WO2007049613A1 - トリフルオロメタンスルホン酸無水物の製造方法 - Google Patents
トリフルオロメタンスルホン酸無水物の製造方法 Download PDFInfo
- Publication number
- WO2007049613A1 WO2007049613A1 PCT/JP2006/321157 JP2006321157W WO2007049613A1 WO 2007049613 A1 WO2007049613 A1 WO 2007049613A1 JP 2006321157 W JP2006321157 W JP 2006321157W WO 2007049613 A1 WO2007049613 A1 WO 2007049613A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- trifluoromethanesulfonic acid
- trifluoromethanesulfonic
- anhydride
- acid
- phosphorus pentoxide
- Prior art date
Links
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 60
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000004821 distillation Methods 0.000 claims description 24
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
Definitions
- the present invention relates to a method for producing trifluoromethanesulfonic anhydride useful as a raw material for synthesizing various functional materials including pharmaceuticals and agricultural chemicals.
- Solvents used here include fluoroalkylsulfonic anhydrides, fluoroalkylsulfonic acid esters, perfluoroalkanes, perfluoroalkylamines and perfluoropolyethers, including the desired product.
- these solvents are insufficient in the solubility of polyphosphoric acid. For this reason, after the reaction, in order to sufficiently recover the produced trifluoromethanesulfonic anhydride by distillation, it is necessary to add water and phosphoric acid as in the conventional method.
- Patent Document 1 US Patent No. 5004829
- Patent Document 2 Japanese Patent Application Laid-Open No. 02-268148
- Patent Document 3 Japanese Patent Laid-Open No. 09-227498
- Patent Document 4 JP-A-10-114734
- Patent Document 5 Japanese Patent Laid-Open No. 11-236365
- Patent Document 6 Japanese Patent Laid-Open No. 11-236366
- the present invention solves the above-mentioned problems in conventional production methods in the production of trifluoromethansulfonic acid anhydride by reaction of trifluoromethanesulfonic acid and phosphorus pentoxide.
- the method for producing trifluoromethanesulfonic acid anhydride of the present invention comprises the step of reacting trifluoromethanesulfonic acid and phosphorus pentoxide to produce trifluoromethanesulfonic acid anhydride.
- the amount of phosphorus pentoxide with respect to trifluoromethanesulfonic acid may be 0.3 or less in molar ratio.
- the molar ratio of phosphorus pentoxide to trifluoromethanesulfonic acid may be 0.05 to 0.2.
- the produced trifluoromethanesulfonic anhydride is recovered by distillation, followed by distillation to distill unreacted trifluoromethanesulfonic acid. It may further include a step of collecting ⁇ It may further include a step of distilling and recovering the produced trifluoromethanesulfonic anhydride under reduced pressure.
- reaction solution does not solidify!
- distillation may be continued as it is. It is not necessary to add phosphoric acid or trifluoromethanesulfonic acid metal salt, etc. used in the conventional method to the distillation residue, and it is possible to effectively recover unreacted trifluoromethanesulfonic acid.
- the method for producing trifluoromethanesulfonic acid anhydride comprises the step of reacting trifluoromethanesulfonic acid with phosphorus pentoxide to produce trifluoromethanesulfonic acid anhydride. An excess of trifluoromethanesulfonic acid is used. This prevents caking of the reaction solution due to the by-product of polyphosphoric acid.
- the conventional production method uses trifluoromethanesulfonic acid to increase the reaction rate of trifluoromethanesulfonic acid. Excess amount (2-4 moles) of pentaacid relative to romethanesulfonic acid I am using Yi Lin.
- the production method of the present invention uses an excess of trifluoromethanesulfonic acid relative to pentalin phosphorus, contrary to the conventional production method.
- the amount of phosphorus pentoxide used is preferably 0.3 or less, more preferably 0.05 to 0.2, in terms of molar ratio with respect to trifluoromethanesulfonic acid.
- the amount of phosphorus pentoxide used is greater than 0.3 by mole with respect to trifluoromethanesulfonic acid, the by-product polyphosphoric acid cannot be sufficiently dissolved, and polyphosphoric acid gradually accumulates in the reaction solution. Then solidify.
