Über die Dicyanierung der 1,4‐Diaminoanthrachinone und die Reaktivität der 1,4‐Diamino‐9,10‐dihydroanthracen‐2,3‐dicarbonitrile gegenüber nucleophilen Reagenzien 3. Mitteilung über Arylierungen und Heterocyclisierungen von Anthrachinonsystemen

The Dicyanation of 1,4‐Diaminoanthraquinones and the Reactivity of 1,4‐Diamino‐9,10‐dioxo‐9,10‐dihydroanthracene‐2,3‐dicarbonitriles towards Nucleophilic Reagents The reaction of 1‐amino‐9, 10‐dioxo‐4‐phenylamino‐9,10‐dihydroanthracene‐2‐sulfonic acid (1, RC6H5) with cyanide in water yields a mixture of 1‐amino‐9,10‐dioxo‐4‐phenylamino‐9,10‐dihydroanthracene‐2‐carbonitrile (3, R  C6H5) and 1‐amino‐4‐(phenylamino)anthraquinone (4, R  C6H5) under the usual reaction conditions (Scheme 1). In dimethylsulfoxide, however, a second cyano group is introduced, and 1‐amino‐9,10‐dioxo‐4‐phenylamino‐9,10‐dihydroanthracene‐2,3‐dicarbonitrile (7) is formed (Scheme 2). The cyano groups are very reactive towards nucleophiles. The cyano group in 2‐position can be substituted by hydroxide and aliphatic amines (Schemes 5 and 6). The cyano group in 3‐position can be eliminated by aliphatic amines and hydrazine (Scheme 7). Nucleophilic attack at the cyano C‐atom of the 2‐cyano group by suitable reagents leads to ring formation, yielding e.g. 2‐(Δ2‐1, 3‐oxazolin‐2‐yl)‐, 2‐(benz[d]imidazol‐2‐yl)‐ and 2‐(1H‐tetrazol‐5‐yl)anthraquinones (Schemes 8 and 10).