DE10126929A1 - Production of compounds with perfluoroalkanesulfonic acid residues, used e.g. in electrolytes and batteries, involves reacting perfluoroalkanesulfonic anhydride with dialkyl carbonate in presence of perfluoroalkanesulfonic acid - Google Patents
Production of compounds with perfluoroalkanesulfonic acid residues, used e.g. in electrolytes and batteries, involves reacting perfluoroalkanesulfonic anhydride with dialkyl carbonate in presence of perfluoroalkanesulfonic acidInfo
- Publication number
- DE10126929A1 DE10126929A1 DE10126929A DE10126929A DE10126929A1 DE 10126929 A1 DE10126929 A1 DE 10126929A1 DE 10126929 A DE10126929 A DE 10126929A DE 10126929 A DE10126929 A DE 10126929A DE 10126929 A1 DE10126929 A1 DE 10126929A1
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- perfluoroalkanesulfonic
- perfluoroalkanesulfonic acid
- alkyl
- salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 5
- 150000008064 anhydrides Chemical class 0.000 title claims description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003990 capacitor Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000011987 methylation Effects 0.000 claims description 6
- 238000007069 methylation reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 4
- 229910052731 fluorine Inorganic materials 0.000 abstract 3
- 229910052801 chlorine Inorganic materials 0.000 abstract 2
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- AKGOLHAGFGPGKB-UHFFFAOYSA-N methyl 1,1,2,2,2-pentafluoroethanesulfonate Chemical compound COS(=O)(=O)C(F)(F)C(F)(F)F AKGOLHAGFGPGKB-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- DOYSIZKQWJYULQ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n-(1,1,2,2,2-pentafluoroethylsulfonyl)ethanesulfonamide Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)C(F)(F)F DOYSIZKQWJYULQ-UHFFFAOYSA-N 0.000 description 1
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 description 1
- YFQPRQIVKLIGMR-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethylsulfonyl 1,1,2,2,2-pentafluoroethanesulfonate Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)C(F)(F)F YFQPRQIVKLIGMR-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WLQRTXOOEGUPJY-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;trifluoromethanesulfonate Chemical compound CN1C=C[N+](C)=C1.[O-]S(=O)(=O)C(F)(F)F WLQRTXOOEGUPJY-UHFFFAOYSA-M 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- -1 Current Progress Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- UQWLFOMXECTXNQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F UQWLFOMXECTXNQ-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- BOJSGWOJLRZTJR-UHFFFAOYSA-M triethyl(methyl)phosphanium;trifluoromethanesulfonate Chemical compound CC[P+](C)(CC)CC.[O-]S(=O)(=O)C(F)(F)F BOJSGWOJLRZTJR-UHFFFAOYSA-M 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65688—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphonium compound
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Verbindungen mit Perfluoralkansulfonsäureresten sowie die Verwendung von Leitsalzen in Batterien, Kondensatoren, Superkondensatoren und galvanischen Zellen.The present invention relates to a method for producing Compounds with perfluoroalkanesulfonic acid residues and the Use of conductive salts in batteries, capacitors, Supercapacitors and galvanic cells.
Die Verbreitung von tragbaren elektronischen Geräten, wie z. B. Laptop- und Palmtop-Computern, Mobiltelefonen, oder Videokameras und damit auch der Bedarf nach leichten und leistungsfähigen Batterien hat in den letzten Jahren weltweit dramatisch zugenommen.The proliferation of portable electronic devices, such as. B. laptop and palmtop computers, cell phones, or video cameras and thus also the need for light and powerful batteries has increased dramatically worldwide in recent years.
Angesichts dieses sprunghaft gestiegenen Bedarfs nach Batterien und den damit verbundenen ökologischen Problemen kommt der Entwicklung von wiederaufladbaren Batterien mit einer langen Lebensdauer eine stetig wachsende Bedeutung zu.Given this surge in demand for batteries and the associated ecological problems Development of rechargeable batteries with a long Lifetime a growing importance.
