Fluorinating nitro-compounds

摘要

Organic compounds containing at least one terminal gem dinitro grouping of the formula wherein M is hydrogen or a metal, are fluorinated by reaction with fluorine in the presence of a moderator which is less reactive with fluorine than the compound being fluorinated. The terminal grouping is converted to Suitable moderators are water, alkanols, alkylene glycols, alkanes, haloalkanes, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, ketones, ethers, and alkyl substituted amides; many suitable organic moderators are specified. The organic radical attached to the terminal gem dinitro grouping may be a substituted or unsubstituted alkyl, cycloalkyl, aryl, or heterocyclic radical or a radical interrupted by a hetero atom, e.g. S, N, or O, or by an ester grouping. When the organic compound treated contains two gem dinitro groups, the link between these groups may be a substituted or unsubstituted alkylene or arylene radical which may be interrupted by nitrogen, nitraza, sulphur, or oxygen. The dinitro compound may be dissolved or suspended in the moderator; fluorine, diluted if desired, with helium or nitrogen, is passed through the liquid. Many fluoro compounds which may be formed are specified and examples are given of the preparation of the following: 1-fluoro-1,1 dinitroethanol, phenyl dinitro fluoromethane, 1 - fluoro - 1,1 - dinitroethane, 1,3 - difluoro-1,1,3,3 - tetranitro - propane, bis - (3 - fluoro-3,3 - dinitropropyl) maleate, N,N1 - bis - (2-fluoro - 2,2 - dinitroethyl) hydrazine, di - (3-fluoro - 3,3 - dinitropropyl) ether, -N - nitro-2,21 - difluoro - 2,2,21,21 - tetranitrodiethylamine, 1 - fluoro - 1,1 - dinitro - 3,3 - dichloropropane, 1 - fluoro - 1,1,3,3 - tetranitrobutane, 4 - fluoro-2,2,4,4 - tetranitrobutylacetate, 3,31 - difluoro -3,3,31,31 - tetranitro - 2,21 - dichlorodipropylamine, 1 - fluoro - 1,1 - dinitro - 4 - nitraza heptane, 2 - fluoro - 2,2 - dinitroethyl benzoate. Moderators used in the examples are water, chloroform, ethylene glycol, benzene, dimethyl acetamide, hexane, 1-propanol, diethyl ether, nonane, dimethyl ketone, dimethyl formamide. The fluoro dinitro compounds are useful as explosives, for example in a missile as described in United States Specification 2,470,162, or as oxidizers for liquid rocket fuels such as hydrazine. In Example 5, bis-(3,3-dinitropropyl) maleate is prepared by esterification of the alcohol with the acid, and is subsequently converted to its barium salt by reaction with barium hydroxide. In Example 14, 2,2-dinitroethyl benzoate is prepared by esterification of the acid with the alcohol.