SYNTHESIS AND REACTIONS OF SOME NEW THIENO[2,3-b]-PYRIDINES AND THE ANTIMICROBIAL EFFECTS

Abstract

3,5-Dicyano-6-mercapto-4-phenylpyridin-2(1H)-one (1) was reacted with ethyl chloroacetate to give compound (II) which on reaction with hydrazine hydrate gave the corresponding hydrazide derivative (III). Acylation of (III) with acetic acid, phenylisocyanate, or phenylisothiocyanate gave different monoacyl derivatives (IV-VI). Condensation of III with aromatic aldehydes and acetylacetone gave compounds VII_a-c, VIII respectively. Compound I was reacted with chloroanilides, bromoacetone and phenacyl bromide to yield the IX-XI; these and compound II gave thieno[2,3-b]-pyridines (XU-XV) on treatment with sodium ethoxide solution. Reaction of XII with acetic anhydride gave the diacetyl derivative XVI. Hydrolysis of compound XII with sodium hydroxide gave the corresponding acid (XVII) which on treatment with acetic anhydride gave the oxazine derivative (XVIII). Reaction of oxazine compound XVIII with ammonium acetate and hydrazine hydrate gave pyrido[3′,2′:4,5] thieno[3,2-d]pyrimidin-4.7-dione derivative (XIX) and (XX) respectively. The N-amino derivative (XX) was reacted with 4-nitrobenzaldehyde to give the corresponding azomethine (XXI).

Significant in vitro gram-positive and gram negative antibacterial activities as well as anti-fungal effect were observed for some members of the series.     

A NOVEL SYNTHESIS OF 2-SUBSTITUTED-4H-THIENO [2,3-d][1,3] OXAZIN-4-ONE AND 2,3-DISUBSTITUTED THIENO [2,3-d]PYRIMIDIN-4(3H)-ONE DERIVATIVES

Abstract

The synthesis of acetic 2-{[1-methyl-2-(4-oxo-5,6,7,8-tetrahydro-4H-benzo [4,5]-thieno [2,3-d] [1,3-oxazin-2-yl)ethylidene]amino}-4,5,6,7-tetrahydrohenzo[b]thiophene ?3-carboxylic acid anhydride 5 and 2-(oxopropyl)-5,6,7,8-tetrahydro-4H-benzo-[4,5] thieno[2,3-d][1,3]oxazin-4-one 7, has been achieved in three steps from ethyl 2-amino-4,5,6,7-tetrahydrobenzo(b]thiophene-3-carboxlate 1 via the reaction with ethyl acetoacetate followed by hydrolysis and acetic anhydride-induced cyclization. The 2-substituent in compound 5 has two functional groups i.e. active methylene and acid anhydride which are suitably located for intramolecular transformation. Thermal and/or base catalyzed intramolecular cyclization of 5 afforded 2-(4-acetoxy-(hydroxyl)-2-methyl-5,6,7,8-tetrahydrobenzo[4,5] thieno[2,3-b]pyridin-3-yl)-5,6,7,8- tetrahydro-4H-benzo[4,5]thieno[2,3-d] [1,3]oxazin-4-one 10 and 9 respectively. Treatment of 5 with hydrazine hydrate, aromatic and/or heterocyclic amines induced the same intramolecular cyclization with a concomitant oxazine-pyrimidine interconversion to give 3-amino(aryl or heteryl)-2-(4-hydroxy-5,6,7,8-tetrdhydrobenzo-[4,5]thieno[2,3-b]pyridin-3-yl)-3,4,5,6,7,8-hexahydrobenzo[4,5] thieno[2,3-d] pyrimid in-4-one 11–14 respectively.     

2,5-二(2-菲基)-[3,2-b]并二噻吩的合成、表征及在有机薄膜晶体管中的应用

本文合成了2,5-二(2-菲基)-[3,2-b]并二噻吩(PhTT), 表征了其基本的物理和化学性质, 制备了相应的有机薄膜晶体管.     

