三硝基间苯三酚1,5-二氨基四唑盐的制备、晶体结构及热分析

通过1,5-二氨基-1,2,3,4-四唑（DAT）与等摩尔的2,4,6-三硝基-1,3,5-苯三酚（TNPG）反应,制备了新型离子型含能化合物DATH⁺TNPG^-。通过X射线单晶衍射、元素分析、FT-IR光谱和¹H NMR对其进行了表征。晶体结构测试表明：该化合物的晶体属于单斜晶系,P2(1)/c空间群,a = 1.3399(3),b= 0.47088(9),c = 2.0127(4) nm,β= 92.83(3) ^o,V = 1.2684(4) nm³, Z= 4。在氢键、静电引力和范德华力的作用下该化合物形成了稳定的三维网状结构。对DAT和DATH⁺TNPG^-晶体进行了DFT-B3LYP/6-31G**周期性计算研究,得到其Mulliken电荷分布和重叠布居,从理论上说明DAT质子化位置是在四唑环的N(4)原子。采用TG-DTG和DSC技术对目标化合物的热分解进行了研究,并采用Kissinger和Ozawa-Doyle法对热分解过程的非等温反应动力学进行了计算。     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

N-[2-(1H-吲哚-3)乙基]-2-乙酰噻唑-4-甲酰胺及其类似物的合成

N-[2-(1H-吲哚-3)乙基]-2-乙酰噻唑-4-甲酰胺是最近从海洋细菌中分离得到的一种新型的天然杀藻剂, 以D-丙氨酸为原料合成了该化合物, 并用类似的方法首次合成了它的类似物2, 3和4. 其关键步骤为通过将取代的4-噻唑甲酸制成混酐与色胺连接的偶联反应. 各中间体都通过¹H NMR和¹³C NMR得到证实. 最终产品通过¹H NMR, ¹³C NMR和HRMS证实, 与文献所报道相一致.     

硫（醇）代N-对甲苯基/苯基磺酰基氨基羧酸酯类化合物的合成与神经营养活性

根据官能团的组合,设计合成了硫（醇）代N-对甲苯基/苯基磺酰基氨基羧酸酯类化合物,这些化合物的结构¹H NMR, ¹³C NMR, MS 和 HRMS证实,初步的实验结果表明：在10μg/mL浓度下,化合物4a, 4b, 4d, 5c, 5d, 5g, 6b和 6d显示对PC12细胞缺氧损伤具有显著的保护作用,化合物4c, 5b和 6c显示对PC12细胞缺氧损伤具有一定的保护作用;在5μg/mL浓度下,4d和 6d显示对PC12细胞缺氧损伤具有一定的保护作用;初步的实验也表明：在10μg/mL浓度下,4c, 5a, 5c, 5d, 5e和 6b显示对PC12细胞具有一定的促分化作用。     

3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

以乙腈和芳基腈为原料, 经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪, 并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物, 通过元素分析, ¹H NMR, IR和HRMS对这些化合物进行了表征. 对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明: 其属于单斜晶系, P2_{1 /c空间群, 晶胞参数a＝1.3941(6) nm, b＝0.5675(2) nm, c＝2.0614(8) nm; α＝γ＝90°, β＝102.055(6)°; V＝1.5949(11) nm³, 此类化合物的四嗪环采用不对称船式结构, 且具有同芳香性.}     

4-(N-取代苯基)氨基喹唑啉类化合物的合成及抗磷酸化活性研究

以4-氯喹唑啉为起始原料, 经环化、氯化、取代三步反应, 合成了8个新的4-取代苯基氨基喹唑啉类化合物. 采用¹H NMR, ¹³C NMR, MS, IR及元素分析对目标化合物的结构进行了表征. 生物活性测试表明, 化合物1f在1 μmol• L^－1 浓度下对PC3细胞增殖抑制活性达到88.6%, 进一步研究表明该化合物具有较高的抑制细胞外信号调节激酶(ERK)磷酸化的活性.     

