PROCESS FOR PREPARING FLUOROCARBOXYLIC ACID HALIDES

Abstract: A process for preparing fluorocarboxylic acid halides comprises the steps of (a) forming a starting composition comprising (i) at least one fluorosulfonic acid halide comprising at least one halosulfonyldifluoromethyl group (-CF2SO2X, wherein X is halogen); and (ii) at least one Group III or Group V Lewis acid; and (b) allowing the fluorosulfonic acid halide and the Lewis acid to react to form a product composition comprising at least one fluorocarboxylic acid halide. The process enables the preparation of even higher molecular weight fluorocarboxylic acid halides in good yield.

Description: PROCESS FOR PREPARING FLUOROCARBOXYLIC ACID HALIDES Field of the Invention This invention relates to processes for preparing fluorinated carboxylic acid halides. Background of the Invention Many products of commercial value (such as oil- and water-repellent finishes for textiles, paper, electronic articles, and the like; stain-repellent finishes for leather; and surfactants for a variety of applications) can be made from fluorocarboxylic acid halides. Fluorocarboxylic acid fluorides can be prepared from telomers of tetrafluoroethylene followed by appropriate oxidation, but a characteristic of this method is that a distribution of molecular weights is obtained. Fluorocarboxylic acid fluorides can also be prepared by electrochemical fluorination (ECF) ofthe corresponding hydrocarbon carboxylic acid (or a derivative thereof), using either anhydrous hydrogen fluoride (Simons ECF) or KF 2HF (Phillips ECF) as the electrolyte. However, a drawback of Simons ECF is that side reactions often occur, and low purity and low yields (particularly at higher molecular weights) are often obtained due to the formation of rearrangement and degradation products. (See, e.g., the discussion by T. Abe et al. in Preparation, Properties, and Industrial Applications of Organofluorine Compounds, edited by R. E. Banks, John Wiley & Sons, pages 24-28, New York (1982).) Although Phillips ECF (KF 2HF) or direct fluorination (F 2 ) can be employed to reduce the occurrence of side reactions and provide high yields of a desired fluorinated product, higher molecular weight hydrocarbon carboxylic acids cannot be fluorinated by such techniques without undergoing decarboxylation and/or other side reactions. Hydrocarbon carboxylic acid halides are extremely water-sensitive and difficult to handle, and hydrocarbon carboxylic acid chlorides yield chlorine-substituted fluorochemical products. Thus, improved routes to fluorocarboxylic acid halides are highly desired in the art. Summary of the Invention Briefly, this invention provides a process for preparing fluorocarboxylic acid halides. The process comprises the steps of (a) forming a starting composition comprising (i) at least one fluorosulfonic acid halide (e.g., perfluorooctanesulfonyl fluoride) comprising at least one halosulfonyldifluoromethyl group (-CF 2 SO 2 X, wherein X is halogen); and (ii) at least one Group III or Group V Lewis acid (e g , antimony pentafluoride); and (b) allowing the fluorosulfonic acid halide and the Lewis acid to react to form a product composition comprising at least one fluorocarboxylic acid halide Preferably, the fluorosulfonic acid halide is a perfluoroalkanesulfonic acid fluoride, and the Lewis acid is antimony pentafluoride or aluminum chloride Surprisingly, the process ofthe invention enables the formation and retention ofthe carbonyl halide moiety and provides higher yields of fluorocarboxylic acid fluorides than can be obtained by the Simons ECF of hydrocarbon carboxylic acids (or derivatives thereof). Even higher molecular weight fluorocarboxylic acid halides can be prepared in good yield in a simple, one-step process. Furthermore, the process utilizes fluorosulfonic acid fluorides