Research in Energetic Compounds.
Abstract
3,3-Dinitrooxetane was synthesized by the oxidative nitration of 3-nitrooxetane. 3,3-Dinitrooxetane underwent addition of triflic acid under mild conditions. Polymerization of 3-azidooxetane with BF3 gave diol with a molecular weight of 2100. Process studies were initiated to enable the preparation of larger quantities of this polymer. The reaction sequence consisted of adding acetic acid to epichlorohydrin, blocking the resulting hydroxyl with dihydropyran, cyclization with sodium hydroxide, and deblocking to give 3-hydroxyoxetane. The latter was converted to the tosylate, which underwent displacement with sodium azide. The relatively expensive blocking agent, dihydropyran, was replaced with ethyl vinyl ether with similar results. The yield in the tosylate preparation step was improved with 4-dimethylaminopyridine catalysis. The azide displacement step was carried out with the inexpensive and nontoxic solvent, triethylene glycol, in place of hexamethyl phosphoramide. An alternative route, consisting of the addition of IN3 to allyl alcohol followed by reaction with base, failed to give 3-azidooxetane. Synthesis of 1-fluoro-1-nitroethylene was improved by using alumina for the dehydration of 2-fluoro-2-nitroethanol. Polymers with molecular weight as high as 30,000 were obtained from fluorodinitroethyl glycidyl ether and the triethylaluminum-water catalyst, but reproducibility and functionality were poor.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1981
- Accession Number
- ADA096192
Entities
People
- Kurt Baum
- Phillip T. Berkowitz
- Wayne A. Vinson