Synthesis of 11H-Indeno[1,2-b]quinolines via the Friedlnder Reaction

The quinoline nucleus occurs in several natural compounds (cincona alkaloids) andpharmacologically active substances displaying a broad range of biological activity1.The biological activity of quinoline compounds has been found to possess antiasthmatic,an…     

One-Pot Synthesis of Thieno[2,3-b]pyridine and Pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine Derivatives

Russian Journal of Organic Chemistry - 2-Acyl-4,5,6-trialkyl-3-aminothieno[2,3-b]pyridines,...     

Synthesis and antitumor evaluation of novel tetrahydrobenzo[4′,5′]thieno[3′,2′:5,6]pyrimido[1,2-b]isoquinoline derivatives

In the present study, a novel 8,9,10,11-tetrahydro-7H,14H-benzo[4′,5′] thieno[2′,3′:4,5]-1,3-oxazino[3,2-b]isoquinoline-7,14-dione 5 was prepared by condensation of 2-amino-3-carbethoxy-4,5,6,7-tetrahydrobenzothiophene with homophthalic anhydride under microwave irradiation, followed by alkaline hydrolysis and cyclization using acetyl chloride. Compound 5 was further allowed to react with different nitrogen nucleophiles to get new tetrahydrobenzothienopyrimido isoquinolinone derivatives. The structures of the prepared compounds were elucidated by IR, ¹H-NMR, ¹³C-NMR, and mass spectroscopy. The newly prepared compounds were tested in vitro against a panel of two human tumor cell lines, namely, hepatocellular carcinoma (liver) HepG2, and mammary gland breast MCF-7. Almost all the tested compounds showed satisfactory activity.     

Synthesis and photophysical properties of dinaphtho[2,3-b:2′,3′-i]dihydrophenazine derivatives

A dinaphtho[2,3-b:2′,3′-i]dihydrophenazine (DNP) derivative was synthesized by Buchwald-Hartwig cross-coupling, and its electronic spectrum was compared with that of dinaphtho[b,i]dihydrophenazine-5,18-dione (DNP-dione) as an anthraquinone analog. An absorption band of DNP is attributed to extension of π-conjugation over the entire molecule via the N atom. DNP-dione showed a broad absorption band in the range 450–490?nm due to intramolecular charge-transfer interactions. Additionally, the absolute fluorescence quantum yield of DNP was larger than that of DNP-dione. DNP-dione exhibited reversible oxidation peaks and a similar oxidation potential to DNP, since there are very weak electronic interactions between the anthracene and anthraquinone units across the N atoms with the 4-octyloxyphenyl substituent.     

Synthesis of novel tricyclic 2H,7H-furo[3′,4′:6,7]cyclohepta-[1,2-b]pyran system

The reaction of 8-hydroxy-1,3-dimethyl-4H-cyclohepta[c]furan-4-one with the ethoxymethylene derivatives of malononitrile or ethyl cyanoacetate in the presence of KOH gave noncyclic cyanovinyl derivatives as their potassium salts rather than the expected α-pyrone derivatives. They are smoothly cyclized to the target α-pyrones by refluxing with acid. The corresponding 3-benzamido-2H-pyran-2-ones can be obtained in a single vessel from the 2-aryl-4-ethoxymethylene-4H-1,3-oxazol-5-ones using the same scheme. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1632–1638, November, 2008.     

Synthesis of a new heterocyclic system of 2-amino-3-cykanO-5h-4,5-dihydropyrido[3′,2′:4,5]-pyrrolo[1,2-a]indole

Alkylatio of 2-piperidinomethylene-2H-pyrrolo[1,2-a]indole-3,9-dione with dimethyl sulfate, followed by hydrolysis of the intermediate immonium salts. yielded 2-formyl derivatives, the reaction of which with substances possessing on active methylene unit leads to the formation of 2-substituted vinyl-3-oxo-9-alkoxypyrrolo[1,2-aindoles. Cyclization of the 9-methoxy derivative yielded a new heterocyclic system of 2-amino-3-cyano-5H-4,5-dihydropyrodol[32:4,5]pyrroloindoledione-4,11.Center for the Chemistry of Drugs, S. Ordzhonikidze All-Russian Scientific Research Institute Moscow119021 Translated from Khimiya Geterotsiklicheskikh Soedinenii.No. 8, pp, 919–925, August, 1994. Orginally article submitted June 22, 1994.     

A Clean and Expedient Synthesis of Pyrido[1,4]oxazepino Spiropyrrolidines Through One-Pot,Three-Component [3 + 2] Cycloaddition Reaction

One-pot three component synthesis of novel pyrido[1,4]-oxazepine fused spiropyrrolidines has been accomplished in good yields by 1,3-dipolar cycloaddition reaction of azomethine ylide, derived from paraformaldehyde and sarcosine with (E)-4-benzylidene-hexahydro-1H-pyrido[2,1-c][1,4]-oxazepine-3(7H)-one as dipolarophiles derived from Baylis-Hillman adducts. The effect of solvent on the [3 + 2]-cycloaddition reaction is also studied.     

