Reactions of Aziridines with Acetyl Chloride and Related Compounds

Abstract

When aziridines (1) were treated with acetyl compounds, such as acetyl chloride, acetic acid, acetic anhydride, and thioacetic acid, the corresponding acetamide derivatives were obtained in good yields. In the case of acetyl chloride, some derivatives of N-(2-chloroethyl)acetamide (5) were found to be unstable in the face of moisture; they were easily hydrolyzed to give N-(2-hydroxyethyl) acetamide hydrochlorides (3). The NMR spectrum of N-(2-mercaptoethyl)-N-benzylacetamide (12) was discussed.

Mechanistic Studies of the Copolymerization Reaction of Aziridines and Carbon Monoxide to Produce Poly-β-peptoids

“…This is apparent in that for a copolymerization reaction carried out using complex 1 as precatalyst in the presence of excess PPh 3 , copolymer formation is greatly retarded as seen in the initial rate plots depicted in Figure . Although, there is no precedent for aziridines or phosphines interacting at the carbonyl center of metal acyl derivatives, aziridine insertion into acetyl chloride has been reported to occur via formation of an intermediate as shown below . Furthermore, the hydrolysis, alcoholysis, and aminolysis of acylcobalt tetracarbonyl are proposed to involve nucleophilic attack of the respective nucleophiles on the acyl group .…”

“…A pivotal reaction to the copolymerization of CO and imines to form poly-α-peptides has been previously reported which involves the insertion of an imine into a Pd-acyl bond, however, CO/imine copolymerization has not yet been achieved. Although aziridine insertion into metal carbon bonds was not known, an insertion into an acetyl chloride bond had been previously described . On the basis of this, Jia and co-workers reported aziridine insertion into a cobalt-acyl bond coupled with CO formed poly-β-peptide and peptoid .…”

Copolymerization of carbon monoxide and aziridine

“…(2)]. 11 It is well established (2) that some metal-acyl species resemble organic acyl chlorides and undergo nucleophilic cleavage by alcohols and amines to afford esters and amides. By such analogy, insertion of aziridine into metal-acyl bonds might also occur.…”

Acetyl Chloride

“…215 Also, aziridines react with AcCl (PhH, 0 • C) to afford chloroethylacetamides. 216 Allylic amines react with in situ-generated AcI (AcCl/CuI, THF, rt) to afford acetamides. 217 AcCl also activates pyridines toward nucleophilic addition.…”