(12) United States Patent (10) Patent N0.: US 8,304,580 B2 Nanmyo Et A]

US008304580B2

(12) United States Patent (10) Patent N0.: US 8,304,580 B2 Nanmyo et a]. (45) Date of Patent: Nov. 6, 2012

(54) METHOD FOR PRODUCING TRIS(PER FOREIGN PATENT DOCUMENTS FLUORO-ALKANESULFONYL)METHIDE EP 0813521 B1 * 9/2000 ACID SALT JP 2000-226392 A 8/2000 JP 2000-256348 A 9/2000 (75) Inventors: Tsutomu Nanmyo, Ube (JP); Shintaro JP 2000-256348 A * 9/2000 Sasaki, Ube (JP); Takashi Kume, OTHER PUBLICATIONS KaWagoe (JP) English translation of JP-2000-256348-A; “machine translation” (73) Assignee: Central Glass Company, Limited, from JPO link at: http://WWW4.ipd1.inpit.go.jp/Tokujitu/ Ube-shi (JP) tj sogodbenkipdl accessed Oct. 25, 201 1; relevant part of document.* European Search Report dated Jun. 8, 2011 (four (4) pages). ( * ) Notice: Subject to any disclaimer, the term of this Waller et al., “Tris (tri?uoromethanesulfonyl) methide (“Tri?ide”) patent is extended or adjusted under 35 Anion: Convenient Preparation, X-ray Crystal Structures, and U.S.C. 154(b) by 528 days. Exceptional Catalytic Activity as a Counterion With Ytterbium (III) and Scandium (111)”, Journal of Organic Chemistry, vol. 64, 1999, pp. (21) Appl. N0.: 12/520,17s 2910-2913, XP-002636992. Turowsky et al., “Tris ((tri?uoromethyl) sulfonyl) methane, HC (22) PCT Filed: Dec. 18, 2007 (SO2CF3)3”, Journal of Inorganic Chemistry, vol. 27, 1988, pp. 2135-2137, XP-002636993. (86) PCT No.: PCT/JP2007/074296 International Search Report and PCT/ISN237 W/translation dated Feb. 12, 2008 (Seven (7) pages). § 371 (0X1)’ LutZ Turowsky et al., “Tris((tri?uoromethyl)sulfonyl)methane, (2), (4) Date: Jun. 19, 2009 HC(SO2CF3)3”, American Chemical Society, 1988, Inorg. Chem., vol. 27, No. 12, pp. 2135-2137. (87) PCT Pub. No.: WO2008/075672 A. Y. Il’Chenko, Tetraheterosubstituted Methanes With a Carbon PCT Pub. Date: Jun. 26, 2008 Halogen Bond, Science of Synthesis, 2005, pp. 1135-1201. Djamila Benrabah et al., “Comparative Electrochemical Study of (65) Prior Publication Data New Poly(oxyethylene)-Li Salt Complexes”, Journal of the Chemi cal Society, Faraday Transactions, 1993, vol. 89, No. 2, pp. 355-359. US 2010/0022803 A1 Jan. 28, 2010 * cited by examiner (30) Foreign Application Priority Data Primary Examiner * Shailendra Kumar Dec. 20, 2006 (JP) ...... 2006-342043 (74) Attorney, Agent, or Firm * CroWell & Moring LLP Dec. 7, 2007 (JP) ...... 2007-317315 Dec. 17, 2007 (JP) ...... 2007-324490 (57) ABSTRACT (51) Int. Cl. There is provided a method for producing a tris(per?uoroal C07C 315/00 (2006.01) kanesulfonyl)methide acid salt represented by formula [1], (52) US. Cl...... 568/35 including the steps of (a) reacting a methylmagnesium halide (58) Field of Classi?cation Search ...... 568/35 represented by formula [2] With a per?uoroalkanesulfonyl See application ?le for complete search history. ?uoride represented by formula [3], thereby obtaining a reac tion mixture; and (b) directly reacting the obtained reaction (56) References Cited mixture With at least one selected from the group consisting of alkali metal halides, quaternary ammonium salts, and quater U.S. PATENT DOCUMENTS nary phosphonium salts. By this method, it is possible to 5,273,840 A * 12/1993 Dominey ...... 429/307 easily produce the target methide acid salt With high yield. 6,410,190 B1 * 6/2002 Ignatiev et al...... 429/347 6,664,380 B1 12/2003 Barrett et al. 17 Claims, No Drawings US 8,304,580 B2 1 2 METHOD FOR PRODUCING TRIS(PER salt industrially more easily With a loWer cost, as compared FLUOROALKANESULFONYL)METHIDE With conventional production methods. ACID SALT According to the present invention, there is provided a method for producing a tris(per?uoroalkanesulfonyl)methide This application is a 371 of PCT/JP2007/074296, ?led acid salt represented by formula [1] Dec. 18, 2007. [Chemical Formula 2] TECHNICAL FIELD IRTSOQhCnM [1] The present invention relates to a method for producing a [In the formula, Rf represents a C1_9 straight-chain or tris(per?uoroalkanesulfonyl)methide acid salt. branched-chain per?uoroalkyl group, n represents an integer that is identical With valence of the corresponding cation, and BACKGROUND OF THE INVENTION M is a cation representing an alkali metal, quaternary ammo nium represented by (R1) 4N, or quaternary phosphonium rep Tris(per?uoroalkanesulfonyl)methide acid salt is a sub resented by (R1)4P. Herein, Rl’s represent C1_9, identical or stance that is useful as a LeWis acid catalyst or ion conducting different, straight-chain or branched-chain, saturated or material in the ?elds of organic syntheses, cell electrolyte, unsaturated aliphatic hydrocarbon groups or aryl groups etc. Hitherto, there have been knoWn many of the method for (herein, the hydrogen atoms may partially or entirely be producing a tris(per?uoroalkanesulfonyl)methide acid salt, replaced With halogen (?uorine, chlorine, bromine, or Which is the target of the present invention. For example, 20 iodine), alkyl group, amino group, nitro group, acetyl group, Non-patent Publication 1 discloses that a tris(per?uoroal cyano group or hydroxyl group)], comprising the steps of: kanesulfonyl)methide acid salt is obtained by reacting trif (a) reacting a methylmagnesium halide represented by for luoromethanesulfonyl ?uoride With a methylmagnesium mula [2] halide (Grignard reagent). Furthermore, Patent Publication 1 discloses a method for 25 [Chemical Formula 3] obtaining a methide acid salt by conducting a reaction betWeen a per?uoroalkanesulfonyl halide and an alkali metal CH3MgX [2] methane in organic solvent. [In the formula, X represents a chlorine, bromine or iodine.] Non-patent Publication 1: Inorg. Chem., Vol. 27, pages 2135 With a per?uoroalkanesulfonyl ?uoride represented by for 2137, 1988 30 mula [3] Patent Publication 1 : Japanese PatentApplication Publication 2000-226392 [Chemical Formula 4]

