Organic heterocyclothiazenes. Part 14. Aminotrithiadiazepines and trithiadiazepyne

Abstract

Amino derivatives of the trithiadiazepine ring are described for the first time, as moderately stable crystalline solids. They are readily formed from the monobromo derivative by nucleophilic substitution under remarkably mild conditions, though only via the 6,7-didehydrotrithiadiazepine (trithiadiazepyne) intermediate. The aryne mechanism is established by hydrogen-deuterium exchange and by trapping and competitive trapping of the aryne, generated from chloro-, bromo-, and iodotrithiadiazepine, with dienes and nucleophiles.