Heterocyclic analogs of 5,12-naphthacenequinone 6. Synthesis of 4,11-dimethoxy derivatives of anthra-[2,3-<Emphasis Type="Italic">b</Emphasis>]thiophene-5,10-dione and anthra[2,3-<Emphasis Type="Italic">d</Emphasis>]isothiazole-5,10-dione

Condensation of 2-formyl-or 2-cyano-3-chloro-1,4-dimethoxyanthraquinone with methyl thioglycolate in the presence of base gave methyl 4,11-dimethoxyanthra[2,3-b]thiophene-5,10-dione-2-carboxylate and its 3-amino derivative respectively. Hydrolysis of the ester group in methyl 4,11-dimethoxyanthra[2,3-b]thiophene-5,10-dione-2-carboxylate and subsequent decarboxylation of the carboxylic acid formed gave 4,11-dimethoxyanthra[2,3-b]thiophene-5,10-dione. Condensation of 3-chloro-2-formyl-1,4-dimethoxyanthraquinone with ammonia in the presence of sulfur gave 4,11-dimethoxyanthra[2,3-d]isothiazole-5,10-dione __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 538–543, April, 2007.     

Naphthoindoles. 10. Synthesis of 4,11-Dihydroxynaphtho[2,3-f]indole-5,10-dione and Some of Its Derivatives

4,11-Dihydroxynaphtho[2,3-f]indole-5,10-dione (pyrroloquinizarin), its 11-dehydroxy derivative, and Mannich base were synthesized by demethylation of previously obtained methoxynaphtho[2,3-f]indole-5,10-diones.     

Heterocyclic analogs of 5,12-naphthacene-quinone. 3. Synthesis of 4,11-diaminonaphtho-[2,3-f]indole-5,10-dione and certain of its derivatives

Nucleophilic substitution of methoxy groups in 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione by the action of primary and secondary alkylamines, or arylamines leads to the formation of N-alkyl or N-aryl derivatives of 4,11-diaminonaphtho[2,3-f]indole-5,10-dione respectively. 4,11-Diamino-1H-naphtho-[2,3-f]indole-5,10-dione is obtained by the dealkylation of 4,11-bis[(1-phenylethyl)amino]-1Hnaphtho[ 2,3-f]indole-5,10-dione in the presence of a Lewis acid (BBr₃). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 854–861, June, 2006.     

Heterocyclic analogs of 5,12-naphthacenequinone 7*. Synthesis of naphtho-[2,3-f]isatin-5,10-dione derivatives

On chlorination of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione with sulfuryl chloride in chloroform, its mono-, di-, and trichloro derivatives are formed depending on the conditions. Hydrolysis of the di- and trichloro derivatives gives a new polycondensed derivative of isatin, 4,11-dimethoxynaphtho-[2,3-f]isatin-5,10-dione. Its demethylation occurs effectively on extended heating with HBr in acetic acid and leads to 4,11-dihydroxynaphtho[2,3-f]isatin-5,10-dione (4,11-di-hydroxynaphtho[2,3-f]indole-2,3,5,10-tetraone). *For Communication 6 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1532–1536, October, 2008.     

Heterocyclic Analogs of 5,12-Naphthacenequinone. 1. Synthesis of Heterocyclic Analogs Starting from 2,3-Diaminoquinizarine

The amination of 2-nitroquinizarine using hydroxylamine gives 2-amino-3-nitroquinizarine, which, upon reduction, gives previously unreported 2,3-diaminoquinizarine, a key intermediate in the synthesis of heterocyclic analogs of 5,12-naphthacenequinone, namely, 4,11-dihydroxyanthra[2,3-d]imidazole-5,10-dione (imidazoloquinizarine), 4,11-dihydroxyanthra[2,3-d][1,2,3]triazole-5,10-dione (triazoloquinizarine), and 5,12-dihydroxynaphtho[2,3-g]quinoxaline-6,11-dione (pyrazinoquinizarine). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1081–1088, July, 2005.     

Heterocyclic analogs of 5,12-naphthacenequinone. 2. Synthesis of 4,11-dihydroxynaphtho[2,3-f]indazole-5,10-dione and its n-methyl derivatives

On methylating 4,11-dimethoxynaphtho[2,3-f]indazole-5,10-dione with methyl iodide in the presence of base a mixture is formed of its 1-and 2-methyl derivatives. Demethylation of the methoxy groups of the starting material and of the products of its alkylation leads to the formation of 4,11-dihydroxynaphtho[2,3-f]indazole-5,10-dione (pyrazoloquinizarine) and its 1-and 2-methyl derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–696, May, 2006.     

