5,7′-(亚甲胺基)-二-8-羟基喹啉的合成及其理论研究

以4-甲基苯磺酸作催化剂、用三乙胺调节pH值约为9的条件下,由5-甲酰基-8-羟基喹啉和5-氨基-8-羟基喹啉合成了新的5,7′-(亚甲胺基)-二-8-羟基喹啉,利用IR,UV,1H NMR,MS确认了分子结构,比较研究了其光致发光特性,运用Gaussian 98量子化学程序包,采用B3LYP密度泛函(DFT)的方法,在6-31G(d,p)水平上对分子的几何构型进行结构优化;并对目标化合物的稳定结构通过计算预测其振动光谱,计算结果与实验值基本相符.     

5,7′-(亚甲胺基)-二-8-羟基喹啉的合成及其理论研究

以4-甲基苯磺酸作催化剂、用三乙胺调节pH值约为9的条件下, 由5-甲酰基-8-羟基喹啉和5-氨基-8-羟基喹啉合成了新的5,7′-(亚甲胺基)-二-8-羟基喹啉, 利用IR, UV, ¹H NMR, MS确认了分子结构, 比较研究了其光致发光特性, 运用Gaussian 98量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在6-31G(d,p)水平上对分子的几何构型进行结构优化; 并对目标化合物的稳定结构通过计算预测其振动光谱, 计算结果与实验值基本相符.     

甲酰基-8-羟基喹啉的合成

以8-羟基喹啉为原料,通过Reimer-Tiemann反应合成了5-甲酰基-8-羟基喹啉(收率15.0%)和7-甲酰基-8-羟基喹啉(收率21.5%),其结构经1HNMR和IR表征。     

5-[2'-氟-4'-溴-苯甲亚胺]-8-羟基喹啉铝的量子化学研究

应用密度泛函PBE0方法优化5-[2'-氟-4'-溴-苯甲亚胺]-8-羟基喹啉铝(AlA3)及5-[2'-氟-4'-溴-苯甲亚胺]-8-羟基喹啉(HA)的几何构型, 用TDDFT法计算其电子光谱, 对电荷转移及金属原子与配体的结合能进行了讨论. 计算结果表明: (1) AlA3配合物较稳定, 但结合能略低于8-羟基喹啉铝(AlQ3). 与AlQ3相比, AlA3的轨道作用较强, 静电作用较弱, 两者之和相近, 但AlA3排斥能较大. (2) 计算AlA3的两个电子吸收峰与实验结果相符. AlA3中的电荷由羟基喹啉基团通过Al原子在不同配体间转移呈现出最大吸收峰, 属于AlQ3类衍生物的特征吸收峰. 因为体系的共轭程度增大使LUMO轨道能降低, 电子跃迁需要的能量减少, 故吸收峰比AlQ3红移; (3) 290 nm吸收峰是电荷由CN基团向羟基喹啉基团转移产生的. 在喹啉环接上5-[2'-氟-4'-溴-苯甲亚胺]基团可望制备出波长更长的发光材料, 且增加了一个较强的吸收峰.     

5-[2''-氟-4''-溴-苯甲亚胺]-8-羟基喹啉铝的量子化学研究

应用密度泛函PBE0方法优化5-[2′-氟-4′-溴-苯甲亚胺]-8-羟基喹啉铝(AlA3)及5-[2′-氟-4′-溴-苯甲亚胺]-8-羟基喹啉(HA)的几何构型,用TDDFT法计算其电子光谱,对电荷转移及金属原子与配体的结合能进行了讨论.计算结果表明:(1)AlA3配合物较稳定,但结合能略低于8-羟基喹啉铝(AlQ3).与AlQ3相比,AlA3的轨道作用较强,静电作用较弱,两者之和相近,但AlA3排斥能较大.(2)计算AlA3的两个电子吸收峰与实验结果相符.AlA3中的电荷由羟基喹啉基团通过Al原子在不同配体间转移呈现出最大吸收峰,属于AlQ3类衍生物的特征吸收峰.因为体系的共轭程度增大使LUMO轨道能降低,电子跃迁需要的能量减少,故吸收峰比AlQ3红移;(3)290 nm吸收峰是电荷由C N基团向羟基喹啉基团转移产生的.在喹啉环接上5-[2′-氟-4′-溴-苯甲亚胺]基团可望制备出波长更长的发光材料,且增加了一个较强的吸收峰.     