新型2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮的超声辅助一锅法合成及乙酰胆碱酯酶抑制活性研究

以取代苯甲醛、溴乙腈和6-苄基-3-硫代-3,4-二氢-1,2,4-三嗪-5(2H)-酮为起始原料,在超声辅助下,一锅合成了9个新型6-苄基-2-亚苄基-2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮类化合物,结构经_¹H NMR,_¹³C NMR和MS（ESI）表征并对其合成机理进行了初步研究。测试了目标化合物(4a~4i)的体外乙酰胆碱酯酶的抑制活性,其中4a和4d抑制活性最好,有进一步研究的价值。     

两个二茂铁基查尔酮衍生物的合成及超快三阶非线性光学响应

合成两种新颖的含二茂铁基团的查尔酮衍生物：1-二茂铁基-3-(4-叔丁基苯基)丙烯酮(a)和1-二茂铁基-3-联苯基丙烯酮(b),经₁H NMR、₁₃C NMR、HR-MS对其结构进行了表征;测定了该两化合物的热力学性质;采用量子化学方法计算了它们的分子轨道能量和极化率,给出了轨道电子云图;采用紫外-可见吸收光谱和Z-扫描技术测定了其线性和非线性光学性质。结果表明：与原料相比,化合物a和b的紫外吸收明显增加,且b的吸收波长更长;化合物a和b均存在分子内电荷转移现象,表现出超快三阶非线性光学响应。     

2,5-二取代的噻酚类化合物的合成,液晶及光谱性能研究

本文合成了两系列2,5-取代的噻吩类衍生物1a-1f: 2,5-二（对烷氧基苯基乙炔基）噻吩和2a-2b: 2,5-二[(对烷氧基苯基乙炔基）-对-苯基乙炔基]噻吩)]并通过¹H NMR, ¹³C NMR, HRMS和元素分析对其结构进行了表征。研究了结构与液晶性和光谱性之间的关系，结果表明：化合物1a-1f均为互变型向列相液晶，其液晶相通过DSC、PXRD和偏光显微镜得到确证，而具有更长共扼结构的化合物2a-2b却没有液晶性。分子结构中增加苯基乙炔基团，吸收光谱和发射光谱均发生红移，发光量子效率也显著提高。     

三聚联苯醚类大环化合物的合成

在温和条件下, 以3,3 -二溴-4,4 -联苯二酚和1,2-二溴乙烷或1,4-二溴丁烷为原料, 经过两步反应方便地合成了三聚联苯醚类大环化合物4a和4b, 并通过¹H NMR, ¹³C NMR, HRMS对中间体和目标化合物的结构进行了表征.     

Synthesis and pharmacological properties of N‐substituted‐N′‐(4,6‐dimethylpyrimidin‐2‐yl)‐thiourea derivatives and related fused heterocyclic compounds

A series of new N‐Substituted‐N′‐(4,6‐dimethylpyrimidin‐2‐yl)‐thiourea derivatives ( 3a , 3b , 3c , 3d ) and related fused heterocyclic compounds ( 4a , 4b , 4c , 4d ) were synthesized using tetrabutylammonium bromide as phase transfer catalyst (PTC). N‐[(2E)‐5,7‐dimethyl‐2H‐[1,2,4] thiadiazolo [2,3‐a] pyrimidin‐2‐ylidene] derivatives ( 4a , 4b , 4c , 4d ) were prepared by oxidative cyclization of 3a , 3b , 3c , 3d . The structures of these novel compounds were characterized by IR, ¹H NMR, ¹³C NMR, mass spectrometry, and the elemental analysis. The crystal structures were determined from single crystal X‐ray diffraction data. The results indicated that the compounds possessed a broad spectrum of activity against the tested microorganisms and showed higher activity against fungi than bacteria. Compounds 3d and 3a exhibited the greatest antimicrobial activity. J. Heterocyclic Chem., 2011.     