Naphthoindoles. 9. Synthesis of N-derivatives of 4,11-Dimethoxynaphtho-[2,3-f]indole-5,10-dione

N-Acetylation and several N-alkylation reactions have been carried out for the previously synthesized 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione.     

Heterocyclic analogs of 5,12-naphthacenequinone 8.* Synthesis of furano-anthraquinones

During the condensation of 2,3-dichloroquinizarine with methyl pivaloylacetate in the presence of potassium carbonate in dimethyl sulfoxide the main reaction products are derivatives of angular 3-pivaloylanthra[1,2-b]furan-2,6,11(3H)-trione (about 70%) and anthra[2,1-d][1,3]dioxole-6,11-dione (15%), whereas the yield of the targeted linear methyl 2-tert-butyl-4,11-dihydroxyanthra[2,3-b]furan-5,10-dione-3-carboxylate is only 2%. Methods are developed for modification of the obtained 3-pivaloylanthra[1,2-b]furan-2,6,11(3H)-trione, making it possible to use it for the synthesis of the tert-butyl derivatives of linear anthra[2,3-b]furan-5,10-dione or angular anthra[1,2-b]furan-6,11-dione. *For Communication 7 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 191–202, February, 2009.     

Heterocyclic analogs of 5,12-naphthacenequinone. 5. Synthesis of 2,3-diamino-1,4-dimethoxyanthraquinone and its heterocyclic derivatives

A new method for the synthesis of 2,3-diamino-1,4-dimethoxyanthraquinone from quinizarin has been developed. Heterocyclic analogs of 5,12-naphthacenequinone have been synthesized based on this o-diamine-4,11-dimethoxyanthra[2,3-d]imidazole-5,10-dione, 4,11-dimethoxyanthra[2,3-d][1,2,3]triazole-5,10-dione, and 5,12-dimethoxynaphtho[2,3-g]quinoxaline-6,11-dione. On the 70th Birthday of Professor E. Lukevics. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No.1, 96–102, January 2007.     

Pd-catalyzed cross-coupling/heterocyclization domino reaction: facile access to anthra[2,3-b]furan-5,10-dione scaffold

A new facile route to the synthesis of 4,11-dimethoxyanthra[2,3-b]furan-5,10-dione and its novel 2-substituted derivatives was proposed. The developed scheme was based on a Pd-catalyzed cross-coupling/heterocyclization domino reaction of 3-bromo-2-hydroxy-4,11-dimethoxyanthraquinone with terminal alkynes.     

Heterocyclic analogs of 5,12-naphthacenequinone. 4. Synthesis of 4,11-dimethoxy-anthra[2,3-d]isoxazole-5,10-dione

A preparative synthetic method has been developed for 3-chloro-2-formyl-1,4-dimethoxyanthraquinone starting from available 2-methylquinizarine. The condensation of the α-chloroaldehyde obtained with acetone oxime gives 4,11-dimethoxyanthra[2,3-d]isoxazole-5,10-dione. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1421–1427, September, 2006.     

Synthesis of Some New Fused and Polyfused [1,2,4]Triazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazepines

7-[1,3-Dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]thiadiazepine-6,8-dione and 7-[5-oxo-1,3-dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4-b][1,3,4]-thiadiazepine-6,8-diones were obtained by treating 3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo-[3,4-b][1,3,4]thiadiazepine-6,8-diones with CS₂ and chloroacetyl chloride, respectively. Treatment of the above compounds with mercaptoacetic acid gave 1,2-dibromoethane or the corresponding spiro polyfused heterocycles. Some other triazolothiadiazepine derivatives including spiro polyfused compounds were also synthesized. __________ Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1256–1264, August, 2005.     

Naphthoindazoles. Synthesis of 4,11-Dimethoxynaphtho[2,3-f]indazole-5,10-dione

The previously unknown 4,11-dimethoxynaphtho[2,3-f]indazole-5,10-dione has been obtained by the thermal cyclization of N-nitroso derivative of 2-acetamido-3-methyl-1,4-dimethoxyanthraquinone.     

