1,5-苯并二氮杂(艹卓)衍生物的合成及其生物活性的研究进展

1,5-苯并二氮杂(艹/卓)是一类具有广泛的生理活性和药理活性的七元杂环化合物,很多化合物已作为临床药物,具有很高的研究价值和应用前景,而其合成方法的研究已成为有机化学的一个热点,综述了1,5-苯并二氮杂(艹/卓)的生理活性、医药方面的应用,以及双环化合物合成方法的最新研究进展.     

合成1,5-苯并二氮杂卓衍生物的催化剂研究进展

根据催化剂种类的不同,综述了近十年在1,5-苯并二氮杂(草)衍生物的合成过程中使用的催化剂的研究进展,包括路易斯酸、布朗斯特酸、有机酸、负载催化剂、离子液体催化剂、哌啶类催化剂、介孔材料等,分析了各方法的优缺点,期望能够为探索出更好的催化剂提供启发.     

1,5-苯并二氮杂卓的一步合成综合性实验探索

设计了一个有机合成综合性实验,该实验以邻苯二胺、乙酰乙酸乙酯、苯甲醛为原料,在磷钨酸催化、乙醇作溶剂、冰水浴条件下一步3组分合成1,5-苯并二氮杂卓化合物。实验实现了该化合物由原来的多步合成转化为一步合成,不但避免了中间产物的分离,而且反应条件温和、操作简便、产物收率高、环境友好等,是绿色化学在有机合成中的实际应用,以及现代有机合成方法的具体体现,也是培养学生创新实验能力的较好途径和方法。     

酸性离子液体催化合成1,5-苯并二氮衍生物

以邻苯二胺和酮为原料,酸性离子液体[hmim]HSO4和乙醇为催化体系,合成了一系列1,5-苯并二氮衍生物,其结构经1^H NMR,IR和元素分析表征。催化体系可循环使用3次。     

六氟磷酸/聚苯胺催化合成1,5-苯并二氮杂类化合物

以聚苯胺和六氟磷酸为原料制备了六氟磷酸/聚苯胺(HPF6/PANI)催化剂,研究了该催化剂在邻苯二胺与酮环化缩合反应合成1,5-苯并二氮杂化合物中的催化活性,考察了催化剂用量、温度、溶剂对反应的影响及催化剂的重复使用性.结果表明,该催化剂具有较高的催化活性及较好的重复使用性.     

1,5-苯并二氮杂的合成及其生物活性研究

采用两种方法: 以三氧化铝为载体邻苯二胺与查尔酮为原料的无溶剂合成法和以PPA(多聚磷酸)为催化剂邻苯二胺与苯乙酮的一锅合成法, 合成了1,5-苯并二氮杂, 产物收率为53.7%～74.5%. 通过¹H NMR, ¹³C NMR, MS, IR, 元素分析等手段对所合成的化合物进行了结构确定, 并测试了它们对菌和乙酰胆碱酶的抑制活性.     

新型1,5-苯并二氮杂卓衍生物的结构与抑菌活性的理论分析

采用密度泛函理论(DFT)方法,在B3LYP/6-31G(d,p)水平上对一系列新型1,5-苯并二氮杂卓衍生物进行了几何结构全优化和理论计算研究,得到分子的几何结构、NPA电荷、红外振动光谱及轨道贡献。研究结果表明:1,5-苯并二氮杂卓分子的七元环是扭船式构型;分子不同位置连接不同的取代基,对分子的电荷分布有一定影响;红外光谱理论计算结果与实验结果相吻合。通过探讨前线轨道与抑菌活性的关系发现,所研究的杂卓分子对不同菌株的抑菌活性具有选择性和特异性,其中分子中的N(11)和C=N可能分别是所合成的该类化合物与细菌(枯草杆菌)和真菌(白色念珠菌和新型隐球菌)发生作用的主要活性部位。     

羧基功能化离子液体催化合成1,5-苯并二氮衍生物

在无溶剂条件下,以邻苯二胺和丙酮为原料,羧基功能化离子液体CmmimBF_4(IL)为催化剂,合成了1,5-苯并二氮衍生物(2),其结构经~1H NMR和IR表征.在IL用量为10 mol%,于40 ℃反应1.5 h的条件下,2的产率达93%.IL无需再生处理,可连续循环使用5次,且活性无明显下降.     

苯二氮杂卓类化合物的合成及抗血吸虫活性研究

化合物B30属于苯二氮杂卓类化合物.体外实验表明,在50μM具有100％的杀灭血吸虫效果.本文利用药物化学生物电子等排等原理,设计、合成了4个B30衍生物6、10、13、16,并对其抗血吸虫活性进行初步体外评价.结果显示4个化合物均具有一定的杀虫能力.尤其化合物16有较好的抗血吸虫活性,在50μM浓度下血吸虫的存活率降...     

