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Wo 2U11/1U4724 A2 (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 1 September 2011 (01.09.2011) WO 2U11/1U4724 A2 (51) International Patent Classification: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, C07C 303/02 (2006.01) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (21) International Application Number: NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, PCT/IN20 11/000106 SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (22) International Filing Date: TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. 23 February 201 1 (23.02.201 1) (84) Designated States (unless otherwise indicated, for every (25) Filing Language: English kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, (26) Publication Language: English ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, (30) Priority Data: TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, 522/MUM/2010 26 February 2010 (26.02.2010) IN EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, (72) Inventor; and SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, (71) Applicant : GHARDA, Keki Hormusji [IN/IN]; Gharda GW, ML, MR, NE, SN, TD, TG). House, 48 Hill Road, Bandra (West), Mumbai 400 050, Maharashtra (IN). Declarations under Rule 4.17 : — as to the identity of the inventor (Rule 4.17(i)) (74) Agent: DEWAN, Mohan; R. K. Dewan & Company, Trade Mark & Patent Attorneys, Podar Chambers, — as to the applicant's entitlement to claim the priority of SA.Brelvi Road, Fort, Mumbai 400 001 Maharashtra the earlier application (Rule 4.17(Hi)) (IN). — of inventorship (Rule 4.1 7(iv)) (81) Designated States (unless otherwise indicated, for every Published: kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, — without international search report and to be republished CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, upon receipt of that report (Rule 48.2(g)) DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, < o o (54) Title: A PROCESS FOR THE MANUFACTURE OF TRIFLIC ACID (57) Abstract: The present invention relates to a process for the preparation of triflic acid by chloroxidation. A PROCESS FOR THE MANUFACTURE OF TRIFLIC ACID FIELD OF THE INVENTION The present invention relates to synthesis of Triflic acid. BACKGROUND Triflic acid (Trifluoromethanesulfonic acid) is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest acids and is mainly used in research as a catalyst for esterification. Triflic acid is a hygroscopic, colorless liquid at room temperature. It is soluble in polar solvents such as DMF, DMSO, acetonitrile and dimethyl sulfone. Triflic acid is a non-oxidizing thermally stable compound and is resistant to both oxidation and reduction. In the laboratory, triflic acid is useful in protonations because the conjugate base of triflic acid is non-nucleophilic. Triflic acid promotes other Friedel-Crafts-like reactions including the cracking of alkanes and alkylation of alkenes, which are very important to the petroleum industry. These triflic acid derivative catalysts are very effective in isomerizing straight chain or slightly branched hydrocarbons that can increase the octane rating of particular petroleum based fuel. Triflic acid is also used in pharmaceutical, agrochemical and fine chemical industries. Derivatives of Triflic acid are used as a component of lithium batteries, thus finds use in various electronic items viz. calculators, laptops, digital cameras, mobiles, watches and the like. There are various processes available for the synthesis of Triflic acid, viz. Oxidation of bis (tnfluoromethylthio) mercury with hydrogen peroxide, formation of its barium salt, followed by its reaction with sulfuric acid to evolve Triflic acid (Hazeldine & Kidd, JCS 1954, 4228). However, mercury is a poisonous metal and hence the process is not desirable. Trifluoromethanesulfonic acid is also produced by electrochemical fluorination (ECF) of methanesulfonic acid: CH3SO3H + 4 HF CF3SO2F + H20 + 1.5 H2 The resulting CF3S0 2F is hydrolyzed and the resulting triflate salt is preprotonated. Alternatively, trifluoromethanesulfonic acid arises by oxidation of trifluoromethylsulfenyl chloride: CF3SCI + 2 Cl2 + 2 H20 CF3S0 2OH + 4 HC1 Triflic acid is then purified by distillation from triflic anhydride. Oxidation of bis-(trifluoromethyl) disulphane to Triflic acid by various oxidizing agents is disclosed in United States Patent No. 5059711. However, Bis- (trifluoromethyl)disulphane can not be readily synthesized and is not easily available. Accordingly, it is desirable to develop a synthetic route for Triflic acid using readily available raw material and which obviates the use of poisonous chemicals. OBJECTS OF THE INVENTION It is an object of the present invention to provide a synthetic route for Triflic acid using easily available raw materials. It