SUMMARY OF THE INVENTION M50; [3] 35 [In the formula, Rf represents a C l_9 straight-chain or In the method of Non-patent Publication 1, as shoWn in the branched-chain per?uoroalkyl group.], thereby obtaining a folloWing scheme, a methide acid magnesium bromide salt reaction mixture; and produced by a reaction betWeen a Grignard reagent and trif (b) directly reacting the obtained reaction mixture With at luoromethanesulfonyl ?uoride is once turned into a methide least one selected from the group consisting of alkali metal acid by sulfuric acid, and furthermore a metal carbonate 40 halides, quaternary ammonium salts, and quaternary phos (herein cesium carbonate) causes this to obtain a methide acid phonium salts. salt (Scheme 1). We have found that a tris(per?uoroalkanesulfonyl)methide acid salt is obtained With short steps and With high purity and [Chemical Formula 1] high yield, thereby completing the present invention. 45 According to the method described in Non-patent Publica tion 1, after a reaction betWeen methylmagnesium halide and per?uoroalkanesulfonyl ?uoride, a tris(per?uoroalkane sulfonyl)methide acid magnesium halide represented by for mula [4] 50 [Chemical Formula 5]

1/2CO2 (Scheme 1) This method, hoWever, has had a burden on productivity [In the formula, Rf is the same as above, and X represents a and a di?iculty someWhat industrially, since the reaction steps 55 chlorine, bromine or iodine.] are long and since Waste treatment takes time due to use of of a methide acid magnesium bromide salt and the like, Which sulfuric acid. is the obtained reaction mixture, is reacted With sulfuric acid, On the other hand, in Patent Publication 1, it is a production thereby producing a tris(per?uoroalkanesulfonyl)methide method, in Which a methide acid salt is obtained by one step, acid represented by formula [5] and therefore is a very useful method, in contrast With Non 60 patent Publication 1. This method, hoWever, has had a di?i [Chemical Formula 6] culty in industrial production due to that the alkyl metal methane has a high price, that there is a problem of Waste since it is treated With hydrochloric acid after the reaction, [In the formula, Rf is the same as above.] and that the reaction is conducted at around —550 C. 65 and a metal carbonate (herein cesium carbonate) causes this It is an object of the present invention to provide a method to obtain a tris(per?uoroalkanesulfonyl)methide acid salt rep for producing a tris(per?uoroalkanesulfonyl)methide acid resented by formula [1]. In this method, hoWever, a burden is US 8,304,580 B2 3 4 placed on productivity, and furthermore purity and yield of during the reaction step. It is possible to cite, for example, the target product loWer. Thus, there has been a di?iculty even ethers such as diethyl ether, diisopropyl ether, t-bu in industrial production. toxymethane, ethylene glycol dimethyl ether, tetrahydrofu The present inventors, hoWever, have obtained surprising ran, and dioxane, and the like. The amount of the solvent used ?ndings that the target product can be obtained by short steps, is suitably selected normally from the range of 05-10 times easily, and With high selectivity and high yield by directly by volume, preferably from the range of 5-7 times by volume, reacting a tris(per?uoroalkanesulfonyl)methide acid magne methylmagnesium halide represented by formula [2]. sium halide With an alkali metal halide (cesium chloride, For the per?uoroalkanesulfonyl ?uoride represented by potassium chloride, or the like), a quaternary ammonium salt formula [3], a C l_9 straight-chain or branched-chain per?uo (tetramethylammonium bromide or the like), or a quaternary roalkyl group is normally used, preferably C1_6, particularly phosphonium salt (tetrabutylphosphonium bromide or the preferably Cl (tri?uoromethyl group). As speci?c com like), Without going through a tris(per?uoroalkanesulfonyl) pounds, it is possible to cite tri?uoromethanesulfonyl ?uo methide acid (Scheme 2). ride, penta?uoroethanesulfonyl ?uoride, hepta?uoropro

[Chemical Formula 7]

Acid Treatment Step Post-treatment Step Puri?cation Step ______> ______>

- Alkali Metal Halide Metal Carbonate - Quaternary Ammonium Salt - Quaternary Phosphonium Salt (Cs2CO3) Filtration Step Recrystallization Step ‘

[1]

_ _ _ _ _ .> Route of Non-patent Publication 1

—’ Route in Which the present invention is used