One‐Pot Approach to Organo‐Phosphorus–Chalcogen Macrocycles Incorporating Double OP(S)SCn or OP(Se)SeCn Scaffolds: A Synthetic and Structural Study

The development of new methodology for the preparation of functional macrocycles with practical applications is an important research area in macromolecular science. In this study, we report a new one‐pot route for the synthesis of a series of macro‐heterocycles by incorporating two phosphorus atoms and two chalcogen atoms and two oxygen atoms (double OP(S)SC_n or OP(Se)SeC_n scaffolds). The three‐component condensation reactions of 2,4‐diferrocenyl‐1,3,2,4‐diathiadiphosphetane 2,4‐disulfide ( FcLR , a ferrocene analogue of Lawesson's reagent) or 2,4‐bis(4‐methoxyphenyl)‐1,3,2,4‐dithiadiphosphetane 2,4‐disulfide ( LR , Lawesson's reagent), or 2,4‐diphenyl‐1,3,2,4‐diselenadiphosphetane 2,4‐diselenide ( WR , Woollins’ reagent), disodium alkenyl‐diols, and dihalogenated alkanes are performed, giving rise to soluble and air or moisture‐stable macrocycles in good‐to‐excellent yields (up to 92 %). This is the first systemically preparative and readily scalable example of one‐pot ring opening/ring extending reaction of three‐components to prepare phosphorus–chalcogen containing macrocycles. We also provide a systematic crystallographic study.     

Heterocyclic analogs of xanthiones: 5,6‐fused 3‐methyl‐1‐phenylpyrano[2,3‐c]pyrazol‐4(1H) thiones—synthesis and NMR (1H, 13C, 15N) data

Various [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐thiones were synthesized in high yields by treatment of the corresponding [5,6]pyrano[2,3‐c]pyrazol‐4(1H)‐ones with Lawesson's reagent. Detailed NMR spectroscopic studies were undertaken of the title compounds. Complete and unambiguous assignment of chemical shifts (¹H, ¹³C, ¹⁵N) and coupling constants (¹H,¹H; ¹³C,¹H) was achieved by the combined application of various one‐ and two‐dimensional (1D and 2D) NMR spectroscopic techniques. Unequivocal mapping of most ¹³C,¹H spin coupling constants is accomplished by 2D (δ, J) long‐range INEPT spectra with selective excitation. Copyright © 2010 John Wiley & Sons, Ltd.     

1—羟基—2（1H）—吡啶硫酮及其甲基衍生物与Cr（Ⅲ）配合物的合成和性质

Edrissi认为Cr(Ⅲ)与1-羟基-2(1H)-吡啶硫酮(HPT)的甲基衍生物不能给出任何反应,并且将与HPT的配合物注明为绿色溶液。本文在过去工作的基础上合成了S-(1-氧化-2-吡啶基)硫代苯甲酸酯(PTB)和3-CH_3-PTB;并合成了3个铬配合物。通过元素分析,紫外-可见,红外光谱,摩尔电导和TG-DTA-DTG作了表征。探讨了形成机理并研究了抑菌活性。     

Zur Synthese von Imidazo(2,1-b)-1,3,4-thiadiazolo(3,2-a)-pyrimidonen-(6)

2-Amino-6-aryl-imidazo(2,1-b)-1,3,4-thiadiazoles (1 a-f) were condensed with 1,3-ketocarboxylates e. g. ethyl-butyroacetate, ethyl-benzoylacetate, 4-nitrobenzoylacetate or ethyl-cyclopentanone(2)-carboxylate and ethyl-cyclohexanone(2)-carboxylate directly to imidazo(2,1-b)-1,3,4-thiadiazolo(3,2-a) pyrimidones-(6) (4 a-f, 5 a-f, 6 d, e, 7 a-f, 8 a, d).

