新型手性胺膦-铱体系催化芳香酮的不对称转移氢化

合成了含-CH_3取代基的PNNP型手性双胺双膦配体, 并采用核磁共振、质谱、红外光谱及圆二色光谱等方法对其进行了表征. 在异丙醇溶液中, 考察了该配体与[IrHCI_2(COD)]_2组成的手性胺膦-铱体系对多种芳香酮的不对称转移氢化性能. 结果表明, 该手性胺膦-铱体系是催化多种芳香酮不对称氢转移氢化的优秀催化剂. 在室温下, 用该体系催化1,1-二苯基丙酮时, 可得到99%的转化率和99% ee的对映选择性.     

双负载双金属催化剂催化芳香卤化物水相脱卤的研究

用PVP（聚乙烯吡咯烷酮）配合双金属Pd—Mn后,再负载于PEG400（平均分子量为400的聚乙二醇）官能化的高岭土上,制成双负载双金属催化剂PVP—PdCl2-MnCl2／GLM—PECA00,用于催化不溶于水的芳香卤化物水相脱卤,对芳香氯化物呈现出高的脱氯活性,重复使用六次转化率仍可达到62．14％,通过IR,TEM,XPS的表征对催化剂各组分在催化脱卤中的作用进行了探讨．     

A mild,efficient and selective iodination of aromatic compounds using iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate

A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate.     

o-，m-，p-IC6H4OCH3的电子结构和取代基效应

采用紫外光电子能谱（UPS）手段结合理论计算研究了有机卤化物o-,m-,p-IC6H4OCH3的电子结构和取代基效应．在碘原子和甲氧基两个供电子基团的共同作用下,这三种碘代苯甲醚的第一电离能均低于相应的碘苯和苯甲醚．通过取代基效应研究表明碘代苯甲醚为富电子体,因此在有机合成反应中具有较高的反应活性．     

气相色谱-质谱联用法测定橡胶制品中多环芳烃（蒽）含量不确定度评定

目的对气相色谱-质谱联用仪法测定橡胶制品中多环芳烃（蒽）含量不确定度进行评定,确定影响不确定度的关键因素。方法依据《ZEK01.4-2008 GS认证过程中PAHs的测试和验证》,使用气相色谱-质谱联用仪法测定橡胶制品中多环芳烃（蒽）含量,并对结果的不确定度进行评定,分析影响测量不确定度的各个因素,对各个分量进行计算和合成。结果扩展不确定度U=5.7 mg/kg,置信概率95%。结论该实验的不确定度主要影响因素是曲线校准。     

Magnesium bistrifluoromethanesulfonimide as an efficient catalyst for the hydroalkylation of aromatic olefins with 1,3-diketones under solvent-free conditions

An efficient magnesium bistrifluoromethanesulfonimide[Mg(NTf_2)_2]catalyzed hydroalkylation of aromatic olefins with 1,3- diketones under solvent-free conditions has been developed.The reactions proceed smoothly to give the desired products in good yields in short reaction times.     

Negishi cross-coupling of organotellurium compounds: synthesis of biaryls, aryl-, and diaryl acetylenes

A functional group tolerant palladium-catalyzed Negishi coupling of diaryl tellurides with organozinc has been developed. This methodology permits efficient preparation of biaryls, aryl acetylenes and diaryl acetylenes in moderate to good yields. A preliminary study to gain further insight into the reaction was performed using in situ ReactIR technology.     

Difluoroalkylamines from high temperature vapor phase reactions of nitrogen trifluoride with alkanes, ethers and benzene

At temperatures around 400 °C, nitrogen trifluoride (NF₃) readily reacts with alkanes and benzene as well as ethers. In all cases, products were N,N-difluoroamines. This is in contrast to difluoroamination of benzylic substrates where the initial N,N-difluoroamines underwent eliminations or rearrangements and were not isolated. Cyclic and acyclic alkanes generated N,N-difluoroaminoalkanes. Benzene substituted on the ring to form N,N-difluoroaniline. Ethers reacted to generate α-N,N-difluoroamino ethers. Little direct fluorination was observed.     

Solid–liquid equilibria based on an equation of state for chain fluids

Solid–liquid equilibria were studied using an equation of state previously developed for fluids containing chain-like molecules. The method was used to correlate solubilities of normal alkanes and aromatic compounds with high molecular mass in hydrocarbon solvents. With one temperature independent parameter for the interaction energy, good agreement can be obtained between calculated results and experimental data for selected systems.     

15N and 13C NMR chemical shifts of 6‐(fluoro,chloro, bromo,and iodo)purine 2′‐deoxynucleosides: measurements and calculations

The ¹⁵N and ¹³C chemical shifts of 6‐(fluoro, chloro, bromo, and iodo)purine 2′‐deoxynucleoside derivatives in deuterated chloroform were measured. The ¹⁵N chemical shifts were determined by the ¹H? ¹⁵N HMBC method, and complete ¹⁵N chemical‐shift assignments were made with the aid of density functional theory (DFT) calculations. Inclusion of solvation effects significantly improved the precision of the calculations of ¹⁵N chemical shifts. Halogen‐substitution effects on the ¹⁵N and ¹³C chemical shifts of purine rings are discussed in the context of DFT results. The experimental coupling constants for ¹⁹F interacting with ¹⁵N and ¹³C of the 6‐fluoropurine 2‐deoxynuleoside are compared with those from DFT calculations. Copyright © 2009 John Wiley & Sons, Ltd.