Quinazoline Chichibabin amination

The application of the Chichibabin amination to effect a direct amination of quinazoline has been reported. It gives 4-aminoquinazoline (60MII) as well as 2,4-diaminoquinazoline (59GEP958197). No mechanistic details were discussed, but it can be expected (based on the experience with the amination with 4-phenyl- and 5-phenylpyrimidine) that amination of quinazoline would also involve, at least partly, participation of the Sn(ANRORC) mechanism. Amination with N-labeled potassium amide/liquid ammonia will certainly shed some light on the mechanism operative in this Chichibabin amination. 

Numerous substituted and benzo-fused quinazoline-2- and -4-amines are accessible by direct amination via the Chichibabin reaction. Quinazoline is aminated at position 4 on heating with sodium amide in iV,A-dimethylaniline or by a mild amination oxidation procedure using potassium amide, liquid ammonia, and potassium permanganate. The latter method comprises oxidation with potassium permanganate of an anionic c-adduct w hich is easily formed when quinazoline is dissolved in liquid ammonia containing potassium amide. 

Quinazolin-2-amines, e.g. quinazoline-2,4-diamine, are similarly obtained from 4-substituted quinazolines by substitution/amination via the Chichibabin reaction. ... 

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