Direct Polynitroaliphatic Alcohol Addition to Alkenes. 2. One-Step Synthesis ofbeta-Substituted Polynitroalkyl Vinyl Ethers via an Alternative Transetherification Pathway

摘要

Beta-Substituted polynitroalkyl vinyl ether compounds represent monomeric polymerprecursors which potentially could be useful chemical components in solid propellant or explosive formulations. Their preparation is limited by the inherent instability of the beta-substituted polynitroalkyl structure in alkaline solution and by the weak nucleophilic nature of the polynitroaliphatic alcohol precursors possessing either the geminal 2,2-dinitroalkyl or terminal 2,2,2-trinitroethyl structure. this precludes using the common vinyl ether synthesis procedure where an alcohol and acetylene are reacted via base catalysis because these polynitroaliphatic alcohol reactants readily deformylate in alkaline solution forming formaldehyde plus their respective polynitroalkyl anion. This paper reports our discovery of a novel reaction which permits the one-step, high-yield synthesis of beta-substituted polynitroalkyl ethers under mild refluxing CH2Cl2 solvent conditions.