In the route in Which the present invention is used, it is panesulfonyl ?uoride, nona?uorobutanesulfonyl ?uoride, possible to greatly shorten the steps as compared With the 35 undeca?uoropentanesulfonyl ?uoride, trideca?uorohexane past, and an acid such as sulfuric acid is not used. Therefore, sulfonyl ?uoride, pentadeca?uoroheptanesulfonyl ?uoride, it has become possible to greatly reduce a Waste liquid, such heptadeca?uorooctanesulfonyl ?uoride, nonadeca?uo as Waste organic solvent and Waste Water, Which is discharged rononanesulfonyl ?uoride, and the like. Tri?uoromethane in the post-treatment step. Furthermore, it has become pos sulfonyl ?uoride, penta?uoroethanesulfonyl ?uoride, hep sible to easily obtain the target product by methods that are 40 ta?uoropropanesulfonyl ?uoride, nona?uorobutanesulfonyl even industrially easy, such as ?ltration and recrystallization. ?uoride, undeca?uoropentanesulfonyl ?uoride, and tridecaf Thus, it is possible to greatly simplify the steps and the luorohexanesulfonyl ?uoride are preferable. Tri?uo production time. Therefore, it is also possible to easily supply romethanesulfonyl ?uoride is particularly preferable. the target product Without taking much effort in operation, The amount of the per?uoroalkanesulfonyl ?uoride is nor and it is a very excellent method in terms of production in 45 mally 0.75 to 2.0 moles, preferably 0.75 moles to 1.20 moles, particularly preferably 0.8 moles to 1.0 mole, relative to 1 industrial scale. mole of the methylmagnesium halide. The present reaction is possible in a temperature range of DETAILED DESCRIPTION —780 C. to 1000 C., preferably —100 C. to 60° C. In the case of using a per?uoroalkanesulfonyl ?uoride of loW-boiling According to the present invention, it is possible to produce 50 point, it is preferable to conduct that under pressurization, to a tris(per?uoroalkanesulfonyl)methide acid salt, Which is maintain the reactor at loW temperature, or to conduct that by useful as organic synthesis and a cell electrolyte, more easily using a condenser of loW-temperature. and With higher purity and higher yield as compared With the In the case of conducting the reaction under pressurization, past. Furthermore, it achieves an effect that can greatly reduce the reactor is charged With methylmagnesium halide repre Waste liquid, such as Waste organic solvent and Waste Water, 55 sented by formula [2] and solvent, then the reactor is sealed, Which is discharged upon production. and per?uoroalkanesulfonyl ?uoride is added. The addition is In the folloWing, the present invention is explained in more conducted, While suitably purging methane produced as a detail. As speci?c compounds of methylmagnesium halide by-product, in order to control pressure. represented by formula [2], it is possible to use methylmag The pressure is normally 0.1-10 MPa (absolute pressure, nesium iodide, methylmagnesium bromide, and methylmag 60 hereinafter the same), preferably 0.1-5 MPa, more preferably nesium chloride. Methylmagnesium chloride is preferable. 0.1-2 MPa. It is possible to produce methylmagnesium halide, Which As to a reactor used upon conducting the reaction under becomes the raW material, by a conventional publicly knoWn pressurization, it is possible to conduct that by using a metal method, but it is also possible to use one on the market as the container such as stainless steel, Hastelloy, and Monel. In the product. A person skilled in the art can suitably select it. 65 case of conducting the reaction under ordinary pressure, a As an organic solvent usable, an inert solvent is preferable person skilled in the art can make a suitable selection regard that does not react With the raW materials and the product ing the reactor, too. US 8,304,580 B2 5 6 In the present invention, the obtained reaction mixture is group, nitro group, acetyl group, cyano group or hydroxyl reacted With at least one selected from the group consisting of group). Of these, Cl_7 is preferable, and Cl_4 is particularly alkali metal halides, quaternary ammonium salts, and quater preferable. nary phosphonium salts, thereby obtaining tris(per?uoroal As the quaternary phosphonium salt, it is possible to use kanesulfonyl)methide acid salt represented by formula [1]. those combined at random, Which correspond to the above As the alkali metal, it is possible to cite at least one selected mentioned formula. Of those, it is preferable to use tetraphe from the group consisting of lithium (Li), sodium (Na), potas nylphosphonium ?uoride, tetraphenylpho sphonium chloride, sium (K), rubidium (Rb), and cesium (Cs). tetraphenylphosphonium bromide, tetraphenylphosphonium As speci?c compounds of the alkali metal halide used in iodide, tetrabutylphosphonium ?uoride, tetrabutylphospho the present invention, it is possible to cite at least one selected nium chloride, tetrabutylphosphonium bromide, tetrabu from the group consisting of lithium ?uoride, lithium chlo tylphosphonium iodide, butyltriphenylphosphonium ?uo ride, lithium bromide, lithium iodide, sodium ?uoride, ride, butyltriphenylphosphonium chloride, sodium chloride, sodium bromide, sodium iodide, potassium butyltriphenylphosphonium bromide, butyltriphenylphos ?uoride, potassium