Lithium-Ionen-Batterien und Doppelschichtkondensatoren mit sehr hohen Kapazitäten (sogenannte Super- oder Ultracapacitors) stellen den derzeitigen Stand der Technik dar. In beiden Systemen werden mit LiPF6 bzw. N(C2H5)4BF4 derzeit hydrolyseempfindliche und thermisch instabile Substanzen als Leitsalz verwendet. Im Kontakt mit feuchter Luft bzw. mit Restwasser aus den Lösungsmitteln kann schnell HF entstehen. Neben den toxischen Eigenschaften wirkt HF sehr negativ auf das Zyklenverhalten und somit auf die Performance der elektrochemischen Zellen.Lithium-ion batteries and double-layer capacitors with very high capacities (so-called super or ultra capacitors) represent the current state of the art. In both systems, LiPF 6 and N (C 2 H 5 ) 4 BF 4 are currently hydrolysis-sensitive and thermally unstable Substances used as conductive salt. HF can quickly develop in contact with moist air or with residual water from the solvents. In addition to the toxic properties, HF has a very negative effect on the cycle behavior and thus on the performance of the electrochemical cells.
Als Alternative wurden Imide, wie das Bis(trifluormethylsulfonyl)imid oder das Bis(pentafluorethylsulfonyl)imid oder Methanide, wie das Tris(trifluormethylsulfonyl)methanid und deren Derivate vorgestellt.As an alternative, imides such as the bis (trifluoromethylsulfonyl) imide or the bis (pentafluoroethylsulfonyl) imide or methanides such as that Tris (trifluoromethylsulfonyl) methanide and its derivatives presented.
Aber auch quaternäre Ammonium- und Phosphoniumsalze mit Perfluoralkansulfonat-Anionen wurden als Leitsalze für galvanische Zellen entwickelt. Die Synthese dieser Salze ist jedoch relativ aufwendig, da ein Zwischenprodukt, der Trifluormethansulfonsäuremethylester (Methyltriflat), schwer darzustellen ist.But also quaternary ammonium and phosphonium salts Perfluoroalkanesulfonate anions have been used as conductive salts for galvanic Cells developed. However, the synthesis of these salts is relative complex, because an intermediate product, the Trifluoromethanesulfonic acid methyl ester (methyl triflate), heavy is to be presented.
Das Methyltriflat ist ein starkes Methylierungsreagenz. Es wird in der präparativen Chemie zur Einführung von Methylgruppen genutzt, z. B. bei der Methylierung von heterocyclischen Verbindungen (Yu, Teylor, Tetrahedron Letter, 1999 (36), 6661-6664) oder der Methylierung von Schwefel-organischen Verbindungen (Tsuge, Hatta, Chem. Letter, 1997 (9), 945-946). Methyltriflat ist wesentlich reaktiver als Methyliodid, Dimethylsulfat und Methyltoluensulfonat, die üblicherweise verwendeten Methylierungsreagenzien bei der Synthese von quaternären Ammonium- und Phosphoniumsalzen.The methyl triflate is a strong methylation reagent. It will be in the preparative chemistry used to introduce methyl groups, e.g. B. in the methylation of heterocyclic compounds (Yu, Teylor, Tetrahedron Letter, 1999 (36), 6661-6664) or the methylation of Organic sulfur compounds (Tsuge, Hatta, Chem. Letter, 1997 (9), 945-946). Methyl triflate is much more reactive than methyl iodide, Dimethyl sulfate and methyl toluenesulfonate, which are common used methylation reagents in the synthesis of quaternary ammonium and phosphonium salts.
Es gibt verschiedene Synthesewege für das Methyltriflat (Gramstad, J. Chem. Soc., 1956, 173-180 oder Beard, J. Org. Chem., 1973 (21), 3673-3677). Alle beschriebenen Synthesewege eignen sich nicht für eine Übertragung in einen großen Maßstab, da sie entweder sehr toxische Ausgangsmaterialien, wie z. B. Dimethylsulfat, verwenden, die Ausbeuten sehr niedrig sind, das Reaktionsprodukt aufgereinigt werden muß, oder gefährliche Neben- bzw. Abfallprodukte anfallen, wie z. B. Schwefelsäure die mit Dimethylsulfat verunreinigt ist.There are various synthetic routes for methyl triflate (Gramstad, J. Chem. Soc., 1956, 173-180 or Beard, J. Org. Chem., 1973 (21), 3673 to 3677). All of the synthetic routes described are not suitable for a transfer on a large scale since it is either very toxic starting materials such as B. dimethyl sulfate, use the Yields are very low, the reaction product can be purified must, or dangerous by-products or waste products arise, such. B. Sulfuric acid contaminated with dimethyl sulfate.
