United States Patent 19 (11) 4,183,873 Baxamusa et al. (45) "Jan. 15, 1980 (54) LIQUID PHASE FLUORINATION PROCESS Attorney, Agent, or Firm-Peter F. Casella; William J. Crossetta, Jr.; Arthur S. Cookfair 75 Inventors: Yusuf A. Baxamusa, Tonawanda; Stephen Robota, North Tonawanda, 57 ABSTRACT both of N.Y. A process for the preparation of compounds of the 73 Assignee: Hooker Chemicals & Plastics Corp., formula: Niagara Falls, N.Y. *) Notice: The portion of the term of this patent subsequent to Jul. 4, 1995, has been disclaimed. comprises contacting compounds of the formula: 21 Appl. No.: 912,629 22 Filed: Jun. 5, 1978 in the liquid phase, with hydrogen fluoride in the pres ence of molybdenum chloride wherein Related U.S. Application Data Ar is aryl 63 Continuation-in-part of Ser. No. 737,626, Nov. 1, 1976, R is a substituent on the aryl nucleus selected from Pat. No. 4,098,832. the group consisting of aryl, substituted aryl, halo gen, alkyl, alkoxy, substituted alkyl, and substituted (51 int.C. ... C07C 25/14 alkoxy; 52 U.S. C. ................................................. 260/651 F n is 0 to 9; (58) Field of Search..................................... 260/651 F X is halogen atom other than fluorine; w is 0 to 2; 56) References Cited 8 p is 1 to 3; U.S. PATENT DOCUMENTS w' is 1 to 3, and is greater than w; 3,131,226 4/1964 Olstowski et al. ................ 260/653.8 p' is 0 to 2, and is less than p; 3,435,082 3/1969 Ager ............... ... 260/653.8 w--p is 3; 3,859,372 l/1975 Robota ............................. 260/651 F w'--p' is 3; 4,079,089 3/1978 Klauke ............................. 260/651 F Z is 1-10; and 4,079,090 3/1978 Bittner et al. ................... 260/651 F 4,093,669 6/1978 Klaukeet al. .................... 260/651 F the maximum value of n--Z is 10. Primary Examiner-C. Davis 16 Claims, No Drawings 4,183,873 2 reaction with hydrogen fluoride, wherein the hydrogen LIQUID PHASE FLUORINATION PROCESS fluoride may be employed in either concentrated or dilute form. It is a still further object to provide a multi This is a continuation-in-part of Ser. No. 737,626, step fluorination process comprising both a vapor phase filed Nov. 1, 1976 and now U.S. Pat. No. 4,098,832. and a liquid phase reaction wherein substantial im BACKGROUND OF THE INVENTION provements in the effective utilization of hydrogen This invention relates to a process for the preparation fluoride reactant are achieved and the amount of hydro of organic fluoride compounds, and in particular, to a gen fluoride waste product is substantially reduced. process for the liquid phase replacement of halogen 10 SUMMARY OF THE INVENTION atoms with fluorine in organic compounds. In accordance with the present invention, there is A variety of fluorination processes are known provided a process for the preparation of fluorinated wherein fluorine replaces substituents of organic com aromatic compounds which comprises reacting a halo pounds, such as halogen atoms, hydrogen atoms, and methyl aromatic compound, wherein the halo is other the like. Such known processes include both vapor 15 phase fluorination reactions and liquid phase fluorina than fluorine, with a fluorinating agent in the presence tion reactions. Typically, such processes involve the of a catalytic amount of molybdenum pentachloride, reaction of an organic halide with hydrogen fluoride, The halomethyl aromatic compound may also contain sometimes in the presence of catalyst, such as antimony stable ring constituents, such as halogen, alkyl, alkoxy, pentachloride, at atmospheric or super-atmospheric substituted alkyl and the like, or other substituents that pressures. Many of the known processes, while suitable will not adversely affect the reaction. for laboratory investigations and experiments, are un In particular, this invention is directed to a process suitable for commercial use for various reasons, such as for the preparation of compounds of the formula: the low purity of product obtained, the high cost of equipment which must be employed, or the need for 25 frequent replacement of the catalyst, due to loss or which comprises contacting compounds of the formula: deactivation, One of the common difficulties encoun tered in vapor phase fluorination reactions results from RhAr(CFX)2 the highly exothermic nature of such reactions. The heat evolved frequently results in a temperature rise 30 in the liquid phase, with hydrogen fluoride in the pres sufficient to cause thermal decomposition of some of the ence of molybdenum pentachloride wherein organic starting materials and a resultant carbonization Ar is aryl; of the catalyst. Furthermore, such vapor phase reac R is a substituent on the aryl nucleus selected from tions commonly require the use of substantial stoichio the group consisting of aryl, substituted aryl, halo metric excess of hydrogen fluoride with the attendant 