Synthesis and transformations of metallacycles. 30. Aluminacyclopentanes in the synthesis of secondary and tertiary alcohols

A method for the synthesis of secondary and tertiary alcohols was developed. The method is based on cycloalumination of olefins with trialkylalanes in the presence of Zr-containing catalysts followed by the CuCl-catalyzed in situ reaction of the corresponding aluminacyclopentanes with aldehydes or ketones.     

A practical synthesis of 2-(N-substituted)-aminobenzimidazoles utilizing CuCl-promoted intramolecular cyclization of N-(2-aminoaryl)thioureas

A practical protocol for synthesis of 2-(N-substituted)-aminobenzimidazoles was developed. N-(2-Aminoaryl)thioureas undergo a CuCl-promoted intramolecular cyclization to give the corresponding 2-(N-substituted amino)benzimidazoles in good to excellent isolated yields.     

分散法制备的CuCl/MCM-41上C3H6选择催化还原NO反应的研究

研究了由分散法制备的两种CuCl/MCM-41催化剂上丙烯在过量氧存在下选择催化还原NO反应, 发现所制备的CuCl/AlMCM-41催化剂的反应活性明显高于CuCl/SiMCM-41. XRD, IR, TPR及ESR的研究结果表明, CuCl/AlMCM-41催化剂上的主要活性中心是与骨架铝配位的铜离子(Cu2+/Cu+).     

氧化羰化法合成碳酸甲乙酯热力学及催化性能的研究

研究了在甲醇、乙醇温和溶液中,氧化羰化一步合成不对称碳酸甲乙酯(MEC)反应。通过热力学计算考察了反应的可行性及程度。计算结果表明,在298.2K下主反应平衡常数为2.39×1080,说明此反应的可行性和程度均很大。实验发现在氧化羰化合成碳酸甲乙酯的过程中,不仅存在氧化羰化过程,同时也存在酯交换过程;含氮席夫碱(Schiff)的种类,甲醇和乙醇相对用量,反应温度和压力对碳酸甲乙酯(MEC)的合成均有影响。当以氯化亚铜(CuCl) 1,10 菲罗啉(phen) N 甲基咪唑(NMI)为催化剂时,摩尔比n(CuCl)∶n(NMI)∶n(phen)=1∶1.25∶1.25,在393K,2.4MPa,VMeOH∶VEtOH=2∶8,CuCl浓度为0.20mol L的条件下,反应2h,甲醇的转化率为44.3%,乙醇的转化率为22.3%,MEC产率为10.4%。与单纯CuCl催化剂相比,甲醇和乙醇的转化率分别提高17倍和9倍,MEC产率提高74倍。对氧化羰化反应机理也进行了探讨。     

周期性密度泛函理论研究氯气在CuCl(111)表面上的吸附与解离

运用广义梯度密度泛函理论(Generalized Gradient Approximation，GGA)的PBE(Perdew-Burke-Ernzerh)方法结合周期性平板模型，研究了氯气分子和氯原子在CuCl(111)表面上的吸附。通过对不同吸附位和不同单层覆盖度下的吸附能和几何构型参数的计算和比较发现：氯气分子在CuCl(111)表面的吸附为解离吸附；单层覆盖度为0.50时的吸附构型为稳定的吸附构型；氯气分子平行吸附在CuCl(111)表面时最稳定，吸附能最大，达364.5 kJ·mol^-1；伸缩振动频率的计算结果表明，吸附后的氯气分子的伸缩振动频率与自由氯气分子的伸缩振动频率相比，都发生了红移；布居分析结果表明整个吸附体系发生了由Cu原子向氯气分子的电荷转移。氯原子吸附的计算结果显示氯原子以穴位稳定的吸附在CuCl(111)表面。     

纳米CuCl晶簇室温光吸收谱

实验测定了平均尺寸４．２ｎｍＣｕＣｌ晶簇的室这紫外和可见光吸收谱线，给出了Ｈｅ－Ｎｅ激光束辐照下的光吸收谱线，在３．１８７ｅＶ处有宽度０．６２ｍｅＶ的吸收尖峰。     

An evidence of contact ion pair in β-(acyloxy)alkyl radical heterolysis during copper(I)-mediated synthesis of trisubstituted alkenes

The first evidence for a unified mechanism of heterolysis in β-(acyloxy)alkyl radical involving contact ion pair (CIP) is presented for both fragmentation and rearrangement of the acyloxy group in the reaction of 1-alkoxy-2,2,2-trichloroethyl acetate with 2 mol equiv each of CuCl and bpy in refluxing DCE under a N₂ atmosphere and availed this reaction for the synthesis of Z-stereoselective trisubstituted alkenes. The stereochemistry of the trisubstituted alkenes was assigned by the uniform pattern of the chemical shift values of some relevant signals in ¹H and ¹³C NMR spectra. This assignment was further supported by the X-ray diffraction spectroscopy of Z-1-chloro-2-(4-nitrobenzyloxy)vinyl acetates.     

Sonochemical Preparation of Micro- and Nanometer Cu2O

Cu2O particles with different morphologies and scales were prepared sonochemically on the solid-liquid interface of CuCl and water, by adjusting the reaction factors. The products were characterized by powder X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The formation and morphology of Cu2O crystals were influenced by high-intensity ultrasound, reaction temperature, and addition of CuCl. The results indicate that micrometer Cu2O was crystallized in cubic and octahedral shapes, whereas, nanometer Cu2O was not produced in well-shaped crystals.     

可见光谱法研究核酸酶P1与氯化铜(Ⅱ)的相互作用

首次采用ＶＩＳ与酶活性测定的方法,研究了溶液中核酸酶Ｐ１与无机氯化铜（Ⅱ）（ＣｕＣｌ２）的直接相互作用。结果发现：在水溶液中核酸酶Ｐ１活性中心的Ｚｎ（Ⅱ）离子可被外加氯化铜（ＣｕＣｌ２）中的Ｃｕ（Ⅱ）部分诱导、交换出来,而Ｃｕ（Ⅱ）进入酶的活性中心,形成相应“Ｃｕ（Ⅱ）－Ｐ１”酶衍生物,并随着溶液ｐＨ值的变化,形成酶的衍生物结构亦随之变化,相应地也影响了酶的催化活性。