纳米2,4-二羟基苯甲酸铅(Ⅱ)配合物的合成及其燃烧催化性能研究

采用液相分散沉淀法制备了纳米2,4-二羟基苯甲酸-Pb(Ⅱ)配合物粉体,并用TG,XRD,TEM,IR和元素分析对产物进行了表征.研究了反应条件对产物粒径和粒子形貌的影响.用DSC考察了产物对吸收药热分解的催化作用.结果表明,在水溶液中得到的产物为15nm×40nm的棒状粒子,而在乙醇溶液中得到的是粒径约为50nm的球形粒子.产物对吸收药热分解有显著的催化效果,使吸收药的分解峰温降低5.6℃,分解热增加918J/g.     

Photoluminescence and Electroluminescence of Organic Light Emitting Diodes Based on Tris‐(8‐quinolinolato) Aluminum Nanoparticles

利用共沉淀方法制备出平均粒径为20nm的有机物8-羟基喹啉铝纳米粒子,8-羟基喹啉铝纳米粒子呈球形且粒度不随老化时间的增加而改变。本文研究了8-羟基喹啉铝纳米粒子的光致发光及基于8-羟基喹啉铝纳米粒子制作的电致发光器件的电致发光特性。8-羟基喹啉铝形成纳米粒子后,其光致发光及电致发光发射光谱的谱峰均出现蓝移。随着驱动电压的增加,器件中8-羟基喹啉铝纳米粒子的发射峰逐渐红移。在驱动电压为16伏时,8-羟基喹啉铝纳米粒子器件的最大亮度达600cd/m²,电流密度为150mA/cm^-2时,器件的发光效率为0.19cd/A。基于8-羟基喹啉铝纳米粒子器件的发射光谱证实了AlQ₃纳米粒子具有量子尺寸效应的存在,这为有机纳米电致发光器件的研究开辟了一条新的研究路线,同时也为那些传统的有机材料如有机分子晶体的基础研究探索出新的研究方向。     

溶剂热法直接合成酞菁铜晶体

以喹啉为溶剂, 在反应釜中将1,3-二异吲哚、钼酸铵和二水乙酸铜在喹啉中反应, 降至室温后得到长10.5 mm针状的酞菁铜单晶, 最佳的反应条件: 以10 mL喹啉为溶剂, 于270 ℃反应8 h, 产率为51.3%.     

Pb(Ⅱ)与8-羟基喹啉沉淀反应及其分析应用

研究了在乙酸盐络合保护作用下,8-羟基喹啉与Pb(Ⅱ)沉淀反应条件,测得了8-羟基喹啉铅螯合物的红外光谱图及差热分析数据,结果表明,8-羟基喹啉铅螫合物适合于重量分析,应用于巴氏合金中高含量铅的分析测定,获得了满意的结果。     

表面引发接枝聚合法制备接枝微粒PHEMA/SiO2及其8-羟基喹啉功能化转变研究

通过用表面引发接枝聚合和高分子反应制备8-羟基喹啉型复合螯合微粒.首先使用γ-氨丙基三甲氧基硅烷(AMPS)对微米级硅胶微粒进行表面改性,制得改性微粒AMPS-SiO2;使改性微粒AMPS-SiO2表面的氨基与溶液中的过硫酸盐构成氧化-还原引发体系,实施了甲基丙烯酸羟乙酯(HEMA)在硅胶微粒表面的高效引发接枝聚合,制得了接枝微粒PHEMA/SiO2.又以5-氯甲基-8-羟基喹啉(CHQ)为试剂,使接枝的PHEMA发生大分子反应,实现了接枝微粒PHEMA/SiO2的8-羟基喹啉功能化转变,制得了复合微粒HQ-PHEMA/SiO2.采用多种手段对两种微粒进行了表征,重点研究了氨基-过硫酸盐表面引发接枝体系的接枝聚合机理,并研究了CHQ与接枝PHEMA的醇羟基之间取代反应的机理,还初步考察了功能微粒HQ-PHEMA/SiO2对重金属离子的螯合吸附性能.研究结果表明,氨基-过硫酸盐表面引发接枝聚合体系具有很高的引发活性,在室温(30℃)即可制得高接枝密度(40 g/100g)的接枝微粒PHEMA/SiO2;CHQ与接枝PHEMA的醇羟基之间的取代反应遵循SN1的反应历程,使用强极性溶剂有利于反应的进行.微粒HQ-PHEMA/SiO2对重金属离子呈现很强的螯合吸附能力,是一种功能复合微粒.     

钯/乙酸亚铜共同促进的嘧啶硫醚的脱硫碳碳偶联反应

报道了一种钯催化、乙酸亚铜盐促进的嘧啶硫醚/喹啉硫醚与炔烃或芳基硼酸的脱硫碳碳偶联反应,合成了一系列2-炔基嘧啶和2-芳基嘧啶/喹啉衍生物,产率良好(64%～87%).所用的乙酸亚铜盐廉价、稳定,反应产率高,底物适用范围较广.     

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.     

聚N-[5-(8-羟基喹啉)甲基]苯胺/硅杂化材料的制备与性能

以8-羟基喹啉、甲醛和苯胺为原料,制备了5-[(苯胺基)甲基-8-羟基喹啉,并以此为单体,以过硫酸铵作为氧化剂,采用化学氧化聚合法,在酸性水溶液中合成了聚N-[5-(8-羟基喹啉)甲基]苯胺.通过正硅酸乙酯表面修饰聚N-[5-(8-羟基喹啉)甲基]苯胺获得了具有荧光特性的聚N-[-5-(8-羟基喹啉)甲基]苯胺/硅杂化材料.该杂化材料不仅在480 nm附近发出较强的荧光,而且在强酸和弱酸电解质溶液中均表现出了较好的氧化-还原可逆性.     

7-取代-8-羟基喹啉的合成

由2-氯辛烷与8-羟基喹啉钠反应制得7-(1′-甲基庚基)-8-羟基喹啉.用长碳链脂肪醛在碱性介质中与8-羟基喹啉反应,合成了一系列7-烯基-8-羟基喹啉(1);对不同结构长碳链脂肪醛合成作了研究.     

5-[2-(5-甲基-1,3,4-噻二唑)偶氮]-8-羟基喹啉的合成及其与铜的显色反应研究

合成了新型偶氮显色剂:5-[2(5-甲基-1,3,4-噻二唑)偶氮]-8-羟基喹啉(简称MTADQ),并研究了它与铜的显色反应。实验结果表明:在pH 5.8~7.8的水溶液中该试剂与铜离子形成一种稳定的黄色络合物,其最大吸收波长位于530 nm处,表观摩尔吸光系数ε=9.5×104L.mol-1.cm-1,配合物的组成比为1∶1。铜离子质量浓度在0~1.2 mg/L范围内服从朗伯-比尔定律。已用于测定矿石样品中的微量铜。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.