The role of pH in the synthesis of diaziridines

Abstract

In the synthesis of diaziridines from amines, carbonyl compounds, and NaOCl in water, the yields of 1,2-dialkyldiaziridines and of 1,2,3-trisubstituted diaziridines prepared from amines with electron-withdrawing substituents in the side chain are less sensitive to changes in pH than the yields of 1,2,3-trialkyldiaziridines with simple alkyl substituents. The formation of 1,5-diazabicyclo[3.1.0]hexanes is insensitive to the pH in 6.5–13.0 range. This difference is explained by the occurrence of two competing pathways to the key intermediate,N-chloroaminal.