2-(5,7-二氯/二溴-8-喹啉氧甲基)-4-苯基喹啉-3-羧酸乙酯的便捷合成(英文)

在K2CO3作为碱、乙腈作为溶剂的条件下,将2-氯甲基-4-苯基喹啉-3-羧酸乙酯(3)分别与5,7-二氯-8-羟基喹啉(4a)和5,7-二溴-8-羟基喹啉(4b)发生Williamson反应,以高收率得到结构新颖的二氯或二溴取代的双喹啉类目标化合物2-(5,7-二氯/二溴-8-喹啉氧甲基)-4-苯基喹啉-3-羧酸乙酯(2a,2b);其结构经波谱数据和元素分析证实.     

5-[2-(8-羟基喹啉-2-基)乙烯基]-2-甲基-8-羟基喹啉的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了5-[2-(8-羟基喹啉-2-基)乙烯基]-2-甲基-8-羟基喹啉(5), 用IR, UV, ¹H NMR, MS和元素分析确认其结构. 利用DPPH•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性及调控鼠骨髓间质干细胞(MSCs)增殖的作用. 结果表明, 目标产物有较强的抗氧化活性, 在低浓度时对鼠骨髓间质干细胞有促进作用.     

2-乙烯基硝基苯-8-羟基喹啉锌配合物的合成及紫外、荧光性质研究

设计合成了3种8-羟基喹啉衍生物配体:(E)-2-[2-(2-硝基苯基)乙烯基]-8-羟基喹啉(4a),(E)-2-[2-(3-硝基苯基)乙烯基]-8-羟基喹啉(4b),(E)-2-[2-(4-硝基苯基)乙烯基]-8-羟基喹啉(4c)及其相应的锌配合物5a～5c,产物经1H NMR,IR,MS和元素分析技术进行了结构表征.通过紫外滴定模拟了金属锌与配体的配位过程,分别测定了它们固态和溶液状态下的荧光性质:光谱显示化合物5a～5c固体荧光光谱的λmax分别是596,625,592 nm,在DMF溶液中的λmax分别是562,536,618 nm.荧光光谱显示硝基位置的改变可以调控8-羟基喹啉锌配合物的发光性质.     

8-羟基喹啉席夫碱衍生物及其金属配合物的合成及荧光性质研究

设计合成了三种新的8-羟基喹啉席夫碱衍生物4-(8-羟基喹啉-5-亚胺甲基)-7-甲氧基苯并吡喃-2-酮(3a),4-(8-羟基喹啉-5-亚胺甲基)-7-己氧基苯并吡喃-2-酮(3b)和4-(8-羟基喹啉-5-亚胺甲基)-7-十八烷氧基苯并吡喃-2-酮(3c)及其铝、锌配合物,产物结构经1H(13C)NMR,MS,HRMS,IR和元素分析表征,研究了它们的荧光发光性能.     

L-(8-羟基-5-甲基喹啉)半胱氨酸修饰电极的制备及其对汞离子选择性检测

利用Shifft碱反应将L-半胱氨酸和5-甲酰基-8-羟基喹啉一步合成L-(8-羟基-5-甲基喹啉)半胱氨酸,通过金-硫键将L-(8-羟基-5-甲基喹啉)半胱氨酸自组装到金电极表面制备L-(8-羟基-5-甲基喹啉)修饰金电极。L-(8-羟基-5-甲基喹啉)半胱氨酸分子中的羟基氧和氮可与Hg2+形成稳定的五元环配合物,因此该修饰电极能选择性吸附Hg2+,结合方波伏安法用于Hg2+电化学检测。在0.01mol/L HCl中,富集时间为160s,Hg2+浓度在1.0×10-9~1.0×10-8 mol/L、1.0×10-8~1.0×10-7 mol/L浓度范围内与方波伏安峰电流分段呈现良好的线性关系,检出限为0.92×10-9 mol/L。     

TD-DFT Study on the Electronic Spectrum Properties of 2,7＇-（Ethylene）- bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7＇-（ethylene）-bis-8-hydroxyqulnoline and its derivatives were optimized by CIS/6-31G（d）. The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory （TD-DFT） by the B3LYP method with the 6-31G（d） basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.     

TD-DFT Study on the Electronic Spectrum Properties of 2,7′-(Ethylene)-bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized by CIS/6-31G(d). The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory (TD-DFT) by the B3LYP method with the 6-31G(d) basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.     

