Synthesis of new terpene derivatives via ruthenium catalysis: rearrangement of silylated enynes derived from terpenoids

Enyne rearrangement of silylated modified terpenoids has been used as the key step for the synthesis of new terpenes and terpenoids. The catalytic system generated in situ from [RuCl₂(p-cymene]₂, 1,3-bis(mesityl)imidazolinium chloride and cesium carbonate is able to perform the transformation of silylated 1,7-enynes into cyclic siloxanes. Selective cleavage of the silicon-carbon and silicon-oxygen bonds by simple reactions has been performed to afford new terpenes and terpenoids by formal addition of a C5 unit.     

Olefin terpolymerizations. II. 4-vinylcyclohexene and cyclooctadiene

4-Vinylcyclohexene (VCH) and cyclooctadiene (COD) were investigated as termonomers in EPDM (ethylene/propylene/diene) synthesis by using rac-ethylenebis (1-η⁵-indenyl) zir-conium dichloride ( 1 ) as a catalyst precursor. Homopolymerizations of VCH, vinylcycloh-exane and cyclohexene were compared. The parameter K_πκ_p, which is the apparent rate constant for Ziegler-Natta polymerization, is about the same for VCH and vinylcyclohexanebut is 10 times smaller for cyclohexene. Therefore, the linear olefinic double bond is more active than the cyclic internal double bond. VCH reduces ethylene polymerization rate but not propylene polymerization rate in copolymerizations. In terpolymerizations, VCH tends to suppress ethylene incorporation especially at elevated polymerization temperature and Lowers the polymer MW by about two-fold. COD has very low activity as a termonomer. © 1995 John Wiley & Sons, Inc.     

Paper-like Microfibrous Nickel Catalyst for Hydrogen Production via NH3 Decomposition in Fuel Cell Applications

Recently, miniature H2 generator to power fuel cells for portable/micro electronic devices and passenger propulsion has been the focus of intense research activities1-3. One of the strategies is to find simple CO-free H2 production with novel microreactor…     

孤立分散在SiO2基质中的半导体InSb纳米颗粒界面效应的MS-XANES研究

利用MS-XANES计算研究了嵌入在SiO₂介质中的InSb纳米颗粒的界面效应, 结果显示Sb K-XANES实验谱在白线峰强度增大和白线峰向高能一侧展宽这两个特点的起因是: 1. SiO₂介质透过界面处强的Sb-O共价键间接地影响和改变了InSb团簇中Sb原子内部的势分布; 2. 通过InSb纳米颗粒界面处存在着强的Sb-O共价键使得Sb原子的5p电子被耗尽来提高InSb纳米颗粒Sb原子的5p的空穴数. 这两方面共同决定了InSb纳米颗粒的Sb K-XANES实验谱在白线峰 强度的增大. 此外, 由于纳米颗粒的界面效应, 仅仅把白线峰的强度增大归因于吸收原子电荷转移带来的空穴数增加, 并依此通过白线峰的强度计算吸收原子的空穴数是不合理的.     

Ruthenium-catalyzed regioselective synthesis of 2-substituted indoles via ring-opening of epoxides by anilines

Anilines react with epoxides in dioxane at 180°C in the presence of a catalytic amount of a ruthenium catalyst along with tin(II) chloride to afford 2-substituted indoles in moderate to good yields.     

A ring-closing metathesis approach to a synthesis of the B ring of eleutherobin

A short and efficient RCM route is reported for the construction of the key nine-membered B ring of eleutherobin starting from the readily available 1,2,5,6-diisopropylidene-d-glucose.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶 凝胶法以磷钼酸 (MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2 催化剂 .使用ICP、XRD、TG DTA、IR、TPD MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能 .杂多钼酸盐与TiO2 通过O2 -在TiO2 表面发生了键合 .在 6 2 3K下 ,杂多阴离子仍保持原有的Keggin结构 .CO2 在Lewis酸位Ni(Ⅱ )和Lewis碱位Ni-O -Mo的桥氧协同作用下生成CO2 卧式吸附态Ni(Ⅱ )←O - (CO)← (O--Ni) .丙烯有多种吸附态在催化剂上吸附 .在 5 6 3K、1MPa和空速 15 0 0h-1的反应条件下 ,丙烯的摩尔转化率为 3.2 % ,产物MAA选择性为 95 % .     

Study on deactivation and regeneration of Pd/Al2O3 catalyst in hydrogen peroxide production by the anthraquinone process

Deactivated palladium catalysts in the hydrogenation of anthraquinione were regenerated with ethanol, nitric acid, hydrogen peroxide, boiling water and steam, respectively. The deactivated and regenerated catalysts were characterized by XPS, ICP, TG, FTIR, TPD, XRD, etc., and studied in the hydrogenation of anthraquinone. The results showed that the main cause of catalyst deactivation is the coverage of the active component by deposits. The treatments by hydrogen peroxide and boiling water can effectively regenerate the deactivated catalysts. This revised version was published online in August 2006 with corrections to the Cover Date.     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.