chloride, potassium bromide, potassium phonium iodide, trioctylethylpho sphonium ?uoride, trioctyl iodide, rubidium ?uoride, rubidium chloride, rubidium bro ethylphosphonium chloride, trioctylethylphosphonium bro mide, rubidium iodide, cesium ?uoride, cesium chloride, mide, trioctylethylphosphonium iodide, cesium bromide, and cesium iodide. Sodium ?uoride, sodium benzyltriphenylphosphonium ?uoride, benzyltriphenylphos chloride, sodium bromide, sodium iodide, potassium ?uo phonium chloride, benZyltriphenylphosphonium bromide, ride, potassium chloride, potassium bromide, potassium 20 benzyltriphenylphosphonium iodide, ethyltriphenylphos iodide, rubidium ?uoride, rubidium chloride, rubidium bro phonium ?uoride, ethyltriphenylphosphonium chloride, eth mide, rubidium iodide, cesium ?uoride, cesium chloride, yltriphenylphosphonium bromide, and ethyltriphenylphos cesium bromide, and cesium iodide are preferable. Potassium phonium iodide. ?uoride, potassium chloride, potassium bromide, potassium In the present invention, methylmagnesium halide repre iodide, rubidium ?uoride, rubidium chloride, rubidium bro 25 sented by formula [2] is reacted With per?uoroalkanesulfonyl mide, rubidium iodide, cesium ?uoride, cesium chloride, ?uoride represented by formula [3]. Then, the obtained reac cesium bromide, and cesium iodide are particularly prefer tion mixture is directly added to an aqueous solution dissolv able. ing at least one selected from the group consisting of alkali As the quaternary ammonium salt used in the present metal halides, quaternary ammonium salts, and quaternary invention, it is possible to cite (Rl)4N+.X_ (in the formula, 30 phosphonium salts to conduct a reaction. After the reaction, Rl’s represent C1_9, identical or different, straight-chain or the solvent used is distilled out. With this, the target tris branched-chain, saturated or unsaturated aliphatic hydrocar (per?uoroalkanesulfonyl)methide acid salt is precipitated. bon groups or aryl groups (herein, the hydrogen atoms may partially or entirely be replaced With halogen (?uorine, chlo In the present invention, although details are described hereinafter in Examples, it is possible to easily obtain the rine, bromine, or iodine), alkyl group, amino group, nitro 35 group, acetyl group, cyano group or hydroxyl group), X rep methide acid salt With high purity by even industrially easy resents a halogen (?uorine, chlorine, bromine, or iodine), methods that are ?ltration and recrystallization. acetate, alkanesulfonate, or arylsulfonate (herein, the hydro Then, the ?ltration step is explained. The ?ltration step is gen atoms may partially or entirely be replaced With halogen not particularly limited. Upon this, in the case of a tris(per (?uorine, chlorine, bromine, or iodine), alkyl group, amino 40 ?uoroalkanesulfonyl)methide acid salt that has loW solubility group, nitro group, acetyl group, cyano group or hydroxyl in Water, the crystals are precipitated after distilling the sol group). Of these, Cl_7 is preferable, and Cl_4 is particularly vent out. Therefore, it can be isolated by ?ltration. preferable. On the other hand, in the case of a salt having high solu As the quaternary ammonium salt, it is possible to use bility, an extraction is conducted by using a solvent having those combined at random, Which correspond to the above 45 high solubility to the tris(per?uoroalkanesulfonyl)methide mentioned formula. Of those, it is preferable to use tetram acid salt, for example, an organic solvent such as ethyl ethylammonium ?uoride, tetramethylammonium chloride, acetate, isopropyl ether, or diethyl ether, and the solvent is tetramethylammonium bromide, tetramethylammonium distilled out. Then, the after-mentioned recrystallization iodide, tetraethylammonium ?uoride, tetraethylammonium operation is conducted. With this, it is possible to obtain a chloride, tetraethylammonium bromide, tetraethylammo 50 tris(per?uoroalkanesulfonyl)methide acid salt of high purity. nium iodide, tetrapropylammonium ?uoride, tetrapropylam It is possible to easily remove inorganic salts, Which are monium chloride, tetrapropylammonium bromide, tetrapro contained in the methide acid salt and are derived from meth pylammonium iodide, tetrabutylammonium ?uoride, ylmagnesium halide and alkali metal halide, by conducting tetrabutylammonium chloride, tetrabutylammonium bro the ?ltration step. mide, and tetrabutylammonium iodide. 