Ionic liquid-promoted ring-closure reactions between 1,4-dihydroxyanthraquinone and diamines

The reaction of 1,4-Dihydroxyanthraquinone with diamines was carried out in the presence of CuCl(2), CuCl in the ionic liquid [Bmim]PF(6), [Bmim]BF(4) or [Bmim]Cl x CuCl.     

Ionic liquid as an efficient promoting medium for fixation of carbon dioxide: a clean method for the synthesis of 5-methylene-1,3-oxazolidin-2-ones from propargylic alcohols, amines, and carbon dioxide catalyzed by Cu(I) under mild conditions

[reaction: see text] The reactions of propargylic alcohols, aliphatic primary amines, and CO2 were conducted in CuCl/[BMIm]BF4 system to produce the corresponding 5-methylene-1,3-oxazolidin-2-ones under relatively mild conditions. The products could be conveniently isolated by means of liquid-liquid extraction. The solvent ionic liquid as well as CuCl catalyst can be recovered and reused three times without appreciable loss of activity. By this green approach, several new 5-methylene-1,3-oxazolidin-2-ones were prepared in excellent yields and purity and were well-characterized.     

主链含联萘的聚吡啶手性离子探针的合成和性质

合成了一种主链含联二萘基团的聚吡啶类共轭聚合物, 并通过圆二色谱(CD) 和紫外可见光谱(UV-Vis) 研究了其对Cu2+和Pd2+的识别能力, 并初步推测了识别机理.     

On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4]2- in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)

The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C(4)Py](2)[CuCl(4)] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl(4)](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl(4)](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.     

CuCl对Et3NHCl/AlCl3离子液体催化性能的影响

 用CuCl对Et3NHCl/AlCl3离子液体进行改性,并考察了其对异丁烷-丁烯烷基化反应的催化性能. 结果表明,烷基化油的收率达到178%,C8组分的含量达到85%,辛烷值(RON)达到94.8. 通过结构组成及电荷分布分析可知,在CuCl改性的Et3NHCl/AlCl3离子液体中形成了新的配位结构AlCl4CuCl-,它作为更好的碳正离子受体,在反应过程中可降低碳正离子的浓度,进而降低烯烃的聚合程度,抑制较长碳链烷烃的生成,改善烷基化油的组成.     

复合离子液体催化碳四烷基化反应性的研究

合成了一种新型的酸性离子液体催化剂——复合离子液体，该离子液体的阴离子具有双金属的配位中心。同时，研究了复合离子液体催化异丁烷与丁烯烷基化反应的规律。结果表明，在搅拌速率大于1500r/min，反应低于20℃，烃酸比2∶1~3∶1，烷烯比大于15，反应停留5min~10min，使用丁烯-2为碳四烯烃反应原料下，复合离子液体催化碳四烷基化所得烷基化油的研究法辛烷值（RON）最高可达100以上，明显优于常规氯铝酸离子液体催化所得烷基化油的质量。     

Speciation of copper(II) complexes in an ionic liquid based on choline chloride and in choline chloride/water mixtures

A deep-eutectic solvent with the properties of an ionic liquid is formed when choline chloride is mixed with copper(II) chloride dihydrate in a 1:2 molar ratio. EXAFS and UV-vis-near-IR optical absorption spectroscopy have been used to compare the coordination sphere of the cupric ion in this ionic liquid with that of the cupric ion in solutions of 0.1 M of CuCl(2)·2H(2)O in solvents with varying molar ratios of choline chloride and water. The EXAFS data show that species with three chloride ions and one water molecule coordinated to the cupric ion as well as species with two chloride molecules and two water molecules coordinated to the cupric ion are present in the ionic liquid. On the other hand, a fully hydrated copper(II) ion is formed in an aqueous solution free of choline chloride, and the tetrachlorocuprate(II) complex forms in aqueous choline chloride solutions with more than 50 wt % of choline chloride. In solutions with between 0 and 50 wt % of choline chloride, mixed chloro-aquo complexes occur. Upon standing at room temperature, crystals of CuCl(2)·2H(2)O and of Cu(choline)Cl(3) formed in the ionic liquid. Cu(choline)Cl(3) is the first example of a choline cation coordinating to a transition-metal ion. Crystals of [choline](3)[CuCl(4)][Cl] and of [choline](4)[Cu(4)Cl(10)O] were also synthesized from molecular or ionic liquid solvents, and their crystal structures were determined.     

Wacker oxidation of terminal olefins in a mixture of [bmim][BF4] and water

A simple and efficient PdCl₂/CuCl catalyzed oxidation of alkenes has been successfully developed using a mixture of water and the ionic liquid [bmim][BF₄] as solvent. Starting from various types of terminal olefins, the corresponding ketones have been prepared under mild reaction conditions and obtained in good to excellent yields after a simple extraction with diethyl ether. Furthermore, it was possible to recycle and reuse the ionic liquid and the catalytic system.     

