微波辐射下2-氨基苯并[h]喹唑啉衍生物的合成

2-芳亚甲基-3，4-二氢-2H-1（2H）-萘酮和碳酸胍在以乙二醇为溶剂、微波辐 射下反应，生成一系列新的2-氨基-4-芳基-5，6-二氢化苯并[h]喹啉衍生物，产物 的结构通过单晶X射线衍射分析确证。     

微波辐射下"一锅煮"法合成2-氨基-3-氰基-4-芳基-4H,5H-吡喃-[3,2-c]苯并吡喃-5-酮

以芳醛、4-羟基香豆素、丙二腈为原料,乙醇为能量转移剂,哌啶为催化剂,在微波辐射下一步合成了一系列2-氨基-3-氰基-4-芳基-4H,5H-吡喃-[3,2-c]苯并吡喃-5-酮,反应在40～60s时间内完成,产率60%～97%.     

Synthesis of cyclopropa[c]indeno[1,2-b]quinolines through a MCR/Staudinger/aza-Wittig sequence

Spirocyclopropanes were prepared from aromatic aldehydes, 1,3-indandione and acetophenones through a halogenation/S_N2-displacement/Michael-initiated ring-closing sequence by a pyridinium-ylide-assisted multicomponent reaction, and their further use was also researched in the construction of cyclopropa[c]indeno[1,2-b]quinolines through subsequent Staudinger/aza-Wittig reactions.     

Keto‐benzo[h]‐Coumarin‐Based Near‐Infrared Dyes with Large Stokes Shifts for Bioimaging Applications

Fluorescence imaging is a promising tool for the visualization of biomolecules in living systems and there is great demand for new fluorescent dyes that absorb and emit in the near‐infrared (NIR) region. Herein, we constructed three new fluorescent dyes ( NBC dyes) based on keto‐benzo[h]coumarin ( k‐BC ) and benzopyrilium salts. These dyes showed large Stokes shifts (>100 nm) and NIR emission (>800 nm). The relationship between the structures and optical properties of these dyes was further investigated by using density functional theory calculations at the B3LYP/6‐3G level of theory. Fluorescence images indicated that the fabricated dyes exhibited good photostability and low cytotoxicity and, thus, have potential applications as imaging agents in living cells and animals.     

Zur Synthese von 4-Aryl-5,6-dihydro-benzo[h]chinolinen

A new route to the benzo[h]quinoline system3 byMichael-addition of malononitrile to 2-arylidene-1-tetralones1 is presented. The mechanism of this reaction is elucidated by isolation of the intermediate 4H-naphtho[1,2—b]-pyrane2 and its reaction to3. The reaction is proposed to be a sequence of addition, cyclisation,Dimroth-rearrangement and disproportionation.

1. Mitt.:H.-H. Otto, Arch. Pharm. [Weinheim]307, 444 (1974).     

水中苯并[h]色烯衍生物的洁净合成

在三乙基苄基氯化铵(TEBA)存在下的水介质中，芳亚甲基丙二腈与1-萘酚发生 加成、环化反应生成2-氨基-3-氰基-4-芳基苯并[h]色烯．产物的结构通过元素分 析、红外光谱和核磁共振氢谱确证，该方法具有操作简单、产率高、环境友好的优 点．     

One-Pot Multicomponent Synthesis of Methoxybenzo[h]quinoline-3-carbonitrile Derivatives; Anti-Chagas,X-ray,and In Silico ADME/Tox Profiling Studies

Several methoxybenzo[h]quinoline-3-carbonitrile analogs were designed and synthesized in a repositioning approach to developing compounds with anti-prostate cancer and anti-Chagas disease properties. The compounds were synthesized through a sequential multicomponent reaction of aromatic aldehydes, malononitrile, and 1-tetralone in the presence of ammonium acetate and acetic acid (catalytic). The effect of the one-pot method on the generation of the target product has been studied. The compounds were in vitro screened against bloodstream trypomastigotes of T. cruzi (NINOA and INC-5 strains) and were most effective at showing a better activity profile than nifurtimox and benznidazole (reference drugs). A study in silico on absorption, distribution, metabolism, excretion, and toxicity (ADME/Tox) profiling to help describe the molecular properties related to the pharmacokinetic aspects in the human body of these compounds was reported. In addition, X-ray data for the compound 2-Amino-5,6-dihydro-4-(3-hydroxy-4-methoxy-phenyl)-8-methoxybenzo[h]quinoline-3-carbonitrile 6 was being reported. Spectral (IR, NMR, and elemental analyses) data on all final compounds were consistent with the proposed structures.     

