10H-茚并[1,2-b]喹啉及其衍生物的合成

杂环化合物大多具有一定的生物活性,而喹啉类杂环化合物是具有生物活性和药理活性最常见的一类杂环化合物.很多喹啉衍生物具有杀菌、抗菌、抗高血压、抗抑郁、抗过敏、抗疟疾、抗肿瘤和抗癌等生物活性和药理活性[1].大部分喹啉衍生物是通过化学方法合成出来的,如磷酸氯喹(Chloroquine phosphate)、扑疟喹(Plasmoquine)、磷酸伯喹(Primaquine phosphate)等抗疟疾药物[2].     

N(—2-羟基乙基)—水杨醛亚胺稀土配合物的合成与性质研究

J.J.Calienni等以水杨醛及取代水杨醛与取代氨基乙醇反应制得多种希夫碱,并合成了它们与铕的希夫碱配合物。N-(2-羟基乙基)-水杨醛亚胺(HESI)与Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)配合物的合成和抗癌活性的研究也有报道,但该希夫碱稀土配合物尚未见文献报道。鉴于有些稀土化合物具有消炎、抗癌活性,合成稀土希夫碱配     

6,7-二氧亚甲基-3-硫杂-1(2H,4H)吖啶酮的Beckmann重排及硫杂吖啶并六员杂环的合成

吖啶类化合物是一类颇受人们注意的抗疟药物,具有抗癌活性的吖啶合成也引起了有机化学工作者的极大兴趣。虽然对吖啶的化学已经进行了相当深入的研究,但硫杂吖啶酮     

6,7-亚甲二氧基-3-硫杂-1(2H,4H)吖啶酮的氨类衍生物及五元杂环并硫杂吖啶的合成

吖啶类化合物在抗疟和抗癌的药用研究中具有显著的作用^[1,2]，尤其在临床抗疟中广泛地应用了该类药物。为了深入进行吖啶化学的研究,我们将杂原子引入到吖啶环系中,完成了氧杂吖啶的合成^[3]、硫杂吖啶酮及其并六元杂环的研究工作^[4]。本文进一步报告6,7-亚甲二氧基-3-硫杂-(2H,4H)吖啶酮的氨类衍生物及其并五元杂环化合物的合成。     

染料木素的化学修饰研究进展

大豆异黄酮染料木素具有抗氧化活性、心血管保护、抗癌、抗炎、抗溃疡及雌激素等多种药理功能。本文综述了染料木素的化学修饰研究进展,为进行前药分子设计、寻找活性化合物提供依据。     

抗癌性吲哚喹唑啉衍生物的定量构效关系

用量子化学密度泛函理论(DFT)、分子力学(MM＋)及回归分析方法,对一系列抗癌性吲哚喹唑啉衍生物进行了定量构效关系(QSAR)的研究.通过回归分析,筛选了影响抗癌活性的主要因素,建立了定量构效关系方程.结果表明,化合物的最低未占据分子轨道(LUMO)与最高占据分子轨道(HOMO)之间的能量差(ΔεL-H)、分子的疏水性(lgP)以及环D上的总电荷(ΣQD)和环D上R1取代基的第一个原子的净电荷(QFR1)是影响化合物抗癌活性的主要因素.所得模型对化合物抗癌活性有较好的预测效果. 同时, 与ΔεL-H密切相关的LUMO轨道能量及共轭平面面积对药物的DNA-结合及其活性起着十分重要的作用,可通过选取具有较强的拉电子性质同时又能与本系列化合物的骨架形成更大共轭体系的取代基R1,设计抗癌活性较高的化合物.     

HPLC法测定人体尿液中的4'-羟基和6-甲氧基黄烷酮

黄烷酮(Flavanone)属于黄酮类化合物(Flavonoids),具有2-苯基色原酮化学结构.黄烷酮类化合物广泛存在自然界,其衍生物大多从天然植物中提取而得,取代基多为羟基、甲氧基、苄氧基、异戊烯基、香叶基等,是多种药用植物有效成分之一.据有关文献报道,许多黄烷酮类化合物具有抗菌、消炎、抗肿瘤、抗HIV病毒、抗诱变、抗氧化、抗癌活性等诸多生物活性~([1]).由于其显著的生物、药理活性及独特的可靼性结构,引起了化学和医药工作者浓厚的研究兴趣.     

白杨素衍生物的合成及生理活性研究进展

黄酮类化合物白杨素具有抗氧化、抗肿瘤、抗癌、抗病毒、抗高血压、抗糖尿病、抗菌、抗过敏等广泛的生理活性.近年来,许多国内外学者对其衍生物的合成及生理活性进行了研究,以期开发出活性更高,更具有临床应用价值的药物.本文着重对各类白杨素衍生物的合成及生理活性研究进展进行综述.     

卟啉介导抗癌药物研究

卟啉是一类具有特别生物功能的化合物，对于增殖异常的组织具有一定的亲和 力．利用这一特性，合成了四—对羟基苯卟啉(Zn^Ⅱ)甲氨蝶呤衍生物，并使用红 外、紫外、质谱、核磁和元素分析等手段对该化合物进行了表征．做了该化合物在 细胞水平上抗艾氏腹水型肿瘤实验，其IC50值为0.28μg/mL。同时在小鼠体内做了 抗艾氏腹水型肿瘤实验，抑瘤率为75．82％．初步实验表明，该化合物具有良好的 抗癌体内外活性及较小的毒副作用．从配位化学的角度提出了该化合物具有良好的 抗癌作用的可能机理．     

2—杂环色酮的合成

近十年来国外对于黄酮类化合物的类似物——2-或3-杂环色酮的生理活性产生了极大兴趣,例如探索了具有抗癌活性的8-羧甲基黄酮的类似物2-(2-呋喃;2-噻吩)-8-羧甲基色酮的抗癌活性,以及发现了2-(3-吡啶)-6,8-二氯色酮具有驱虫作用。本文作为研究杂环色酮构效关系的一部分,首先合成了心血管药物立可定——7-乙氧羰甲氧基黄酮的类似     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.