Aufgabe der Erfindung war es daher, ein einfaches Verfahren für die Synthese von Perfluoralkansulfonsäurealkylestern und daraus herstellbare Leitsalze zur Verfügung zu stellen.The object of the invention was therefore to provide a simple method for Synthesis of perfluoroalkanesulfonic acid alkyl esters and therefrom to provide conductive salts that can be produced.
Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung von
Verbindungen mit Perfluoralkansulfonsäureresten, unter der
Verwendung eines Verfahrensschrittes bei dem
Perfluoralkansulfonsäureanhydrid in Gegenwart von
Perfluoralkansulfonsäure mit Dialkylcarbonat zu
Perfluoralkansulfonsäurealkylester umgesetzt wird.
The object is achieved by a process for the preparation of compounds having perfluoroalkanesulfonic acid residues, using a process step in which perfluoroalkanesulfonic anhydride is reacted with dialkyl carbonate to give perfluoroalkanesulfonic acid alkyl ester in the presence of perfluoroalkanesulfonic acid.
Überraschend wurde gefunden, daß die Umsetzung von Perfluoralkansulfonsäureanhydrid nahezu quantitativ zum Perfluoralkansulfonsäurealkylester erfolgt. Es sind nur katalytische Mengen an Perfluoralkansulfonsäure erforderlich. Es werden nur 0,01-0,1 mol Perfluoralkansulfonsäure pro 1 mol Perfluoralkansulfonsäureanhydrid benötigt.It was surprisingly found that the implementation of Perfluoroalkanesulfonic anhydride almost quantitative for Perfluoroalkanesulfonsäurealkylester takes place. They are only catalytic Amounts of perfluoroalkanesulfonic acid required. Only 0.01-0.1 mol Perfluoroalkanesulfonic acid per 1 mol Perfluoroalkanesulfonic anhydride is required.
Über das erfindungsgemäße Verfahren erhält man Perfluoralkansulfonsäurealkylester, die als Methylierungsreagenzien verwendet werden können. Sie können zur Methylierung von heterocyclischen Verbindungen oder Phosphor- und Schwefel- organische Verbindungen verwendet werden, oder zur Darstellung von N-Methylaminosäure mit geringer Racematbildung.One obtains via the method according to the invention Perfluoroalkanesulfonic acid alkyl esters used as methylation reagents can be used. You can use it to methylate heterocyclic compounds or phosphorus and sulfur organic compounds are used, or for the representation of N-methyl amino acid with low racemate formation.
Das Reaktionsprodukt muß nicht isoliert werden, da nicht umgesetzte
Dialkylcarbonate bei einer Umsetzung mit
The reaction product does not have to be isolated, since unreacted dialkyl carbonates react with
XR1R2R3,
XR 1 R 2 R 3 ,
wobei
X P oder N und
R1, R2, R3
unabhängig voneinander H, Alkyl, Alkylaryl oder Aryl bedeuten, und
mindestens ein R + H ist, zu den entsprechenden Salzen für die
Verwendung in Elektrolyten für galvanische Zellen als Lösungsmittel
enthalten sein kann.in which
XP or N and
R 1 , R 2 , R 3
independently of one another denote H, alkyl, alkylaryl or aryl, and at least one R + H is, to the corresponding salts for use in electrolytes for galvanic cells can be contained as a solvent.
Beispielsweise können folgende Umsetzungen erfolgen:
For example, the following implementations can take place:
CF3SO2OCH3 + (C2H5)3N → ((C2H5)3NCH3]+ CF3SO2O-
CF 3 SO 2 OCH 3 + (C 2 H 5 ) 3 N → ((C 2 H 5 ) 3 NCH 3 ] + CF 3 SO 2 O -
oder
or
CF3SO2OCH3 + (C2H5)3P → [(C2H5)3PCH3]+ CF3SO2O-.CF 3 SO 2 OCH 3 + (C 2 H 5 ) 3 P → [(C 2 H 5 ) 3 PCH 3 ] + CF 3 SO 2 O - .
