氯化锆催化芳胺和正丁醛合成喹啉衍生物

以ZrCl4为催化剂,芳胺和醛为原料,采用"一锅法"合成了喹啉衍生物;考察了空气、催化剂用量、原料比例以及芳胺的取代基等因素对反应收率的影响;利用高分辨质谱和核磁共振谱(1 H NMR、13 C NMR)表征了产物的分子结构.结果表明,以苯胺和正丁醛为原料时,3-乙基-2-丙基喹啉的收率可达65%,同时生成27%的N-丁基苯胺;工艺经改进后,反应条件温和、操作简便、催化剂用量少、产物收率高.     

白鲜碱的合成

以苯胺为原料经取代、关环、甲基化、还原、消除反应合成了呋喃喹啉类生物碱白鲜碱,总收率17%,其结构经1H NMR,13C NMR和MS确证.     

豆腐果苷-喹啉和黄酮衍生物的合成及镇静活性研究

以L-脯氨酸为有机催化剂一步合成了豆腐果苷-喹啉酮(2),在此基础上合成了一系列豆腐果苷-喹啉衍生物3a～3c,4和5a～5c;以苄溴、豆腐果苷、邻羟基苯乙酮,氨基脲盐酸盐、羟胺盐酸盐、甲氧基胺盐酸盐为原料合成出豆腐果苷-黄酮衍生物8和9a～9c.产物结构经1H NMR,IR和HRMS确认.初步生物活性测试结果表明5b和9b具有较好的镇静催眠活性.     

4,4'-二氨基三苯胺的合成与纯化

以苯胺和对硝基氯苯为原料,K2CO3作催化剂,合成出了中间产物4,4'-二硝基三苯胺(DNTPA).将中间产物用10%(质量分数)的Pd/C催化剂加氢催化还原,得到纯度为96.6%的目标产物4,4'-二氨基三苯胺(DATPA),合成总产率为38%.与其它方法相比,该方法原料便宜易得,纯度很高,产物可作为反应的单体原料.     

一类新型硅烷基Schiff碱亚胺络合过渡金属催化剂的合成及催化乙烯性能研究

以γ-氨丙基三乙氧基硅烷和水杨醛为原料,通过席夫碱反应合成一类硅烷基Schiff碱亚胺配体;分别以六水氯化镍和六水氯化钴为络合试剂,通过络合反应合成两类硅烷基Schiff碱亚胺络合过渡金属催化剂.元素分析、FT-IR、1H NMR和ICP证实合成的硅烷基Schiff碱亚胺配体及其相应的过渡金属催化剂的结构与其理论结构相...     

离子液体作相转移剂催化合成N,N-二乙基苯胺的研究

用离子液体作相转移催化剂,在常压下以苯胺和溴乙烷为原料合成N,N-二乙基苯胺,考察了多种反应因素对目的产物产率的影响,得到了适宜的反应条件是:苯胺和溴乙烷的摩尔比为1∶2.5(苯胺,11mL,溴乙烷,22.5mL),催化剂用量1.20g(0.004mol),在50mL50%(质量分数)的氢氧化钠溶液中,反应温度60℃,常压反应6h,产品收率高于97%.     

4,4'-二氨基三苯胺的合成与纯化

以苯胺和对硝基氯苯为原料, K₂CO₃作催化剂, 合成出了中间产物4,4'-二硝基三苯胺(DNTPA). 将中间产物用10%(质量分数)的Pd/C催化剂加氢催化还原, 得到纯度为96.6%的目标产物4,4'-二氨基三苯胺(DATPA), 合成总产率为38%. 与其它方法相比, 该方法原料便宜易得, 纯度很高, 产物可作为反应的单体原料.     

4-溴-N,N-二(2-氨基苯氧乙基)苯胺的合成

以对溴苯胺为原料,经4步反应合成了4-溴-N,N-二(2-氨基苯氧乙基)苯胺,其结构经1H NMR, IR和MS表征.     

可见光诱导邻烯基甲酰苯胺环化合成2-喹啉酮

使用廉价易得的邻烯基甲酰苯胺在可见光的诱导下发生自由基环化反应, 以良好至优秀的产率合成了15种2-喹啉酮衍生物. 该方法简单高效、 条件温和、 产率较高, 具有优异的官能团兼容性, 不仅拓展了邻烯基甲酰苯胺参与的新型有机反应, 也为光催化合成喹啉酮类化合物提供了一条新途径.     