11. Mitt. über Heterocyclen; 10. Mitt.Paul, H., Sitte, A., Wessel, R., Arch. Pharm. (Weinheim), im Druck.     

Highly efficient synthesis of chromeno[2,3-b]pyridine using Graphene-Oxide/N1,N3-bis (pyridin-2-ylmethyl)propane-1,3-diamine-Copper nanocomposites as a novel catalyst

Recent studies about innovations in GO/N-Ligand-Cu Nano-Composites have been done. Graphene-Oxide is improved with N¹,N³-bis (pyridin-2-ylmethyl)propane-1,3-diamine and after that is matched with copper (Cu). The chemical composition and the structure of the catalyst were analyzed by TGA/DTG, EDX, XRD, FT-IR, TEM, and SEM. The results demonstrated that GO/N-Ligand-Cu was able to catalyze the chromeno[2,3-b]pyridine compounds to obtain high yields in short reaction time. The results of the present work are hoped to assist the growth of a new class of heterogeneous catalysts as the high-function candidate for industrial applications.     

聚亚胺酮的合成与性能研究

聚酰胺(PA)、聚醚酮(PEK)和聚酰亚胺(PI)等作为高性能材料已被开发并得到应用.这些高性能材料可用于航空、航天、微电子等高新技术领域[1~5].与此同时,为了满足人们对新材料的需求,科学界对新型高性能材料的开发和应用始终没有停止,且备受关注.本文首先通过傅-克酰基化反应合成     

Synthesis and in vitro cytotoxic evaluation of 2-hydrazinylpyrido[2,3-b]pyrazin-3(4H)-one derivatives

A series of novel 2-hydrazinylpyrido[2,3-b]pyrazin-3（4H）-one derivatives were synthesized and evaluated for their cytotoxic activities against A549,MDA-MB-231 and HT-29 cell lines in vitro.Pharmacological data indicated that compounds 5b,5c,10a and 10g possessed marked cytotoxicity,especially 10a(with IC₅₀ values of 0.81,2.56 and 1.63μmol/L against A549,MDA-MB- 23 1 and HT29 cell lines,respectively),which had emerged as a lead compound.     

聚酯酸酐的合成与表征

聚酸酐具有优良的表面溶蚀性能，作为药物控释体系材料得到广泛的应用．以对（２ 羟基 乙氧基）苯甲酸和对（２ 甲基 ２羟基 乙氧基）苯甲酸分别与丁二酸酐，顺丁烯二酸酐和丁二酰氯反应得到六个含有酯基的新型二元酸单体，经熔融聚合得到聚酯酸酐．单体和聚合物经ＩＲ，１Ｈ ＮＭＲ和元素分析等表征．研究了催化剂对聚合物结构的影响．     

SYNTHESIS OF THE BIOLOGICALLY ACTIVE 5-(INDOLYL-3-METHYLENE)THIAZOLIDINE-2,4-DIONE DERIVATIVES

Abstract

The cycloaddition reaction of the biologically active 5-(indolyl-3-methylene) derivatives of thiazolidi-none-4-thiones 2a-c to acrylonitrile, ethyl acrylate, N-phenylmaleimides and dimethyl fumarate has been evaluated.     

Nitrate and perchlorate salts of a silver(I) complex from 5-methyl-2-(2,3-diaza-4-(5-methyl-2-thienyl)buta-1,3-dienyl)thiophene

Bis(5-methyl-2-(2,3-diaza-4-(5-methyl-2-thienyl)buta-1,3-dienyl)thiophene) silver(I) complex was synthesized in high yield by refluxing 5-methyl-2-(2,3-diaza-4-(5-methyl-2-thienyl)buta-1,3-dienyl)thiophene (L) with silver nitrate or silver perchlorate in anhydrous acetonitrile. The product thus formed was well characterized by NMR, IR, UV–Vis and mass spectroscopies as well as elemental analysis and electrochemical analysis. Molecular structures of compounds L, [L₂Ag]NO₃ and [L₂Ag]ClO₄ were determined by single crystal X-ray diffraction analysis. It was found that the C=N double bond of the ligand rotated during the course of ligand coordination in the case of the perchlorate salt but not in the case of the nitrate salt.     