which, unlike fluorocarboxylic acid fluorides, can be effectively prepared in good yields (even at higher molecular weights) by the Simons ECF of readily available starting materials Detailed Description of he Invention Fluorosulfonic acid halides suitable for use in the process ofthe invention are those which contain at least one halosulfonyldifluoromethyl group A class of useful compounds is that which can be represented by the general formula (I) below Rf-CF2-SO 2 X(I) wherein Rf is selected from the group consisting of perfluorinated alkyl groups having from 1 to about 11 carbon atoms, partially-fluorinated alkyl groups having from 1 to about 1 1 carbon atoms, unsubstituted or perfluoroalkyl-substituted perfluorocycloalkyl groups having from 4 to about 8 (preferably, 5 to 6) carbon atoms, and unsubstituted or perfluoroalkyl-substituted, partially-fluorinated cycloalkyl groups having from 4 to about 8 (preferably, 5 to 6) carbon atoms; and X is selected from the group consisting of fluorine and chlorine. Preferably, X is fluorine and Rf is perfluoroalkyl (more preferably, perfluoroalkyl having from about 3 to about 7 carbon atoms) Fluorosulfonic acid fluorides (and indirectly, the chlorides) can be prepared by the Simons ECF of hydrocarbon sulfonic acid halides, as described by T Abe et al in Preparation, Properties, and Industrial Applications of Organofluorine Compounds, R E. Banks (editor), pages 37-39, John Wiley & Sons, New York (1982) The hydrocarbon sulfonic acid halide precursors can be prepared by oxidative chlorination ofa mercaptan followed by, if desired, exchange with fluoride ion (as described, e.g., by Davies et al. in J. Chem Soc. 1932, 483) or by direct conversion of alkylthiols to the corresponding sulfonyl fluorides using nitrogen dioxide (as described, e.g., by Comnineliis et al. in Synthesis 1974, 887) In particular, perfluoroalkanesulfonic acid fluorides (and, indirectly, the chlorides) are readily available by the electrochemical fluorination ofthe corresponding alkanesulfonic acid fluorides, as described in U.S. Pat. No 2,732,398 (Brice et al.) (See also P W Trott et al , 126th National Meeting ofthe American Chemical Society, abstract at page 42-M, New York, N Y (1954).) Perfluorooctanesulfonyl fluoride is commercially available from 3M Co under the tradename Fluorad™ fluorochemical sulfonyl fluoride FX-8. Routes to perfluoroalkanesulfonic acid chlorides are described by P J Stang et al in Synthesis 1982, 85 and by R. N. Haszeldine et al. in J. Chem. Soc 1955, 2901 The chlorides of the ω-hydrofluorinated acids are described by Coffrnan and Raasch in J Org Chem. j4, 747 (1949), by H Weiyuan et al. in Chemistry 2, 31 (1987), and by W. Y Huang, J Fluorine Chem 32, 179 (1986) See also the method described in U S Patent No 2,950,317 (Brown et al ) Representative examples of fluorosulfonic acid halides suitable for use in the process ofthe invention include C 2 F5SO F, C 2 F 5 SO 2 Cl, GjFgSOJ, C4F9SO2CI, C 8 F 17 SO 2 F, C 8 F 17 SO 2 Cl, FSO 2 (CF 2 ) 4 SO 2 F, C 10 F 21 SO 2 F, C 10 F 21 SO 2 C1, cyclo-(C 6 F,,)CF 2 SO 2 F, cyclo-(C 6 F n )CF 2 SO 2 Cl, C 2 F 5 -cyclo-(C6F 10 )CF 2 SO 2 F, C 2 F 5 - cyclo-(C 6 F 10 )CF 2 SO 2 Cl, H(CF 2 ) 2 SO 2 Cl, H(CF 2 ) 4 SO 2 Cl, H(CF 2 ) 8 SO 2 Cl, H(CF 2 ) 10 SO 2 C1, H(CF 2 ) 4 SO 2 F, H(CF 2 ) 8 SO 2 F, cyclo-(C 6 F I0 H)CF 2 SO 2 F, cyclo- (C 6 F, 0 H)CF 2 SO 2 C1, C 2 F5-cycIo-(C 6 F 9 H)CF 2 SO 2 F, and C 2 F 5 -cyclo- (C6F 9 H)CF 2 SO 2 Cl Preferably, perfluoroalkanesulfonic acid fluorides and chlorides are utilized, most preferably, perfluorooctanesulfonyl fluoride and perfluorobutanesulfonyl fluoride because of their high yields from the electrochemical fluorination process and correspondingly low costs (see, e g , T Abe et al , supra, page 37) Lewis acids suitable for use in the process ofthe invention are those