35 gen, alkyl, alkoxy and substituted alkyl; problem of disposal of the hazardous hydrogen fluoride n is 0 to 9; containing effluent gases. X is halogen atom other than fluorine; Some of the problems associated with vapor phase w is 0 to 2; fluorination processes may be avoided through the use p is 1 to 3; of liquid phase fluorination. However, although atmo 40 w' is 1 to 3, and is greater than w; spheric liquid phase fluorination processes are known p' is 0 to 2, and is less than p; and are used in laboratory preparations, they have not w--p is 3; received widespread acceptance for larger scale com w'+p' is 3; mercial use for various reasons. Heretofore, the most Z is 1-10; and widely used catalyst for liquid phase fluorinations has 45 the maximum value of n--Z is 10. been antimony pentachloride or a mixture of antimony The designation Ar or aryl represent an aromatic pentachloride and antimony trichloride. However, anti structure such as benzene, naphthalene, anthracene and mony chlorides, although highly effective in the cataly the like, preferably of up to 14 carbon atoms. The pre sis of fluorination reactions, are very volatile materials. ferred compounds prepared in accordance with this To avoid the problems associated with the volatility of 50 invention are those of the above formula wherein Ar is antimony chlorides, such fluorination reactions are benzene. often carried out in closed systems under superatmos Among the R substituents encompassed within the pheric pressure, necessitating the use of pressure equip formula shown above, are alkyl radicals of from 1 to ment. In addition it has been found that to obtain desir about 20 carbon atoms, and preferably of from 1 to ably high yields, antimony chloride catalysts must be 55 about 12 carbon atoms, such as methyl, ethyl, propyl, employed in relatively large concentrations. Thus, al butyl, amyl, octyl, decyl, dodecyl, pentadecyl, eicosyl, though antimony chlorides provide an effective catalyst as well as their various isomer forms, such as isopropyl for fluorination reactions, a need exists for a still more and isobutyl, said alkyl radical being a monovalent radi effective catalyst that will overcome the aforemen cal derivable from an aliphatic hydrocarbon alkane by tioned disadvantages. 60 the removal of 1 hydrogen atom; substituted alkyl of It is an object of the present invention to provide an from 1 to about 30 carbon atoms and preferably of from improved process for the liquid phase fluorination of 1 to about 15 carbon atoms, said alkyl group being organic halides. It is a further object to provide an substituted by one or more of aryl, substituted aryl, and improved catalyst for fluorination reactions that is rela the like; alkoxy and substituted alkoxy of from 1 to tively low in cost, of low volatility, and that may be 65 about 20 carbon atoms, and preferably of from 1 to effectively employed at relatively low concentrations. about 12 carbon atoms, such as methoxy, ethoxy, It is a further object to provide an improved process for propoxy, butoxy, pentoxy, octoxy, dodecoxy, pen the fluorination of organic halides in the liquid phase by tadecoxy, eicosoxy, as well as their varius isomer 4,183, 873 3 4. forms, such as iso-propoxy, iso-butoxy, and the like; and halogen. Various other R substituents may be present on the haloalkyl aromatic compound reactants and cor responding products will be obtained. The number (n) 5 of R substituents present on the aromatic nucleus is O Cl O Cln (OCCln from 0 to 9 and preferably from 0 to 5. Where n is more A A A III than 1, the R substituents may be the same or different. The number (Z) substituents on the aromatic nucleus is or mixtures thereof. Similarly, a compound of the above from 1 to 10 and preferably 1 or 2. The maximum num- 0 formula wherein Z is 2, such as, ber of substituents (n+Z) is equal to the total number of positions available on the aromatic nucleus. Thus when CCl3 Ar is benzene, the maximum value of n--Z is 6, and in this instance, for example, if the value of n is 3, the 15 CCl3 maximum value of Z will be 3. Similarly when Ar is Cln naphthalene, the maximum value of n--Z is 8 and when Ar is anthracene the maximum value of n--Z is 10. The wherein n is 0 to 2, is reacted with hydrogen fluoride in preferred compounds which may be fluorinated in ac the presence of molybdenum pentachloride to prepare cordance with this invention are those of the above compounds such as: formula wherein Aris benzene, R is chlorine, n is 0 to 2, and Z is 1 or 2. CFCl2 CF2Cl CFCl2 DESCRIPTION OF PREFERRED 25 EMBODIMENTS CCl3 CCl3 CFCl In a preferred embodiment the present invention is Cl Cln Cln directed to a process for fluorination of compounds of the above formula wherein Aris benzene; Z is 1 or 2; R BI B II B III is a halogen, preferably fluorine, chlorine, or bromine CF CF2Cl CFCl2 and n is 0 to 2.