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.     

8,19-Dimethyl-tetraepoxy[22]annulen(2.1.2.1): ein erstes Tetraepoxy-Verbrücktes aromatisches [22]Annulen

8,19-Dimethyl-tetraepoxy[22]annulen(2.1.2.1): The First Tetraepoxy-Bridged Aromatic[22]Annulene By McMurry reaction of 5,5′-ethylidenebis[furan-2-carbaldehyde] ( 15 ), a syn/anti mixture 16 of (E,E)- and (Z,Z)-8,19-dihydro-8,19-dimethyl-tetraepoxy[22]annulene is obtained. The (E/E)-isomers 16 are the first rotation- ally active noncyclic conjugated macrocycles, where the (E)-ethenediyl moieties rotate around the connecting single bonds. The dihydro-tetraepoxy[22]annulenes 16 are dehydrogenated by (Ph₃C)BF₄ as well as by O₂ to give the tetraepoxy[22]annulene 11 . The spectroscopic data support the character of 11 as an aromatic, diatropic ring system, which is rather sensitive towards O₂. In the oxidation mixture obtained from 11 , beside polymeric products, two compounds 19 and 20 can be isolated, carrying one and two CHO groups, respectively, resulting by oxidation of one or both Me-groups but having retained the aromatic 22π system of 11 .     

Reaction of 5-haloanthra[1,9-cd]-6-isoxazolones with aziridine

The reaction of 5-haloanthra[1,9-cd]-6-isoxazolones with aziridine gave 5-aziri-dinoanthra[1,9-cd]-6-isoxazolones. The latter, upon reaction with acids, undergo cleavage of the aziridine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 885–888, July, 1984.     

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.     

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.     

NH3-Eliminierungen aus 2-Äthoxybenzoesäureamid und 2-Äthoxybenzylamin Als Weitere Beispiele [Komplexer] Ortho-Effekte

Using deuterium labelled compounds the mechanisms of the elimination of ammonia from the molecular ions of the title compounds have been elucidated. It can be shown that the fragmentation is preceded by a partial hydrogen scrambling which is favoured by the carbonyl function. In addition to this an unusual oxygen-carbon bond cleavage of the ether moiety can be explained by assuming a neighbouring group participation.     

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.     

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.     

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.