which comprise Group III or Group V elements Such compounds can be prepared by known methods, and many are commercially available Generally, the Lewis acids can be of sufficient strength to cleave the carbon-sulfur bond ofthe fluorosulfonic acid halide Representative examples of suitable Lewis acids include SbF5, AICI3, AJBr , and ASF5, all of which are commercially available Preferred Lewis acids are SbF5 and AICI3, with AICI3 being most preferred The process ofthe invention can be carried out by introducing to a vessel a starting composition comprising (preferably, consisting essentially of) at least one fluorosulfonic acid halide and at least one Group III or Group V Lewis acid The vessel can be made of glass or other corrosion-resistant material and is preferably connected to a suitable condensing system (e.g , condenser(s) and/or trap(s)) for collecting volatile reaction products Preferably, the vessel is also equipped with a suitable mechanical agitator, and, optionally, with a scrubber to remove gaseous inorganic by-products The fluorosulfonic acid halide and Lewis acid starting materials can be introduced to the vessel separately or in combination, and in any order The starting materials and the vessel should preferably be substantially dry, and substantially anhydrous conditions should preferably be maintained to avoid hydrolysis ofthe Lewis acid starting material Inert diluent(s), e.g , perfluorohexane or perfluorooctane, can be utilized, if desired, but are not generally required The process ofthe invention can generally be carried out by heating the contents ofthe vessel (at a temperature in the range of from about 20°C to about 150°C, preferably, from about 80°C to about 100°C, and at pressures equal to or greater than atmospheric) preferably with agitation, until evolution of gas ceases (e g , from about 2 to about 4 hours) The fluorosulfonic acid halide and Lewis acid starting materials can be utilized in mole ratios of from about 1 1 to about 10 1 (acid halide acid), preferably from about 4 1 to about 7 1, most preferably in a ratio of about 5 1 Both the reaction conditions and the proportions of starting materials can vary widely The process ofthe invention can be carried out continuously (e g , by continuously feeding a starting composition to the vessel and continuously withdrawing a product composition from the vessel), semi-continuously (e g , by continuously feeding a starting composition and intermittently withdrawing a product composition, or by intermittently feeding a starting composition and continuously withdrawing a product composition), or batchwise The desired fluorocarboxylic acid halide products ofthe process ofthe invention (as well as by¬ products such as, e g , fluoroalkanes) can be recovered from a product composition by conventional separation means, e g , by decantation, distillation, extraction, chromatography, or adsorption Any unreacted fluorosulfonic acid halide starting material can also be recovered similarly and then recycled, if desired The process ofthe invention provides higher yields of fluorocarboxylic acid fluorides than can be obtained by the Simons ECF of hydrocarbon carboxylic acids (or derivatives thereof) Even higher molecular weight fluorocarboxylic acid halides can be prepared in good yield in a simple, one- step process Fluorocarboxylic acid halides are useful in the preparation of many products of commercial value (such as oil- and water-repellent finishes for textiles, paper, electronic articles, and the like, stain-repellent finishes for leather; and surfactants for a variety of applications) Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention EXAMPLES Example 1 Reaction of Perfluorooctanesulfonyl Fluoride and Antimony Pentafluoride A round bottom flask, equipped with a reflux condenser, a -78°C cold trap, and a