Oxaziridine reactions hydrolysis

Like isomerization of oxaziridines to nitrones, acid hydrolysis of oxaziridines proceeds with conservation of the N—O bond. Both reactions are related mechanistically and are... 

Hydrolysis and rate constants of oxaziridine compounds and nitrones under variation of the pH value and reaction medium... 

The investigations of the UV spectra, the rate constants of hydrolysis and additional investigations of deuterium isotope and temperature effects of TV-t-butylbenzaldoxime and 2-J-butyl-3-phenyloxaziridine57 suggest a mechanism which is shown in Scheme 3. If the protonated nitrone is the intermediate in both reactions, the formation from either nitrone or oxaziridine should have no effect on the subsequent behaviour under identical conditions. 

Hydrolysis by Emmons path 2 has been suggested" as a method for converting amines to ketones, the acid counterpart of a base-catalyzed procedure cited previously. The oxaziridines were obtained by oxidation of the product from amines and acetone, and hydrolyzed with 2M hydrochloric acid at room temperature for 40 hours. The only aliphatic aldehyde produced was not stable under these conditions. This reaction has received further study. ... 

Oxidative deamination of a secondary amine to the ketone can be effected by formation of the imine with 2-pyridinecarboxaldehyde, reaction of the imine with peroxy-acid to form the oxaziridine, and alkaline hydrolysis (KOH-H2O-DMF-MeaCO). The steps are illustrated for 3a-amino-5a-cholestane (235), leading to (239) a IVa-aminoandrostane also gave the corresponding ketone. ... 

Acid-catalyzed hydrolysis of A-aryloxaziridines may proceed via cleavage of either the C—O or N—O bonds, depending upon the ring substitution pattern. These reactions are usually discussed in terms of initial protonation at the oxaziridine oxygen atom <77JHC1393>. Acid-catalyzed isomerization to nitrones has also been reported <64HC(19)624>. 

In some reactions the compounds unsubstituted at nitrogen proved to be typical oxaziridines. So the classification as oxaziridines was never a problem. They can be cleaved by hydrolysis to give carbonyl compounds and hydrox-ylamine and can easily be reduced by iodide in acid solution to form iodine, the carbonyl compound, and ammonia. N-Alkylation by t-butyl chloride leads to the known Ai-t-butyloxaziridine. By the action of ferrous salts the diamide of dodecanedicarboxylic acid is formed, in analogy to the formation of 31. 

Irradiation of the diazepine N-oxide 8 gives a mixture of the 1,2-dihydroquinoxaline (10) and the oxadiazocine 11 through an intermediate oxaziridine (9). The dihydroquinoxaline undergoes acid hydrolysis to the quinoxalinone 12. It was subsequently shown that quinoxalinones of type 12 undergo ready reaction with ammonia or primary or secondary amines, in the presence of titanium tetrachloride, to give 3-amino- or... 

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