Synthesis of Angular [1,2,5]Oxadiazolo[3,4-b]pyrazino-[1′,2′ : 1,2]pyrrolo[2,3-e][1,4]diazepine by Stepwise Reaction of Pyrrolo[1,2-a]pyrazinetrione with 3,4-Diaminofurazan

Russian Journal of Organic Chemistry - Diaminofurazan reacted with 8-benzoyl-2-phenyl-3,4-dihydropyrrolo[1,2-a]pyrazine-1,6,7(2H)- trione to give addition product of the amino group to the double...     

Condensed isoquinolines 32. Synthesis of 4H-thieno-[3′,2′:5,6]-and-[2′,3′: 5,6]pyrimido-[1,2-b]isoquinolines and 6,12-dihydro-5H-isoquino-[2,3-a]quinazoline-5,12-dione derivatives

Treatment of 2-(4-oxo-3,4-dihydrothieno[2,3-d]-and-[3,2-d]pyrimidin-2-ylmethyl)benzoic acids and 2-(4-oxo-3,4-dihydro-2-quinazolinylmethyl)benzoic acid with acetic anhydride gave thieno[3′,2′:5,6]-and-[2′,3′:5,6]pyrimido[1,2-b]isoquinoline-4,11-diones and isoquino[2,3-a]quinazoline-5,12-dione respectively. NMR spectroscopy showed that an intramolecular acylation of the above acids occurs at the atom N-1 of the pyrimidinone part of the bicycle. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1053–1061, July, 2008.     

Study on the Ring Eulargment Reaction: Synthesis of 7,8,13, 13a-tetrahydroisoindolo[1,2-b][3]benzazepine and 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepine

In our research on the ring enlargement of certain N-heterocycles, a general procedure for the ring enlargement with the insertion of an extra -CH2- was improved and shown in Scheme I1.Scheme IThe procedure had been carried out with such N-heterocycles as 2-methyl-1,2,3,4-tetrahydroisoquinoline2, tetrahydroberberine and strychnine3 with expected results. Thus, the procedure shown in Scheme I provides a new approach to the synthesis of larger N-heterocycles.Isoindolo[1,2-b][3]benzazepines a…     

Synthesis of 11H-Indeno[1,2-b]quinolines via the Friedliinder Reaction

The nine new 11H-indeno[1,2-b]quinolines were synthesized in high yield with sodium ethoxide as a catalyst via the Friedlander condensation reaction, The possible reaction mechanism was proposed.     

Three-Component Spiro Heterocyclization of Pyrrolediones with Aminoindenones. Synthesis of Spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-pyrroles]

Russian Journal of Organic Chemistry - 4,5-Dibenzoyl-1H-pyrrole-2,3-diones and 4-benzoyl-5-phenyl-1H-pyrrole-2,3-diones reacted with 3-arylamino-1H-inden-1-ones at a molar ratio of 1:2 to give...     

Condensed isoquinolines. 7.* Synthesis of derivatives of the new heterocyclic system thieno[3′,2′:5,6]-pyrimido[1,2-b]isoquinoline

4-Oxo-6, 11-dihydro-4H-thieno[3, 2.-5,6]-pyrinudo[1, 2-b]isoquinolines have been synthesized by the reaction of o-bromo-methylphenylacetonitrile with esters of substituted 2-aminothiophene-3-carboxylic acids. They were characterized as the hydrobromides and as the fee bases. The tautonterism of the bases in DMSO solution is discussed.For Communication 6. see[1].T. G. Shevchenko Kiev University, Kiev, 252017. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 366–369, March, 1996. Original article submitted September 9, 1995.     

Thieno[2,3-b]pyridine-2-carbohydrazide in Polyheterocyclic Synthesis: The Synthesis of Pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine,Pyrido[3′,2′:4,5]thieno[3,2-d][1,2,3]triazine,and Pyrazolyl,Oxadiazolylthieno[2,3-b]pyridine Derivatives

Pyrdine-2(1H)-thione 1 reacted with ethyl chloroacetate 2 to give 2-S-ethoxy-carbonylmethylpyridine derivative 3, which could be cyclized into thieno[2,3-b]-pyridine-2-carbohydrazide derivative 5 by boiling with hydrazine hydrate. The latter compound reacted with cinnamonitrile derivatives 6a, b, triethylorthoformate, formic acid, dimethylformamide-dimethylacetal, and diethyl carbonate to give the corresponding shiff base 7a, b and pyrido[3′,2′;-4,5]thieno[3,2-d]pyrimidine derivatives 10–13 in respective manner. On the other hand, compound 5 also reacted with carbondisulphide and phenyl isothiocyanate to afford the corresponding 2-(1,3,4-oxadiazolo-2-yl)thieno[2,3-b]pyridine derivatives 18 and 22. Finally, compound 5 reacted with some β-dicarbonyl compounds, such as ethyl acetoacetate, acetylacetone and ethyl β-arylazoacetoacetate, to yield the corresponding 2-(pyrazol-1-yl-carbonyl)thieno[2,3-b]pyridine derivatives 24, 25, and 27 respectively.     

