新型三环系稠杂环[1,2,4]-三唑并[1,5-a][1]-苯并氮杂及[1,2,4]-三唑并[1,5-a]-喹啉的合成

α-四氢萘酮的乙氧羰基腙(1)经LTA氧化,得到α-偶氮-α-乙酰氧基化合物2.在A lC l3作用下,化合物2脱去乙酰氧基产生重氮正离子中间体3,再经与腈的1,3-偶极环加成、[1,2]-迁移扩环、碱性水解和与苦味酸作用,得到新型[1,2,4]-三唑并[1,5-a][1]苯并氮杂苦味酸盐6a~6c.以2,3-二氢-1-茚酮为底物,采用相同的合成路线,合成了1,2,4-三唑并[1,5-a]-二氢喹啉苦味酸盐12a~12c.     

氨基磺酸催化下三组分一锅法无溶剂合成苯并[4,5]咪唑并[1,2-a]嘧啶类衍生物

无溶剂条件下,用氨基磺酸催化芳香醛,2-氨基苯并咪唑和β-二羰基化合物的三组分反应,简单而方便地得到了苯并[4,5]咪唑并[1,2-a]嘧啶类衍生物.该法具有产率高,成本低廉,环境友好,适应性广简捷方便等优点.     

1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂（艹/卓）化合物的合成

苯并二氢吡喃－４－酮的芳腙（１）衍生的偶氮基碳正离子（３）与腈发生１,３－偶极环加成反应,加成产物（４）通过「１,２」－迁移扩环重反应,形成新颖的三环系杂环化合物１,２,４－三唑并「３,２－ｄ」「１,５」－苯并氧氮杂Ｚｈｕｏ化合物５ａ－５ｋ。     

四氢咪啶[2,1-a]并-2,3-二苯基-1,4-二氮杂-3-环己烯的合成与结构

对由二乙烯三胺与联苯甲酰合成的标题化合物进行了MS、IR、UV、NMR谱的表征及X射线单晶衍射结构分析.该化合物M_r=277.39,晶体属P2_1/n空间群,晶胞参数a=0.9442(2)nm,b=1.4344(4)nm,c=1.1824(3)nm.β=112.92(2)°,Z=4,D_c=1.25g·cm~(-3).晶体结构由直接法解出,1827个可观察衍射参与最小二乘法修正,最终偏差因子R=0.050.结果表明标题化合物是一非平面型,具有部分不饱和键的氮杂稠二环化合物,其母体六元环为椅式构型、五元环为半椅式构型,2个取代苯基间的夹角为73.5°.     

1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成

近年来稠杂环化合物的合成及其生物活性的研究日益成为杂环化学研究的热门课题。3,6-二取代-1,2,4-三唑并噻二唑衍生物是具有广谱生物活性的稠杂环化合物,如抗菌、消炎、杀微生物、调节植物生长、除草等,因而引起各国化学家的广泛兴趣。此类化合物的生物活性,     

新型4-芳氧基吡啶并[3′,2′∶4,5]噻吩并[3,2-d]嘧啶衍生物的合成

2-氯-3-氰基吡啶与巯基乙酸乙酯经闭环反应制得3-氨基吡啶并[3,′2′∶4,5]噻吩-2-甲酸乙酯(1);1与甲酰胺第二次成环生成吡啶并[3,′2′∶4,5]噻吩并[3,2-d]嘧啶-4-酮(2);2经氯化后与取代苯酚反应合成了12个新型的4-芳氧基吡啶并[3,′2′∶4,5]噻吩并[3,2-d]嘧啶衍生物,其结构经1H NMR,13C NMR,IR和元素分析表征。     

3-氧代-3-[3-三氟甲基-5,6-二氢[1,2,4]三唑并[4,3-α]吡嗪-7(8H)-基]-1-苯基丙烷-1-胺的合成

三唑类衍生物是重要的化工和药物合成中间体,而稠合三唑类衍生物因其独特的生理活性更是得到了广泛关注[1-2],其中3-三氟甲基-5,6,7,8-四氢[1,2,4]三唑并[4,3-α]哌嗪与β-氨基酸缩合得到的化合物是一类重要的二肽基肽酶-Ⅳ抑制剂 [3-4],可作为2型糖尿病的治疗药物,如2006年经美国FDA批准在美国上市的西他列汀(sitagliptin),此外二肽基肽酶-Ⅳ抑制剂还可用于肥胖症和高血压等疾病的预防和治疗[5].     