8-羟基喹啉的高分子化及其Eu(Ⅲ)配合物的制备和表征

在合成含有8-羟基喹啉(8HOQ)配位基单体的基础上,将其与甲基丙烯酸甲酯(MMA)共聚得到含有8-羟基喹啉侧基的聚甲基丙烯酸甲酯(PMMA8q),实现了8-羟基喹啉的高分子化;通过PMMA8q和小分子协同配体与稀土离子Eu(Ⅲ)的配位反应,制备了两个稀土高分子发光配合物:Eu(PMMA8q)(8HOQ)2(H2O)3和Eu(PMMA8q)2(TTA)(H2O)3(TTA:噻吩甲酰三氟丙酮)。利用元素分析、红外光谱方法对各阶段产物进行了表征,用荧光光谱研究了两个稀土高分子配合物的荧光特性及发光机理。     

8-hydroxyquinoline monomer, water adducts, and dimer. Environmental influences on structure, spectroscopic properties, and relative stability of cis and trans conformers

The low fluorescence quantum yield of 8-hydroxyquinoline cannot be correctly interpreted without knowing the form that such a compound assumes in different environments. The commonly accepted emission-quenching excited-state proton transfer can follow different reaction paths if 8-hydroxyquinoline is dimeric or monomeric or if it exists in the form of cis and trans conformers; in this light, the knowledge of the compound form in a particular environment is basic. We have performed a spectroscopic and computational investigation aimed at the determination of the form of 8-hydroxyquinoline in different solvents. UV-vis, fluorescence, and IR spectral features have been assigned by ab initio computations based on the density functional theory and time-dependent density functional theory; the density functional theory and MP2 computations have been applied to the determination of the relative stability of the dimeric and monomeric cis and trans forms of 8-hydroxyquinoline in different solvents. Molecular dynamics computations have been used to determine the compound behavior in water solutions. According to our results, 8-hydroxyquinoline shows a clear preference for the cis conformation (as dimer or monomer), but, in water solutions, a small fraction of the trans conformation is also present.     

含8-羟基喹啉铝配合物的高分子聚合物的合成与表征

通过甲基丙烯酸甲酯(MMA)和含有8-羟基喹啉的单体共聚合成模板聚合物,再与二配体的8-羟基喹啉铝配合物(AlQ2)配位,实现了8-羟基喹啉铝配合物的高分子化,获得了一种高分子量金属配合物发光聚合物,并利用元素分析,FTIR,UV,PL光谱,GPC等方法对其结构和性能作了表征．     

4-Aryl-8-hydroxyquinolines from 4-chloro-8-tosyloxyquinoline using a Suzuki-Miyaura cross-coupling approach

4-Chloro-8-tosyloxyquinoline was successfully cross-coupled with various arylboronic acids in anhydrous Suzuki-Miyaura conditions. The protective tosyl group was stable during the anhydrous coupling. The use of tosyl protection in association with anhydrous Suzuki-Miyaura reaction conditions allows the use of commercially available but relative inert 5-chloro-8-hydroxyquinoline for the synthesis of 5-phenyl-8-hydroxyquinoline. Deprotection could easily be made by using suitable nucleophiles to afford the final 5-phenyl and 4-aryl-8-hydroxyquinolines in high yields. Under acidic conditions the tosyloxy group is sufficiently stable to allow selective further modification of acid labile functional groups.     

Analysis of vibratinal spectra of 8-hydroxyquinoline and its 5,7-dichloro, 5,7-dibromo, 5,7-diiodo and 5,7-dinitro derivatives based on density functional theory calculations

The geometry, frequency and intensity of the vibrational bands of 8-hydroxyquinoline and its 5,7-dichloro, 5,7-dibromo, 5,7-diiodo and 5,7-dinitro derivatives were obtained by the density functional theory (DFT) calculations with Becke3-Lee-Parr (B3LYP) functional and 6-31G* basis set. The effects of chloride, bromide, iodide and nitro substituent on the vibrational frequencies of 8-hydroxyquinoline have been investigated. The assignments have been proposed with aid of the results of normal coordinate analysis. The observed and calculated spectra are found to be in good agreement.      

DFT studies and vibrational spectra of isoquinoline and 8-hydroxyquinoline

The geometry, frequency and intensity of the vibrational bands of isoquinoline (IQ) and 8-hydroxyquinoline (8-HQ) were obtained by the density functional theory (DFT) calculations with the B3LYP functional and 6-31 G* basis set. The vibrational spectral data obtained from the solid phase mid and far FT-IR and FT-Raman spectra of IQ and 8-HQ are assigned based on the results of the normal coordinate calculations. The observed and the calculated spectra are found to be in good agreement.     

新型8-羟基喹啉席夫碱的合成与抑菌活性

以2-甲基-8-羟基喹啉为原料,经羟基保护、甲基氧化、水解后得到2-甲酰基-8-羟基喹啉(L)。L分别与苯胺衍生物缩合得到三种新型喹啉衍生物。经元素分析、红外光谱、紫外光谱、核磁共振谱表征,确定了席夫碱的组成。产物分别与大肠杆菌、产气杆菌、枯草杆菌、变形杆菌、金黄色葡萄球菌进行抑菌活性实验,配体与席夫碱均有较好的抑菌活性。