N-Cyanoaziridines and 1-alkylalkylidenecyanamides from cyanogen azide and olefins

Abstract

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.

On the functionalization and characterization of hydroxyl‐terminated polybutadiene with octyl‐1‐azide and the evaluation of polyurethane elastomers based on such modified HTPB

“…Herein the proposed reaction mechanism is revised, based on infrared and nuclear magnetic resonance evaluations and with the help of other published results. 15,26,27 Unlike the mechanism previously proposed in, 4 four different paths are shown in Figure 3 for the rupture of the triazoline ring. The first ring rupture (a) involved imine formation through proton H 2 transfer; in the second one (b) it was assumed an addition reaction resulting in the aziridine heterocyclic formation.…”

“…The paths (c) and (d) are presented as the both ways to form amine in which the first involves proton H 1 transfer to nitrogen and the other through the sigmatropic intramolecular reaction from imine. 27 Concerning the possible applications for propellant, the incorporation of aziridine groups in the HTPB is remarkably interesting. The hydrogen of the aziridine groups are expected to form linkages with the perchlorate anion and therefore increase the compatibility of the ammonium perchlorate (AP) with the binder.…”

Some reactions of N-substituted-1,2-dihydropyridines with cyanogen azide. Synthesis of 1,2,3,4-tetrahydropyridylidene-4-cyanamides

“…General Procerlure A Cyanogen azide was prepared iil sitci using the procedure of Hermes and Marsh (2). Cyanogen bromide (2.65 g, 25 mmol) in acetonitrile (25 ml) was added slowly with vigorous stirring to a suspension of sodium azide (8.12 g, 0.125 mol) in 75 ml dry acetonitrile at 0°C under a nitrogen atmosphere.…”

Small Rings by Azide Chemistry

“…For example, N -cyanotriazolines decompose at temperatures between 0 ° C and 35 ° C, leading to the formation of mixtures of N -cyanoaziridines 32 (R 1 = CN) and alkylidenecyanamides 33 (R 1 = CN). 68 In reactions wherein aziridines are isolated but triazolines are neither isolated nor detected it can be diffi cult to distinguish between nitrene and triazoline mechanisms. An example of this is the reaction of 2 -azido -1 -methylindole and methyl acrylate at room temperature which led directly to the isolation of the aziridine 34 in 78% yield.…”