新显色剂 1-[2,3,5-三氮唑偶氮]-2-萘酚的合成及其与钴(Ⅱ)的分光光度研究

合成了新显色剂 1-[2,3,5-三氮唑偶氮]-2-萘酚(简称TZAN ) ,并研究了其性质及与钴显色反应的条件,测定了试剂有关参数.在 pH 6.08 的 HAc-NaAc 介质中,试剂与钴形成红色络合物,其最大吸收波长为 578.2 nm,摩尔络合比 Co2+∶R=1∶2,用双波长测定,表观摩尔吸光系数为 3.15×104 L/mol.cm,钴量在 0～1.0 μg/mL 范围内遵守比耳定律.     

5-卤代-1H-1,2,4-三氮唑-3-羧酸乙酯及其衍生物的合成

以5-氨基-1H1,2,4-三氮唑-3-羧酸乙酯为原料,经Sandmeyer反应合成了5-X-1H-1,2,4-三氮唑-3-羧酸乙酯(X=C1,Br,I)(1a-1c),1a-1c再分别与α-2′,4′-二氟苯乙酮反应合成了3个5-卤代-1-1H-1,2,4-三氮唑-3-羧酸乙酯衍生物(2a-2c),其结构通过元素分析,IR,UV和^1H NMR进行了表征。     

1，3-偶极环加成合成新型4，5-二氢-2′，5′-二氧杂吡咯啉并[4，5-c]异嗯唑衍生物

N-取代苯基马来酰亚胺与a-氯代-1，2，3-三唑-4-甲醛肟和a-氯代-喹喔啉-2-甲醛肟在三乙胺作用下通过1，3-偶极环加成合成了一系列4，5-二氢-2′，5′-二氧杂吡咯啉并[4，5-c]异噁唑衍生物．化合物结构经元素分析，IR，^1H NMR及MS得到确证．     

Synthesis,design, and antimicrobial activity of pyrido[2,3-d][1,2,4]triazolo[4,3-a]pyrimidinones based on quinoline derivatives

The pyrido[2,3-d]pyrimidine moieties are one of the most biologically widespread heterocyclic compounds as antimicrobial, antioxidant, antitubercular, antiviral and anti-inflammatory. Hence, we synthesized an efficient new series of 2-thioxo-pyrido[2,3-d]pyrimidinone, 2-hydrazinyl-(quinolin-2-yl)pyrido[2,3-d]pyrimidinone,N′-(quinolin-2-yl)-pyrido[2,3-d]pyrimidine-(formo/aceto)-hydrazide and substituted-(quinolin-2-yl)pyrido[2,3-d][1,2,4]triazolo[4,3-a]pyrimidinone derivatives. The characterization of new compounds was corresponded by using spectroscopic techniques, IR, NMR and Mass spectra. In vitro, all compounds were evaluated as antimicrobial activity compared with cefotaxime sodium and nystatin as the standard drug. This work deals with the exploration of the new heterocyclic compounds and medicinal diversity of quinoline-pyrido[2,3-d][1,2,4]triazolo[4,3-a]pyrimidine derivatives that might pave the way for long in the discovery of therapeutic medicine for future drug design.     

Synthesis of 8,9-dihydro[1,2,4]triazolo[1,5-a]-quinazolin-6(7H)-one derivatives

Regioselectivity of the reactions of 1H-1,2,4-triazol-3-amines with 2-acyl-5,5-dimethylcyclohexane-1,3-diones and 2-dimethylaminomethylidene-5,5-dimethylcyclohexane-1,3-dione was studied. In all cases, the products were substituted 8,9-dihydro[1,2,4]triazolo[1,5-a]quinazolin-6(7H)-ones whose structure was determined by ¹H and ¹³C NMR spectroscopy.     