1,2,3‐Triazole derivatives of 3‐ferrocenylidene‐2‐oxindole: Synthesis,characterization, electrochemical and antimicrobial evaluation

A series of bioactive, triazole‐linked benzyl, aryl, sugar and aliphatic conjugates of 3‐ferrocenylidene‐oxindole have been synthesized. A facile 1,3‐dipolar‐Huisgen coupling reaction of the respective azides with the 3‐ferrocenylidene‐oxindole N‐propargyl moiety ( 3 ) gave the corresponding conjugates ( 5a–n ). All the newly synthesized compounds ( 5a–n ) were characterized by ¹H‐NMR, ¹³C‐NMR, HRMS, Fourier transform‐infrared spectroscopy and elemental analysis. The UV–Vis and electrochemical studies of these compounds were performed in dimethylsulfoxide solutions. The structure of compound ( 3 ) was determined by single crystal X‐ray diffraction study. These compounds exhibited moderate to good antimicrobial activity against Gram‐positive and Gram‐negative strains.     

Synthesis and antimicrobial and pharmacological properties of new thiosemicarbazide and 1,2,4‐triazole derivatives

Reaction of 4‐phenyl‐4H‐1,2,4‐triazole‐3‐thione with ethyl bromoacetate has led to the formation of ethyl [(4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)sulfanyl]acetate 1 , the structure of which was confirmed by X‐ray analysis. In the next reaction with 80% hydrazide hydrate, appropriate hydrazide 2 was obtained, which in reaction with isothiocyanates was converted to new acyl derivatives of thiosemicarbazides 2 , 3 , 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h . The cyclization of these compounds in alkaline media has led to formation of new derivatives of 5‐{[(4‐phenyl‐4H‐1,2,4‐triazole‐3‐yl)sulfanyl]methyl}‐4H‐1,2,4‐triazole‐3(2H)‐thiones 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4j . The structure of the compounds was confirmed by elementary analysis and IR, ¹H‐NMR, ¹³C‐NMR, and MS spectra. Compounds 2 , 3 , 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h and 4a , 4b , 4c , 4d , 4e , 4f , 4g were screened for their antimicrobial activities, and the influence of the compounds 4a , 4b , and 4e , 4f , 4g on the central nervous system of mice in behavioral tests was examined. J. Heterocyclic Chem., (2011).     

Synthesis and growth regulatory activity of pyrazolesulfanyl‐ and isoxazolesulfanyl‐1H‐[1,2,4]triazoles and their azinyl derivatives

By cyclocondensation of 3‐(1H‐[1,2,4]triazol‐3‐ylsulfanyl)‐pentane‐2,4‐dion with hydroxylamine, hydrazine, methylhidrazine, and arylsulfonyl‐hydrazides, the 3‐(3,5‐dimethyl‐isoxazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazole ( 2 ) and 3‐(3,5‐dimethyl‐1‐R‐pyrazol‐4‐ylsulfanyl)‐1H‐[1,2,4]triazoles ( 3a , 3b , 3c , 3d ) are synthesized. Under the action of quaternary ammonium salts of azines with limited heating in acetone they form a series of compounds ( 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h ), which molecules simultaneously contain three different heterocyclic rings. Structures of compounds were confirmed by ¹H and ¹³C NMR, MS, and elemental analysis. The plants growth regulatory activities of compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h were investigated. Data of biological tests testify that these compounds can be of interest to search for new growth stimulators. J. Heterocyclic Chem., (2010).     

Synthesis,Antimicrobial Evaluations,and DNA Photo Cleavage Studies of New Bispyranopyrazoles

The bispyranopyrazoles ( 4a , 4b , 4c , 4d , 4e , 4f , 4g ) were synthesized from the reactions of dibenzaldehydes ( 2a , 2b , 2c , 2d , 2e , 2f , 2g ) with 3‐methylpyrazole‐5‐one 3 and malononitrile by refluxing under alcoholic medium. The dibenzaldehydes were obtained from the O‐alkylation of 3‐hydroxybenzaldehyde with suitable 1,ω‐dibromoalkanes under the alkaline conditions in the presence of dry EtOH/DMF. The structures of bisheterocyclics were determined from rigorous analysis of their spectral parameters (IR, ¹H‐NMR, ¹³C‐NMR, and ESI‐MS). The newly prepared compounds were screened for their antimicrobial activity against seven bacterial and five fungal strains. The DNA photo cleavage potential of these compounds was also evaluated by using agarose gel electrophoresis, and bispyranopyrazoles 4b , 4d and 4e exhibited significant level of DNA photocleavage activity.     