取代8-羟基喹啉钌络合物催化Friedl?nder反应合成喹啉衍生物

Friedl?nder喹啉合成法是以邻胺基芳基醛或酮与有α-亚甲基的酮环化制备喹啉的反应,报道了一种喹啉钌络合物催化Friedl?nder法合成喹啉的方法.首先,以8-羟基喹啉钌络合物为催化剂,对模板反应邻氨基苯甲醇和苯乙酮合成2-苯基喹啉进行了反应条件优化实验.重点对比研究了8-羟基喹啉钌络合物配体上不同取代基对反应收率的影响,其中5-甲基-8-羟基喹啉(1e)钌络合物催化邻氨基苯甲醇和苯乙酮合成2-苯基喹啉获得了73%的最高收率.结合IR, UV以及密度泛函理论(DFT)计算讨论了配体结构与催化性能之间的关系.提出了β-H消除形成醛过渡态,交叉aldol反应再亚胺环化,最后脱水生成目标产物的可行机理.以(1e)₃Ru为催化剂,在优化的反应条件下进行了底物扩展研究,以69%～94%的收率合成了32个不同取代的喹啉衍生物,验证了方法的普适性.     

Selective oxidation of ethylbenzene to acetophenone over Cr(III) Schiff base complex intercalated into layered double hydroxide

A new heterogeneous catalyst, Cr(III) Schiff base‐containing layered double hydroxide, was synthesized using the intercalation method. The Cr(III) Schiff base complex derived from 2‐hydroxy‐1‐naphthaldehyde and 4‐aminobenzoic acid was intercalated into the layered double hydroxide. The synthesized materials were characterized using inductively coupled plasma atomic emission spectrometry, energy‐dispersive X‐ray analysis, scanning electron microscopy, X‐ray diffraction, Brunauer–Emmett–Teller surface area measurement, Fourier transform infrared spectroscopy, thermogravimetric analysis, diffuse reflectance UV–visible spectroscopy and electron paramagnetic resonance spectroscopy. The catalytic activity was investigated for the oxidation of ethylbenzene with tert‐butylhydroperoxide as an oxidant under solvent‐free conditions as well as with lower chromium concentrations. In the oxidation reaction, ethylbenzene was oxidized to acetophenone and benzaldehyde. The catalyst was recycled ten times without significant loss of catalytic activity. Leaching studies performed with hot filtration experiments showed that the chromium catalyst was heterogeneous in nature and stable under the reaction conditions.     

中孔MCM-41锚合Zr（IV）-salen催化剂制备及用于硫化物氧化制亚砜和Knoevenagel缩合反应

通过NH2-MCM-41与水杨醛反应得到席夫碱配体,然后加入八水氧氯化锆形成络合物,制得Zr(IV)-salen-MCM-41催化剂。采用X射线衍射、N2吸附-脱附、热重、红外光谱、电感耦合等离子体发射光谱和能量散射谱等分析手段对催化剂结构进行了表征。在含有该催化剂的体系中进行了硫化物选择氧化为亚砜以及醛与丙二腈和氰乙酸乙酯的Knoveonagel缩合反应,并考察了催化剂的循环使用性能。     

钴-席夫碱-壳聚糖/凹凸棒土对苯乙烯环氧化的催化性能

以NaOH固化法制备的壳聚糖/凹凸棒土（CS/ATP）复合树脂为载体,以水杨醛和天冬氨酸合成的席夫碱为配体,分别合成Co、Mn、Cu、Fe和Ni的席夫碱金属配合物及其负载型席夫碱金属配合物,并通过FT-IR对其进行结构表征,且以苯乙烯为底物,分子氧为氧源,分别考察了各种催化剂对苯乙烯的环氧化性能。 实验结果表明,在小分子席夫碱金属配体中,Co-Schiff碱催化性能较好。 将Co-Schiff碱负载到CS/ATP复合树脂中,综合考察了Co-Schiff碱-CS/ATP的用量、温度、时间对苯乙烯催化环氧化性能的影响,结果表明,反应温度为80 ℃,反应时间为8 h,苯乙烯的转化率达93.1%。     

