engleski

Observation of the Second and Concurrent Pathway in the Interaction of Acyl Chlorides With C-nitroso Group ; Can C-nitroso Group Attack Acetyl Cation-Chloride Contact Ion Pair ?

The interaction of acyl chlorides with nitrosobenzenes in 99.9% acetonitrile and in the presence of excess HCl over the nitrosobenzene concentration, leads exclusively to the corresponding N-p-chlorophenyl hydroxamic acids (Eq. 1) However, when nitrosobenzene was in excess over the HCl concentration, the main reaction product (> 80%) appears to be N-phenyl hydroxamic acid, with N-p-chlorophenyl hydroxamic acid as the minor product (Eq.2). The available evidence suggests that the reaction (Eq. 2) could be initiated by the attack of the nitroso group on the acetyl cation-chloride contact ion pair (4) (or perhaps also on a solvent separated acetyl cation-chloride ion pair). This leads to the intermediate acetylnitroso cation-chloride ion pair (5) and after N-Cl bond breaking of the subsequent intermediate (6), gives N-phenyl hydroxamic acid. The observation that p-methylnitrosobenzene reacts with acetylchloride to give a mixture of N-phenylacetohydroxamic acid and N-2-chlorophenylacetohydroxamic acid is in support of the mechanism proposed.

nije evidentirano

nije evidentirano