magnetic stir bar, was charged with perfluorooctanesulfonyl fluoride (4 1 g, 8 2 mmol) and antimony pentafluoride (0 4 g, 1 8 mmol) and was heated to 100°C for 2 5 hours with stirring Initially the resulting mixture was homogeneous, but two separate phases developed as the reaction progressed The colorless, transparent upper layer (3 61 g) was separated from the lower layer. Gas chromatographic analysis ofthe upper layer showed the following components perfluorooctanoyl fluoride (24 area %), perfluorooctane (36 area %), and unreacted perfluorooctanesulfonyl fluoride starting material (39 area %) The contents ofthe cold trap was analyzed by gas chromatography/Fourier transform infrared spectroscopy (GC FTIR) and determined to be a mixture of SOF2 and SO2 Example 2 Reaction of Perfluorooctanesulfonyl Fluoride and Antimony Pentafluoride Using essentially the procedure of Example 1, perfluorooctanesulfonyl fluoride (10 1 g, 20 mmol) and antimony pentafluoride (0 66 g, 3 mmol) were combined and heated to 105-110°C for 3 hours The resulting mixture was then distilled, and the fraction (8 3 g) boiling up to 106°C was collected Gas chromatographic analysis ofthe collected fraction showed the following components perfluorooctanoyl fluoride (24 area %), perfluorooctane (65 area %), and unreacted perfluorooctanesulfonyl fluoride starting material (9 area %) Example 3 Reaction of Perfluorooctanesulfonyl Fluoride and Antimony Pentafluoride Using essentially the procedure of Example 1, perfluorooctanesulfonyl fluoride (5 0 g, 9 9 mmol) and antimony pentafluoride (0 64 g, 2 9 mmol) were combined and heated to 98°C for 1 hour Gas chromatographic analysis ofthe resulting mixture showed the following components perfluorooctanoyl fluoride (27 area %), perfluorooctane (56 area %), and unreacted perfluorooctanesulfonyl fluoride starting material (15 area %) An additional 5 0 g of perfluorooctanesulfonyl fluoride was added to the mixture, and the resulting mixture was heated at 1 10°C for four hours Gas chromatographic analysis ofthe mixture then revealed 18 area % perfluorooctanesulfonyl fluoride starting material Five additional grams ofthe sulfonyl fluoride was added to the mixture, and the resulting mixture was refluxed at 125°C for 16 hours The resulting upper layer (12 6 g) was separated from the lower, dark, viscous layer and was distilled from 0 2 g of NaF, collecting the fraction in the range of 102-108°C (10 3 g) Gas chromatographic analysis ofthe collected fraction showed the following components perfluorooctanoyl fluoride (27 area %), perfluorooctane (67 area %), and unreacted perfluorooctanesulfonyl fluoride starting material (6 area %) Example 4 Reaction of Perfluorooctanesulfonyl Fluoride and Aluminum Chloride Using essentially the procedure of Example 1, perfluorooctanesulfonyl fluoride (4 0 g, 8 0 mmol) and aluminum chloride (1 0 g, 8 0 mmol) were combined and heated to 100-1 10°C for five hours The resulting mixture was distilled, and the fraction boiling at 50-86°C at 30 torr was collected (1 83 g) Gas chromatographic analysis of the collected fraction showed the following components perfluorooctanoyl chloride (13 area %), perfluorooctane (9 area %), 1 -chloro-perfluorooctane (23 area %), and perfluorooctanesulfonyl chloride (56 area %) Example 5 Reaction of Perfluorooctanesulfonyl Fluoride and Boron Trifluoride A dry 180 mL Hastelloy™ B pressure reactor equipped with a mechanical stirrer was charged with perfluorooctanesulfonyl fluoride (51 g, 0 1 1 mol), was sealed, was cooled with solid carbon dioxide, and was attached to a vacuum pump to further reduce the internal pressure Anhydrous gaseous boron trifluoride (8 g, 0 12 mol) was added to the reactor, and the reactor was then heated at 140°C for 16 hours with stirring The reactor was cooled, and the excess boron trifluoride pressure was