engleski

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.

An unexpected and previously unknown reaction sequence in the interactions of the acyl halides with nitrosobenzenes which involves the carbon-nitrogen bond formation followed by the 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 N-phenylchlorohydroxylamine intermediate, formed in the first reaction step, with the acyl halide in the second step of the complex sequence, which leads to a N-acyl-N-chlorophenylhydroxylamine cation intermediate. The key reaction step involves the interaction of 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.

C-Nitroso compounds; hydroxamates; acyl halides; kinetic; mechanismn

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