Nach der Umsetzung muß lediglich der nicht umgesetzte Perfluoralkansulfonsäurealkylester abdestilliert werden, die restliche Perfluoralkansulfonsäure kann für weitere Umsetzungen genutzt werden.After the implementation, only the unconverted must Perfluoroalkanesulfonsäurealkylester be distilled off, the rest Perfluoroalkanesulfonic acid can be used for further reactions become.
Diese Salze können sowohl in reiner Form als auch in Form ihrer Mischungen als Leitsalze in primären und sekundären Batterien, Kondensatoren, Superkondensatoren und galvanischen Zellen eingesetzt werden. Es ist auch möglich, die Salze gemeinsam mit weiteren, dem Fachmann bekannten Salzen als Leitsalz zu verwenden.These salts can be in both pure form and in the form of their Mixtures as conductive salts in primary and secondary batteries, Capacitors, supercapacitors and galvanic cells be used. It is also possible to use the salts together to use further salts known to the person skilled in the art as the conductive salt.
Die Leitsalze werden im Elektrolyten mit geeigneten Lösungsmitteln eingesetzt. Besonders bevorzugt werden als Lösungsmittel solche Lösungsmittel oder deren Gemische eingesetzt, die zur Anwendung in einer primären oder sekundären Batterie, einem Kondensator, einem Superkondensator oder einer galvanischen Zelle geeignet sind, wie beispielsweise Dimethylcarbonat, Diethylcarbonat, Propylencarbonat, Ethylencarbonat, Ethylmethylcarbonat, Methylpropylcarbonat, 1,2- Dimethoxyethan, 1,2-Diethoxyethan, Methylacetat, γ-Butyrolacton, Ethylacetat, Methylpropionat, Ethylpropionat, Methylbutyrat, Ethylbutyrat, Dimethylsulfoxid, Dioxolan, Sulfolan, Acetonitril, Acrylnitril, Tetrahydrofuran, 2-Methyl-Tetrahydrofuran oder deren Gemische, hergestellt.The conductive salts are in the electrolyte with suitable solvents used. Such solvents are particularly preferred Solvents or mixtures thereof are used in a primary or secondary battery, a capacitor, a Supercapacitor or a galvanic cell are suitable, such as for example dimethyl carbonate, diethyl carbonate, propylene carbonate, Ethylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2- Dimethoxyethane, 1,2-diethoxyethane, methyl acetate, γ-butyrolactone, Ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Ethyl butyrate, dimethyl sulfoxide, dioxolane, sulfolane, acetonitrile, acrylonitrile, Tetrahydrofuran, 2-methyl-tetrahydrofuran or mixtures thereof, manufactured.
Die so erhaltenen Elektrolyte eignen sich zum Einsatz in primären Batterien, sekundären Batterien, Kondensatoren, Superkondensatoren und galvanischen Zellen und stellen ebenfalls einen Gegenstand der vorliegenden Erfindung dar.The electrolytes thus obtained are suitable for use in primary ones Batteries, secondary batteries, capacitors, supercapacitors and galvanic cells and also represent an object of present invention.
Gegenstand der Erfindung sind auch primäre Batterien, sekundäre Batterien, Kondensatoren, Superkondensatoren und galvanische Zellen, die wenigstens ein Salz, erhalten durch die Umsetzung von Perfluoralkansulfonsäurealkylester mit einer Verbindung gemäß der Formel XR1R2R3, und ggf. weitere Salze und/oder Zusatzstoffe enthalten. Diese weiteren Salze und Zusatzstoffe sind dem Fachmann z. B. aus Doron Aurbach, Nonaqueous Electrochemistry, Marc Dekker Inc., New York 1999; D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995 und G. Mamantov und A. I. Popov, Chemistry of Nonaqueous Solutions, Current Progress, VCH Verlagsgemeinschaft, Weinheim 1994 bekannt. Sie werden hiermit als Referenz eingeführt und gelten somit als Teil der Offenbarung. The invention also relates to primary batteries, secondary batteries, capacitors, supercapacitors and galvanic cells which contain at least one salt obtained by reacting alkyl perfluoroalkanesulfonic acid ester with a compound of the formula XR 1 R 2 R 3 , and optionally further salts and / or Contain additives. These other salts and additives are known to the expert z. B. from Doron Aurbach, Nonaqueous Electrochemistry, Marc Dekker Inc., New York 1999; D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995 and G. Mamantov and AI Popov, Chemistry of Nonaqueous Solutions, Current Progress, VCH Verlagsgemeinschaft, Weinheim 1994. They are hereby introduced as a reference and are therefore considered part of the disclosure.
