3-乙酰基取代吡咯衍生物的合成及其晶体结构

本文通过Knorr合成法制备了四个3-位乙酰基取代的吡咯衍生物:1, 2-二甲基-4-异丙基-5-苯基-3-乙酰基-吡咯(5a); 1, 2, 4-三甲基-5-对甲氧苯基-3-乙酰基-吡咯(5b); 1, 2, 5-三甲基-4-苯基-3-乙酰基-吡咯(5c); 1, 2, 5-三甲基-4-对甲氧苯基-3-乙酰基-吡咯(5d)。通过红外, 质谱, 核磁等方法对其结构进行了表征。测定了其中三个化合物的晶体结构。对这类吡咯环上4或5-位有芳环取代基时化合物的晶体结构特征进行了扼要讨论, 晶体衍射实验结果表明,4, 5-位上的芳环与吡咯环本身处于非共平面结构。     

Pd/C催化氢化芳香族硝基化合物合成芳胺

以5%Pd/C为催化剂,芳香族硝基化合物在温和条件(30℃,H2/0.1 MPa)下还原成芳胺。研究了芳环上的取代基对催化加氢反应的影响。结果表明:对位取代的芳硝基化合物的加氢反应速率为:HCH3CO2CH3CF3FOCH3;间位取代芳硝基化合物加氢反应速率为:HCH3CF3FCO2CH3OCH3CN;邻位取代芳硝基化合物加氢反应速率为:HCF3CH3OCH3FCO2CH3CN。     

芳氧基稀土化合物引发开环聚合的活性

综述了近十年来芳氧基稀土化合物在引发内酯、丙交酯和环碳酸酯开环聚合的研究进展,在整理聚合条件、聚合产物收率和分子量、聚合反应动力学和机理的基础上,比较了苯环上不同位置不同取代基的芳氧基配体对开环聚合反应活性的影响,得到以下结论:(1) 三(2,6-二叔丁基-4-甲基苯氧基)稀土化合物[Ln(26B4M)3]的活性最高,无取代基芳氧基稀土化合物(La(P)3)没有活性;(2)邻位叔丁基能提高活性,一个叔丁基与两个甲基效果相近;(3)甲基影响作用相对叔丁基较小,甲基越多活性越大.     

钝化芳环的溴化反应研究

研究了钝化芳环的溴化方法，对三氟甲基苯等一系列含有不同钝化基团的芳环 化合物用KBrO3-H2SO4直接溴化，取得了良好的结果。对影响该反应的因素，如硫 酸的浓度和用量、反应温度和不同钝化基团的影响等进行了分析。     

双环戊二烯基二(芳氧基)钛、锆、铪衍生物的13C核磁共振谱

第Ⅳ副族金属的双环戊二烯基二卤化物及取代双环戊:二烯基二卤化物的¹³C NMR谱已有一些报道.但关于双环戊二烯基二(芳氧基)钛、锫、铪类型化合物的¹³C NMR谱则尚未见系统报道.我们研究其¹³C NMR谱,目的在于探讨第Ⅳ副族的不同金属以及芳环对位不同取代基对¹³C化学位移的影响.我们发现环戊二烯环的¹³C化学位移随金属周期数的增加而有规律地移向高场.同时,在钛、锆、铪三个系列的化合物中,不论是芳环还是环戊二烯环,其相应碳原子的¹³C化学位移之间存在着非常好的线性关系,相关系数等于或优于0.99.     

2-芳胺基-3H-1,3,4-噻二唑-5-硫醇类介离子化合物的X射线光电子能谱研究

用XPS表征2-芳胺基-1,3,4-噻二唑-5-硫酮(1)在ω-溴代-ω-(1H-1,2,4-三唑)-苯乙酮诱导下生成的2-芳胺基-3H-1,3,4-噻二唑-5-硫醇类介离子化合物(4).结果表明,化合物4分子中的C_1s,N_1s,S_2p电子结合能均高于化合物1,尤其以N_1s,S_2p结合能谱最为特征.例如在含3个氮原子的化合物4中由于噻二唑环的两个氮环境不同,故产生3个峰,而在与其结构相近的对照物1中,由于噻二唑环的两个氮环境相近,故产生2个峰.S_2p诸状态结合能加合值化合物4均大于化合物1,在化合物4中均是杂环内硫大于杂环外硫.     

新型萘酰亚胺衍生物的合成及抗肿瘤活性评价

本文合成了三种新的萘酰亚胺衍生物,并对其体外抗肿瘤活性进行了评价.初步实验结果表明,以芳基修饰氨萘菲特芳环上氨基所得化合物体外活性不如阳性对照氨萘菲特.而利用1,4-丁二醇修饰4-溴-1,8-萘酐芳环上溴原子得到的化合物3与阳性对照及其它两种衍生物相比对肝癌细胞HepG2具有较低的IC_(50)值.     

