C–N bond formation followed by N–Cl bond breaking. One more and unexpected case of the formation of a hydroxamic group via heterolytic bond cleavage

Abstract

An unexpected and previously unknown reaction sequence in the interactions of the acyl halides with nitrosobenzenes, which involves carbon–nitrogen bond formation followed by heterolytic nitrogen–chlorine bond cleavage giving the corresponding unsubstituted N-phenylalkylhydroxamic acids (or N-phenylarylhydroxamic acids) and chlorine as the products has been observed. The kinetic and other evidence obtained suggest that the carbon–nitrogen bond formation is the consequence of a nucleophilic interaction of an N-phenylchlorohydroxylamine intermediate, formed in the first reaction step, with the acyl halide in the second step of the complex sequence, which leads to an N-acyl- N-chlorophenylhydroxylamine cation intermediate. The key reaction step involves the interaction of an N-acyl- N-chlorophenylhydroxylamine cation intermediate with chloride ion, which leads to the N–Cl heterolytic bond cleavage and the final formation of the hydroxamic group and a molecule of chlorine.