Heterocyclic analogs of 5,12-naphthacenequinone 9*. Study of the synthesis and reactivity of 4,11-dimethoxynaphtho[2,3-<Emphasis Type="Italic">f</Emphasis>]isatin-5,10-diones

A preparative method has been developed for N-alkyl 4,11-dimethoxynaphtho[2,3-f]isatin-5,10-diones. Condensation reactions with several N- and C-nucleophiles have been carried out to give the corresponding derivatives at position 3. An efficient method has been discovered for the demethylation of the N-alkyl-4,11-dimethoxynaphtho[2,3-f]isatin-5,10-diones to give a high yield of N-substituted 4,11-dihydroxynaphtho[2,3-f]isatin-5,10-diones. Successive halogenation using phosphorus penta-chloride and acylation of tert-butylamine by the intermediate 2-chloro derivative converted 4,11-di-methoxynaphtho[2,3-f]isatin-5,10-dione to the 2-amino-3H-naphtho[2,3-f]indole-3,5,10-trione derivative.     

Synthesis and fluorescence of anthra[2,3-<Emphasis Type="Italic">b</Emphasis>]furan-5,10-dione derivatives

4,11-Dialkoxyanthra[2,3-b]furan-5,10-diones containing various substituents in the 3-position were synthesized. Reactions of these compounds with primary and secondary amines resulted in nucleophilic replacement of one or two alkoxy groups by the corresponding amine residues. 4,11-Dialkoxy derivatives of anthra[2,3-b]furan-5,10-dione showed fluorescence with large Stokes shifts (170–200 nm).     

Oxidative cyclocondensation of cyclic thio-and selenoureas. 5. 2-Thioxothieno-and 2-thioxopyrido[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4-ones

A study was carried out on the oxidative cyclocondensation of 2-thioxothieno-and 2-thioxopyrido[2,3-d]pyrimidin-4-ones. The thiophene ring with excess π-electron density facilitates the reaction, while the pyridine ring with diminished π-electron density hinders it. 2-Thioxothieno-[2,3-d]pyridimin-4-ones were converted into previously unreported 7H,13H-[1,2,4]thiadiazolo-[3,2-b:5,4-b′]bis(thieno[2,3-d]pyridimine-7,13-diones). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1424–1427, September, 2007.     

Synthesis and properties of (thieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridin-3-yl)iminotriphenylphosphoranes. Molecular structure of (2-benzoyl-4-methoxymethyl-6-methylthieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridin-3-yl)iminotriphenylphosphorane

Iminophosphoranes containing a thieno[2,3-b]pyridine fragment were obtained through a sequence of reactions: 1) alkylation of 3-cyano-2(1H)-pyridinethiones in alkaline medium by an -halocarbonyl compound with subsequent Thorpe-Ziegler cyclization of the resultant 2-thioalkylpyridines to give 3-aminothieno[2,3-b]pyridines, 2) diazotization of the amino group and nucleophilic substitution of the diazonium group by an azido group without isolation of the diazonium salts, and 3) reaction of the 3-azidothieno[2,3-b]pyridines with triphenylphosphine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1853–1862, December, 2004.     

An efficient three-component reaction involving [3 + 1 + 1] furannulation leading to furanonaphthoquinones in water

An efficient and clean green synthesis of highly substituted linear naphtho[2,3-b]-furan-4,9-dione derivatives, starting from 2-hydroxy-1,4-naphthoquinone, alkyl isocyanides and a variety of aldehydes, is described. This new method provides the first example of an efficient regioselective synthetic method for the synthesis of linear naphtho[2,3-b]-furan-4,9-dione ring systems by formation of three bonds. This [3 + 1 + 1] furannulation strategy affords furanonaphthoquinones in moderate to high yields, using water as a cheap, non-toxic, environmentally friendly solvent, in a one-step reaction, without the need of complicated work-up procedures. Correspondence: Mohammad Bagher Teimouri, Petrochemical Department, Iran Polymer and Petrochemical Institute, P.O. Box 14965-115, Tehran, Iran.     

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.     

Original synthesis of 2-substituted-4,11-dimethoxy-1-(phenylsulfonyl)-2,3-dihydro-1H-naphtho[2,3-f]indole-5,10-diones using TDAE and Cu-catalyzed reaction strategy

We report herein an original and rapid synthesis of 2-substituted-4,11-dimethoxy-1-(phenylsulfonyl)-2,3-dihydro-1H-naphtho[2,3-f]indole-5,10-diones by TDAE mediated synthesis of N-benzylsulfonamides followed by an intramolecular N-arylation using Cu-catalyzed system.