is another object of the present invention to provide a synthetic route for Triflic acid that obviates the use of poisonous/toxic chemicals. It is still another object of the present invention to provide a simple and commercially attractive route for the synthesis of triflic acid. SUMMARY OF AN INVENTION In accordance with the present invention there is provided a process for the preparation of triflic acid, said process comprising the following steps: a) treating a mixture of benzyl trifluoro methyl sulphide and water with chlorine gas in a reactor maintained at a temperature of about 5°C to about 30°C and at a pressure of about 0.1 to 1.2 kg/cm to form a reaction mixture; b) maintaining the reaction mixture at a temperature of about 5°C to about 20°C for a period of about 4 to about 8 hours at 0.1 to 1.0 kg/cm2 pressure; c) raising the temperature of the reaction mixture to about 25 °C to about 45°C followed by maintaining the reaction mixture at 25 °C to 45°C and at pressure of about 0.1 to 1.0 kg/cm to form a biphasic mixture containing an organic layer and an aqueous layer; d) separating the organic layer from the biphasic mixture followed by distilling said organic layer to obtain trifluoromethyl sulphonyl chloride; and f hydrolyzing trifluoromethyl sulponyl chloride to form triflic acid having a purity of about 99.5 %. Typically, benzyl trifluoro methyl sulphide is at least one selected from the group consisting of unsubstituted benzyl trifluoro methyl sulphide and substituted benzyl trifluoro methyl sulphide. In accordance with one of the embodiments of the present invention benzyl trifluoro methyl sulphide is a substituted benzyl trifluoro methyl sulphide. Typically, the substituent is at least one selected from the group consisting of aromatic group and halogen group. Typically, the aromatic group is at least one selected from the group consisting of aromatic hydrocarbon, heterocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon. Typically, the aromatic hydrocarbon is at least one selected from the group consisting of Benzene, Toluene, o, p, m-Xylene, Benzophenone, substituted benzophenone, acetophenone, substituted acetophenone, tri methyl benzene, tetramethyl benzene and pentamethyl benzene. Typically, the heterocyclic aromatic hydrocarbon is at least one selected from the group consisting of furan, pyridine, pyrazine, imidazole, Pyrazole, oxazole and thiophene. Typically, the polycyclic aromatic hydrocarbon is at least one selected from the group consisting of naphthalene, anthracene and phenanthrene. Typically, the halogen group is at least one selected from the group consisting of fluorine, chlorine, bromine and iodine. In accordance with one of the embodiment the substituent is at least one selected from the group consisting of ortho chlorobenzyl chloride, 4-chloromethyl methylene dioxy benzene, 1-chloromethyl naphthalene, bis-2, 4-chloromethyl toluene and tris 2,4,6-chloromethyl toluene and bis-9,10-chloromethyl anthracene. Typically, the ratio of benzyl trifluoro methyl sulphide to chlorine is in the range of about 1: 6 moles. Preferably, step (a) is carried out at a pressure of about 0.5 to 0.9 kg/cm2. In accordance with one of the embodiments of the present invention the hydrolyzing step comprises hydrolyzing trifluoromethylsulponyl chloride with water to form a triflic acid monohydrate and dehydrating triflic acid monohydrate with thionyl chloride at a temperature of about 40 to about 80°C to yield crude anhydrous triflic acid followed by removing the impurities from the crude triflic acid by vacuum distillation to obtain pure triflic acid. Typically, the hydrolyzing step is carried out at a temperature of about 70 to about 120°C and at a pressure of about 3 to 6 kg/cm 2. Preferably, the hydrolyzing step is carried out at a temperature of about 80 to about 100°C and at a pressure of about 4 to 5 kg/cm . Typically, the amount of thionyl chloride is about 1 to about 1.5 moles per mole of triflic acid monohydrate. Preferably, the amount of thionyl chloride is about 1.1 to about 1.2 moles per mole of triflic acid monohydrate. Preferably, the step of dehydrating triflic acid monohydrate with thionyl chloride is carried out at a temperature of about 50 to about 60°C. In accordance with another embodiment of the present invention the hydrolyzing step comprises hydrolyzing trifluoromethylsulponyl chloride in presence of at least one inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide and at least one aliphatic alcohol selected from the group consisting of methanol, ethanol, isopropyl alcohol and mixtures thereof to form a hydrolyzed mass followed by neutralization using at least one mineral acid selected from the group consisting of hydrochloric acid and sulphuric acid and distillation to obtain pure triflic acid.
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