Reactions of 2-Fluoro-2-nitro-1,3-propanediol. Trifluoromethanesulfonates and 3-Fluoro-3-nitrooxetane

Article abstract of DOI:10.1021/jo01312a010

The reaction of diethyl fluoronitromalonate with base and formaldehyde provided a convenient synthesis of 2-fluoro-2-nitro-1,3-propanediol.This diol reacted with triflic anhydride to give 2-fluoro-3-hydroxy-2-nitro-1-propyl triflate and 2-fluoro-2-nitro-1,3-propylene ditriflate.The monotriflate reacted with base to give 3-fluoro-3-nitrooxetane.The ditriflate underwent displacement reactions with sodium azide, 2-fluoro-2,2-dinitroethanol, and methanol.Reactions of 3-fluoro-3-nitrooxetane with strong acids resulted in ring opening to give 3-substituted 2-fluoro-2-nitropropanols.The oxetane was polymerized with phosphorus pentafluoride.Triflates derived from 2,2-dinitro-1,3-propanediol and 2-(hydroxymethyl)-2-nitro-1,3-propanediol did not cyclize.