¹⁵N Labeling Studies of the Reactions of 4-t-Butyl-2,6-dimethyl-4-nitrocyclohexa-2,5-dienone and 2,4-Di-t-butyl-6-methyl-4-nitrocyclohexa-2,5-dienone With Nitrogen-Dioxide; the Mechanism of Formation of 2,5,6-Trinitrocyclohex-3-enones

Abstract

Reaction of the ¹⁵N-labelled 4-nitro dienone (15b) with nitrogen dioxide in benzene gives the 2,5,6-trinitrocyclohex-3-enones (19), (20), (22) and (24) with retention of some ¹⁵N-label at C6. Similar reaction of ¹⁵N-labelled 4-nitro dienone (18b) gives the 2,5,6-trinitrocyclohex-3-enones (30), (31), (34) and (38), and the 2-hydroxy-5,6- dinitrocyclohex-3-enones (33) and (37) all with retention of some ¹⁵N-label at C6. These results are rationalized in terms of 2,5-addition of nitrogen dioxide to corresponding intermediate 6-nitro dienones (27) and (40).