Research in Energetic Compounds.
Interim summary rept. 1 Mar 79-29 Feb 80,
FLUOROCHEM INC AZUSA CALIF
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3-Chloro-2-hydroxy-1-propyl acetate, obtained from acetic acid and epichlorohydrin, was converted to its tetrahydropyranyl ether which was cyclized with base. Hydrolysis gave 3-hydroxyoxetane in 37 overall yield. This compound was converted to the tosylate, the bromide and the iodide, none of which underwent displacement by nitrite ion. The reaction of 3-oxetyl tosylate with potassium azide gave 3-azidooxetane which on hydrogenation gave 3-aminooxetne, also obtained from the tosylate and ammonia. Oxidation of the amine with m-chloroperbenzoic acid gave 3-nitrooxetane. Fluoronitromalonate esters were hydrolyzed to fluoronitroacetates, which, with formaldehyde gave the 2-fluoro-3-hydroxy-2-nitropropionates. The hydroxyls were protected as the tetrahydropyranyl ethers. Base hydrolysis of the ester groups followed by acid hydrolysis of the tetrahydropyranyl groups gave 2-fluoro-2-nitroethanol. Subsequently a one step synthesis of this compound from diethyl fluoronitromalonate, potassium carbonate and formaldehyde was developed. 1-Fluoro-1-nitroethylene was prepared by reactions of 2-fluoro-2-nitroethanol with acetic anhydride and potassium acetate, wth phthalic anhydride and also with dicyclohexyl carbodiimide. 2-Fluoro-2,2-dinitroethyl glycidyl ether was polymerized with triflic acid, triflic acid hydrates and triflic anhydride to give polymers with molecular weights up to 1800. NMR evidence indicated that triflate esters were intermediates. Author
- Polymer Chemistry