Oxidation and nitration of oximes

6 OXIDATION AND NITRATION OF C-N BONDS 1.6.1 Oxidation and nitration of oximes 

Methods used for the oxidation or nitration of C-N bonds have found wide use for the synthesis of novel polynitropolycycloalkanes as can be seen in Chapter 2. The conversion of readily 

Yields are frequently moderate for Scholl reactions. Aldoximes are not usually compatible with these harsh reaction conditions and are very sensitive to factors such as temperature and reaction time. Consequently, oxidation to the corresponding carboxylic acid is a major side-reaction. However, both the ketoxime (51) and the aldoxime (53) are reported to give good yields of the corresponding m-dinitro compounds, (52) and (54) respectively, on treatment with absolute nitric acid in methylene chloride followed by hydrogen peroxide. 

The nitration of oximinocyanoacetic acid esters with mixed acid at room temperature yields dinitrocyanoacetic acid esters which are precursors to dinitroacetonitrile and its salts. a-Oximinonitriles can be nitrated to Q ,Q -dinitronitriles with anhydrous nitric acid containing ammonium nitrate, and then subjected to ammonolysis with aqueous ammonia to give the ammonium salt of the corresponding m-dinitroalkane.  

A series of a ,a -dinitroesters have been synthesized from the reaction of a-oximinoesters with cold nitric acid containing ammonium nitrate, followed by oxidation of the resulting pseudonitroles with oxygen. 

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