ES2523689B1 - IONIC LIQUIDS, PREPARATION PROCESS AND ITS USE AS ELECTROLYTES FOR ELECTROCHEMICAL DEVICES FOR ENERGY STORAGE - Google Patents
IONIC LIQUIDS, PREPARATION PROCESS AND ITS USE AS ELECTROLYTES FOR ELECTROCHEMICAL DEVICES FOR ENERGY STORAGE Download PDFInfo
- Publication number
- ES2523689B1 ES2523689B1 ES201330612A ES201330612A ES2523689B1 ES 2523689 B1 ES2523689 B1 ES 2523689B1 ES 201330612 A ES201330612 A ES 201330612A ES 201330612 A ES201330612 A ES 201330612A ES 2523689 B1 ES2523689 B1 ES 2523689B1
- Authority
- ES
- Spain
- Prior art keywords
- bis
- amide
- trifluoromethylsulfonyl
- ethyl
- thiazolium
- 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- Withdrawn - After Issue
Links
- 239000002608 ionic liquid Substances 0.000 title claims description 29
- 239000003792 electrolyte Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000004146 energy storage Methods 0.000 title description 2
- -1 2-methoxyethoxy Chemical group 0.000 claims description 35
- 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 claims description 25
- 150000001450 anions Chemical class 0.000 claims description 15
- 150000004820 halides Chemical class 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- JDPPQKZBYDQVQA-UHFFFAOYSA-N 5-[2-(2-methoxyethoxy)ethyl]-3,4-dimethyl-1,3-thiazol-3-ium Chemical compound COCCOCCc1sc[n+](C)c1C JDPPQKZBYDQVQA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012039 electrophile Substances 0.000 claims description 6
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000012983 electrochemical energy storage Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010934 O-alkylation reaction Methods 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- GXQLEZWFWSFMDK-UHFFFAOYSA-N 5-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3,4-dimethyl-1,3-thiazol-3-ium Chemical compound C[N+]1=CSC(=C1C)CCOCCOCCOC GXQLEZWFWSFMDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005649 metathesis reaction Methods 0.000 claims description 3
- 239000012038 nucleophile Substances 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- DVDGMAPTWHPYDE-UHFFFAOYSA-N FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOC)CCOCCOCCOC Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOC)CCOCCOCCOC DVDGMAPTWHPYDE-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- QYLCHMMKYAKPCV-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 5-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3-[2-(2-methoxyethoxy)ethyl]-4-methyl-1,3-thiazol-3-ium Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOCCOC)CCOCCOC QYLCHMMKYAKPCV-UHFFFAOYSA-N 0.000 claims description 2
- FKFXMURHYSYDSP-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 5-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]-3-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-4-methyl-1,3-thiazol-3-ium Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOCCOCCOC)CCOCCOCCOC FKFXMURHYSYDSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229910052696 pnictogen Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 1
- 150000001912 cyanamides Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005481 NMR spectroscopy Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- ZUTMHOFPJBCIIG-UHFFFAOYSA-N 5-(2-methoxyethyl)-4-methyl-1,3-thiazole Chemical compound COCCC=1SC=NC=1C ZUTMHOFPJBCIIG-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- WHCCVTZDQCOILU-UHFFFAOYSA-N 5-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-4-methyl-1,3-thiazole Chemical compound CC=1N=CSC=1CCOCCOCCOC WHCCVTZDQCOILU-UHFFFAOYSA-N 0.000 description 5
- BBSIJPAIZKJFCT-UHFFFAOYSA-N 5-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]-4-methyl-1,3-thiazole Chemical compound CC=1N=CSC=1CCOCCOCCOCCOC BBSIJPAIZKJFCT-UHFFFAOYSA-N 0.000 description 5
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 5
