Acetoxylation, accompanying nitration

The kinetics of nitration in acetic anhydride are complicated. In addition to the initial reaction between nitric acid and the solvent, subsequent reactions occur which lead ultimately to the formation of tetranitromethane furthermore, the observation that acetoxylation accompanies the nitration of the homologues of benzene adds to this complexity. 

Acetoxylation is found to accompany nitration of fairly reactive aromatics by nitric acid in acetic anhydride and gives rise to zeroth-order kinetics76. The electrophile is believed to be protonated acetyl nitrate the formation of which is rate-determining, hence the kinetic order (see p. 37). Acetoxylation can also accompany halogenation by positive halogenating agents in acetic acid solvent, especially in the presence of sodium acetate137, but no kinetic studies have been carried out. 

The fact that nitration with acetyl nitrate is sometimes accompanied by acetoxylation has been mentioned ( 5.3.3). In proposing the ion pair ACONO2H+ NOg- as the nitrating agent, Fischer, Read and Vaughan also suggested that it was responsible for the acetoxylation, which was regarded as an electrophilic substitution. 

Acetoxylation has been found to accompany the nitration of o- and m-xylene... 

Nitration is widely applicable, can be carried out under a variety of conditions, can usually be stopped cleanly after mononitration, is usually effected by the nitronium ion, can take place on a neutral molecule or a cation, and in many cases can be considered as the standard aromatic electrophilic substitution. However, this last point must be treated with caution. Depending on the reaction conditions and reagents, the mechanism of the reaction does vary, and accompanying reactions such as oxidation (due to the oxidative action of nitric acid), acetoxylation (by acetyl nitrate), and migration of nitro groups following ipso attack (80MI1) can occur. Ipso nitration processes have been extensively studied by Fischer and co-workers. 

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