- the amount ratio of phosphorus pentoxide to trifluoromethanesulfonic acid is less than 0.05, the amount of anhydride produced is not preferable. For industrial production, it is better to use more than the above amount.
- the trifluoromethanesulfonic acid anhydride produced by the dehydration condensation reaction of trifluoromethanesulfonic acid can recover the internal force of the system by distillation.
- trifluoromethanesulfonic anhydride is recovered by distillation in the presence of trifluoromethanesulfonic acid, when the distillation temperature increases, the resulting trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid interact with the following side reactions. Is known to produce.
- the internal pressure is preferably 500 torr or less, particularly 300 to 30 torr.
- high purity trifluoromethanesulfonic acid anhydride can be obtained by collecting fractions with an internal pressure of 90 torr and an internal temperature of 90 ° C.
- the internal pressure is preferably lOOtorr or less, more preferably 50 torr or less.
- the internal temperature is preferably 200 ° C or less, although it depends on the degree of vacuum. Specifically, for example, after collecting trifluoromethanesulfonic anhydride under reduced pressure distillation, the fraction is switched, and distillation is continued to an internal pressure of 10 torr and an internal temperature of about 200 ° C, thereby contributing to the reaction. Powerful excess of unreacted trifluoromethanesulphonic acid can be efficiently recovered.
- a reaction vessel equipped with a thermometer, a reflux condenser, and a stirring blade was charged with 450 g (3.0 mol) of trifluoromethanolenolephonic acid, and further 85.2 g (0.60 mol) of phosphoric acid pentalin was added thereto. This was stirred at room temperature for 18 hours to be reacted. Immediately after the addition of phosphorus pentoxide, it was a dispersion (a state where phosphorus pentoxide powder was dispersed in the solution), but it became a uniform solution in about 8 hours. Thereafter, the internal pressure was reduced to 90 torr, and a fraction having an internal temperature of 90 ° C. was collected to obtain trifluoromethanesulfonic acid anhydride.
- the amount of trifluoromethanesulfonic anhydride obtained was 185.5 g, and the purity by gas chromatography was 99%.
- the yield of the anhydride formed relative to the amount of trifluoromethanesulfonic acid charged is 43%.
- Trifluoromethanesulfonic anhydride was produced in the same manner as in Example 1 except that the amount of trifluoromethanesulfonic acid and the amount of phosphorus pentoxide added were adjusted as shown in Table 1. Fluorosulfonic acid was recovered. The results are shown in Table 1.
- T iO! L is rifluorene sulfone ?
- Trifluoromethanesulfonic anhydride was produced in the same manner as in Example 1 except that the amount of trifluoromethanesulfonic acid and the amount of phosphorus pentoxide added were adjusted as shown in Table 1. Fluorosulfonic acid was recovered. The results are shown in Table 1.
- the reaction efficiency can be increased and effectively. Unreacted trifluoromethanesulfonic acid can be recovered. For this reason, Trifluo It can be suitably applied to the production process of romethanesulfonic anhydride.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06822137A EP1942102B1 (en) | 2005-10-25 | 2006-10-24 | Process for producing trifluoromethanesulfonic anhydride |
CN2006800393733A CN101291906B (zh) | 2005-10-25 | 2006-10-24 | 三氟甲磺酸酐的制备方法 |
US12/064,113 US7741518B2 (en) | 2005-10-25 | 2006-10-24 | Method for producing trifluoromethanesulfonic anhydride |