- SRBOBHWPXYDHBJ-UHFFFAOYSA-N 5-[2-(2-methoxyethoxy)ethyl]-4-methyl-1,3-thiazole Chemical compound CC=1N=CSC=1CCOCCOC SRBOBHWPXYDHBJ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZVBYUKOCPFDQLZ-UHFFFAOYSA-N 5-(2-hexoxyethyl)-4-methyl-1,3-thiazole Chemical compound CCCCCCOCCC=1SC=NC=1C ZVBYUKOCPFDQLZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- JNDSBRBUOKZGJM-UHFFFAOYSA-N FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C(CCCCC)OCCC1=C([N+](=CS1)C)C Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C(CCCCC)OCCC1=C([N+](=CS1)C)C JNDSBRBUOKZGJM-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DLGFZOSPWIUMKY-UHFFFAOYSA-N 1-[2-(2-iodoethoxy)ethoxy]-2-methoxyethane Chemical compound COCCOCCOCCI DLGFZOSPWIUMKY-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QPIIRKSLYVDXHT-UHFFFAOYSA-N 5-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]-3-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-4-methyl-1,3-thiazol-3-ium Chemical compound COCCOCCOCCOCCc1sc[n+](CCOCCOCCOC)c1C QPIIRKSLYVDXHT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HUXJXNSHCKHFIL-UHFFFAOYSA-N 1-(2-bromoethoxy)-2-methoxyethane Chemical compound COCCOCCBr HUXJXNSHCKHFIL-UHFFFAOYSA-N 0.000 description 1
- CJXAGOKSVZAZAI-UHFFFAOYSA-N 1-(2-iodoethoxy)-2-methoxyethane Chemical compound COCCOCCI CJXAGOKSVZAZAI-UHFFFAOYSA-N 0.000 description 1
- LCCCTXULXHJDLA-UHFFFAOYSA-N 1-[2-(2-bromoethoxy)ethoxy]-2-methoxyethane Chemical compound COCCOCCOCCBr LCCCTXULXHJDLA-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 1
- BKAWJIRCKVUVED-UHFFFAOYSA-N 5-(2-hydroxyethyl)-4-methylthiazole Chemical compound CC=1N=CSC=1CCO BKAWJIRCKVUVED-UHFFFAOYSA-N 0.000 description 1
- XYUPDUREFXWVED-UHFFFAOYSA-N 5-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3-[2-(2-methoxyethoxy)ethyl]-4-methyl-1,3-thiazol-3-ium Chemical compound CC=1[N+](=CSC=1CCOCCOCCOC)CCOCCOC XYUPDUREFXWVED-UHFFFAOYSA-N 0.000 description 1
- AHALYECKNGGHLP-UHFFFAOYSA-N CC1=C(SC(=[N+]1CCOCCOC)S(=O)(=O)C(F)(F)F)CCOCCOCCOC Chemical compound CC1=C(SC(=[N+]1CCOCCOC)S(=O)(=O)C(F)(F)F)CCOCCOCCOC AHALYECKNGGHLP-UHFFFAOYSA-N 0.000 description 1
- YMOPAMKBOVYKME-UHFFFAOYSA-N C[N+]1=CSC(=C1C)CCOCCOCCOC.FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F Chemical compound C[N+]1=CSC(=C1C)CCOCCOCCOC.FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F YMOPAMKBOVYKME-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical class NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RKMPRIGNYFSCPE-UHFFFAOYSA-N FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C(CCCCC)[N+]1=CSC(=C1C)CCOC Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C(CCCCC)[N+]1=CSC(=C1C)CCOC RKMPRIGNYFSCPE-UHFFFAOYSA-N 0.000 description 1
- JQXPPTXMYPYBKR-UHFFFAOYSA-N FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOCCOCCOC)CCOCCOC Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.CC=1[N+](=CSC1CCOCCOCCOCCOC)CCOCCOC JQXPPTXMYPYBKR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
- C07D277/24—Radicals substituted by oxygen atoms
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Description
DESCRIPCIÓNDESCRIPTION
Líquidos iónicos, procedimiento de preparación y su uso como electrolitos para dispositivos electroquímicos de almacenamiento de energía.Ionic liquids, preparation procedure and their use as electrolytes for electrochemical energy storage devices.
CAMPO DE LA INVENCIÓNFIELD OF THE INVENTION
La presente invención se refiere a la síntesis de nuevos líquidos iónicos, de carácter líquido o bien con una temperatura de fusión próxima a la temperatura ambiente, y su uso potencial como electrolito conductor iónico en dispositivos electroquímicos de almacenamiento de energía (baterías avanzadas de litio/ión litio, condensadores electroquímicos).The present invention relates to the synthesis of new ionic liquids, of a liquid nature or with a melting temperature close to room temperature, and their potential use as an ion-conducting electrolyte in electrochemical energy storage devices (advanced lithium batteries / lithium ion, electrochemical capacitors).
ESTADO DE LA TÉCNICASTATE OF THE ART
El esquema general de un dispositivo electroquímico consta de dos electrodos, de elevada conductividad electrónica, separados por un electrolito, que ha de poseer elevada conductividad iónica a la vez que ser aislante desde el punto de vista electrónico.The general scheme of an electrochemical device consists of two electrodes, of high electronic conductivity, separated by an electrolyte, which must have high ionic conductivity while being insulating from the electronic point of view.