Synthesis of arylamino-substituted pyrazolo[3,4-d][1,2,4]triazolo[4,3-a]pyrimidinones,pyrazolo[4,3-e][1,2,4]triazolo[4,3-a]pyrimidinones,and their thermal isomerization

The reaction of 1-(4-oxo-1-R-5H-pyrazolo[3,4-d]pyrimidin-6-yl)-4-arylthiosemicarbazides with methyl iodide gave rise to 1,2,4-triazolo-pyrazolopyrimidinones of linear structure, and with dicyclohexylcarbodiimide the products had angular and linear structure. The heating of compounds obtained higher than their melting point resulted in their isomerization into 7-aryl-amino-1-R-1,8-dihydro-4H-pyrazolo[3,4-d]-[1,2,4]triazolo[1,5-a]pyrimidin-4-ones.     

异色满并[4,3-b]喹啉衍生物的合成

早在1931年,Hetherington等从念珠状曲菌(Aspergillus Cand inin)和土曲菌(Asperillus tereus)等菌类中分离出带有异色满(Isochroman)环系结构的左旋抗菌素橘霉素(C itrinin),后来又相继发现诸多带有异色满环系的天然产物[1-3],新近在软木木质素中也发现了多种具有异色满结构的     

5-取代-1,2,4-三唑并[4,3-a]喹唑啉衍生物的合成及抗惊厥活性

合成了5-取代-1,2,4-三唑并[4,3-a]喹唑啉衍生物2a～2q.利用最大电惊厥法(MES)和旋转棒法(Rotarod Test),以小鼠腹腔给药,分别测定了其抗惊厥活性和神经毒性.药理实验结果表明,化合物5-正庚氧基-1,2,4-三唑并[4,3 -a]喹唑啉(2d)的抗惊厥活性最强,其半数有效量EDso为19.7 mg/kg,保护指数PI为6.2.由化学物质诱发的抗惊厥实验结果表明,化合物2d能对抗由戊四唑、异烟肼、硫代氨基脲和3-巯基丙酸诱发的惊厥作用,推测其抗惊厥作用是通过增强γ-aminobutyric acid (GABA)神经能系统和活化谷氨酸脱羧酶或抑制GABA转氨酶而起抗惊厥作用.     

Synthesis and positive inotropic evaluation of 1-(benzylamino)-3-(4,5-di-hydro[1,2,4]trizaolo[4,3-a]quinolin-7-yloxy)propan-2-ol derivatives

In an attempt to search for more potent positive inotropic agents,a series of 1-(benzylamino)-3-(4,5-dihydro[1,2,4]trizaolo[4,3- a]quinolin-7-yloxy)propan-2-ol derivatives was synthesized in four steps using 6-hydroxy-3,4-dihydro-2(1H)-quinolinone as a starting material,and their positive inotropic activities were evaluated by measuring the coronary blood flow(CBF)and the left ventricular pressure(LVP)followed by calculating the rate of pressure development(dp/dt_(max)values)in the preparation of rat Lan...     

Synthesis of mesoionic triazolo[4,3-a]quinoxalines

The reaction of 6-chloro-2-(1-methylhydrazino)quinoxaline 4-oxide 1 or 6-chloro-2-(1-methylhydrazino)-quinoxaline 5 with phenyl isothiocyanate under reflux in N,N-dimethylformamide gave 7-chloro-3-methyl-1,2,4-triazolo[4,3-a]quinoxalin-3-ium-1-thioate 4 , which was also obtained by refluxing of 6-chloro-2-[1-methyl-2-(N-phenylthiocarbamoyl)hydrazino]quinoxaline 4-oxide 2b or 6-chloro-2-[1-methyl-2-(N-phenylthiocarbamoyl)hydrazino]quinoxaline 6 in N,N-dimethylformamide.     

A synthesis of 6-functionalized 4,7-dihydro[1,2,4]triazolo[1,5-a]pyrimidines

6-Unsubstituted 7-R-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidines (R = H or Me) were synthesized via two pathways: (a) deacylation of the corresponding 5-acetyl Biginelli-like precursors in KOH/H₂O and (b) reduction of the corresponding 1,2,4-triazolo[1,5-a]pyrimidines using LiAlH₄. The products could be easily formylated at position 6, which is promising for the further synthesis of functionalized 6-substituted derivatives of 4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidines. In contrast, 6-acetyl-7-(4-(N,N-dimethylaminophenyl))-5-methyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine undergoes a cascade process in KOH/H₂O, leading to the formation of a 4,5,8,9-tetrahydro[1,2,4]triazolo[5,1-b]quinazoline derivative.