Aniline, formation Benzanilide

Formation of amide Aniline reacts with acid chloride to form corresponding amide. For example, when aniline is treated with benzoylchloride in the presence of pyridine, it produces benzanilide. 

While these experiments are suggestive of a nitrene mechanism for the non-Curtius products, they do not constitute entirely conclusive evidence. Anselme re-examined some of Homer s earlier work and found that photolysis of benzoyl azide in benzene followed by the addition of aniline to the photolysate produced 30% of benzanilide (117) and 56% of W,A -diphenylurea (118). The same products were isolated when benzonitrile was the solvent, but no cyanoben-zanilide was found, which should have been one of the products had benzanilide (117) been formed directly by nitrene attack on the solvent. To account for the formation of the non-Curtius products Anselme suggested a reaction scheme involving azodibenzoyl (119) as an intermediate. Some support for this mechanism can be found in the work of Lwowski and of Hancock... 

Equation (6) Likewise, aniline i.e., a primary aiyl amine, gives rise to the formation of benzanilide or phenyl benzamide or benzoyl aniline as the final product plus one mole of HCl. 

Anilides are also substrates for the PFR, although their reactivity is lower than that of the analogous phenyl esters. Thus, irradiation of acetanilide leads to 2-aminoacetophenone, 4-aminoacetophenone, and aniline (Scheme 31.5) [62] the quantum yields of product formation (<0.1) are markedly lower than those of phenyl acetate [63,64] and decrease with solvent polarity, dne to excited state quenching. Similar resnlts are obtained with benzanilides [65, 66]. 

Primary amines react less readily with diacyl peroxides than either secondary or tertiary amines. The reaction results in a complex mixture of products . From aniline and benzoyl peroxide, for instance, benzoic acid, benzanilide, azoxybenzene and a little o-hydroxybenzanilide can be isolated . Their formation can be rationalised from an initial attack by benzoyl peroxide to give both 0-benzoylphenylhydroxylamine (34) plus benzoic acid and benzanilide (35) plus perbenzoic acid (Scheme 32). Subsequent hydrolysis. 

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