ALKYL NITRATE NITRATION OF ACTIVE METHYLENE COMPOUNDS .6. NITRATION OF ESTERS IN LIQUID AMMONIA

The nitration of aliphatic and phenyl acetate esters with alkyl nitrates in the presence of potassium amide in liquid ammonia gives not only α-nitro esters 1 but also nitroalkanes 2 and dialkyl carbonates 3. In addition to these compounds, another α-nitro ester 4 forms when the alkoxy portion of the ester and alkyl nitrate are not the same. Compounds 2 and 3 arise from a fragmentation reaction and compound 4 from a transesterification reaction, both of which occur during the nitration step, and not during subsequent acidification. These reactions are not caused by direct base attack on the resulting -nitro ester, however, except when the latter is tertiary. © 1969, American Chemical Society. All rights reserved.