(d)], and single-point Poisson–Boltzmann self-consistent reaction field determination of the free energy of solvation (Jaguar Poisson–Boltzmann self-consistent reaction field), support this mechanism and reproduce the observed order of reactivity, the addition step being 2–4 kcal less favourable for the isomeric 1-hydroxy-1H-pyrazolo[4,3-c](iso)quinolines and provide a rationalisation for the role of strong acid. Received: 27 June 2002 / Accepted: 6 September 2002 / Published online: 14 February 2003     

CH2XH→CH3X (X＝O, S, Se)异构化的量子拓扑研究

利用从头算和量子拓扑方法讨论了CH₂XH→CH₃X (X＝O, S, Se)异构化过程的反应机理. 着重从电子密度拓扑分析计算了反应进程中的各点, 讨论了反应进程中键的断裂和生成, 上述反应都经历了三元环过渡结构, 找到了这类反应的"能量过渡态"和"结构过渡态", 且结构过渡态均在能量过渡态之后出现. 三元结构过渡态结构出现的范围与反应热成正比.     

邻位吡啶自由基多通道分解反应的动力学和反应机理研究

Utilizing Gaussian94 program package, all species involved in decomposition reactions of o-pyridyl radical were optimized fully at B3LYP/6-311＋＋G^＊＊ level. Intrinsic reaction coordinate calculations were employed to confirm the connections of the transition states and products, and transition states were ascertained by the number of imaginary frequency （0 or 1）. The reaction mechanism was elucidated by the vibrational mode analysis and electronic population analysis, and the reaction rate constants were calculated with transition state theory.     

Reverse permeation of sodium ions driven by pH difference across a liquid membrane: time dependencies of membrane resistance and membrane potential in a reverse permeation system

The diffusional flux of sodium ions across a liquid membrane was observed as a reverse permeation phenomenon: sodium ions were transported across the membrane against their own concentration difference. A supported liquid membrane having stearic acid as an ionic carrier was used. The internal aqueous phase contained NaCl and HCl and the external aqueous phase contained NaOH of the same initial concentration as NaCl in the internal aqueous phase. The reverse permeation occurred with a long time delay. During the delay, sodium ions flowed from the acidic to alkaline solution. The diffusion coefficient of sodium ion estimated from the flux equation taking into account the Donnan equilibrium at the interface was found to be much greater than that in the membrane solvent, 1-octanol. In the same membrane system as for the flux measurement, the membrane conductance and the membrane potential were measured as a function of time. The time dependence of the membrane potential in the presteady state showed a biphasic behavior. The initial rapid phase could be attributed to the change in the phase boundary potential and the subsequent slow step to the change in the diffusion potential within the membrane. Before the steady membrane potential had been reached, the reverse permeation of sodium ions against their own concentration difference was not observed. During the slow relaxation process of the membrane potential, the membrane resistance decreased to approach the steady state. Moreover, the oscillation of membrane potential abruptly started at a time in the slow step of the potential change and continued during the steady state. It was suggested that, at the presteady state, the increase in the amount of water in the membrane would drive a drastic change in the state of the liquid membrane in the filter pore, e.g. an inverted micellar structure making.     

Fast and reversible migrations of N,S-centered groups around the perimeter of cyclopropene and cycloheptatriene rings

The kinetics and mechanism of circumambulatory rearrangements of N-centered (NCS) and S-centered (SPh, SC₃Ph₃, SC(OEt)=S) groups in corresponding derivatives of 1,2,3-triphenylcyclopropene and cycloheptatriene were studied by dynamic¹H and¹³C NMR spectroscopy. Migrations of the isothiocyanate group occur by the dissociation-recombination mechanism with intermediate formation of a tight ionic pair. Migrations of the phenylthio group around the perimeter of cyclopropene and cycloheptatriene rings occur by the 1,2-shift mechanism. It was found that rearrangements of theO-ethyl dithiocarbonate group inS-(1,2,3-triphenylcyclopropen-3-yl)-O-ethyl dithiocarbonate occur by the 3,3-sigmatropic shift mechanism. The molecular and crystal structure ofO-ethylS-(1,2,3-triphenylcyclopropen-3-yl) dithiocarbonate was studied by X-ray analysis.     

以对-(4-烯丙氧基苯甲酰氧基)苯甲酸对-甲氧基苯酚酯为单体的液晶聚硅氧烷的合成与表征

侧链型液晶聚合物是目前很有兴趣的研究课题之一。在国内,有关的研究报道也逐渐增多,本工作设计并合成了对-(4-烯丙氧基苯甲酰氧基)苯甲酸对-甲氧基苯酚酯单体,其结构式为:     

开放式声化学反应体系中的反应动力学

采用气液传质的双膜理论建立了开放体系中声化学反应的动力学模型，同时用声源频率为500 kHz，声强为3 W·cm^-2的超声波在开放式声化学反应器内引发被空气饱和溶解的KI纯水溶液中的声化学反应，并检测反应过程中溶液的电导率，pH值改变及KI溶液中I₂的析出量，结果表明，它们与超声辐照时间之间呈线性关系，与理论模型吻合。     

The Mitsunobu Reaction: Origin,Mechanism, Improvements,and Applications

The Mitsunobu reaction is a widely used and versatile method for the dehydrative oxidation–reduction condensation of an acid/pronucleophile usually with a primary or secondary alcohol that requires the combination of a reducing phosphine reagent together with an oxidizing azo reagent. The utility of this reaction stems from the fact that it is generally highly stereoselective and occurs with inversion of the stereochemical configuration of the alcohol starting material. Furthermore, as carboxylic acids, phenols, imides, sulfonamides, and other compounds can be used as the acid/pronucleophile, this reaction is useful for the preparation of a wide variety of functional groups. This Focus Review of the Mitsunobu reaction summarizes its origins, the current understanding of its mechanism, and recent improvements and applications.     

Suzuki-Miyaura coupling reaction of aryl chlorides using di(2,6-dimethylmorpholino)phenylphosphine as ligand

Suzuki-Miyaura coupling was achieved on a variety of aryl chlorides by using di(2,6-dimethylmorpholino)phenylphosphine (L1) as a bulky electron-rich monoaryl phosphine ligand. We report the couplings of various chlorobenzenes and heteroaryl chlorides.