vented to a scrubber filled with potassium hydroxide The remaining clear fuming liquid (49 5 g) from the reactor was analyzed by gas chromatography (GC) No low boiling components were detected Only unreacted perfluorooctanesulfonyl fluoride starting material was detected by GC analysis Example 6 Reaction of Perfluorooctanesulfonyl Chloride and Antimony Pentafluoride Using essentially the procedure of Example 1, perfluorooctanesulfonyl chloride (5 74 g, 1 1 mmol) and antimony pentafluoride (0 47 g, 2 mmol) were combined and heated to 100-130°C for four hours The resulting upper layer (4 96 g) was separated from precipitated antimony halides on the bottom Gas chromatographic analysis ofthe separated upper layer showed the following components, perfluorooctanoyl fluoride (27 area %), perfluorooctane (37 area %), perfluorooctanesulfonyl fluoride (16 area %), and unreacted perfluorooctanesulfonyl chloride starting material (18 area %) Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention

Claims: We claim: 1. A process for preparing fluorocarboxylic acid halides comprising the steps of (a) forming a starting composition comprising (i) at least one fluorosulfonic acid halide comprising at least one halosulfonyldifluoromethyl group; and (ii) at least one Group III or Group V Lewis acid; and (b) allowing said fluorosulfonic acid halide and said Lewis acid to react to form a product composition comprising at least one fluorocarboxylic acid halide 2 The process of Claim 1 wherein said fluorosulfonic acid halide is a perfluoroalkanesulfonic acid fluoride 3 The process of Claim 1 wherein said fluorosulfonic acid halide is represented by the general formula Rf-CF 2 -S0 2 X (I) wherein Rf is selected from the group consisting of perfluorinated alkyl groups having from 1 to about 11 carbon atoms, partially-fluorinated alkyl groups having from 1 to about 1 1 carbon atoms, unsubstituted or perfluoroalkyl-substituted perfluorocycloalkyl groups having from 4 to about 8 carbon atoms, and unsubstituted or perfluoroalkyl-substituted, partially-fluorinated cycloalkyl groups having from 4 to about 8 carbon atoms, and X is selected from the group consisting of fluorine and chlorine 4 The process of Claim 1 wherein said fluorosulfonic acid halide is selected from the group consisting of perfluorooctanesulfonyl fluoride, perfluorooctanesulfonyl chloride, and perfluorobutanesulfonyl fluoride 5 The process of Claim 1 wherein said starting composition consists essentially of (i) at least one fluorosulfonic acid halide comprising at least one halosulfonyldifluoromethyl group, and (ii) at least one Group III or Group V Lewis acid 6 The process of Claim 1 wherein said Lewis acid is of sufficient strength to cleave the carbon-sulfur bond of said fluorosulfonic acid halide 7 The process of Claim 1 wherein said Lewis acid is selected from the group consisting of SDF5, AJCI3, AlBr3, and ASF5 8 The process of Claim 1 wherein said fluorosulfonic acid halide and said Lewis acid are utilized in mole ratios of from about 1 1 to about 10 1 9 The process of Claim 1 further comprising the step of recovering said fluorocarboxylic acid halide from said product composition 10 A process for preparing fluorocarboxylic acid halides comprising the steps of (a) forming a starting composition comprising (i) at least one perfluoroalkanesulfonic acid fluoride, and (ii) at least one Lewis acid selected from the group consisting of aluminum chloride and antimony pentafluoride, and (b) allowing said perfluoroalkanesulfonic acid fluoride and said Lewis acid to react to form a product composition comprising at least one fluorocarboxylic acid halide

Inventors: BEHR FREDERICK E, CHEBURKOV YURI, BEHR, FREDERICK, E., CHEBURKOV, YURI
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1996
Main classification: C07C51
IPC codes: C07C51, C07C53