锆氢化反应研究 Ⅰ.酯类及双官能团化合物的锆氢化反应

本工作以一氯一氢二茂锆为还原试剂,对苯甲酸苯乙酯和苯甲酸甲酯进行还原,对还原的条件及水解产物的分离鉴定进行了研究。并对同时含酯基与其它官能团的几种化合物进行了选择性还原,列出了官能团还原先后的顺序,对结果进行了讨论。     

Photocatalytic Properties of Titanium Dioxide Heterostructures with Cyanine Dyes and Polyepoxy Propylcarbazole

We have obtained novel photosensitive materials containing a semiconductor photocatalyst and a dye sensitizer. We have studied the activity of the latter in the reaction of photoreduction of methylene blue, and we consider possible mechanisms for the photocatalytic effect.     

手性氨基醇催化的前手性芳酮的不对称还原反应

首次以天然D-樟脑的衍生物为原料, 合成了两个新型龙脑基氨基醇配体, 研究了它们与硼烷原位制备成手性噁唑硼烷后, 在不对称催化氢化还原前手性芳酮中的性能, 得到的手性仲醇的对映体过量(ee)值最高可达96%, 还考察了反应温度、时间、溶剂等因素对苯乙酮的不对称氢化还原的化学产率和光学收率的影响.     

Application of thermal analysis to study smelting reduction kinetics

A thermal analysis study on the reduction of iron oxide rich slags under different conditions is presented in this paper. The effects of important process variables such as time, temperature, lime-silica ratio, FeO level in slag etc. are discussed. It is shown that the mechanism of reduction by externally added graphite is different from that by a carbon saturated bath although the activation energy values are similar.     

制备高比表面积碳化硅的几种影响因素

采用溶胶凝胶法，以蔗糖和正硅酸乙酯(TEOS)为原料，草酸为TEOS水解的催化剂，制备均相碳化硅前驱体，在氩气氛和高温条件下(1 350～1 600 ℃)将碳化硅先驱体进行碳热还原，制备出高比表面积的SiC。考察了水/TEOS物质的量的比、碳/硅物质的量的比及镍盐等因素对碳化硅比表面积的影响。结果表明，当n_water/n_TEOS=7.5，n_C/n_Si=4时，适宜的镍催化剂(n_Ni/n_TEOS=0.005)，凝胶形成的时间最短，镍盐的加入可使碳热还原温度降低200 ℃。     

The lion and man problem revisited

A pursuerP, whose speed is bounded by 1, wants to get closer to an evaderE, whose speed is bounded by >1.P wants to reduce his distancePE fromE below the capture radius . Both players are confined to a circular arena. This problem is equivalent to a problem discussed by Flynn, who characterized and gave numerical bounds to the least upper boundd* on the values ofPE thatE can maintain. He used direct methods and did not use Isaacs' theory.We solve our problem relying on the theory of singular surfaces in differential games. We construct and investigate barriers of the game of kind, and we replace Flynn's bounds ond* by analytical (exact) values for various speeds .The support of the TW Department of THT, Enschede, Holland, is gratefully acknowledged.     

On the initial layer solution of the Boltzmann equation with small Knudsen number

We extend our method of systematic removal of secular terms in a singular perturbation treatment of the Boltzmann equation with small Knudsen numbers to the initial layer. The requirement that the solution through the initial layer should connect smoothly to the normal solution removes an ambiguity noted in our previous paper. We show that removal of secular terms improves Grad's solution for the initial layer and reintroduces soundlike modes associated with higher moments, first found by Wang Chang and Uhlenbeck.     

New Aspects of Cyclodextrin Chemistry Induced by Outside Type Complex Formation; Asymmetric Reduction of Indol-3-Pyruvic Acid with NaBH4 in Aqueous Solution

Asymmetric reduction of indol-3-pyruvic acid (IPA) with NaBH₄ in aqueous solution in the presence of various cyclodextrins (α-, β-, γ-, mono-6-amino-6-deoxy-β- and di-6^ABamino-6^AB-deoxy-β-cyclodextrin) was investigated. From the NMR and circular dichroism spectral studies, the conformation of the CyD–substrate complexes is suggested; the part of carboxylic group stay in the cavity of α-CyD, whole of IPA in β-CyD, two molecules in a γ-CyD cavity, and IPA(s) is/are on the rim of the cavity of mono-6-amino-6-deoxy-β- and di-6^ABamino-6^AB-deoxy-β-CyD (AβCyD, DAβCyD) with electrostatic interaction between amino group and carboxylic group. This conformational difference provides in the difference in the optical selectivity of reduction.     

Cu(OTf)2-catalyzed Et3SiH-reductive etherification of various carbonyl compounds with trimethylsilyl ethers

A triethylsilane-reductive etherification of the trimethylsilyl ethers with a variety of carbonyl compounds in good yields at room temperature employing 0.5 mol% Cu(OTf)₂ as an extremely efficient catalyst is described here.     

Synthesis and properties of novel dialkylaminocarbenium salts

Novel dialkylaminocarbenium salts with metallocomplex counter ions were prepared by the reaction of phosgene with either DMF or tetramethylurea in the presence of metal chlorides. Reactions of organosilicon amides with phosgene gave corresponding carbenium salts, while organosilicon ureas yielded aminoiminocarbenium salts. Dialkylaminochlorocarbenium salts were reduced with hydrosilanes to give dialkylaminocarbenium, salts and can be easily hydrolyzed to afford either amides or ureas. Pathways of the reaction with water and alcohols depend on the nature of reagent and the reaction conditions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1035–1040, May 1997.