Im folgenden wird die Erfindung anhand von Beispielen erläutert. Diese Beispiele dienen lediglich der Erläuterung der Erfindung und schränken den allgemeinen Erfindungsgedanken nicht ein.In the following the invention will be explained with the aid of examples. This Examples serve only to illustrate the invention and limit it the general idea of the invention.
In einem 1-l-Rundhalskolben werden 646 g (2,29 mol)
Trifluoressigsäureanhydrid und 36 g (0,24 mol) Trifluoressigsäure
vorgelegt. Unter ständigem Rühren und Rückflußkühlung werden 206 g
(2,29 mol) Dimethylcarbonat bei Raumtemperatur zugegeben.
Innerhalb von 10 min erwärmt sich die Lösung auf 50-60°C und wird
anschließend noch eine Stunde bei dieser Temperatur weiter gerührt.
Anschließend wird die Lösung mit einem Ölbad auf 100-110°C erwärmt
und weitere 2 Stunden gerührt. Es werden nach einer Destillation 733 g
Methyltrifluormethansulfonat mit einer Reinheit über 99% isoliert.
Siedebereich: 98-99°C, Ausbeute: 97,7%
19F und 1H-NMR sind identisch mit den Literaturdaten (Paquette,
Encyclopedia of Reagents for Organic Synthesis, 1995, 3617-3622).646 g (2.29 mol) of trifluoroacetic anhydride and 36 g (0.24 mol) of trifluoroacetic acid are placed in a 1 liter round-necked flask. 206 g (2.29 mol) of dimethyl carbonate are added at room temperature with constant stirring and reflux cooling. The solution heats up to 50-60 ° C. within 10 minutes and is then stirred at this temperature for a further hour. The solution is then heated to 100-110 ° C. with an oil bath and stirred for a further 2 hours. After distillation, 733 g of methyl trifluoromethanesulfonate with a purity of over 99% are isolated.
Boiling range: 98-99 ° C, yield: 97.7%
19 F and 1 H NMR are identical to the literature data (Paquette, Encyclopedia of Reagents for Organic Synthesis, 1995, 3617-3622).
Zu dem Rückstand werden 731 g (2,59 mol) Trifluoressigsäureanhydrid
und 232 g (2,58 mol) Dimethylcarbonat gegeben und der oben
beschriebene Prozeß wiederholt. Es werden 837 g
Methyltrifluormethansulfonat mit einer Reinheit über 99% isoliert.
Ausbeute: 99,1%.731 g (2.59 mol) of trifluoroacetic anhydride and 232 g (2.58 mol) of dimethyl carbonate are added to the residue and the process described above is repeated. 837 g of methyl trifluoromethanesulfonate with a purity of over 99% are isolated.
Yield: 99.1%.
Der Prozeß kann mehrmals wiederholt werden. The process can be repeated several times.
In einem 10-ml-Rundhalskolben werden 5,74 g (15,0 mmol)
Pentafluorethansulfonsäureanhydrid und 0,31 g (1,55 mmol)
Pentafluorethansulfonsäure vorgelegt. Unter ständigem Rühren und
Rückflußkühlung werden 1,35 g (15,0 mmol) Dimethylcarbonat bei
Raumtemperatur zugegeben. Die Lösung wird eine Stunde bei einer
Temperatur von 60°C und anschließend bei 110°C 3 Stunden weiter
gerührt. Es werden nach einer Destillation 5,41 g
Methylpentafluorethansulfonat isoliert.