KR1020087005501A KR101294531B1 (ko) | 2005-10-25 | 2006-10-24 | 트리플루오로메탄술폰산 무수물의 제조방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005310245 | 2005-10-25 | ||
JP2005-310245 | 2005-10-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007049613A1 true WO2007049613A1 (ja) | 2007-05-03 |
Family
ID=37967724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/321157 WO2007049613A1 (ja) | 2005-10-25 | 2006-10-24 | トリフルオロメタンスルホン酸無水物の製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7741518B2 (ja) |
EP (1) | EP1942102B1 (ja) |
KR (1) | KR101294531B1 (ja) |
CN (1) | CN101291906B (ja) |
RU (1) | RU2419604C2 (ja) |
WO (1) | WO2007049613A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5874353B2 (ja) | 2011-11-30 | 2016-03-02 | セントラル硝子株式会社 | フルオロアルカンスルホン酸無水物の製造方法 |
US8377406B1 (en) | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
CN103450050B (zh) * | 2013-09-10 | 2015-11-25 | 中国船舶重工集团公司第七一八研究所 | 三氟甲磺酸酐的纯化方法 |
CN111689878A (zh) * | 2020-07-14 | 2020-09-22 | 江西国化实业有限公司 | 一种三氟甲磺酸酐制备工艺 |
CN113877482B (zh) * | 2021-10-27 | 2022-12-27 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种三氟甲磺酸酐制备的加料装置及方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02268148A (ja) | 1989-04-10 | 1990-11-01 | Central Glass Co Ltd | 無水トリフルオロメタンスルホン酸の製造方法 |
JPH09227498A (ja) | 1995-12-20 | 1997-09-02 | Central Glass Co Ltd | 高純度フルオロアルキルスルホン酸無水物の製造方法 |
JPH10114734A (ja) | 1996-10-15 | 1998-05-06 | Central Glass Co Ltd | 高純度フルオロアルキルスルホン酸無水物の製造方法 |
JPH11236365A (ja) | 1998-02-23 | 1999-08-31 | Central Glass Co Ltd | トリフルオロメタンスルホン酸無水物の製造方法 |
JPH11236366A (ja) | 1998-02-23 | 1999-08-31 | Central Glass Co Ltd | トリフルオロメタンスルホン酸無水物の製造方法 |
JP2005310245A (ja) | 2004-04-20 | 2005-11-04 | Seiko Epson Corp | メモリコントローラ、半導体集積回路装置、マイクロコンピュータ及び電子機器 |
-
2006
- 2006-10-24 RU RU2008109759/04A patent/RU2419604C2/ru not_active IP Right Cessation
- 2006-10-24 WO PCT/JP2006/321157 patent/WO2007049613A1/ja active Application Filing
- 2006-10-24 KR KR1020087005501A patent/KR101294531B1/ko not_active IP Right Cessation
- 2006-10-24 US US12/064,113 patent/US7741518B2/en not_active Expired - Fee Related
- 2006-10-24 CN CN2006800393733A patent/CN101291906B/zh not_active Expired - Fee Related
- 2006-10-24 EP EP06822137A patent/EP1942102B1/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02268148A (ja) | 1989-04-10 | 1990-11-01 | Central Glass Co Ltd | 無水トリフルオロメタンスルホン酸の製造方法 |
US5004829A (en) | 1989-04-10 | 1991-04-02 | Central Glass Company, Limited | Method of preparing trifluoromethanesulfonic acid anhydride |
JPH09227498A (ja) | 1995-12-20 | 1997-09-02 | Central Glass Co Ltd | 高純度フルオロアルキルスルホン酸無水物の製造方法 |
JPH10114734A (ja) | 1996-10-15 | 1998-05-06 | Central Glass Co Ltd | 高純度フルオロアルキルスルホン酸無水物の製造方法 |
JPH11236365A (ja) | 1998-02-23 | 1999-08-31 | Central Glass Co Ltd | トリフルオロメタンスルホン酸無水物の製造方法 |
JPH11236366A (ja) | 1998-02-23 | 1999-08-31 | Central Glass Co Ltd | トリフルオロメタンスルホン酸無水物の製造方法 |
JP2005310245A (ja) | 2004-04-20 | 2005-11-04 | Seiko Epson Corp | メモリコントローラ、半導体集積回路装置、マイクロコンピュータ及び電子機器 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1942102A4 |
Also Published As
Publication number | Publication date |
---|---|
US7741518B2 (en) | 2010-06-22 |
KR20080059153A (ko) | 2008-06-26 |
KR101294531B1 (ko) | 2013-08-07 |
EP1942102A4 (en) | 2010-10-27 |
US20090118543A1 (en) | 2009-05-07 |
RU2419604C2 (ru) | 2011-05-27 |
EP1942102B1 (en) | 2012-07-04 |
RU2008109759A (ru) | 2009-12-10 |
CN101291906A (zh) | 2008-10-22 |
CN101291906B (zh) | 2012-02-01 |
EP1942102A1 (en) | 2008-07-09 |
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