Reactions of 1‐ and 3‐bromoisoquinoline with potassium amide in liquid ammonia. Nucleophilic substitution of 3‐bromoisoquinoline by the ANRORC mechanism

Both 1‐ and 3‐bromoisoquinoline are converted by potassium amide in liquid ammonia into the corresponding amino derivatives in excellent yields. It is shown that the amination of 3‐bromoisoquinoline proceeds as for 55% by the SN(ANRORC) mechanism via an open‐chain compound, while the remaining 45% substitution, as well as the substitution in 1‐bromoisoquinoline, occurs probably by the AE mechanism. When heated with ethanolic ammonia at 130°C 3‐bromoisoquinoline is transformed into 3‐aminoisoquinoline to the extent of 27% by the SN(ANRORC) mechanism; thus this mechanism may well occur with other reagents also.