3—（3,5—二氨基—2,4,6—三硝基苯基）氨基—5—硝基—1,2,4—三唑的合成

多硝基多氨基三唑类衍生物作为含能材料,具有高氮、致密、钝感等优点。本文通过3-氨基-1,2,4-三唑和三硝基三氯苯的缩合,再经过三唑碳原子上的硝化反应和芳环上的氨化反应,合成并鉴定了标题化合物。     

2-（5-芳氧甲基-4-苯基-1，2,4-三唑-3-硫基）乙酰芳胺的水相合成、晶体结构及生物活性

在无催化剂存在下,以水为溶剂通过5-芳氧甲基-4-苯基-1,2,4-三唑-3-硫酮与氯乙酰芳胺的硫烷基化反应,合成了14个未见文献报道的2-(5-芳氧甲基-4-苯基-1,2,4-三唑-3-硫基)乙酰芳胺.其结构经元素分析,IR和1HNMR进行了表征,利用单晶X射线衍射法测定了化合物5n的单晶结构.该化合物通过分子间氢键自组装成三维网状结构的超分子.生物活性试验表明部分化合物对小麦的根有促进作用而对所有的茎都有抑制活性.     

含吡啶环的芳香醚-噁二唑类化合物的合成及其光谱研究

为开发新的高强度的有机电致发光材料, 用含烷氧基的取代苯甲酸(2)与2,6-吡啶二甲酰肼(3)在POCl3作用下, “一锅煮”法合成6个结构对称的含吡啶环的芳香醚-噁二唑4a～4f. 通过MS, IR, 1H NMR, 元素分析等手段对其结构进行了表征. 化合物的荧光性能测定结果显示此类化合物具有良好的荧光性, 其荧光发射波长均在347～507 nm范围内, 最大荧光发射波长在384 nm附近处, 且荧光强度较强. 在芳环上引入5-Br基团(4e, 4f), 化合物的荧光发射波长发生红移, 荧光强度有所减弱. 以硫酸奎宁作参比, 测定6个目标产物的荧光量子产率, 5-Br基团的引入对荧光量子产率没有明显影响. 同时讨论了代表性产物4a在不同溶剂中最大荧光激发波长处的荧光量子产率, 发现溶剂极性对该类化合物的荧光量子产率基本没有影响.     

Guanidiniocarbonylpyrrole–Aryl Derivatives: Structure Tuning for Spectrophotometric Recognition of Specific DNA and RNA Sequences and for Antiproliferative Activity

We present a systematic study of different guanidiniocarbonylpyrrole‐aryl derivatives designed to interact with DNA or RNA both through intercalation of an aromatic moiety into the base stack of the nucleotide and through groove binding of a guanidiniocarbonylpyrrole cation. We varied 1) the size of the aromatic ring (benzene, naphthalene, pyrene and acridine), 2) the length and flexibility of the linker connecting the two binding groups, and 3) the total number of positive charges present at different pH values. The compounds and their interactions with DNA and RNA were studied by UV/Vis, fluorescence and CD spectroscopy. Antiproliferative activities against human tumour cell lines were also determined. Our studies show that efficient interaction with, for example, DNA requires a significantly large aromatic ring (pyrene) connected through a flexible linker to the pyrrole moiety. However, a positive charge, as in 12 , is also needed. Compound 12 allows for base‐pair‐selective recognition of ds‐DNA at physiological pH values. The antiproliferative activities of these compounds correlate with their binding affinities towards DNA, suggesting that their biological effects are most probably due to DNA binding.     

Proton-ionizable crown compounds. 10. Preparation and structural studies of macrocyclic ligands containing two sulfonamide units and with seventeen to twenty-six ring members

Eight new macrocylic ligands each containing two sulfonamide groups have been prepared. Six of these compounds have both the sulfur and nitrogen atoms of the sulfonamide units substituted with aromatic rings. The nitrogen atoms of the other two compounds have alkyl ring connections. X-ray crystal structure data were obtained for new macrocyclic compounds of 20 and 23 ring members. Each crystal structure showed two molecules in the asymmetric unit. Molecule A of 5 and both molecules of 7 exist in a compact conformation suggesting that they could wrap around a metal ion during complexation. Some of these compounds will be used as cation carriers in a bulk liquid membrane system.     

噻唑类化合物应用研究新进展

噻唑环是一类重要的含氮硫杂原子的五元芳杂环,其特殊的结构使得噻唑类化合物在化学、药学、生物学和材料科学等诸多领域具有广阔的应用前景,显示出巨大的开发价值,受到广泛关注.本文结合作者的研究工作,参考国内外近五年文献,系统地综述了噻唑类化合物在医药、农药、材料、生物染色剂和超分子化学领域应用研究进展.     