Synthesis and Structure Elucidation of Pyrimidobenzimidazoles and Fused Derivatives II [1]. Dodecahydrobenzimidazo-[2,1-b]quinazolines and Decahydrobenzimidazo-[2,1-b]benzo[h]quinazolines [2]

Summary.  The cyclization reactions of trans-3a-hexahydro-2-benzimidazolamine with 2-alkylidene- and 2-benzylidenecyclohexanones and α-tetralones, respectively, yield mixtures of two isomeric condensates each. Thorough high resolution NMR analyses (¹H and ¹³C NMR, HH-COSY, gs-HSQC, gs-HMBC, 1D TOCSY, and 1D NOE difference spectra) revealed that the corresponding isomers are in all cases linearly fused diastereomeric 12α- and 12β-substituted trans-6aα-dodecahydrobenzimidazo[2,1-b]quinazolines and 7α-substituted trans-8aβ- and trans-8aα-decahydrobenzimidazo[2,1-b]benzo[h]quinazolines, respectively. The formation of corresponding angularly fused regioisomers was not observed so far. The stereochemistry and the tautomerism of some bases and their hydrochlorides as well as the regiospecific course of the cyclization reactions are discussed. Biological tests showed that the novel compounds don’t exert remarkable antibacterial and antimycotic effects. Received November 3, 1999. Accepted November 30, 1999     

Synthesis and characterization of 9,9-dialkylfluorene capped benzo[c]thiophene/benzo[c]selenophene analogs as potential OLEDs

The synthesis of soluble benzo[c]thiophene analogs capped with 9,9-dialkylfluorene at one end is described.     

An Efficient One-pot Synthesis of 4H-Pyrrolo[3,2,1-ij]quinolines

Summary. Dialkyl 4H-pyrrolo[3,2,1-ij]quinoline-4,5-dicarboxylates are obtained in quantitative yields from the 1:1:1 addition reaction between triphenylphosphine, dialkyl acetylenedicarboxylates, and indole-7-carboxaldehyde.     

Microwave Assisted Synthesis of Some Novel Thiopyrano[2,3-b]quinolines as a New Class of Antimicrobial Agent

A series of novel substituted thiopyrano[2,3-b]quinolines 4a–e , 5a–e , and 6a–e were prepared from substituted 3-formyl-2-mercapto quinolines 2a–e , on reaction with ethyl acetoacetate, diethyl malonate, and ethyl cyanoacetate 3a–c by microwave irradiation in the presence of piperidine. Synthesized compounds were evaluated for antimicrobial activities. Among the compounds tested, 7-chloro-2-oxo-2H-thiopyrano[2,3-b]quinoline-3-carbonitrile 6d and 7-nitro-2-oxo-2H-thiopyrano[2,3-b]quinoline-3-carbonitrile 6e were highly active against S. aureus and M. roseus.     

Synthesis of furo[3,2-c]- and pyrano[3,2-c]quinolines by lanthanide triflate catalyzed imino-Diels-Alder reaction

Imino Diels-Alder reaction of imines with 2,3-dihydrofuran or 3,4-dihydro-2H-pyran proceeded smoothly in the presence of a catalytic amount (0.5 mol %) of ytterbium triflate to afford furo[3,2-c]- and pyrano[3,2-c] quinolines conveniently in high yield.     

2-薁基取代的苯并[b]呋喃类化合物的合成

以溴代丁二酰亚胺为溴化试剂, 对1-氰基-2-甲基薁进行了溴代反应研究, 将溴甲基化产物与水杨醛类衍生物在通常的加热反应及微波辐射条件下进行缩合, 以较高的收率得到2-薁基取代苯并[b]呋喃, 其结构经¹H NMR, IR及元素分析等得以证实.     

Conversion of novel palladacycles into oxopyrrolo[3,4-b]quinolines

The quinolinylcyclopalladated complexes 3a–b were synthesised in good yields (81% and 77%) by the insertion reaction of the prepared dinuclear palladium complexes [Pd(C,N-2-C₉H₄N-CHO-3-R-6)Cl(PPh₃)]₂ [(R = H (2a), R = OMe (2b)] with isonitrile XyNC (Xy = 2,6-Me₂C₆H₃). The cyclopalladated complexes 3a–b were also obtained in low yields (39% and 33.5%) via a one pot oxidative addition reaction of quinoline chloride 1a–b with isonitrile XyNC:Pd(dba)₂ (4:1). The reactions of 3a–b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of the complexes to provide the corresponding organic compounds 4a–b, 5a–b and 6a–b in yields (41%, 27% and 18–19%). The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures of 2a, 3a and 3b were determined by X-ray diffraction studies.     

