The reaction of molecular cyanogen azide with hydrocarbon olefins at 0-35°g ives 1-alkylalkylidenecyanamides and/or 1-cyanoaziridines in high yields. Evidence is presented favoring a 1,3-dipolar concerted addition of the azide followed by opening of the resulting triazoline to a diazonium zwitterion and loss of nitrogen from this labile species to yield products. Linear and simple cyclic olefins generally produce alkylidenecyanamides as the major product, often to the exclusion of A-cyanoaziridines. With selected cyclic olefins this reaction is an effective means of forming either ring-enlarged or ring-contracted product. Ring-enlargement products and aziridines are also formed by reacting cyclic alkylidenecyanamides with diazomethane. The 1-alkylalkylidenecyanamides are readily hydrolyzed to ketones; the cyanogen azide reaction thus permits facile, low-temperature conversion of olefins to ketones. More highly substituted olefins often produce W-cyanoaziridines, and these compounds are obtained in high yield from polycyclic olefins such as norbornene and dicyclopentadiene. The W-cyanoaziridine produced from norbornene, 3-cyano-3-azatricyclo[4.2.1.02•4]octane, is cleaved with LiAlH, to the parent aziridine, which is readily converted to 7-aminonorbornane (by hydrolysis and dehalogenation) and sj/w-7-aminonorbornene (by hydrolysis and dehydro chlorination).Since we reported the synthesis of cyanogen azide (N3CN) in 1964,1 two broad areas of chemical reactivity for this highly reactive compound have been defined. We disclosed at that time the facile addition of the molecular azide to olefins accompanied by nitrogen loss (1) F. D. Marsh and . E.
Cyanazid (I) reagiert mit Isobutylen (II) zunächst zu einem Triazol (III), das zu 34% in N‐Cyan‐aziridin (IV) und zu 48% in Alkylalkyliden‐cyanamid (V) übergeht.
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