The use of iodine in triethylamine is presented as a superior alternative to the commonly used silver oxide pro-cedure for the oxidation of diaziridinesto diazirines. However, in acidic media this oxidation is not stoichiometric. A study of the iodine-iodide ion redox system with 1, 1-hydrazicyclohexane disclosed that a catalytic cyclic process is operative andleads todisproportionation of the diaziridine. Conversely, overconsumption of iodine under conditions of rapid titration is also possible, perhaps owing to the formation of an N, N'-diiododiaziridine intermediate. A variety ofsimple diazirine-containing aliphatic acids, acid chlorides, esters, alcohols, ace-tals, aldehydes, amines, amides, etc., were prepared either from the corresponding ketone or by subsequent transformations. The diazirine group was stable to a variety of reagents. The physical properties (pK „, uv, ir, nmr) of some of these functionalized diazirine-containing molecules are discussed. The effect of the diazirine function on p. Kais approximately comparable with that exerted by a keto group or a chlorine atom, but it is less diminished by increasing distance.

Considerable interest has been generated by the diazirine and diaziridine groupssince their unequivocal discovery about ten years ago. 2 In continuation of our study concerning the effect of the diazirine group on biological activity, 1 we have found it necessary to prepare a variety of small, otherwise functionalized mole-cules which contain this group. In addition to the preparation of some of these compounds, we report herein our observations concerning the compatibility of the diazirine group with a number of common chemical reagents and certain interactions between the diazirine group and neighboring functions. A subsequent re-port3 will describe some of the biological properties of these and derived compounds. The diazirine group is generally introduced by oxida-tion ofthe diaziridine obtained from the corresponding ketone by treatment with ammonia and hydroxyl-amine-O-sulfonic acid or chloramine (Scheme I). Us-ually, the oxidation (reaction b) is effected by silver oxide which, however, is not an entirely satisfactory reagent for this purpose. Certain functional groups, amines in particular, interfere with thereagent. Fur-thermore, preprepared silver oxide which is sufficiently active is rather difficult to obtain and, when prepared