Los electrolitos que se emplean en este tipo de dispositivos pueden presentar tanto carácter sólido (poliméricos o inorgánicos), como líquido (acuosos u orgánicos). Desde un punto de vista práctico el electrolito consta de una sal que puede ser tanto de carácter orgánico como inorgánico, disuelta en una matriz, que puede ser tanto líquida como sólida. El electrolito ha de poseer una elevada conductividad iónica, alta estabilidad electroquímica en el intervalo de potencial de trabajo del dispositivo, buena estabilidad térmica, compatibilidad con los electrodos (ha de dar lugar a la formación de interfases estables), ser económico y en la medida de lo posible respetuoso con el medio ambiente. Los electrolitos sólidos, ya sean de carácter polimérico o inorgánico presentan por lo general buena estabilidad electroquímica, si bien el valor de la conductividad es menor que la de un líquido como resultado de la menor movilidad iónica, lo que conduce a que los dispositivos comerciales actuales empleen por lo general electrolitos de tipo líquido, tanto acuoso como orgánico, si bien éstos últimos presentan problemas asociados a su carácter inflamable y en algunos casos altamente contaminante.The electrolytes used in this type of devices can have both solid character (polymeric or inorganic) and liquid (aqueous or organic). From a practical point of view the electrolyte consists of a salt that can be both organic and inorganic, dissolved in a matrix, which can be both liquid and solid. The electrolyte must have a high ionic conductivity, high electrochemical stability in the range of working potential of the device, good thermal stability, compatibility with the electrodes (must lead to the formation of stable interfaces), be economical and to the extent of the possible respectful with the environment. Solid electrolytes, whether polymeric or inorganic in nature, generally exhibit good electrochemical stability, although the conductivity value is lower than that of a liquid as a result of reduced ionic mobility, which leads to current commercial devices they generally use liquid-type electrolytes, both aqueous and organic, although the latter have problems associated with their flammable and in some cases highly polluting character.
Los electrolitos líquidos orgánicos, basados normalmente en carbonatos del tipo carbonato de etileno o propileno, dimetil carbonato, etc, y sus correspondientes mezclas presentan inconvenientes como su bajo punto de ebullición, alta inflamabilidad e inestabilidad electroquímica en las condiciones de trabajo (se degradan o descomponen en los electrodos, inhibiendo el paso de la corriente) y elevada toxicidad. Como sales normalmente se emplean derivados de litio del tipo hexafluorofosfato de litio (LiPF6), tetrafluoroborato de litio (LiBF4) o perclorato de litio (LiClO4), compuestos que experimentan procesos de degradación en presencia de trazas de agua para dar lugar a acido fluorhídrico (HF) o acido clorhídrico (HCl).Organic liquid electrolytes, normally based on carbonates of the ethylene or propylene carbonate type, dimethyl carbonate, etc., and their corresponding mixtures have drawbacks such as their low boiling point, high flammability and electrochemical instability in working conditions (they degrade or decompose on the electrodes, inhibiting the passage of current) and high toxicity. How do you normally come out lithium derivatives of the type lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4) or lithium perchlorate (LiClO4), compounds that undergo degradation processes in the presence of traces of water to produce hydrofluoric acid (HF) or hydrochloric acid (HCl).
Los líquidos iónicos (LIs) son sales, completamente disociadas, que poseen una temperatura de fusión inferior o próxima a la temperatura ambiente, si bien por convenio, entran en esta definición aquellos que presentan naturaleza líquida por debajo de 100oC. Constan de un catión, generalmente de naturaleza orgánica, y un anión de naturaleza orgánica o inorgánica. Debido a su naturaleza iónica, los LIs poseen una serie de propiedades de gran importancia práctica. De entre ellas, destacan: elevada conductividad, similar a las de los electrolitos comerciales actuales basados en carbonatos orgánicos, una presión de vapor prácticamente inexistente, nula inflamabilidad, amplia ventana electroquímica, elevada estabilidad térmica y un precio moderado. La combinación de estas propiedades les hace ser materiales atractivos a la hora de su empleo como electrolitos en dispositivos electroquímicos de almacenamiento de energía, con mejoras sustanciales en términos de seguridad.Ionic liquids (LIs) are salts, completely dissociated, that have a melting temperature below or close to room temperature, although by agreement, those that have a liquid nature below 100oC fall into this definition. They consist of a cation, usually of an organic nature, and an anion of an organic or inorganic nature. Due to their ionic nature, LIs possess a series of properties of great practical importance. Among them, they stand out: high conductivity, similar to those of the current commercial electrolytes based on organic carbonates, a vapor pressure practically nonexistent, no flammability, wide electrochemical window, high thermal stability and a moderate price. The combination of these properties makes them attractive materials when used as electrolytes in electrochemical energy storage devices, with substantial improvements in terms of safety.
