A REARRANGEMENT OF S-SUBSTITUTED CYCLOHEX ANONE THIOXIMES

Mercaptoheterocycles like 2-mercaptobenzazoles 5, 2-mercaptouracils 10 , and ketene S,S-acetals 18 are aminated by 1-oxa-2-azaspiro[2.5]octan e (1). The intermediate cyclohexanone thioximes, which can be isolated in some cases (6a-c, 11), undergo a 1,3-shift of the mercapto fragmen t from the nitrogen to the carbon atom followed by cyclization and/or hydrolysis. Thus, new heterocyclic systems as 14-17 or 19 can be creat ed.