Diaziridines addition products

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). 

All diaziridines which contain at least one NH-group give, with chloral, w ell crystallized addition products in molar ratio l ." The adducts liberate tw-o equivalents of iodine and thus retain the CNN three-membered ring [Eq. (38)]. By treatment with alkali the chloro-... 

The rate of the diaziridine formation shows that the chloramine is attacked by the Schiff s base. Although ethereal chloramine solutions are only decomposed after weeks of standing, in the presence of a Schiff s base the chloramine is consumed after a few hours. The Schiff s base therefore does not enter into the reaction merely after the decomposition of the chloramine as it would have to do if formula 39 was an intermediate. Probably the chloramine adds onto the Schiff s base [Eq. (37)] and ring closure of the geminal addition product occurs.39... 

The isoelectronic pyridinium A-ylides, e.g. 110, behave in an analogous manner to the A-oxides. Photolysis in an inert solvent leads to the diazepine 112 as the sole product, probably with intermediate formation of a diaziridine 111, followed by electrocyclic N/C-1 cleavage. Photolysis in benzene yields, in addition to the diazepine 112, the azepine 113 because of a competitive N-N cleavage and interaction of the solvent with the resulting nitrene (by a [2+1] cycloaddition and electrocyclic opening of the diazanorcaradiene) ... 

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