Patent GB-391168-A (GB)
Title: Improvements in or relating to the manufacture of fluorine derivatives of hydrocarbons
IPC: C07C17/20
Filed: 1931-07-13
Abstract: Fluorine derivatives of hydrocarbons are obtained by reacting halides of acyclic hydrocarbons, including paraffins, olefines, and the like, or aryl derivatives thereof with hydrogen fluoride in the presence of a metallic halide catalyst which has the property of mutually exchanging its halogen with hydrogen fluoride, and whose fluoride has the property of mutually exchanging halogen with an acyclic halogen derivative or aryl derivative thereof.  Examples of suitable metallic halides are antimony halides, particularly antimony chloride, Antimony pentachloride with or without antimony trichloride and free chlorine may be used.  During the reaction there may be present a complex of the general formula S6FxHal5-x where Hal stands for a halogen other than fluorine and x is less than six.  The antimony compound may advantageously be maintained in the liquid condition by the presence of an inert material, such as a previously fluorinated compound which is liquid at the temperatures employed, examples of suitable diluents given being benzotrichloride, difluorotetrachloroethane, octachlorodiphenyl, benzotrifluoride, and chloroform.  The presence of excess of the hydrocarbon halide being fluorinated, or of a trivalent antimony compound, may also be resorted to for the same purpose.  Examples of hydrocarbon halides which may be employed as starting materials are carbon tetrachloride, chloroform, methylene chloride, fluorotrichloromethane, ethyl chloride, isopropyl bromide, ethylene dibromide, tetrachloroethane, trichloroethylene, benzotrichloride, and ring chlorinated benzotrichloride obtained by the chlorination of orthochlortoluene in the presence of phosphorus pentachloride. Partially fluorinated compounds containing halogens other than fluorine may be further fluorinated by the process.  When the original hydrocarbon halide contains hydrogen, as in the case of methylene chloride or tetrachloroethane, a substitution of halogen for hydrogen may take place during the reaction, particularly if free chlorine be present. When the hydrocarbon halide is unsaturated, the addition of halogen and introduction of fluorine both occur.  For example, from trichloroethylene, particularly if free chlorine is present, a product containing fluorine derivatives of ethane is obtained.  The reaction may be carried out at temperatures between 0 DEG  C. and the boiling point of antimony fluoride, the preferred range being 45-95 DEG  C. Sub-atmospheric, atmospheric, or super-atmospheric pressures may be employed.  The separation of the products by distillation, fractional or otherwise, may be carried out simultaneously or in separate steps, and in the latter case the pressures of the two steps may be different.  Two forms of apparatus and methods of carrying out the process, either in a continuous manner or by batch operation, are described in detail.  Parts of the apparatus coming into contact with hydrogen halides and antimony halides are usually made of corrosion resisting material such as copper, but when the invention is carried out on a small scale the reaction vessel and subsequent parts may be made of glass.  Examples describing the fluorination of carbon tetrachloride, chloroform, benzotrichloride, and ring chlorinated benzotrichloride obtained from orthochlortoluene are given, products of which specific mention is made being fluorotrichloromethane, difluorodichloromethane, trifluorochloromethane, benzotrifluoride, benzodifluorochloride, ring chlorinated benzotrifluoride, and orthochlorobenzotrifluoride.