蒙脱土负载碘催化多组分合成咪唑衍生物

以苯偶酰(1)、苯甲醛(2a)、苯胺(3)和醋酸铵（4)为原料,蒙脱土负载碘和三乙烯二胺（DABCO）为催化剂,通过多组分法合成了6种1,2,4,5-四芳基-1,3-咪唑衍生物,其结构经¹H NMR和IR确证。对反应条件进行了优化。结果表明：在最优反应条件｛以10 mol%MMT/I₂为催化剂,10 mol%DABCO为碱,正丁醇为溶剂,原料配比r［n(1）：n(2a) ：n(3) ：n(4)］=1.0：2.0：2.0：8.0,于110 ℃反应16 h｝下,产率最高为91.5%。     

Lewis Acid Catalyzed Synthesis of Cyanidophosphates

Salts containing new cyanido(fluorido)phosphate anions of the general formula [PF_6?n(CN)_n]^? (n=1–4) were synthesized by a very mild Lewis‐acid‐catalyzed synthetic protocol and fully characterized. All [PF_6?n(CN)_n]^? (n=1–4) salts could be isolated on a preparative scale. It was also possible to detect the [PF(CN)₅]^? but not the [P(CN)₆]^? anion. The best results with respect to purity, yield, and low cost were obtained when the F^?/CN^? substitution reactions were carried out in ionic liquids.     

Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives Catalyzed by p-Dodecylbenezenesulfonic Acid in Water

With the increasing concerns of the environment, more and more chemists are devoted to the research of the "green synthesis" which means that the reagent, solvent and catalyst are environmentally friendly in the organic chemical reactions. The importance of aqueous reaction is now generally recognized, and development of carbon-carbon bond-forming reactions that can be carried out in aqueous media is now one of the most challenging topics in organic synthesis.[1]Herein, we report a clean synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-octahydroxanthene derivatives from aromatic aldehyde and 5,5-dimethyl-1,3-cyclohexadione using p-dodecylbenezenesulfonic acid (DBSA) as the catalyst in water.This method provides several advantages such as high yield, simple work-up procedure and environmental friendliness and water was chosen as a green solvent. All the products were characterized by m.p., 1H NMR, IR and elemental analyses.     

Synthesis of novel 3-substituted 1,5-benzodiazepine derivatives

This paper describes an improved method for the synthesis of 3-(3-chloroquinoxalin-2-yl)-1,2-dihydro-1-formyl-2-oxo-3H-1,5-benzodiazepine (2) and its conversions into novel 3-substituted 1,5-benzodiazepine derivatives (3a,b and 4a,b).     

Solvent Free Synthesis of N-Substituted Pyrrole Derivatives Catalyzed by Silica Sulfuric Acid

Russian Journal of General Chemistry - Sulfuric acid immobilized on silica gel is used as an efficient catalyst in the synthesis of N-substituted pyrrole derivatives by the Clauson–Kaas...     

Synthesis of Quinoline Derivatives by Multicomponent Reaction Using Niobium Pentachloride as Lewis Acid

The aim of this work was to investigate the use of NbCl₅ as a Lewis acid in multicomponent reactions between benzaldehyde, aniline derivatives and phenylacetylene in the synthesis of quinoline derivatives. The effects of the temperature and substituents in the aromatic ring of the aniline were also evaluated. The reactions were carried out at low concentration of niobium and in relatively short reaction times, resulting in yields ranging from 67 to 96%.     

Synthesis of 1,5-benzodiazepine heterocycles containing a trifluoromethyl group

Summary 2,3-Dihydro-1,5-benzodiazepines containing a trifluoromethyl group were obtained by the reaction of ,-unsaturated ketones CF₃COCH=CR¹R² with o-phenylenediamine.M. V. Lomonosov State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10. pp. 1429–1431, October, 1994. Original article October 11, 1994.     

蒙脱土负载碘催化合成双吲哚甲烷衍生物

以蒙脱土负载碘(MMT/I2)作催化剂,醛(1a~1g)与吲哚(2)反应合成双吲哚甲烷衍生物(3a~3g),其结构经1H NMR和IR确证。以3a的合成为例,研究了催化剂、溶剂、反应时间、温度和物料比r[n(1)∶n(2)]对3产率的影响。结果表明:在最佳合成条件(2 1 mmol,r=1.1∶2.0,10 mol%MMT/I2,乙腈1 m L,于25℃反应5min)下,3a~3g产率67.9%~96.2%。MMT/I2循环使用3次,3a产率78.6%。     

Synthesis of Tetrahydrofuran and Tetrahydropyran Derivatives Catalyzed by Tungstophosphoric Acid in Ionic Liquid

Synthesis of tetrahydrofuran and tetrahydropyran derivatives catalyzed by tungstophosphoric acid （H3PW12040） were conveniently performed with high yield from the corresponding unsaturated alcohols in ionic liquid. Sufuric acid （H2SO4）, trifluoromathanesulfonic acid （TfOH） and p-toluenesulfonic acid （TsOH） were also explored for preparing these products in ionic liquid. The catalysts and ionic liquid can be easily recovered and reused.