手性胺—铜配合物的合成及其在菊酸不对称合成中的应用

报导了新型希夫碱－铜配合物的合成，及其对菊酸不对称合成的催化诱导效应，用降解脱氢松香胺和水杨醛反应，形成希夫碱，再与醋酸铜反应，制行希夫碱－铜配合物。将该配合物作为手性催化剂，催化重氮乙酸乙酯及重氮乙酸冰片酯与２，５－二甲基－２，４－己二烯合成菊酸的反应，讨论了重饩     

KF/Al2O3催化合成2-甲基-3-(3,4-亚甲二氧基苯基)丙烯醛

缩合;催化剂;洋茉莉醛;KF/Al2O3催化合成2-甲基-3-(3;4-亚甲二氧基苯基)丙烯醛     

Polyethylene glycol clicked Co(II) Schiff base and its catalytic activity for the oxidative dehydrogenation of secondary amines

Copper catalyzed [3+2] cycloaddition "click method" provided an efficient and high yielding immobilization of cobalt(II) Schiff base to the azido-functionalized MeOPEG(5000); whereas the direct reaction between MeOPEG(5000) and Co(II) Schiff base did not produce any immobilization. The prepared catalyst was tested for the oxidative dehydrogenation of various secondary amines using TBHP as oxidant and could be easily recovered by precipitation with diethyl ether at the end of the reaction.     

呋喃胺水杨醛Schiff碱铜(Ⅱ)配合物的合成与结构

以4,5-二甲基-3-腈基-2-呋喃胺与水杨醛为原料,合成了4,5-二甲基-3-腈基-2-呋喃胺水杨醛Schiff碱化合物,再与醋酸铜反应得到一种新型的呋喃胺水杨醛Schiff碱铜(Ⅱ)配合物.目标化合物通过IR、UV,元素分析及摩尔电导分析等进行了表征.应用荧光光谱法研究了该配合物与牛血清白蛋白(BSA)之间的相互作用.实验表明,该配合物能强烈猝灭BSA的内源荧光.     

Synthesis and characterization of a polymer-anchored palladium(II) Schiff base complex and its catalytic efficiency in phosphine-free Sonogashira coupling reactions

A polymer-anchored Pd(II) Schiff base complex has been synthesized by reacting a polymeric amine with 2-pyridinecarboxaldehyde to get the polymer-anchored Schiff base, which was then reacted with palladium acetate. The catalyst was characterized by physicochemical and spectroscopic methods. It shows excellent catalytic activity in the Sonogashira coupling of phenylacetylene with aryl halides using triethylamine as a base and copper iodide as a co-catalyst in water under open air at 70 °C. We have also studied the effects of base and solvent on the coupling reaction. Sonogashira reactions of phenylacetylene with a variety of functionalized aryl halides were performed under the optimized reaction conditions. This catalyst gives excellent yields without the use of phosphine ligands. Further experiments showed that the catalyst can be used five times without much loss in the catalytic activity.     

Metal complexes of novel Schiff base derived from the condensation of 2‐quinoline carboxaldehyde and ambroxol drug with some transition metal ions

A new Schiff base was prepared as the condensation product of the reaction of 2‐quinoline carboxaldehyde and ambroxol drug. The Schiff base ligand thus obtained (HL; trans‐4‐[(2‐(2‐quinolinoimino)‐3,5‐dibromobenzyl)amino]cyclohexanol) was further employed as a tridentate ligand for the synthesis of new complexes through reaction with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions. The synthesized HL and its metal complexes were characterized using various physicochemical techniques including elemental analysis, Fourier transform infrared and UV–visible spectroscopies, conductimetric and magnetic susceptibility measurements, mass spectrometry and thermal analyses. ¹H NMR data indicated that complex formation was through the amino group rather than the aliphatic hydroxyl group. Thermal analysis gave an idea about the decomposition pattern of HL and its complexes. Also, it revealed the number of water molecules in the inner and outer spheres of the complexes. An octahedral geometry for all the complexes has been suggested. HL and its complexes were screened for their antimicrobial activity against various species of bacteria and fungi using the disc diffusion method. The Cr(III) complex had the highest antimicrobial activity.