Siedebereich: 114-115°C, Ausbeute: 84,1%
NMR 19F, ppm: (Lösungsmittel: CDCl3; Standard: CCl3F)
-80,44 s (CF3);
-115,34 s (CF2)
NMR 1H, ppm: (Lösungsmittel: CDCl3; Standard: TMS)
4,23 s (CH3).5.74 g (15.0 mmol) of pentafluoroethanesulfonic anhydride and 0.31 g (1.55 mmol) of pentafluoroethanesulfonic acid are placed in a 10 ml round-necked flask. With constant stirring and reflux cooling, 1.35 g (15.0 mmol) of dimethyl carbonate are added at room temperature. The solution is stirred for one hour at a temperature of 60 ° C and then at 110 ° C for 3 hours. After distillation, 5.41 g of methyl pentafluoroethanesulfonate are isolated.
Boiling range: 114-115 ° C, yield: 84.1%
NMR 19 F, ppm: (solvent: CDCl 3 ; standard: CCl 3 F)
-80.44 s (CF 3 );
-115.34 s (CF 2 )
NMR 1 H, ppm: (solvent: CDCl 3 ; standard: TMS)
4.23 s (CH 3 ).
Das Spektrum wurde auf einem Bruker Spektrometer WP 80 SY erstellt.The spectrum was recorded on a Bruker WP 80 SY spectrometer created.
Bei Raumtemperatur wird eine Lösung aus 8,35 g (82,7 mmol)
Triethylamin in 150 cm3 Hexan vorgelegt. Unter ständigem Rühren
werden innerhalb von 10 min 13,56 g (82,7 mmol) Methyltriflat,
hergestellt wie in Beispiel 1, bei Raumtemperatur zugegeben. Die
Lösung erwärmt sich und wird eine halbe Stunde weiter gerührt. Dabei
wird die Lösung wieder auf Raumtemperatur gebracht. Ein weißer
Niederschlag wird abfiltriert und mit Hexan gewaschen. Das Hexan-
Filtrat kann für eine weitere Umsetzung genutzt werden. Nach der
Trocknung im Vakuum bei 60°C werden 21,81 g eines weißen
feinkristallinen Materials werden isoliert.
Ausbeute: 99,5%
NMR 19F, ppm: (Lösungsmittel: Acetonitril D3; Standard: CCl3F)
-78,04 s (CF3SO3 -)
NMR 1H, ppm: (Lösungsmittel: Acetonitril D3; Standard: TMS)
1,25 tm (3CH3);
2,86 s (CH3);
3,26 q (3CH2);
J3 H,H = 7,3 HzA solution of 8.35 g (82.7 mmol) of triethylamine in 150 cm 3 of hexane is initially introduced at room temperature. With constant stirring, 13.56 g (82.7 mmol) of methyl triflate, prepared as in Example 1, are added at room temperature within 10 min. The solution warms up and is further stirred for half an hour. The solution is brought back to room temperature. A white precipitate is filtered off and washed with hexane. The hexane filtrate can be used for a further reaction. After drying in vacuo at 60 ° C., 21.81 g of a white, finely crystalline material are isolated.
Yield: 99.5%
NMR 19 F, ppm: (solvent: acetonitrile D 3 ; standard: CCl 3 F)
-78.04 s (CF 3 SO 3 - )
NMR 1 H, ppm: (solvent: acetonitrile D 3 ; standard: TMS)
1.25 tm (3CH 3 );
2.86 s (CH 3 );
3.26 q (3CH 2 );
J 3 H, H = 7.3 Hz
Bei Raumtemperatur wird eine Lösung aus 8,05 g (68,2 mmol)
Triethylphosphin in 150 cm3 Hexan vorgelegt. Unter ständigem Rühren
werden innerhalb von 10 min 11,19 g (68,2 mmol) Methyltriflat,
hergestellt wie in Beispiel 1, bei Raumtemperatur zugegeben. Die
Lösung erwärmt sich und wird eine halbe Stunde weiter gerührt. Dabei
wird die Lösung wieder auf Raumtemperatur gebracht. Ein weißer
Niederschlag wird abfiltriert und mit Hexan gewaschen. Das Hexan-
Filtrat kann für eine weitere Umsetzung genutzt werden. Nach der
Trocknung im Vakuum bei 60°C werden 19,02 g eines weißen
feinkristallinen Materials isoliert.
