Reaction of Acyl Nitrates formed from Metal Nitrates or Nitric Acid in Carboxylic Anhydrides with Some Aromatic Hydrocarbons

Abstract

The nitrations of naphthalene [1], fluorene [2], o-xylene [ 3 ], and trans-stithene [4] by means of metal nitrates or nitric acid in carboxylic anhydrides were studied. The formation of acyl nitrates from metal nitrates in the carboxylic anhydrides was ascertained by thermographic technique.
The isomer distributions did not depend on the nature of acyl groups in the nitrations of [1] and [2]. The reaction of [3] afforded 4-acyloxy-o-xylenes 17 a-6 in 25-43% yields along with 3-nitro- and 4-nitro-o-xylenes. Acetate ion in the reaction medium was found to be consumed for the formation of [7 a] in the reaction with propionyl nitrate.
trans-Stilbene underwent g-nitroacyloxylation with acetyl or propionyl nitrate to give threo1-acyloxy-1, 2-dipheny1-2-nitroet1iane.
In is reasonably concluded that the acyl nitrates formed under the present conditions behave like acetyl nitrate toward typical aromatic hydrocarbons.