Synthesis and Crystal Structure of 2-(3,3'-Bithiophen-2,2'-yl)dibenzothiazole (BTDB) and 2-(Dithieno[2,3-b:3',2'-d]-thiophen-2,5-yl)dibenzothiazole (DTTDB)

The title compounds, 2-(3,3’-bithiophen-2,2’-yl)dibenzothiazole (BTDB) and 2-(dithieno[2,3-b:3’,2’-d]thiophen-2,5-yl)dibenzothiazole (DTTDB), have been synthesized and characterized by FT-IR, NMR, MS, HRMS and X-ray single-crystal diffraction. The crystal of BTDB crystallizes in triclinic, space group Pī with a=9.2207(17), b=10.453(2), c=10.969(2), V=981.2(3)3 and Z=2. Crystal data of DTTDB: orthorhombic system, space group Pbcn with a=4.5290(8), b=13.576(3), c=32.033(6), V=1969.6(6)3 and Z=4.     

Accessing Dihydropyrrolo[3,4-b]indol-1(2H)-ones via Pd-Catalyzed Intramolecular Aminocarbonylative Ring Closure

Present in a number of small molecule derivatives that display a wide range of biological activities, the dihydropyrrolo[3,4-b]indol-(2H)-one (DHPI) core represents an underexplored heterocyclic scaffold. Given the pharmaceutical potential of the DHPI motif, the development of synthetic methodologies that permit their expedient assembly would be highly desirable. Herein, we describe a novel strategy for the construction of the DHPI core from 3-iodo-1H-indolyl substrates, employing an unprecedented Pd-catalyzed intramolecular aminocarbonylative ring closure. The compatibility of our optimized protocol with various functional groups is highlighted through the synthesis of a range of diversely substituted DHPI derivatives in up to 90 % isolated yield.     

2, 3-二氢蒽并(1, 2-b)(1, 4)恶嗪-7, 12-二酮的合成

2-溴-1, 4-二羟基蒽醌与氨基醇, 缩合可以生成2-取代氨基-1, 4-二羟基蒽醌, 但在较高温度下并延长反应时间, 部分产物可以进行分子内脱水而进一步环化为2, 3-二氢蒽并(1, 2-b)(1, 4)恶嗪-7, 12-二酮的衍生物。用MS和NMR确定其结构。     

SYNTHESIS AND PROPERTIES OF POLY(AROMATIC DIACETYLENE)S CONTAINING FLUORENE

Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by multistep reactions.The structures and properties of the polymers are characterized and evaluated by IR,NMR,TGA,UV, photoluminescence(PL),and cyclic voltammetry analyses.These polymers possess good thermal stability.All the polymers are completely soluble in coammon solvents such as toluene,TH...     

钯催化胺化反应合成高性能材料——聚亚胺砜

利用三(二亚苄基丙酮)二钯(Pd2(dba)3)与1.1′-联萘-2.2′-二苯膦(BINAP)组成的催化体系,高效地催化4,4′-二氯二苯砜和芳香二胺的Buchwald-Hartwig交叉偶联反应,制备出新型聚亚胺砜.聚合物结构通过核磁氢谱、红外谱图、凝胶渗透色谱和元素分析等方法进行表征,表征结果与目标产物相吻合,并具有较高的分子量(Mw>2.5×104).利用DSC、TG和XRD等对其性能进行测试,结果表明,该类聚合物为无定形态,具有较高的玻璃化转变温度(Tg>200℃)、良好的热稳定性(Td>400℃)和溶解性能.其中含异丙基的PIS-3不仅可溶解在强极性溶剂中,并且在室温条件下(25℃)可溶于四氢呋喃中.