REM树脂的制备及亲核加成应用研究

用Mitsunobu反应及丙烯酰氯酰化反应制备了用于固相有机合成的载体REM树脂，将REM树脂与苄胺加成，考查了所合成REM树脂的反应性能，并通过元素分析测定氮含量，推出REM树脂的烯丙基固载量。利用所合成的REM树脂进行了与胺、酚的加成反应动力学研究。结果表明，REM树脂与脂肪族伯胺和促胺的加成反应能够进行，与苯胺不发生反应；REM树脂与酚不能发生亲核加成反应。     

Synthesis of substituted benzene derivatives by homo- and hetero-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by McMurry coupling

A convenient synthetic approach to substituted benzene derivatives by modified Ullmann cross-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by intramolecular McMurry coupling has been developed.     

The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.     

Study of the spontaneous formation of organic layers on carbon and metal surfaces from diazonium salts

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.     

CSR外靶实验终端中子流测量的模拟

随着兰州重离子加速器冷却储存环(HIRFL-CSR)外靶实验终端中子墙的建立, 为实验测量高能中子提供了机遇. 为确定CSR外靶实验终端对中子流测量的可行性, 基于BUU理论模型分别对对称系统(Ni+Ni, Pb+Pb)和非对称系统(Pb+Ni)进行了模拟计算, 发现当系统能量达到几百MeV/u时, 中子流信号相当明显, 并与碰撞参数有明显的依赖关系. 模拟结果表明, 在前角20°的覆盖范围内, 可以较好地实现中子流测量所需要的反应平面确定及碰撞参数选择. 对双击事件及其对中子流的影响进行了简单的讨论.     

On the topological representation of catalytic cycles with nonlinear steps

Reaction route analysis is applied to visualize reaction networks in several heterogeneous catalytic reactions. Combination of the theory of complex reactions with the notion of catalytic cycles results in a topological representation of complex mechanisms with the nodes comprising all possible surface species including free sites and branches indicating interconnections between reactions.     

Synthesis of vinyl-substituted oxiranes and their transformation to dihydrofurans

The reaction of dimethylsulfonium methylide with the carbonyl function of 2-arylidene-cyclohexanones obtained from 2-methylcyclohexanone affords the corresponding spirooxiranes. The application of this reaction to 2,2-dimethyl-6-(5-methylfurfurylidene)cyclohexanone and 2,2-dimethyl-6-(5-chlorofurfurylidene)cyclohexanone leads to substituted 4,4-dimethyl-1-furyl-1,-3,4,5,6,7-hexahydroisobenzofurans.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1439–1443, August, 1994.     

Thermal reaction of clCH2CONH2 in molten acetamide

Mixtures composed of amides and electrolytes exhibit interesting properties such as viscoelastic behaviour and a megavalue of the dielectric constant. In order to improve the dielectric properties, the authors are investigating a large number of molten mixtures of CF₃COONa with different types of amides, including the ternary system sodium trifluoroacetate-chloroacetamide-acetamide. The experimental measurements showed that the ternary mixtures are thermally unstable. A yellow oily product is formed; this was purified and tested by means of IR and NMR techniques. The formula and the kinetic mechanism are proposed.