55 Next, the recrystallization step is explained. Regarding the As the quaternary phosphonium salt used in the present recrystallization step too, there is no particular limitation. As invention, it is possible to cite (R1)4P+.X_ (in the formula, the recrystallization solvent to be used, organic solvent or Rl’s represent C1_9, identical or different, straight-chain or Water can be cited. As the organic solvent, it can be exempli branched-chain, saturated or unsaturated aliphatic hydrocar ?ed by, for example, ethers such as diethyl ether, tetrahydro bon groups or aryl groups (herein, the hydrogen atoms may 60 furan, dioxane, butyl methyl ether, diisopropyl ether, and partially or entirely be replaced With halogen (?uorine, chlo ethylene glycol dimethyl ether; alcohols such as methanol, rine, bromine, or iodine), alkyl group, amino group, nitro ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alco group, acetyl group, cyano group or hydroxyl group), X rep hol, iso-butyl alcohol, sec-butyl alcohol, and tert-butyl alco resents a halogen (?uorine, chlorine, bromine, or iodine), hol; alkanes such as n-pentane, n-hexane, n-heptane, and acetate, alkanesulfonate, or arylsulfonate (herein, the hydro 65 n-octane; alkyl ketones such as acetone, methyl ethyl ketone, gen atoms may partially or entirely be replaced With halogen and methyl isobutyl ketone; halogenated hydrocarbons such (?uorine, chlorine, bromine, or iodine), alkyl group, amino as dichloromethane and chloroform; and aromatics such as US 8,304,580 B2 7 8 benzene, toluene, and xylene. Each of these organic solvents conducted again With 260 g of Water, and the precipitated may be used alone, and a plurality of the organic solvents may crystals Were separated by ?ltration. The obtained crystals be combined. Were dried. With this, cesium tris(tri?uoromethanesulfonyl) Of these, as shoWn in the after-mentioned Examples, even methide Was obtained With a yield of 29.7 g, a yield of 53% in the case of a recrystallization using Water as solvent, it is and a purity of 99%. possible to obtain a tris(per?uoroalkanesulfonyl)methide acid salt of a suf?ciently high purity. Therefore, a recrystal EXAMPLE 2 lization using Water is one of particularly preferable embodi ments in the industrial production method of the present The reactions Were conducted in the same conditions as invention. those of Example 1, except in that rubidium chloride Was used By recrystallization, tris(per?uoroalkanesulfonyl)methide in place of cesium chloride (selectivity 76%). As a result, acid salt is precipitated. To isolate this, it suf?ces to conduct rubidium tris(tri?uoromethanesulfonyl)methide Was a normal operation of organic chemistry. By conducting a obtained With a yield of 58% and a purity of 99%. ?ltration operation (Filtration operation referred herein means a ?ltration operation in the recrystallization step. Here EXAMPLE 3 inafter, the same.), it is possible to obtain a tris(per?uoroal kanesulfonyl)methide acid salt of a still higher purity even as The reactions Were conducted in the same conditions as compared With the above-mentioned ?ltration step. those of Example 1, except in that potassium chloride Was Furthermore, the present inventors have obtained ?ndings 20 used inplace of cesium chloride (selectivity 81%).As a result, that, since the methide acid salt is partly dissolved in the potassium tris(tri?uoromethanesulfonyl)methide Was solution obtained by the ?ltration operation, it is possible to obtained With a yield of 52% and a purity of 99%. recover the obtained ?ltrate and reuse it as a solvent in the recrystallization step (see the after-mentioned Table 1). By EXAMPLE 4 reusing, it is possible to further improve yield of tris(per?uo 25 roalkanesulfonyl)methide acid salt and to greatly reduce The reactions Were conducted in the same conditions as those of Example 1, except in that penta?uoroethanesulfonyl Waste liquid, such as Waste organic solvent or Waste Water, ?uoride and potassium chloride Were respectively used in even as compared With the after-mentioned Reference Example. Therefore, productivity has improved remarkably. place of tri?uoromethanesulfonyl ?uoride and cesium chlo By subjecting a solid obtained by the recrystallization 30 ride (selectivity 64%). As a result, potassium tris(penta?uo roethanesulfonyl)methide Was obtained With a yield of 46% operation to vacuum drying, organic solvent or Water is removed. With this, tris(per?uoroalkanesulfonyl)methide and a purity of 99%. acid salt represented by formula [1] is obtained With high EXAMPLE 5 purity. 35 In the folloWing, the present invention is explained by A 1000 ml, glass, reaction container With a condenser Was Examples, but the present invention is not limited by these charged With 494 g of 1 .6M-methylmagnesium chloride-tet Examples. Herein, “%” of the composition analysis values rahydrofuran solution under nitrogen gas stream, folloWed by represents “mol %” of compositions obtained by measuring cooling With ice. Then, 64 g of tri?uoromethanesulfonyl ?uo the reaction mixtures by nuclear magnetic resonance analyzer 40 ride Was introduced at an inside temperature of 0-200 C. The (NMR; in the case of no particular mention, the measurement temperature Was increased once to 35-500 C., and then trif nuclei is 19F). luoromethanesulfonyl ?uoride Was added again by 32 g. After termination of the addition, it Was aged for all night at room EXAMPLE 1 temperature to conduct the reaction (selectivity 75%). 45 A 1000 ml round-bottom ?ask Was charged With 500 ml of A 300 ml, glass, reaction container With a condenser Was pure Water. 