离子液体的结构及其汽油萃取脱硫性能

用不同金属氯化物与氯代甲基咪唑合成离子液体,采用快原子轰击谱测定了这些离子液体的结构,并评价了这些离子液体对汽油萃取脱硫的能力.实验结果表明,由CuCl合成的离子液体中存在稳定的CuCl-2 ,Cu2Cl-3 和Cu3Cl-4 阴离子.这些阴离子可能通过Cu(I)与S的π络合作用而使离子液体具有较高的萃取脱硫效率.经六次萃取后,汽油中的硫含量可以从 650 μg·g-1降至 20~30μg·g-1.     

Direct electroreduction of solid cuprous chloride to copper powder in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

Direct electroreduction of solid cuprous chloride to prepare copper powder in a “neutral” ambient-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (BMIMBF₄) was investigated. Cyclic voltammetry of the CuCl powder in a Pt-powder cavity microelectrode exhibited that solid CuCl can be electrochemical reduced in the ionic liquid. Chronoamperometry of the salt powder filled Mo-cavity electrode (current collector) in the ionic liquid further demonstrated the conversion of chloride-to metal inside the cavity, as confirmed by scanning electron microscopy, energy-dispersive X-ray, and X-ray diffraction spectra.     

Highly efficient solvent-free synthesis of quinazolin-4(3H)-ones and 2,3-dihydroquinazolin-4(1H)-ones using tetrabutylammonium bromide as novel ionic liquid catalyst

<正>A simple and efficient procedure for the synthesis of 2-arylquinazolin-4(3H)-ones has been developed through cyclocondensation of 2-aminobenzamide with aromatic aldehydes using tetrabutylammonium bromide(TBAB) as novel neutral ionic liquid catalyst in the presence of copper(Ⅱ) chloride(CuCl_2) as oxidizing agent under solvent-free conditions at 100℃.In the absence of CuCl_2 and under a nitrogen atmosphere,the unoxidized intermediates,2-aryl-2,3-dihydroquinazolin-4(1H)-ones,were isolated. Treatment of these intermediates with CuCl_2 in TBAB media gave the oxidized products 2-arylquinazolin-4(3H)-ones.On the other hand,cyclocondensation of 2-aminobenzamide with aromatic aldehydes in TBAB under microwave irradiation directly gave 2- arylquinazolin-4(3H)-ones.     

[CuCl3CPZ(O)H]络合物的合成及电化学行为的研究

盐酸氯丙嗪目前在精神病治疗中作为首选药物之一，在临床上应用于精神分裂症、狂躁症、焦虑症及更年期精神病等症．该药物吩唾咪环比较容易被氧化；1982年Geary等[1]合成了该药物的钯络合物，并对其进行了X-今线结构分析．Kawazura等[2,3]研究了该药物与体内微量元素之间的相互作用；Holbrok山研究表明用盐酸氯丙埃后脑内铜的浓度上升．而服用后药物先与蛋白质结合，与金属离子反应的可能性较小；为此本文制备了该药物的主要代谢产物之一的CPZ（0）HCI，并与体内微量元素铜（11）络合得到KUQa＊Pz问仰，对该络合物进行了元素分析和电…     

Cu(I)Y分子筛的固态离子交换制备及其表征

应用ＩＲ、ＭＳ和ＥＰＲ表征ＣｕＣｌ和ＮＨ４Ｙ固态离子交换过程以及制备Ｃｕ（Ｉ）Ｙ的一些特性。固态离子交换程度依赖于反应温度。和还原Ｃｕ（ＩＩ）Ｙ的方法，固态离子交换是更为有效的制备纯Ｃｕ（Ｉ）Ｙ的方法。     

Ionic liquid crystal precursors for inorganic particles: phase diagram and thermal properties of a CuCl nanoplatelet precursor

We have recently reported (Angew. Chem. Int. Ed. 2004, 43 (40), 5380) the formation of CuCl nanoplatelets from an ionic liquid crystal precursor (ILCP) consisting of a 50/50 (wt/wt) mixture of bis(dodecylpyridinium) tetrachlorocuprate 1 and 6-O-palmitoyl ascorbic acid 2. Here we present the full ILCP phase diagram and the thermal behavior from a mixing ratio of 1/0 (i.e., pure 1) to 0/1 (i.e., pure 2). The ILCP exhibits a crystalline-smectic-isotropic phase transition at all mixing ratios, and the liquid crystal region is up to 90 degrees C wide. DSC shows a broad exothermic peak between ca. 70 and 170 degrees C, which is associated with the thermally induced CuCl formation. The reaction enthalpies reach -150 kJ/mol at around 50/50 (wt/wt) mixtures of the two components, and the activation energy for CuCl formation is ca. 190 kJ/mol. Thermogravimetric analysis shows that the samples degrade above ca. 200 degrees C.     

