An unusual case of carbonnitrogen bond formation. Reactivity of a C-nitroso group toward acyl chlorides

Study of condition-dependent decomposition reactions

“…Formation of nitrosobenzene in the decomposition reacts with acid chlorides to produce the corresponding N-p-chlorophenylhydroxamic acid. The presence of HCl catalyses the reaction [12]. Scheme 6.…”

“…In the reported formation of the hydroxamic acid [12], the reaction takes place in acetonitrile. If the manufacture of the acid chloride takes place in a solvent or solvent mixture containing acetonitrile (which is a quite common approach), the formation of the hydroxamic acid would be more likely to occur.…”

Nitrosobenzene

“…67 The best results are obtained in a mixed solvent systems such as n-hexane-CH 2 Cl 2 and n-pentane-CH 2 Cl 2 . up to 92% ee (51) …”

“…are also prepared from the reaction of nitrosobenzene and acyl chloride in the presence of a catalytic amount of HCl in acetonitrile (eq 42) 51. The reaction is initiated by the formation of an N-chlorohydroxylamine intermediate from nitrosobenzene and hydrogen chloride.…”

Reactions of Nitrosobenzenes with Cyclobutanones by Activation with a Lewis Acid

“…Among reactions of nitrosobenzenes with carbonyl compounds, the nitroso aldol reaction, 1 which is a valuable synthetic method for introduction of nitrogen or oxygen at the α position of a carbonyl group, has been extensively studied, and various regioselective 2 and enantioselective 3 methods have been established. 4 In addition to the nitroso aldol reaction, reactions of nitrosobenzene with carboxylic acid chloride and formaldehyde were reported to give N-(pchlorophenyl)hydroxamic acid 5 and N-phenylhydroxamic acid, 6 respectively. Frongia and Piras reported that organocatalyzed reaction of cyclobutanones with nitrosobenzene gave 5-hydroxy-γ-lactams.…”