53.2 g of tetrapropylammonium chloride Was charged With 203 g of 2M-methylmagnesium chloride-tet added, and it Was completely dissolved. Herein, the obtained rahydrofuran solution under nitrogen gas stream, folloWed by reaction liquid Was added, and the tetrahydrofuran Was dis cooling With ice. Then, 33 g of tri?uoromethanesulfonyl ?uo tilled out under reduced pressure With an evaporator. To the ride Was introduced at an inside temperature of 0-200 C. The 50 remaining solution, 800 ml of ethyl acetate Was added to temperature Was increased once to 35-500 C., and then trif conduct extraction. The obtained organic layer Was evapo luoromethanesulfonyl ?uoride Was added again by 17 g. After rated, and the precipitated crystals Were subjected to recrys termination of the addition, it Was aged for all night at room tallization With 200 ml of ethanol. The precipitated crystals temperature to conduct the reaction (selectivity 71%). Were separated by ?ltration. The obtained crystals Were dried. A 500 ml round-bottom ?ask Was charged With 300 ml of 55 With this, tetrapropylammonium tris(tri?uoromethanesulfo pure Water. 17.3 g of cesium chloride Was added, and it Was nyl)methide Was obtained With a yield of 73.6 g, a yield of completely dissolved. Herein, the obtained reaction liquid 62%, and a purity of 97%. Was added, and the tetrahydrofuran in the reaction system Was EXAMPLE 6 distilled out under reduced pressure With an evaporator 60 (herein, 170 g of Waste organic solvent Was produced as a A 300 ml, glass, reaction container With a condenser Was by-product). With this, cesium tris(tri?uoromethanesulfonyl) charged With 124 g of 1 .6M-methylmagnesium chloride-tet methide Was precipitated. The precipitated crystals Were rahydrofuran solution under nitrogen gas stream, folloWed by separated by ?ltration (herein, 320 g of Waste Water contain cooling With ice. Then, 16 g of tri?uoromethanesulfonyl ?uo ing inorganic salts Was produced as a by-product), folloWed 65 ride Was introduced at an inside temperature of 0-200 C. The by recrystallization With 350 g of Water. The precipitated temperature Was increased once to 35-500 C., and then trif crystals Were separated by ?ltration. Recrystallization Was luoromethanesulfonyl ?uoride Was added again by 8 g. After US 8,304,580 B2 9 10 termination of the addition, it Was aged for all night at room TABLE 1 temperature to conduct the reaction (selectivity 75.4%). Comparison in Amount of Waste Liquid (Waste liquid or ?ltrate after A 500 ml round-bottom ?ask Was charged With 250 ml of recrystalli ation g/l g ofmethide acid salt) pure Water. 9.2 g of tetramethylammonium bromide Was added, and it Was completely dissolved. Herein, the obtained Example 1 Reference Example 1 reaction liquid Was added, and the tetrahydrofuran Was dis Waste organic solvent 0 7.9 (IPE + toluene) tilled out under reduced pressure With an evaporator. To the Waste Water containing THF 5.7 57.9 remaining solution, 200 ml of ethyl acetate Was added to Waste Water containing inorganic salt 10.8 0 Waste liquid in total (g/g) 16.5 65.8 conduct extraction. The obtained organic layer Was evapo Filtrate after recrystallization (reuse)* 20.8 19.6 rated, and the precipitated crystals Were subjected to recrys tallization With 300 ml of Water. The precipitated crystals [PE = diisopropyl ether TH1: = tetrahydrofuran Were separated by ?ltration. The obtained crystals Were dried. *It shows the amount ofthe ?ltrate (usable as a recrystallization solvent ofthe next reaction) With this, tetramethylammonium tris(tri?uoromethanesulfo recovered a?er ?ltration in the recrystallization step. nyl)methide Was obtained With a yield of 26.8 g, a yield of 5 As shoWn in Table 1, it is understood that Example 1 can 48%, and a purity of 99%. greatly reduce Waste liquid as compared With Reference As are clear in Examples 1-6, as compared With the after Example 1. mentioned Reference Example 1, it is possible to easily The invention claimed is: obtain the target product With high yield by industrially easy 1. A method for producing a tris(per?uoroalkanesulfonyl) methods, such as ?ltration and recrystallization, With short methide acid salt represented by formula [1] steps. lRfsoghcnM [1]

REFERENCE EXAMPLE 1 Wherein Rf represents a C 1 _9 straight-chain or branched-chain 25 per?uoroalkyl group, n represents an integer that is identical With valence of the corresponding cation, and A 300 ml, glass, reaction container With a condenser Was M is a cation representing an alkali metal, quaternary charged With 200 g of 2M-methylmagnesium chloride-tet ammonium represented by (Rl)4N, or quaternary phos rahydrofuran solution under nitrogen gas stream, folloWed by phonium represented by (Rl)4P, R1 ’s represent C1_9, cooling With ice. Then, 32 g of tri?uoromethanesulfonyl ?uo identical or different, straight-chain or branched-chain, ride Was introduced at an inside temperature of 0-200 C. The saturated or unsaturated aliphatic hydrocarbon groups or temperature Was increased once to 35-500 C., and then trif aryl groups and hydrogen atoms of R1 ’s may partially or luoromethanesulfonyl ?uoride Was added again by 16 g. After entirely be replaced With halogen, alkyl group, amino termination of the addition, it Was aged for all night at room group, nitro group, acetyl group, cyano group or temperature to conduct the reaction. 