Synthesis and antimicrobial evaluation of the novel heteroannulated furo[3′,2′:6,7]chromeno[2,3-b]pyridines: Part 1

The chemical behavior of 4,9-dimethoxy-5-oxo-5H-furo[3,2-g]chromene-6-carbonitrile ( 1 ) was investigated toward some acyclic and cyclic active methylene ketones namely acetylacetone, ethyl acetoacetate, ethyl benzoylacetate, acetoacetanilide, dimedone, indanedione, pyrazolidine-3,5-dione and 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, barbituric acid and 1-allylthiobarbituric acid, and hippuric acid. A variety of novel heteroannulated furochromenopyridines were efficiently synthesized through a cascade reactions between 4,9-dimethoxy-5-oxo-5H-furo[3,2-g]chromene-6-carbonitrile ( 1 ) and the carbon nucleophilic reagents. Structures of the new products were inferred based on their analytical and spectral data.     

Synthesis of benzothieno[2,3-b]thiophenes, [2,3-b:3′,2′-d]-dithienothiophenes and their selenium derivatives via electrophilic cyclization and McMurry cyclization

Benzothieno[2,3-b]thiophenes, [2,3-b:3′,2′-d]-dithienothiophenes, and their selenium derivatives were synthesized in good yields from readily available 3-ethynyllithio-benzo[b]thiophenyllithio compounds, sulfur or selenium, and 2 equiv of acid chlorides. Two heteroarene rings were constructed by a twofold cyclization via an acid chloride-induced electrophilic ring closing and the McMurry cyclization using Zn/TiCl₄ reagents.     

New convenient synthesis of substituted 6,9-dihydropyrido[3′,2′:4,5]thieno[3,2-b]pyridines and 6,9-dihydropyrido[3′,2′:4,5]thieno[3,2-d]pyrimidines

1,4-Dihydro-3-cyano-2-pyridinethiolates react with 2-bromo-l-(4-bromophenyl)ethylidenemalononitrile or N-cyanochloracetanudine to give 6, 9-dihydropyrido[3, 2': 4, 5]thieno[3. 2-b]pyridines or 6, 9-dihydropyrido-[3.2:4.5Jthieno(3,2-d]pyrimidines, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 553–556, April, 1996.     

Reaction of thieno[2,3-b]pyridines with sodium hypochlorite: An unusual and stereoselective one-pot approach to dimeric pyrrolo[2′,3′:4,5]thieno[2,3-b]pyridines

The oxidation of 3-aminothieno[2,3-b]pyridine-2-carboxamides with commercially available bleach leads to the formation of dimeric pyrrolo[2′,3′:4,5]thieno[2,3-b]pyridines (7a,14a-diamino-7,14-bis(aryl)-7,7a,14,14a-tetrahydro-6H,13H-pyrido[3″″,2″″:4?,5?]thieno[2?,3?:4″,5″]pyrrolo-[3″,4″:3′,4′]pyrrolo[2′,3′:4,5]thieno[2,3-b]pyridine-6,13-diones) in moderate yields (37–52%).     

Synthesis,crystal structure,and properties of 2H-4,8-dimethylfuro[2′,3′:5,6]naphtho[1,2-b]pyran-2-one,a novel DNA intercalator

Summary The furonaphthopyrone6, a novel DNA intercalator, was synthesized in two steps (ca. 56% overall yield) starting from naphthopyrone3. The new naphthopyrone derivatives4 and6 were fully characterized and the absorption and fluorescence spectroscopic properties of6 were determined. The dark interactions of furonaphthopyrone1 and6 with DNA have been investigated by a fluorescence quenching technique and their apparentScatchard binding constants were calculated. The crystal structure of6 was determined. The planarity of6 and the geometry of the active double bond between the -pyrone and the furan moieties of6 suggest that furonaphthopyrones are efficient monofunctional DNA intercalators.

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Synthese, Kristallstruktur und Eigenschaften von 2H-4,8-Dimethylfuro[2,3:5,6]naphtho[1,2-b]pyran-2-on, einem neuen DNA-Intercalator

Zusammenfassung Der neue DNA-Intercalator6 wurde, ausgehend vom Naphthopyron3, in zwei Stufen mit einer Gesamtausbeute vonca. 56% hergestellt. Die neuen Naphthopyronderivate4 und6 wurden vollständig charakterisiert; die Absorptions- und Fluoreszenzeigenschaften von6 wurden bestimmt. Die Dunkelwechselwirkungen von1 und6 mit DNA wurden mittels einer Fluoreszenzquenchtechnik untersucht; ihreScatchard-Bindungskonstanten wurden berechnet. Die Kristallstruktur von6 wurde bestimmt. Die Planarität von6 und die Geometrie der aktiven Doppelbindung zwischen dem -Pyron- und dem Furanteil von6 lassen erwarten, daß Furonaphthopyrone effiziente monofunktionelle DNA-Intercalatoren sind.

     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.