Recent developments in the synthesis of zoanthamine alkaloids

This review provides a compilation of the most recent synthetic approaches and total syntheses of zoanthamine alkaloids, which are structurally unique heptacyclic marine natural products that display a range of interesting biological activities. This review is focused on synthetic methodologies for the construction of the three adjacent quaternary asymmetric carbon atoms on the cyclohexane ring (C-ring) of these compounds. The literature covered in this review dates from 2008 to the end of 2013.     

Synthesis and Bioactivity of Novel N,N′‐Diacylhydrazine Derivatives Containing Furan(I)

The furan ring system possesses electron‐rich properties and exhibits various biological activities, which was introduced into diacylhydrazine to create novel leading compounds that may serve as improved pesticides and pharmaceuticals. A series of novel diacylhydrazine derivatives containing a furan ring were synthesized by the reaction of 5‐fluorophenyl‐2‐furoyl chloride with substituted benzoylhydrazide in anhydrous dichloromethane under reflux. The structures of the resultant compounds were confirmed by IR, ¹H NMR, MS and elemental analysis. Insecticidal and anti‐tumor activities of these new compounds were evaluated.     

The Syntheses of Novel 7-Methyl-3-Substituted-1,2,4-Triazolo[3,4-b] benzothiazoles

Tricyclazole is one of the benzothiazole derivatives, which are well known for developing this synthesis as many compounds with this ring system are associated with diverse biological activities such as application as potent antibacterials^[1,2] and as fungicides for the control of Piricularia oryzae in the prevention of rice blast^[3]. In particular, s-triazolo[3,4-b]benzothiazole derivatives are of interest because of their broad spectra of biological activities. Therefore, it was planned to investigate a system, which combines these three biologic components in a molecule to give a compact system for screening their biologic activities. Recently, we have synthesized a novel 7-methyl-3-substituted-1,2,4-triazolo[3,4-b]benzothiazole from p-methylaniline to 5 with various aromatic carboxylic acids in the presence of phosphorus oxychloride. The structures of these compounds were established by elemental analysis, NMR, MS and IR techniques.     

Synthetic Routes to Coumarin(Benzopyrone)-Fused Five-Membered Aromatic Heterocycles Built on the α-Pyrone Moiety. Part II: Five-Membered Aromatic Rings with Multi Heteroatoms

Coumarins are natural heterocycles that widely contribute to the design of various biologically active compounds. Fusing different aromatic heterocycles with coumarin at its 3,4-position is one of the interesting approaches to generating novel molecules with various biological activities. During our continuing interest in assembling information about fused five-membered aromatic heterocycles, and after having presented mono-hetero-atomic five-membered aromatic heterocycles in Part I. The current review Part II is intended to present an overview of the different synthetic routes to coumarin (benzopyrone)-fused five-membered aromatic heterocycles with multi-heteroatoms built on the pyrone ring, covering the literature from 1945 to 2021.     

Molecular modeling study of tubulosine and other related ipecac alkaloids

A molecular modeling study of two alkaloids, tubulosine and psychotrine, isolated from the sap of Pogonopus speciosus, and other related ipecac alkaloids, showed that these flexible alkaloids favor a nonplanar structure. The biologically active compounds had conformations with a similar angle between aromatic ring A, the nitrogen in ring B, and ring D. This angle was related to the biological activity reported for these compounds. Our results support the hypothesis of two different types of receptor interactions, one for the nonplanar compounds and another for the planar compounds.     

Current perspectives on quinazolines with potent biological activities: A review

Quinazoline is a heterocyclic compound having biological activities. It is aromatic in nature having bicyclic structure containing benzene ring and pyrimidine ring. Quinazoline and its derivatives are found to have wide range of biological activities that is anticancer, analgesic, antimicrobial, antihypertensive, anticonvulsant, antimalarial, antitumor, and anti-tubercular activities. The purpose of this review is to highlight the recent researches made by researchers on various biological activities of quinazoline derivatives on different targets.     

Definition of a pharmacophore for partial agonists of serotonin 5-HT3 receptors

A definition of a partial agonists serotonin 5-HT3 pharmacophore was carried out by considering a three-dimensional model which correlates the chemical structures of series of piperazinopyrrolothienopyrazines, piperazinopyridopyrrolopyrazines, piperazinopyrroloquinolaxines, piperazinopyridopyrroloquinoxalines, aminoalkyloximinopyrroloindoles, aminoalkyloximinothienopyrrolizines, and aminoalkyloximinopyrrolizines with the biological affinities. The model is formed by five features corresponding to two hydrogen bond acceptors, one aromatic ring, one hydrophobic group, and one positive ionizable site (quaternary ammonium ions). The nature of the features and the distances between them explain the partial agonist activities of these compounds.