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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
Author(s) -
Adam JeanMarie,
Winkler Tammo
Publication year - 1983
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19830660203
Subject(s) - chemistry , nucleophile , reagent , medicinal chemistry , reactivity (psychology) , ring (chemistry) , hydrazine (antidepressant) , stereochemistry , cyanide , organic chemistry , medicine , alternative medicine , pathology , chromatography , catalysis
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 , RC 6 H 5 ) with cyanide in water yields a mixture of 1‐amino‐9,10‐dioxo‐4‐phenylamino‐9,10‐dihydroanthracene‐2‐carbonitrile ( 3 , R C 6 H 5 ) and 1‐amino‐4‐(phenylamino)anthraquinone ( 4 , R C 6 H 5 ) 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‐(Δ 2 ‐1, 3‐oxazolin‐2‐yl)‐, 2‐(benz[ d ]imidazol‐2‐yl)‐ and 2‐(1 H ‐tetrazol‐5‐yl)anthraquinones ( Schemes 8 and 10 ).