Ausbeute: 98,9%
NMR 19F, ppm: (Lösungsmittel: Aceton D6; Standard: CCl3F)
-77,82 s (CF3SO3 -)
NMR 1H, ppm: (Lösungsmittel: Aceton D6; Standard: TMS)
1,30 dt (3CH3);
1,95d (CH3);
2,40 dq (3CH2);
J3 H,H = 7,7 Hz
J2 P,H = 13,7 Hz
J2 P,H = 13,8 Hz
J3 P,H = 18,8 Hz
A solution of 8.05 g (68.2 mmol) of triethylphosphine in 150 cm 3 of hexane is initially introduced at room temperature. With constant stirring, 11.19 g (68.2 mmol) of methyl triflate, prepared as in Example 1, are added at room temperature within 10 min. The solution warms up and is further stirred for half an hour. The solution is brought back to room temperature. A white precipitate is filtered off and washed with hexane. The hexane filtrate can be used for a further reaction. After drying in vacuo at 60 ° C., 19.02 g of a white, finely crystalline material are isolated.
Yield: 98.9%
NMR 19 F, ppm: (solvent: acetone D 6 ; standard: CCl 3 F)
-77.82 s (CF 3 SO 3 - )
NMR 1 H, ppm: (solvent: acetone D 6 ; standard: TMS)
1.30 dt (3CH 3 );
1.95d (CH 3 );
2.40 dq (3CH 2 );
J 3 H, H = 7.7 Hz
J 2 P, H = 13.7 Hz
J 2 P, H = 13.8 Hz
J 3 P, H = 18.8 Hz
Zu 6,67 g (81,2 mmol) 1-Methylimidazol werden in einem Rundkolben
unter Rühren und Eisbad-Kühlung 13,70 g (83,5 mmol) Methyltriflat
innerhalb von 10 Minuten zugetropft. Das Reaktionsgemisch erwärmt
sich und wird unter Rückflußkühlung 1 Stunde bei 70-75°C gerührt. Der
Überschuß an Methyltriflat wird im Vakuum bei 60°C entfernt. 20,00 g
eines weißen Pulvers werden isoliert.
NMR 19F, ppm: (Lösungsmittel: Acetonitril D3; Standard: CCl3F)
-78,14 s (CF3SO3 -)
NMR 1H, ppm: (Lösungsmittel: Acetonitril D3; Standard: TMS)
3,82 s (2CH3);
7,35d (2H);
8,53 t (1H);
J4 H;H = 1,6 Hz13.70 g (83.5 mmol) of methyl triflate are added dropwise to 6.67 g (81.2 mmol) of 1-methylimidazole in a round bottom flask with stirring and cooling in an ice bath over the course of 10 minutes. The reaction mixture heats up and is stirred under reflux for 1 hour at 70-75 ° C. The excess methyl triflate is removed in vacuo at 60 ° C. 20.00 g of a white powder are isolated.
NMR 19 F, ppm: (solvent: acetonitrile D 3 ; standard: CCl 3 F)
-78.14 s (CF 3 SO 3 - )
NMR 1 H, ppm: (solvent: acetonitrile D 3 ; standard: TMS)
3.82 s (2CH 3 );
7.35d (2H);
8.53 t (1H);
J 4 H; H = 1.6 Hz
Claims (9)
XR1R2R3,
wobei
X P oder N und
R1, R2, R3
unabhängig voneinander H, Alkyl, Alkylaryl oder Aryl bedeuten, und mindestens ein R ≠ H ist, umgesetzt wird.3. A process for the preparation of perfluoroalkanesulfonic acid residues according to claim 1, characterized in that the perfluoroalkanesulfonic acid alkyl ester with a compound according to the formula
XR 1 R 2 R 3 ,
in which
XP or N and
R 1 , R 2 , R 3
independently of one another denote H, alkyl, alkylaryl or aryl, and at least one R ≠ H is reacted.
