Synthesis and base-catalyzed recyclization of 3-arylamino-carbonylanthra[1,9-cd]-6-isoxazolones

Thermolysis of 1-azido-2-arylaminocarbonylanthraquinones in nonpolar solvents leads to 3-arylaminocarbonylanthra[1,9-cd]-6-isozazolones. By the action of bases, these compounds recyclize in aprotic solvents into 2-arylanthra[1,2-d]-1H-pyrazolin-3,6,11-triones.     

Reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with pyridine bases

In the reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with pyridine bases the chlorine atom is substituted to give the corresponding pyridinium salts. The pyridine ring of the synthesized anthra[1,9-cd]isoxazol-6-one-5-pyridinium chloride was cleaved by the Zincke method. The reduction of the cleavage product, viz., N-(anthra[1,9-cd]isoxazol-6-on-5-yl)-5-amino-2,4-pentadienal, under various conditions was investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1186–1188, September, 1981.     

Reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with oxygen-containing nucleophiles

Facile nucleophilic substitution of the chloride ion to give 5-alkoxy- or 5-aryloxy-anthra[1,9-cd]-6-isoxazolones occurs in the reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with alcohols and phenols. The possibility of conversion of the synthesized isoxazolones to 1-amino-4-alkoxyanthraquinones is demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1329–1331, October, 1983.     

Unusual reaction between 6H-6-oxo-5-haloanthra[1,9-cd]-isoxazoles and quinoline

The reaction of 6H-6-oxo-5-haloanthra[1,9-cd]isoxazoles with quinolines leads to unexpected fragmentation of the quaternized quinoline ring to give xylidine or o-toluidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1682–1686, December, 1986.     

Reactions of 3(5)-halo-6-oxo-6H-anthra[1,9-cd]isoxazoles with arenethiols

The corresponding 3(5)-arylthio-6-oxo-6H-anthra[1,9-cd]isoxazoles are formed as a result of the reaction of 3(5)-halo-6-oxo-6H-anthra[1, 9-cd]isoxazoles with arenethiols.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–824, June, 1993.     

Thermolysis of some 6H-6-oxo-3-aminoanthra[1,9-cd]isoxazoles

The thermolysis of 6H-6-oxo-3-alkylaminoanthra[1,9-cd]isoxazoles leads to derivatives of anthra[1,2-d]imidazole and 1-amino-9,10-anthraquinone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 119–123, January, 1987.     

Transformations of anthra[1,9-cd]isoxazol-6-ones in hydrohalic acids

4-Halo-1-aminoanthraquinones are formed when anthra [1,9-cd]isoxazol-6-ones are refluxed in hydrohalic acids. The 3 position undergoes halogenation when 5-substituted isoxazoles are used. The process takes place via a one-proton mechanism with the participation of halide ion in the rate-determining step, possibly with the intermediate formation of N-haloaminoanthraquinones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1471–1473, November, 1980.     

Ring opening reactions of 6H-anthra[1,9-cd]isoxazol-6-ones and related compounds

Nucleophilic attack of anthra[1,9-cd]isoxazol-6-ones, and of anthra[1,9-cd:5,10-c'd']isoxazole by various sulfoxides, triphenyl phosphine, and aliphatic or aromatic phosphites proceeded with cleavage of the nitrogen? oxygen bond of the isoxazole ring. This method provided ready access to substituted anthraquinones bearing sulfoximido-, triphenylphosphazo-, and dialkyl(aryl)phosphoramidic groups attached to the 1- and the 1,5-positions of the anthraquinone system. The structures of the newly synthesized anthraquinone derivatives were supported by analytical and spectral data. l-S,S-dimethyl-N-(5-benzamidoanthraquinon-1-yl)-sulfoximide yielded in 90% sulfuric acid the l-amino-5-sulfoximido anthraquinone without hydrolyzing the sulfoximido group.     

Synthesis and Acylation of peri-Amino Derivatives of Anthra[1,9-cd]pyrazol-6-one

Heating of 5- and 7-chloro-6H-anthra[1,9-cd]pyrazol-6-ones in butylamine and aniline gives the corresponding peri-amino-substituted anthrapyrazole derivatives. Acylation of the latter occurs at the N¹ atom of the heterocyclic fragment to afford monoacyl derivatives having an ana-quinonimine structure.     

Synthesis of 3-alkyl-5-arylamino-6,11-dihydro-3H-anthra[1,2-d]-[1,2,3]triazole-6,11-dione 2-oxides by nitrosation of 3-alkylamino-5-arylamino-6H-anthra[1,9-cd]isoxazol-6-ones

Nitrosation of 3-alkylamino-5-arylamino-6H-anthra[1,9-cd]isoxazol-6-ones with sodium nitrite in acetic acid leads to the formation of the corresponding unstable N-nitroso derivatives which are converted into 3-alkyl-5-arylamino-6,11-dihydro-3H-anthra[1,2-d][1,2,3]triazole-6,11-dione 2-oxides on heating.     

Anticancer anthrapyrazoles. The synthesis of 2-substituted 5-nitro and 5-aminoanthra[1,9-cd]pyrazol-6(2H)-ones

Synthetic methodologies for the preparation of substituted 5-nitro- and 5-aminoanthra[1,9-cd]-pyrazol-6(2H)-ones, 4 and 5 respectively, substituted with a basic side at N-2 and dioxy substitution in the A-ring, are reported. These compounds are essentially devoid of activity against in vitro L1210 leukemia and in vivo murine P388 leukemia.     

Heteroannulated-9,10-anthracenediones. The synthesis of substituted 5- and 7-chloroanthra[1,9-cd]pyrazol-6(2H)-ones,precursors to anticancer anthrapyrazoles

Synthetic methodologies to a number of 5- and 7-chloroanthra[1,9-cd|pyrazol-6(2H)-ones, 4 and 37 respectively, optionally substituted with side chains at N-2 and dioxy substituents in the A ring, are reported. Reported also are detailed uv, ir and ¹H-nmr spectroscopy for representative compounds.     

Synthesis of 6H-Naphtho[1,2,3-cd]indol-6-ones

S,S-Dimethyl-and S-methyl-S-phenyl-N-(9,10-anthraquinon-1-yl)sulfoximides are converted into 6H-naphtho[1,2,3-cd]indol-6-ones on heating in polar aprotic solvents.