氯化亚铜氧化反应的化学动力学初探

多数被发掘的古代青铜文物表面都附着有某些钢锈,其中以粉状锈(Cu_2(OH)_3Cl)对铜器的腐蚀最为严重.迄今已有一些文献介绍粉状锈的生成机理,但对其反应过程的动力学研究尚未见报导。作为青铜合金中含量最丰的元素铜,被氧化腐蚀是分步进行的.本工作主要用X-光衍射及分光光度法对一价铜锈CuCl在潮湿环境中进行氧化反应的速度常数及表观活化能进行测定核算;对反应的中间产物及伴随现象进行分析探讨。     

The reactivity in the system CuCl-Si related to the activation of silicon in the Direct Synthesis

The reaction between cuprous chloride CuCl and silicon is the classical model reaction for activation of the contact mass in Direct Synthesis. It had been found by several authors that the reactivity of CuCl strongly depends on its quality and the route of synthesis. In the present study the reactivities of two CuCl charges, prepared from the elements at high temperatures and by reduction in aqueous solution, are compared by means of calorimetric studies. The aqueous route CuCl was found to have a higher reactivity, indicated by lower reaction start temperatures and 100% CuCl conversion with respect to the other charge. It was found that the reactivity depends neither on intrinsic properties (defect concentration) nor on properties that can be derived from microscopical or thermoanalytical characterizations or by X-ray powder diffraction. The initial step of reaction between cuprous chloride and silicon was identified as a solid state reaction. Therefore, the role of the CuCl surface is discussed and a model for the initial step is suggested.     

SILAR法制备化学计量CuInS_2薄膜

在室温下,以不同cCu/cIn的CuCl2和InCl3混合溶液作为阳离子前驱体,Na2S水溶液为硫源,利用连续离子层吸附反应法(SILAR)在玻璃基底上制备了CuInS2薄膜。XRD结果表明,当cCu2 /cIn3 在1￣1.5范围内均可形成具有黄铜矿结构的CuInS2薄膜。SEM观察到随cCu2 /cIn3 的升高,薄膜表面颗粒长大并出现团簇聚集。通过XPS测定薄膜表面的化学组成证明当cCu2 /cIn3 =1.25时,CuInS2薄膜接近其标准的化学计量组成。此时薄膜的吸收系数大于>104cm-1,禁带宽度Eg为1.45eV。     

超声法合成3,4-二氢嘧啶-2(1H)-酮衍生物

以取代芳醛（1a~1h）,乙酰乙酸乙酯(2)和脲(3)为原料,MMT/CuCl₂为催化剂,乙醇为溶剂,在超声条件下经Beginelli反应合成了8个3,4-二氢嘧啶-2(1H)-酮衍生物（4a~4h）,其结构经¹H NMR和IR确证。以4a为例,分别采用单因素法和正交实验法研究了催化剂、溶剂、反应温度、超声时间和物料比r［n(1a): n(2) :n(3)］对4a产率的影响。结果表明：在最优反应条件(1a 2.4 mol, r=1.2 : 1.0 : 1.0, MMT/CuCl₂20 mol%, EtOH 1 mL,于90 ℃超声15 min)下,4a产率88.4%。 MMT/CuCl₂循环使用3次,产率基本不变。     

Two solvent and temperature dependent copper(II) compounds formed by a flexible ligand: syntheses, structures and SC-SC transformation

A nonporous neutral framework [CuCl(2)(m-bttmb)(2)](n) (1) was changed into a porous ionic {[Cu(m-bttmb)(2)(H(2)O)Cl]Cl(CH(3)CN)(0.5)(H(2)O)(2.75)}(n) (2) by simply increasing the amount of CH(3)CN in the mixed solvent (CH(3)CN and H(2)O) or temperature in the reactions of CuCl(2)·2H(2)O with 1,3-bis(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (m-bttmb). 1 undergoes transformation into 2 when treated with CH(3)CN. Both 1 and 2 have 2D 4-connected (4,4) network architectures but in different packing arrangements. These compounds have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra and thermogravimetric analysis. This work may provide a way to control the formation of neutral or ionic frameworks, as well as porosities by adjusting the polarity and components of the solvents.     

纤维素基磁性聚偕胺肟树脂的研究——CuCl2的吸附行为

CuCl₂可吸附在碱式纤维素基磁性聚偕胺肟树脂(BMAO)上.接触20min时F=0.69,n([Cu²⁺]a)/n([AO])=0.59,此后吸附速度突然下降.动力学研究和扫描电镜观察表明,吸附后生成了二齿螯合物,随后进行氧化还原反应析出单质铜.BMAO适于在稀溶液中吸附Cu²⁺离子,也适于进行大规模吸附.