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10126929A DE10126929A1 (en) | 2001-06-01 | 2001-06-01 | Production of compounds with perfluoroalkanesulfonic acid residues, used e.g. in electrolytes and batteries, involves reacting perfluoroalkanesulfonic anhydride with dialkyl carbonate in presence of perfluoroalkanesulfonic acid |
CA002449060A CA2449060A1 (en) | 2001-06-01 | 2002-05-04 | Process for the preparation of compounds containing perfluoroalkanesulfonic acid groups |
US10/478,969 US7084290B2 (en) | 2001-06-01 | 2002-05-04 | Method for producing perfluoroalkanesulfonic acid esters |
AT02776502T ATE439340T1 (en) | 2001-06-01 | 2002-05-04 | METHOD FOR PRODUCING PERFLUORALKANSULPHONIC ACID ESTERS |
DE50213765T DE50213765D1 (en) | 2001-06-01 | 2002-05-04 | PROCESS FOR PREPARING PERFLUOROAL KANSULFONIC ACID ESTERS |
EP02776502A EP1399417B1 (en) | 2001-06-01 | 2002-05-04 | Method for producing perfluoroalkanesulfonic acid esters |
PCT/EP2002/004917 WO2002098844A1 (en) | 2001-06-01 | 2002-05-04 | Method for producing perfluoroalkanesulfonic acid esters |
JP2003501834A JP4317918B2 (en) | 2001-06-01 | 2002-05-04 | Method for producing perfluoroalkanesulfonic acid ester |
AU2002344346A AU2002344346A1 (en) | 2001-06-01 | 2002-05-04 | Method for producing perfluoroalkanesulfonic acid esters |
EP09006446A EP2085378A1 (en) | 2001-06-01 | 2002-05-04 | Perfluor alkane sulphonic acid salts |
IN1656KO2003 IN2003KO01656A (en) | 2001-06-01 | 2003-12-22 | |
US11/443,278 US7585994B2 (en) | 2001-06-01 | 2006-05-31 | Process for the preparation of compounds containing perfluoroalkanesulfonic acid groups |
JP2009030513A JP4564092B2 (en) | 2001-06-01 | 2009-02-12 | Method for producing perfluoroalkanesulfonic acid ester |
US12/499,446 US20130316248A9 (en) | 2001-06-01 | 2009-07-08 | Process for the preparation of compounds containing perfluoroalkanesulfonic acid groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10126929A DE10126929A1 (en) | 2001-06-01 | 2001-06-01 | Production of compounds with perfluoroalkanesulfonic acid residues, used e.g. in electrolytes and batteries, involves reacting perfluoroalkanesulfonic anhydride with dialkyl carbonate in presence of perfluoroalkanesulfonic acid |
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Publication Number | Publication Date |
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DE10126929A1 true DE10126929A1 (en) | 2002-12-05 |
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DE10126929A Withdrawn DE10126929A1 (en) | 2001-06-01 | 2001-06-01 | Production of compounds with perfluoroalkanesulfonic acid residues, used e.g. in electrolytes and batteries, involves reacting perfluoroalkanesulfonic anhydride with dialkyl carbonate in presence of perfluoroalkanesulfonic acid |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2085378A1 (en) | 2001-06-01 | 2009-08-05 | Merck Patent GmbH | Perfluor alkane sulphonic acid salts |
CN114156535A (en) * | 2020-09-07 | 2022-03-08 | 比亚迪股份有限公司 | Electrolyte, lithium ion battery and power vehicle |
-
2001
- 2001-06-01 DE DE10126929A patent/DE10126929A1/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2085378A1 (en) | 2001-06-01 | 2009-08-05 | Merck Patent GmbH | Perfluor alkane sulphonic acid salts |
CN114156535A (en) * | 2020-09-07 | 2022-03-08 | 比亚迪股份有限公司 | Electrolyte, lithium ion battery and power vehicle |
CN114156535B (en) * | 2020-09-07 | 2023-09-05 | 比亚迪股份有限公司 | Electrolyte, lithium ion battery and power vehicle |
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