Synthesis of 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles

Several 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐1,3,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles have been synthesized and the structures of these compounds were established by elemental analysis, MS, IR and ¹H NMR spectral data.     

Synthesis of Novel Thioglycoside Derivatives Containing Quinazolinone

A series of novel thioglycoside derivatives containing 4(3H)‐quinazolinone was designed and synthesized from 2‐chloromethyl‐quinazolin‐4(3H)‐ones and 1‐thioglycose. Several 2‐chloromethyl‐quinazolin‐4(3H)‐ones were synthesized on refluxing with 2‐(chloroacetylamino)‐benzoic acid and arylamines in acetonitrile. All of the novel compounds were characterized by IR, ¹H NMR spectra and elemental analysis. The structures of compounds 7b, 8b and 8c have been determined by X‐ray diffraction analysis.     

Synthesis and Characterization of Novel Arylaldehyde (Arylketone)‐(4‐Substituted phenyl‐5‐Substituted phenoxy‐Methyl‐4H‐1,2,4‐Triazole‐3‐yl)‐Thiol Acetyl Hydrazones

Fourteen novel arylaldehyde (arylketone)‐(4‐substituted phenyl‐5‐substituted phenoxy‐methyl‐4H‐1,2,4‐triazole‐3‐yl)‐thiol acetyl hydrazone derivatives ( 5a‐5g, 6a‐6g ) were synthesized by 4‐substituted phenyl‐5‐substituted phenoxy‐methyl‐1,2,4‐triazole‐3‐thione as starting material according to substructure link principle, followed by thioetherification, hydrazide hydrazone reaction. The structures of these compounds were confirmed by IR, ¹H NMR and elemental analysis. Crystal structure of compounds 1b and 6d were determined by the X‐ray diffraction.     

The Synthesis,Spectral, and Electrochemical Characterization of Novel Alkoxybenzoquinone Derivatives

The novel monosubstituted benzoquinone compounds 3e , 3g , 3h ; 2,5‐O‐ substituted benzoquinone compounds 4a , 4b , 4c , 4d , 4e 4g and known compound 4h and 2,6‐O‐ substituted benzoquinone compounds 5e , 5f , 5g , 5h were obtained by the reaction of p‐chloranil ( 1 ) and related alcohol compounds in potassium carbonate (K₂CO₃) solution of acetonitrile or chloroform with Et₃N. The novel cyclic compounds 7 , 8 and 10 , 11 were obtained from the reaction of p‐chloranil ( 1 ) and diols in potassium carbonate (K₂CO₃) solution of acetonitrile at room temperature. The structures of novel compounds were characterized by using micro analysis, FT‐IR, ¹H‐NMR, ¹³C‐NMR, MS and cyclic voltammetry.     

Study of 1,3‐Dipolar Cycloaddition and Ring Contraction of New 1,4‐Phenylene‐bis[1,5]benzothiazepine Derivatives

Some 1,4‐phenylene‐bis[1,2,4]oxadiazolo‐[5,4‐d][1,5]benzothiazepine derivatives ( 4a , 4b , 4c ) were synthesized by 1,3‐dipolar cycloaddition reaction of benzohydroximinoyl chloride with 1,4‐phenylene‐bis(4‐aryl)‐2,3‐dihydro[1,5]benzothiazepine ( 2a , 2b , 2c ); meanwhile, compounds 2a , 2b , 2c also occurred ring contraction under acylating condition to obtain bis[2‐aryl‐2′‐(β‐1,4‐phenylenevinyl)‐3‐acetyl]‐2,3‐dihydro[1,5]benzothiazoles ( 3a , 3b , 3c ). The structures of some novel compounds were confirmed by IR, ¹H‐NMR, elemental, and X‐ray crystallographic analysis.