Studies on Hydroiodination and Deconjugation of 5—Aryloxy—（thiophenyl）—3—pentyn—2—one

One-pot hydroiodination and deconjugation of 5-aryloxy(or thiophenyl)-3-pentyn-2-one with a reagent system of sodium iodide/trimethylsilyl chloride/water in acetonitrile at 25℃ have been described.The plasuible mechanism was discussed.The reaction provided a simple and useful method for the preparation of (Z)-β-substituted β，γ-enones and (Z)-β-substituted α，β-unsaturated ketones.     

过硫酸胺与N－［（3－二甲氨基）丙基］丙烯酰胺氧化还原引发体系的研究

过硫酸胺与Ｎ－［（３－二甲氨基）丙基］丙烯酰胺氧化还原引发体系的研究司堃，郭新秋，丘坤元（北京大学化学与分子工程学院北京１００８７１）关键词Ｎ－取代丙烯酰胺，氧化还原体系，反应动力学，端基分析，反应机理Ｎ－［（３一二甲氨基）两基］丙烯酸胺（ＤＭＡＰＡ...     

含酮基团对煤焦异相还原NO的影响

基于量子化学密度泛函理论和过渡态理论研究了含酮基团对煤焦异相还原NO的影响及其产物发生氧脱附的微观反应机理。计算结果表明，NO更易于吸附在含酮基团煤焦表面。椅形含酮基团强化了煤焦异相还原NO；锯齿形含酮煤焦表面与NO异相反应决速步能垒值（495.45 kJ/mol）大于锯齿形纯碳基煤焦表面与NO决速步能垒值（331.32 kJ/mol），基于锯齿形含酮煤焦模型中的氧浓度不在利于NO还原的范围内而不易于NO的还原。中间产物P1在无CO存在情况下，较纯碳基煤焦表面更易于发生氧脱附而产生表面缺陷；在CO存在条件下，含酮煤焦表面为氧脱附过程提供自由活性位点，降低了过程能垒消耗。     

One-pot Sequential Reaction for the Synthesis of Polysubstituted 3-（3-Nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates

The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-（3-nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates in good yields and with high diastereoselectivity. Reaction mechanism was believed involving the initial formation of β-enamino ester and sequential Michael addition.     

An expedient one-pot synthesis of highly substituted imidazoles using supported ionic liquid-like phase（SILLP） as a green and effcient catalyst and evaluation of their anti-microbial activity

An effcient method for the synthesis of imidazole derivatives by a three-component condensation of benzil or 9,10-phenanthrenequinone,aldehydes and ammonium acetate using supported ionic liquidlike phase（SILLP）catalyst under ultrasonic irradiation or classical heating conditions is reported.The present methodology offers several advantages,such as excellent yields,simple procedures,short reaction times,simple work-up and mild conditions.The catalyst is easily separated from the products by fltration and also exhibits remarkable reusable activity.These highly substituted imidazoles were also evaluated for their anti-microbial activity.     

三光气与酚制备三氯甲氧基甲酸芳酯研究

研究了不同取代酚与三光气的反应,得到七种未见报道的新化合物,以IR、MS、1H NMR、13C NMR对产物进行了表征,并探索得到合适的反应催化剂、反应物浓度配比、反应时间,讨论了酚上不同取代基对反应的影响,收率在78.5～90.5%之间。     

炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质

以四苯基环戊二烯酮为起始原料,经过八步连续反应,成功地合成了3个炔桥联不对称五苯基取代双二茂铁衍生物Fc''-C≡C-Fc（1）、Fc''-C≡C-C≡C-Fc（2）和Fc''-C≡C-C≡C-Fc''（3）（Fc''=五苯基二茂铁基,Fc=二茂铁基）。在设计合成双二茂铁衍生物的过程中,首先经过4步反应,制备出已知化合物Fc''-H（4）,再连续进行3步反应,分别得到3个中间化合物Fc''-COCH₃（5）,Fc''-CCl=CHCHO（6）和Fc''-C≡CH（7）,最后利用偶联反应,得到目标化合物1~3。利用X射线单晶衍射和循环伏安法,测定了化合物1、2和5、7的晶体结构,研究了化合物1~7的电化学性质。研究结果表明,分子的C-H…π键相互作用和空间位阻是导致化合物1和2分子中Fc''和Fc基空间排布取向不同的主要原因。当二茂铁的一个环戊二烯环上引入5个苯取代基时,铁中心的氧化还原电位将升高（E_p^a（Fc''-H）=0.658 V,E_p^a（Fc-H）=0.511 V）。与已知化合物Fc-C≡C-Fc（ΔE=0.215 V）和Fc-C≡C-C≡C-Fc（ΔE=0.134 V）相比,化合物1~3的氧化电位差值（ΔE）均有不同程度地提高（ΔE₁=0.236 V;ΔE₂=0.170 V;ΔE₃=0.146 V）。将1与Fc-C≡C-Fc,2与Fc-C≡C-C≡C-Fc和3进行比较发现,当炔桥两端连接不同的基团Fc''和Fc时,其氧化电位差值（ΔE）将明显提高。     

Design and Synthesis of Tri-substituted Chiral Pyrrolidin-2-one Derivatives as CCR4 Antagonists

A series of tri-substituted chiral pyrrolidin-2-one derivatives have been designed and synthesized as CC chemokine receptor 4 （CCR4） antagonists. The structure of CCR4 was built by homology modeling. Asymmetric synthesis was applied to synthesize the R,R configuration chiral pyrrolidin-2-one scaffold. The stereoisomeric con- figurations of the compounds were identified by 2D I H-~H COSY spectroscopy and 1D NOESY spectroscopy. This method was more economical and convenient than traditional X-ray single crystal diffraction. In addition, the inter- actions between these compounds and the N-terminal extracellular tail of CCR4 were studied using capillary zone electrophoresis. The CCR4 chemotaxis inhibition effect was tested in CCR4-transfected HEK293 cells. Several compounds showed potent activities as CCR4 antagonists. Among these compounds, lc is the most active one. Its apparent binding constant of CZE experiment result is （1.569±0.11）× 10s L·mol ^-1, and its percentage inhibition of the HEK293/CCR4 cells migration with the concentration of I gmol·L ^-1 in DMSO is 59%. And compound If has slightly higher affinity to N-terminal of CCR4 according to its apparent binding constant than lb because of the in- troduced ester linkage. Further studies on the mechanism of these compounds are in progress.     

PW11O39Co（Ⅱ）（H2O）5-的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B（RhB）的光降解为探针,评估了Keggin型钴取代杂多阴离子PW₁₁O₃₉Co（Ⅱ）（H₂O）^5-（PW₁₁Co）及其异相体系PW₁₁Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW₁₁Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW₁₁Co均相体系及其异相体系PW₁₁Co/D301R对RhB的可见光降解均有较高的光催化活性,但与PW₁₁Co相比,PW₁₁Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW₁₁Co均相体系相比,在PW₁₁Co/D₃₀₁R异相体系中由于PW₁₁Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。