Synthesis of Diaziridines

Chloral forms well-crystallized adducts (126) with diaziridines containing at least one NH group (B-67MI50800). Carbonyl addition products to formaldehyde or cyclohexanone were also described. Mixtures of aldehydes and ammonia react with unsubstituted diaziridines with formation of a triazolidine ring (128). Fused diaziridines like (128) are always obtained in ring synthesis of diaziridines (127) from aldehyde, ammonia and chloramine. The existence of three stereoisomers of compounds (128) was demonstrated (76JOC3221). Diaziridines form Mannich bases with morpholine and formaldehyde (64JMC626), e.g. (129). 

S.08.4.2.1 Synthesis of diaziridines by electrophilic amination of carbonyl-amine adducts... 

Imines and substituted oximes react with several nitrogen-containing nucleophiles to provide a general synthesis of diaziridines or diazirines. ... 

The general methods of synthesis of diaziridines and diazirines were worked out by Schmitz (Equation (12)) <84CHEC-i(7)i95> and Graham (Equation (13)) <65JA4396> at the beginning of the study of these classes of compounds. 

Recently there was a report on the asymmetric synthesis of diaziridines. For example, on reaction of camphor-sulfonylated acetone-oxime with methylamine, optically active 115 is formed with an optical purity of 10%... 

The preparation of diazirines 147, the cyclic isomers of diazoalkanes, almost always proceeds by synthesis of diaziridines from carbonyl compounds followed by dehydrogenation [Eq. (2)]. 

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