AbstractIodine azide adds to cyclohexene in acetonitrile or 4:1 methylene chloride/acetonitrile to givetrans‐1‐azido‐2‐iodocyclohexane. In methylene chloride this reaction gives a mixture of thecis‐andtrans‐iodoazides owing to competing radical addition. Iodine azide adds to 1‐hexene in acetonitrile by an ionic mechanism to give a 3:1 mixture of the 2‐azido‐1‐azido‐ and 1‐azido‐2‐iodohexanes. Dehydroiodination of the model iodoazides proceeds smoothly with potassiumt‐butoxide in diethyl ether or THF in the presence of 5 mol % 18‐crown‐6 at room temperature, giving in the previous example a mixture of 2‐azido‐ andtrans‐1‐azidohexenes. Polybutadiene, carboxyterminated poly(acrylonitrile‐co‐butadiene), and hydroxy‐terminated polybutadiene gave iodoazide derivatives with up to 96% of the theoretical maximum nitrogen content and strong azide IR absorption. High azidoiodination gave polymer with N3/I ratios slightly higher than unity while low percent azidoiodination led to polymer with N3/I ratios of as low as 2:3. All of the nitrogen introduced was in the form of azide function. Dehydroiodination gave polymers with vinyl azide functionality and caused loss of some of the azide groups. All the azidoiodinated polymers decomposed between 120 and 160°C. The dehydroiodinated materials were less stable, decomposing between 100 and 150°C. The temperature of initial decomposition decreased as azide content increased. Polymers with>55–60% of the the