35 hydroxyl group, comprising the steps of: (a) reacting a methylmagnesium halide represented by for After charging a 500 ml separatory funnel With 200 g of mula [2] 10% hydrochloric acid, 225 g of the reaction liquid and 72 g of isopropyl ether Were added, and a liquid separation opera CH3MgX [2] tion Was conducted (herein, Waste hydrochloric acid Was Wherein X represents a chlorine, bromine or iodine, produced by 232 g as a by-product). The obtained organic With a per?uoroalkanesulfonyl ?uoride represented by for layer Was Washed With 450 g of Water tWo times and With 150 mula [3] g of Water, and a liquid separation Was conducted (herein, Waste Water containing organic solvent Was produced by RrSO2F [3] 1365 g as a by-product). Then, the organic layer Was added to Wherein Rf represents a C1_9 straight-chain or branched a 500 ml round-bottom ?ask and Was evaporated (Waste chain per?uoroalkyl group, thereby obtaining a reaction organic solvent Was produced by 123 g as a by-product). To mixture containing a tris(per?uoroalkanesulfonyl)me the obtained crude methide acid, 200 g of Water Was added. Toluene Was added by 44 g><2, and a liquid separation opera thide acid magnesium halide represented by formula [4] tion Was conducted tWo times With a separatory funnel (Waste organic solvent Was produced by 94 g as a by-product). To the obtained aqueous layer, 50% cesium hydroxide aqueous solu Wherein Rf and X are de?ned as above; and tion Was added by 20 g for neutralization and precipitation. (b) directly reacting the tris(per?uoroalkanesulfonyl)me Then, a recrystallization Was conducted by adding 60 g of thide acid magnesium halide from step (a) With at least Water, and the precipitated crystals Were separated by ?ltra one salt selected from the group consisting of alkali tion. Again, a recrystallization Was conducted by 290 g of metal halides, quaternary ammonium salts, and quater Water, and the precipitated crystals Were separated by ?ltra nary phosphonium salts, by directly adding the at least tion. The obtained crystals Were dried. With this, cesium one salt to the obtained reaction mixture from step (a), tris(tri?uoromethanesulfonyl)methide Was obtained With a Wherein the quaternary ammonium salts of step (b) are yield of 27.6 g and a yield of 52%. represented by the formula of (Rl)4N+.X'_ Where Rl’s 60 are de?ned as above, and X' represents a halogen, Thus, in Reference Example 1, as compared With acetate, alkanesulfonate, or arylsulfonate, and hydrogen Examples 1-6, organic matter and Waste Water are drained in atoms of X' may partially or entirely be replaced With large amounts in the post-treatment step. Therefore, a burden halogen, alkyl group, amino group, nitro group, acetyl is placed on industrial operation. group, cyano group or hydroxyl group, Herein, a comparison betWeen Example 1 and Reference 65 Wherein the quaternary phosphonium salts of step (b) are Example 1 in the amount of Waste liquid is summarized in the represented by the formula of (R1)4P+.X'_ Where Rl’s folloWing as Table 1. and X' are de?ned as above. US 8,304,580 B2 11 1 2 2. A method according to claim 1, wherein the alkali metal (a) reacting a methylmagnesium halide represented by for as M in formula [1] is at least one selected from the group mula [2] consisting of lithium, sodium, potassium, rubidium, and CH3MgX [2] cesium. 3. A method according to claim 1, Wherein the alkali metal Wherein X represents a chlorine, bromine or iodine, halide of the step (b) is at least one selected from the group With a per?uoroalkanesulfonyl ?uoride represented by for consisting of lithium ?uoride, lithium chloride, lithium bro mula [3] mide, lithium iodide, sodium ?uoride, sodium chloride, RiSO2F [3] sodium bromide, sodium iodide, potassium ?uoride, potas Wherein Rf represents a C1_9 straight-chain or branched sium chloride, potassium bromide, potassium iodide, chain per?uoroalkyl group, thereby obtaining a reaction rubidium ?uoride, rubidium chloride, rubidium bromide, mixture; and rubidium iodide, cesium ?uoride, cesium chloride, cesium (b) directly reacting the obtained reaction mixture from bromide, and cesium iodide. step (a) With at least one salt selected from the group 4. A method according to claim 1, Wherein the quaternary consisting of alkali metal halides, quaternary ammo ammonium salt of the step (b) is at least one selected from the nium salts, and quaternary phosphonium salts, group consisting of tetramethylammonium ?uoride, tetram Wherein the quaternary ammonium salts of step (b) are ethylammonium chloride, tetramethylammonium bromide, represented by the formula of (Rl)4N+.X‘_ Where Rl’s tetramethylammonium iodide, tetraethylammonium ?uoride, tetraethylammonium chloride, tetraethylammonium bro are de?ned as above, and X‘ represents a halogen, 20 acetate, alkanesulfonate, or arylsulfonate, and hydrogen mide, tetraethylammonium iodide, tetrapropylammonium atoms of X‘ may partially or entirely be replaced With ?uoride, tetrapropylammonium chloride, tetrapropylammo halogen, alkyl group, amino group, nitro group, acetyl nium bromide, tetrapropylammonium iodide, tetrabutylam group, cyano group or hydroxyl group, monium ?uoride, tetrabutylammonium chloride, tetrabuty Wherein the quaternary