Co-Catalyzed Metal-Ligand Cooperative Approach for N-alkylation of Amines and Synthesis of Quinolines via Dehydrogenative Alcohol Functionalization

Herein we report a cobalt-catalyzed sustainable approach for C−N cross-coupling reaction between amines and alcohols. Using a well-defined Co-catalyst 1 a bearing 2-(phenyldiazenyl)-1,10-phenanthroline ligand, various N-alkylated amines were synthesized in good yields. 1 a efficiently alkylates diamines producing N, N′-dialkylated amines in good yields and showed excellent chemoselectivity when oleyl alcohol and β-citronellol, containing internal carbon-carbon double bond were used as alkylating agents. 1 a is equally compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols. 1H-Indole was synthesized via an intramolecular dehydrogenative N-alkylation reaction, and various substituted quinolines were synthesized by coupling of 2-aminobenzyl alcohol and secondary alcohols. A few control reactions and spectroscopic experiments were conducted to illuminate the plausible reaction mechanism, indicating that the 1 a -catalyzed N-alkylation proceeds through the borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout the reaction; the hydrogen eliminated during dehydrogenation of alcohols was set aside in the ligand backbone and subsequently gets transferred in the reductive amination step to imine intermediates yielding N-alkylated amines. On the other hand, 1 a -catalyzed quinoline synthesis proceeds through dehydrogenation followed by successive C−C and C−N coupling steps forming H₂O₂ as a by-product under air.     

Reaction of 3‐Hydroxyquinoline‐2,4‐diones with Inorganic Thiocyanates in the Presence of Ammonium or Alkylammonium Ions: the Unexpected Replacement of a Hydroxy Group by an Amino Group

3‐Hydroxyquinoline‐2,4‐diones react with KSCN in the presence of the NH$\rm{{_{4}^{+}}}$ ions to generate 2,3‐dihydro‐3‐thioxoimidazo[1,5‐c]quinazolin‐5(6H)‐ones, 2,3‐dihydro‐2‐thioxo‐1H‐imidazo[4,5‐c]quinolin‐4(5H)‐ones, and products of molecular rearrangement of the 3‐aminoquinolinedione intermediates. Starting compounds with a benzyl (Bn) group at C(3) afford 3‐aminoquinolinediones, even when only AcONH₄ is used. The results of the reaction between 3‐hydroxyquinoline‐2,4‐diones and KSCN in the presence of BuNH₂ show that replacing a OH group with a secondary NH₂ group is also possible.     

Quinoline-based aggregation-induced delayed fluorescence materials for highly efficient non-doped organic light-emitting diodes

Three new emitters,namely 10,10'-(quinoline-2,8-diyl)bis(10 H-phenoxazine)(Fene),10,10'-(quinoline-2,8-diyl)bis(10 H-phenothiazine)(Fens) and 10,10'-(quinoline-2,8-diyl)bis(9,9-dimethyl-9,10-dihydroacridine)(Yad),featuring quinoline as a new electron acceptor have been designed and conveniently synthesized.These emitters possessed small singlet-triplet splitting energy(ΔEst) and twisted structures,which not only endowed them show thermally activated delayed fluorescence(TADF)properties but also afforded a remarkable aggregation-induced emission(AIE) feature.Moreover,they also showed aggregation-induced delayed fluorescence(AIDF) property and good photoluminescence(PL) property,which are the ideal emitters for non-doped organic light-emitting diodes(OLEDs).Furthermore,high-performance non-doped OLEDs based on Fene,Fens and Yad were achieved,and excelle nt maximum external quantum efficiencies(EQE_(max)) of 14,9%,13.1% and 17,4%,respectively,were obtained.It was also found that all devices exhibited relatively low turn-on voltages ranging from 3.0 V to3.2 V probably due to their twisted conformation and the AIDF properties.These results demonstrated the quinoline-based emitters could have a promising application in non-doped OLEDs.     

A novel colorimetric chemosensor based on quinoline for the sequential detection of Fe3+ and PPi in aqueous solution

A novel quinoline-functionalized Schiff-base derivative PY was designed and synthesized. Sensor PY displayed highly selective and sensitive fluorescence enhancement and naked-eye color change to Fe³⁺ in the presence of other competing cations. The mechanisms have been supported by Job’s plot evaluation, FT-MS and theoretical calculations. The in situ generated PY-Fe³⁺ complex solution exhibited a high selectivity toward PPi via Fe³⁺ displacement approach. The detection limits of sensor PY to Fe³⁺ and PY-Fe³⁺ complex to PPi were estimated to be 4.24 × 10^?8 M and 8.18 × 10^?8 M, respectively. This successive recognition feature of sensor PY makes it has a potential utility for Fe³⁺ and PPi detection in aqueous solution. A B3LYP/6-31G(d,p) basis set was employed for optimization of PY and PY-Fe³⁺ complex.     

