Improved synthetic routes to polynitroheterocycles

Abstract The preparations of several explosive precursors utilizing oxidative nitration are described. These include 1,3-di-t-butyl-5,5-dinitrohexahydropyrimidine, 3-t-butyl-5,5-dinitrotetrahydro-1,3-oxazine, 2,2-dinitro-1,3-propanediol (ADIOL) and potassium aci-2,2-dinitroethanol. The former pyrimidine and oxazine precursors were nitrolyzed to 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and 3,5,5-trinitrotetrahydro-1,3-oxazine (TriNOx). ADIOL, a widely used reagent in explosives preparation, was prepared by the trans-ketalization of 2,2-dimethyl-5,5-dinitro-1,3-dioxane. The dioxane was prepared in high yield by the oxidative nitration of 5-hydroxymethyl-2,2-dimethyl-5-nitro-1,3-dioxane. The little known explosive, 1,3,3,5,5-pentanitro-piperidine (PNP), has been prepared from potassium aci-2,2,4,4-tetranitrobutanol and t-butylamine hydrochloride. The vacuum thermal stabilities of DNNC, TriNOx and PNP at 100°C are reported.