Efficient One-Pot,Four-Component Synthesis of 1,2,3-Triazole-Linked Tetrahydrobenzo[b]pyrans

A one-pot procedure has been developed for the synthesis of (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene derivatives by concurrent reaction of aryloxy propargylated aldehydes, various azides, active methylene compounds, and 1,3-cyclohexanediones using catalytic amounts of Cu(OAc)₂ / sodium ascorbate and diammonium hydrogen phosphate in aqueous ethanol media. Excellent conversion of starting materials was achieved to the desired (1,2,3-triazolyl) methoxyphenyl tetrahydro-5-oxo-4H-chromene products.     

2-Chloro-3-quinolinecarboxaldehyde in the Synthesis of Condensed Quinoline Systems. 1. Synthesis of Derivatives of 3,4-Dihydro-2H-[1,3]thiazino[6,5-b]quinolines

A method for the synthesis of derivatives of previously unknown heterocyclic systems - 3,4-dihydro-2H-[1,3]thiazino[6,5-b]quinolines - has been developed based on 7,8-dimethyl-2-chloro-3-quinolinecarboxaldehyde via the consecutive steps of conversion into its Schiff's base with a primary amine, reduction to the corresponding aminomethyl derivative, conversion to the thiourea with isothiocyanates, and heterocyclization by intramolecular substitution of the chlorine atom.     

Theophylline as a new and green catalyst for the one-pot synthesis of spiro[benzo[a]pyrano[2,3-c]phenazine] and benzo[a]pyrano[2,3-c]phenazine derivatives under solvent-free conditions

A green, convenient, high yielding and one-pot procedure for the synthesis of novel spiro[benzo[a]pyrano[2,3-c]phenazine] derivatives by domino multi-component condensation reaction between 2-hydroxynaphthalene-1,4-dione, benzene-1,2-diamines, ninhydrine, and malononitrile in the presence of a catalytic amount of 1,3-dimethyl-7H-purine-2,6-dione (theophylline) as an expedient, eco-friendly and reusable solid base catalyst under thermal, microwave irradiation and solvent-free conditions. This procedure has also been applied successfully for the synthesis of benzo[a]pyrano[2,3-c]phenazines.     

Nanomagnetically modified thioglycolic acid (γ‐Fe2O3@SiO2‐SCH2CO2H): Efficient and reusable green catalyst for the one‐pot domino synthesis of spiro[benzo[a]benzo[6,7]chromeno[2,3‐c]phenazine] and benzo[a]benzo[6,7]chromeno[2,3‐c]phenazines

Superparamagnetic nanoparticles of modified thioglycolic acid (γ‐Fe₂O₃@SiO₂‐SCH₂CO₂H) represent a new, efficient and green catalyst for the one‐pot synthesis of novel spiro[benzo[a ]benzo[6,7]chromeno[2,3‐c ]phenazine] derivatives via domino Knoevenagel–Michael–cyclization reaction of 2‐hydroxynaphthalene‐1,4‐dione, benzene‐1,2‐diamines, ninhydrin and isatin. This novel magnetic organocatalyst was easily isolated from the reaction mixture by magnetic decantation using an external magnet and reused at least six times without significant loss in its activity. The catalyst was fully characterized using various techniques. This procedure was also applied successfully for the synthesis of benzo[a ]benzo[6,7]chromeno[2,3‐c ]phenazines.     

A Novel and Facile Synthesis of 2‐(Benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic Acid Derivatives

A simple and concise approach for the synthesis of a series of new heterocyclic systems of 2‐(benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic acid derivatives ( 3a–3g ) is described. The synthetic strategy features the one‐pot reaction of ethyl 2‐(chloromethyl)benzo[h]quinoline‐3‐carboxylate ( 2 ) with various substituted salicylaldehydes as well as 2‐hydroxy‐1‐naphthaldehyde as a key step. The substrate 2 was prepared in good yield by a mild, efficient and direct reaction of 1‐naphthylamine ( 1 ) with Vilsmeier‐Haack reagent. The structures of all the new compounds were identified by spectral data and elemental analysis.