溶剂热合成可调控氧空位的Bi2MoO6纳米晶及其光催化氧化制喹啉和抗生素降解

近年来,半导体光催化在环境净化和有机合成领域的研究引起了广泛的重视.其中,在有机合成领域中,光催化技术已经应用在醇类、环己烷以及芳香族化合物的选择性氧化研究.而另一类具有特殊结构的有机物——N-杂环芳烃,在药物化学和材料科学中具有重要意义.而传统用于合成N-杂化芳烃的脱氢催化氧化反应通常需要高温高压的苛刻环境,传统方法通常还需要使用贵金属催化剂,这也增加了N-杂化芳烃的合成成本;另外,如果合成是均相催化过程,则催化剂难以实现回收利用.因此,开发室温常压条件下的非贵金属多相光催化技术具有巨大的应用前景.本文以能够被可见光驱动的钼酸铋半导体为催化剂,利用氧缺陷策略来提升钼酸铋的光催化氧化性能.不同于传统氧缺陷制备方法(氢气还原热处理、离子掺杂等),本文采用一种低成本的乙二醛辅助溶剂热的方法合成具有可调控的含氧空位Bi₂MoO₆催化剂(OVBMO).通过X射线粉末衍射(XRD)、扫描电镜、透射电镜、紫外可见漫反射吸收光谱、氮气物理吸附脱附、X射线光电子能谱(XPS)、电子自旋共振光谱、光致发光光谱及电化学测试等技术对制备的OVBMO材料进行了物理化学性质及能带研究.XPS,XRD,Raman和FT-IR结果表明,氧空位存在于[Bi₂O₂]²⁺和MoO₆八面体的层间.紫外可见漫反射结果表明,随着氧空位的引入,Bi₂MoO₆的光吸收范围扩大,带隙变窄.结合莫特肖特基和VBXPS分析获得OVBMO的能带位置,发现氧空位的存在不仅会导致禁带中出现缺陷带能级,还会导致价带顶位置上移,促进光生空穴的迁移.PL和电化学结果表明,氧空位的存在使得载流子浓度、载流子的分离能力与界面电荷迁移能力都有较大提升,这是因为氧空位引入的缺陷能级可以浅势捕获电子,抑制光催化剂中的电子与空穴的复合,改变化学反应的速率.同时,氧空位有助于捕获分子氧,分子氧与捕获的光生电子发生反应,产生更多的超氧自由基(·O₂)和空穴(h⁺),从而极大地提升光催化剂的氧化性能.因此,OVBMO在1,2,3,4-四氢喹啉脱氢氧化产生喹啉及系列抗生素(环丙沙星、四环素、盐酸土霉素)的降解反应中,表现出较好的光催化氧化性能.结合多种表征分析,本文还进一步阐明了OVBMO催化剂将1,2,3,4-四氢喹啉脱氢氧化为喹啉的自由基参与的多相催化反应机理.     

Synthesis of New 1,3,4‐Oxadiazol,Thiadiazole, 1,2,4‐Triazole,and Arylidene Hydrazide Derivatives of 4‐Oxo‐1,4‐dihydroquinoline with Antimicrobial Evaluation

A series of substituted 1,3,4‐oxadiazole, 1,2,4‐triazole, and 1,3,4‐thiadiazole derivatives of the substituted 3‐carboethoxy‐1,4‐dihydro‐4‐oxoquinoline have been synthesized through the reaction of the key intermediate thiosemicarbazide derivatives with different reagents. N′‐Arylidene‐4‐oxo‐1,4‐dihydroquinoline‐3‐carbohydrazides were also synthesized through the condensation reaction of the corresponding hydrazides with the appropriate aldehydes. Antimicrobial activity of some of the synthesized compounds was evaluated.     

Synthesis of lodopyridone

The total synthesis of the unusual 4-pyridone marine metabolite lodopyridone has been achieved by late stage manipulation of the related 4-pyrone. Key reactions include a Suzuki–Miyaura coupling to form the tetracyclic core and a modified Corey–Ganem–Gilman reaction to install the ethanolamide side-chain.     

KMnO4-mediated direct selective radical cross-coupling: An effective strategy for C2 arylation of quinoline N-oxide with arylboronic acids

Direct C—H functionalization of quinoline N-oxides with arylboronic acids is achieved using KMnO_4 as the sole and efficient oxidative system.This method provides an efficient protocol to construct regioselectively 2-arylquinoline N-oxides via radical cross-coupling reaction in moderated to good yields under mild conditions.     

Construction of mononuclear transition metal(II) complexes with bi- and tridentate,neutral hydrazone ligands with a quinoxaline hub

A series of Co(II), Ni(II), Cu(II), and Zn(II) complexes of bi- and tridentate hydrazones were prepared. Ligands L¹ and L² were synthesized by the condensation of 2-mercapto-3-hydrazinoquinoxaline with 2-hydroxy-3-formylquinoline and 3-acetylcoumarin, respectively. The compounds were characterized by various spectro-analytical techniques and magnetic moment studies. The complexes are found to be monomeric and non-electrolytes. In these complexes, [CuL¹Cl₂] has square pyramidal geometry and others have octahedral. The copper complexes are electrochemically active in the applied potential range.