phosphonium salts of step (b) are lammonium bromide, and tetrabutylammonium iodide. represented by the formula of (R1)4P+.X‘_ Where Rl’s 5. A method according to claim 1, Wherein the quaternary and X‘ are de?ned as above. phosphonium salt of the step (b) is at least one selected from 10. The method according to claim 9, Wherein the obtained the group consisting of tetraphenylphosphonium ?uoride, tet reaction mixture from step (a) comprises a tris(per?uoroal raphenylphosphonium chloride, tetraphenylphosphonium kanesulfonyl)methide acid magnesium halide represented by bromide, tetraphenylphosphonium iodide, tetrabutylphos 30 formula [4] phonium ?uoride, tetrabutylphosphonium chloride, tetrabu tylphosphonium bromide, tetrabutylphosphonium iodide, [4] butyltriphenylphosphonium ?uoride, butyltriphenylphos Wherein Rf is the same as above, and X represents a chlorine, phonium chloride, butyltriphenylphosphonium bromide, bromine or iodine. butyltriphenylphosphonium iodide, trioctylethylphospho 35 11. The method according to claim 9, Wherein the alkali nium ?uoride, trioctylethylphosphonium chloride, trioctyl metal as M in formula [1] is at least one selected from the ethylphosphonium bromide, trioctylethylphosphonium group consisting of lithium, sodium, potassium, rubidium, iodide, benZyltriphenylphosphonium ?uoride, benZyltriph and cesium. enylphosphonium chloride, benZyltriphenylphosphonium 12. The method according to claim 9, Wherein the alkali bromide, benZyltriphenylphosphonium iodide, ethyltriph 40 metal halide of the step (b) is at least one selected from the enylphosphonium ?uoride, ethyltriphenylphosphonium group consisting of lithium ?uoride, lithium chloride, lithium chloride, ethyltriphenylphosphonium bromide, and ethylt bromide, lithium iodide, sodium ?uoride, sodium chloride, riphenylphosphonium iodide. sodium bromide, sodium iodide, potassium ?uoride, potas 6. A method according to claim 1, Wherein the methylmag sium chloride, potassium bromide, potassium iodide, nesium halide of the step (a) is methylmagnesium chloride. 45 rubidium ?uoride, rubidium chloride, rubidium bromide, 7. A method according to claim 1, Wherein the per?uoro rubidium iodide, cesium ?uoride, cesium chloride, cesium alkanesulfonyl ?uoride of the step (a) is tri?uoromethane bromide, and cesium iodide. sulfonyl ?uoride. 13. The method according to claim 9, Wherein the quater 8. A method according to claim 1, Wherein a product of the nary ammonium salt of the step (b) is at least one selected step (b) is subjected to ?ltration and a recrystallization from 50 from the group consisting of tetramethylammonium ?uoride, Water. tetramethylammonium chloride, tetramethylammonium bro 9. A method for producing a tris(per?uoroalkanesulfonyl) mide, tetramethylammonium iodide, tetraethylammonium methide acid salt represented by formula [1] ?uoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammo 55 nium ?uoride, tetrapropylammonium chloride, tetrapropy Wherein Rf represents a C l_9 straight-chain or branched-chain lammonium bromide, tetrapropylammonium iodide, tetrabu per?uoroalkyl group, n represents an integer that is identical tylammonium ?uoride, tetrabutylammonium chloride, With valence of the corresponding cation, and tetrabutylammonium bromide, and tetrabutylammonium M is a cation representing an alkali metal, quaternary iodide. ammonium represented by (Rl)4N, or quaternary phos 60 14. The method according to claim 9, Wherein the quater phonium represented by (R1)4P, Rl’s represent C1_9, nary phosphonium salt of the step (b) is at least one selected identical or different, straight-chain or branched-chain, from the group consisting of tetraphenylphosphonium ?uo saturated or unsaturated aliphatic hydrocarbon groups or ride, tetraphenylpho sphonium chloride, tetraphenylpho spho aryl groups, and hydrogen atoms of R1 ’s may partially or nium bromide, tetraphenylphosphonium iodide, tetrabu entirely be replaced With halogen, alkyl group, amino 65 tylphosphonium ?uoride, tetrabutylphosphonium chloride, group, nitro group, acetyl group, cyano group or tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxyl group, consisting of the steps of: iodide, butyltriphenylphosphonium ?uoride, butyltriph US 8,304,580 B2 13 14 enylpho sphonium chloride, butyltriphenylpho sphonium bro 15. The method according to claim 9, Wherein the methyl mide, butyltriphenylphosphonium iodide, trioctylethylphos magnesium halide of the step (a) is methylmagnesium chlo phonium ?uoride, trioctylethylphosphonium chloride, ride. trioctylethylphosphonium bromide, trioctylethylphospho 16. The method according to claim 9, Wherein the per?uo nium iodide, benZyltriphenylphosphonium ?uoride, benZyl roalkanesulfonyl ?uoride of the step (a) is tri?uoromethane triphenylphosphonium chloride, benzyltriphenylphospho sulfonyl ?uoride. nium bromide, benzyltriphenylphosphonium iodide, 17. The method according to claim 9, Wherein a product of ethyltriphenylphosphonium ?uoride, ethyltriphenylphos the step (b) is subjected to ?ltration and a recrystallization phonium chloride, ethyltriphenylpho sphonium bromide, and from Water. ethyltriphenylphosphonium iodide.