Reactions of 6-Benzyl-2-t-butyl-4,6-dimethyl-cyclohexa-2,4-dienone and 6-Benzyl-4-t-butyl-2,6-dimethylcyclohexa-2,4-dienone With Nitrogen Dioxide

Abstract

Reaction of the 2-t-butyl-4-methylcyclohexa-2,4-dienone (7) with nitrogen dioxide in benzene gives the four 4,5-dinitrocyclohex-2-enones (9)-(12), the three 2,5-dinitrocyclohex-3-enones (13)-(15), and the 2-hydroxy-5-nitrocyclohex-3-enone (17). Under the same reaction conditions the 4-t-butyl-2-methylcyclohexa-2,4-dienone (8) gives the four 2,5-dinitrocyclohex-3-enones (19)-(22), and the three 2-hydroxy-5-nitrocyclohex-3-enones (23)-(25). X-Ray structure determinations are reported for compounds (9), (10), (13), (14), (19) and (25). In solution at 40 the dinitro ketone (20) rearranges to give dinitro ketone (19) and 2-hydroxy-5-nitro ketones (23) and (24). The reaction mechanisms for the various reactions are discussed.