Multi-component synthesis of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-triones using zinc terephthalate metal-organic frameworks

The present article describes an efficient one-pot method for the preparation of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-trione derivatives from a three-component condensation reaction of 1,3-indandione, aromatic amines and isatins in the presence of a zinc terephthalate metal-organic framework Zn (BDC) MOF as the catalyst under solvent-free conditions. High yields, short reaction times, simple workup and environmentally benign procedure are advantages of this protocol. The Zn (BDC) MOF catalyst can be recovered and reused several times without loss of activity. The catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infra red, X-ray powder diffraction and thermal gravimetric analysis.     

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...     

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.     

A novel three-component method for the synthesis of spiro[chromeno [4′,3′:4,5] pyrimido[1,2-b] indazole-7,3′-indoline]-2′,6(9H)-dione

A green, efficient, and rapid procedure for the synthesis of novel spiro[chromeno[4′,3′:4,5] pyrimido[1,2-b]indazole-7,3′-indoline]-2′,6(9 H)-dione derivatives has been developed by one-pot condensation of 4-hydroxy-2H-chromen-2-one, isatin, and 1H-indazole-3-amine, in the presence of acetic acid in EtOH. This method has the advantages of operational simplicity, and high yield of products via a simple experimental and work-up procedure as compared to the conventional methods. The reaction mechanism and substrate scope of this novel reaction is briefly discussed.     

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.     

5′,5′,6,6-Tetramethyl-6,7-dihydro-3′H-spiro[1,3-benzodithiole-2,1′-cyclohexane]-3′,4(5H)-dione

Russian Journal of Organic Chemistry -     

Dipyrrolo[1,2-a; 2′,1′-c]pyrazines. 5. Azo coupling of dipyrrolo[1,2-a;2′,1′-c]pyrazines and 5,6-dihydrodipyrrolo[1,2-a; 2′,1′-c]pyrazines

We have synthesized a series of previously unreported azo dyes via the azo coupling of alkyl substituted dipyrrolopyrazines with aryldiazonium chloride. For this type of substrate where one or both -positions of the pyrrole rings of the molecules are not occupied by substituents, electrophilic attack was found to occur initially at carbon atom C₍₃₎.For communication 4 see [1]M. V. Lomonosov State University, Moscow 119899, Russia Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 236–240, February, 1999.     

8-氧-二喹啉并[5,6-b;6′,5′-e]-碘六环盐的合成

在已合成的数十种碘杂环类化合物中,绝大多数是二苯并碘杂环化合物,而含生物碱的二喹啉醚类碘杂环化合物至今未见报道。     

Synthesis of New 2′-(2- and 3-Aminopropanoyl)-6′,7′-dimethoxy-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamides

Russian Journal of Organic Chemistry - 6′,7′-Dimethoxy-N-methyl-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamide reacted with...     

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.     

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 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.     

Catalyst-free glycerol-mediated green synthesis of 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones

The development of new catalyst-free green and efficient protocol to access 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones, potential privileged scaffolds for drug discovery, is disclosed. Key feature of this methodology is the dual use of glycerol—a recyclable, bioorganic compound, as a solvent cum promoter. Other highlights include use of inexpensive reagents, mild reaction conditions, operational simplicity, short reaction time, no need for chromatographic purification, and high yields.     

Light-induced synthesis of 3,7-disubstituted bisisothiazolo[4,5-b:4′,5′-e]pyrazines from 3-substituted 4-dibromoamino-5-haloisothiazoles

A new procedure was developed for the synthesis of 3,7-disubstituted bisisothiazolo[4,5-b:4′,5′-e]pyrazines from 3-substituted 4-dibromoamino-5-haloisothiazoles under UV irradiation.N,N′-Bis(5-haloisothiazol-4-yl)diazenes were obtained as by-products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1350–1352, July, 1999.     

Synthesis of some new dispiro[dipyrano-(2,4′:6,4″)bidithiolo(4,5-b:4′,5′-e)-4,8-benzoquinones]

Summary The one pot reaction of acetylacetone, CS₂, and tetrabromobenzoquinone in a 2:2:1 molar ratio affords 2,6-di-(1-acetyl-2-oxopropylidene)-bidithiolo-(4,5-b:45-e)-4,8-benzoquinone (3) which was allowed to react with some active methylene reagents in a 1:2 molar ratio to give the dispiro derivatives5–11. The reaction is assumed to proceedvia a hydrolysis of the two acetyl groups in compound3 followed by a nucleophilic addition of the active methylene reagents at the two ethylenic bonds and subsequent cyclization.

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Synthese einiger neuer Dispiro[dipyrano(2,4:6,4)bidithiolo(4,5-b:4,5-e)-4,8-benzochinone]

Zusammenfassung Die Eintopfreaktion von Acetylaceton, CS₂ und Tetrabrombenzochinon in einem molaren Verhältnis von 2:2:1 liefert 2,6-Di-(1-acetyl-2-oxopropyliden)-bidithiolo-(4,5-b:4,5-e)-4,8-benzochinon (3), das anschließend mit aktivierten Methylenverbindungen im Verhältnis 1:2 zu den Dispiroverbindungen5–11 umgesetzt wurde. Die Reaktion verläuft offenbar über eine Hydrolyse der beiden Acetylgruppen in Verbindung3, gefolgt von einer nucleophilen Addition der aktiven Methylengruppen an die ethylenischen Doppelbindungen und anschließender Cyclisierung.

     

Synthesis of functionalized 5H-spiro[furan-2,2′-indene]-1′,3′,5-triones from primary amines, acetylenic esters and ninhydrin

An effective route to functionalized 5H-spiro[furan-2,2??-indene]-1??,3??,5-triones is described via tandem reaction of primary amines, acetylenic esters and ninhydrin.     

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.     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

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Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

Three-component condensation of 3-aminothiophene derivatives with isatines and Meldrum’s acid. Synthesis of 2,5′-dioxo-3′-phenyl-5′,6′-dihydro-4′H-spiro[indoline-3,7′-thieno[3,2-b]pyridine]-2′-carboxylic acids

A method for the synthesis of 2,5′-dioxo-3′-phenyl-5′,6′-dihydro-4′H-spiro[indoline-3,7′-thieno[3,2-b]pyridine]-2′-carboxylic acids was elaborated based on the three-component condensation of 3-aminothiophenes, Meldrum’s acid, and isatines.     

Acylation of 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro-[naphthalene-1,3′-pyrrol]-4-one with 5-arylfuran-2,3-diones

Russian Journal of Organic Chemistry -