Se han descrito aplicaciones de LIs como electrolitos en dispositivos electroquímicos (Acc. Chem. Res. 2007, 40, 1165-1173, WO 2012169909, WO 2012173694, US 2012107697). Un problema que presentan es su moderada a elevada viscosidad, que limita en alguna forma su empleo como electrolitos en dispositivos electroquímicos si tenemos en cuenta la relación inversa que existe entre viscosidad y conductividad iónica. En general, los LIs basados en aniones fluorados son los más idóneos para ser empleados como electrolitos, ya que presentan bajas viscosidades y, por consiguiente, elevadas conductividades. Existe pues la necesidad de encontrar LIs a temperatura ambiente con utilidad como electrolitos en dispositivos electroquímicos.Applications of LIs have been described as electrolytes in electrochemical devices (Acc.Chem. Res. 2007, 40, 1165-1173, WO 2012169909, WO 2012173694, US 2012107697). One problem they have is their moderate to high viscosity, which in some way limits their use as electrolytes in electrochemical devices if we take into account the inverse relationship between viscosity and ionic conductivity. In general, the LIs based on fluorinated anions are the most suitable to be used as electrolytes, since they present low viscosities and, consequently, high conductivities. There is therefore a need to find LIs at room temperature with utility as electrolytes in electrochemical devices.
Los LIs basados en sales de tiazolio fueron descritos por primera vez en 1999 (Tetrahedron Lett. 1999, 40, 1621-1622). Sin embargo, a diferencia de sus análogos basados en sales de imidazolio, este tipo de LIs han sido mucho menos estudiados. Se han descrito aplicaciones de LIs basados en sales de tiazolio como disolventes en procesos de separación de gases (Ind. Eng. Chem. Res. 2012, 51, 11530-11537), como catalizadores orgánicos (Electrochim. Acta 2010, 55, 3511-3517) y catalizadores termorregulados (Green Chem, 2010, 12, 1196 1200), pero su aplicación en dispositivos electroquímicos de generación y almacenamiento de energía no ha sido descrita. LIs based on thiazolium salts were described for the first time in 1999 (Tetrahedron Lett, 1999, 40, 1621-1622). However, unlike their analogues based on imidazolium salts, this type of LIs have been much less studied. Applications of LIs based on thiazolium salts as solvents in gas separation processes (Ind. Eng. Chem. Res. 2012, 51, 11530-11537), as organic catalysts have been described (Electrochim Acta 2010, 55, 3511- 3517) and thermoregulated catalysts (Green Chem, 2010, 12, 1196 1200), but its application in electrochemical energy generation and storage devices has not been described.
Una estrategia que permite la disminución de la viscosidad de los LIs, y por tanto el aumento de su conductividad, es la introducción de grupos éter en el catión presente en el LI (Chem. Soc. Rev. 2012, 41, 4030-4066). Un tipo de LIs a temperatura ambiente no descritos anteriormente está constituido por sales de tiazolio derivadas de 4-metil-5-tiazoetanol (sulfurol), donde cadenas de naturaleza alquílica o de tipo poliéter están unidas a la posición 3 del anillo de tiazol y al grupo hidroxilo. Una característica estructural de los líquidos iónicos objeto de la presente invención es la presencia de al menos un grupo éter en su estructura.A strategy that allows the decrease of the viscosity of the LIs, and therefore the increase of their conductivity, is the introduction of ether groups in the cation present in the LI (Chem. Soc. Rev. 2012, 41, 4030-4066) . One type of LIs at room temperature not described above is constituted by thiazolium salts derived from 4-methyl-5-thiazoethanol (sulfurol), where alkyl or polyether type chains are attached to position 3 of the thiazole ring and to the hydroxyl group. A structural characteristic of the ionic liquids object of the present invention is the presence of at least one ether group in its structure.
DESCRIPCIÓN DE LA INVENCIÓNDESCRIPTION OF THE INVENTION
La presente invención se refiere a la síntesis de líquidos iónicos a temperatura ambiente con un anillo de tiazolio en su estructura y su uso como electrolitos en dispositivos electroquímicos. La presente invención se refiere a un compuesto de formula general I y que tiene estructura de sal de tiazolio 3,4,5-trisustituido,The present invention relates to the synthesis of ionic liquids at room temperature with a thiazolium ring in its structure and its use as electrolytes in electrochemical devices. The present invention relates to a compound of general formula I and having a 3,4,5-trisubstituted thiazolium salt structure,
en la que los grupos R1 y R2 pueden ser de la misma o diferente naturaleza, seleccionados de entre los grupos:wherein the groups R1 and R2 may be of the same or different nature, selected from among the groups:
. alquilo (C1-C6). alkyl (C1-C6)
. cicloalquilo (C3-C6). cycloalkyl (C3-C6)
. -(CH2CH2O)nCH3, donde n es 1, 2 ó 3. - (CH2CH2O) nCH3, where n is 1, 2 or 3
X- es un anión, seleccionado entre los siguientes:X- is an anion, selected from the following:
. Bis(perfluoroalcanosulfonil)imidas (el término "amida” en vez de "imida” es a menudo empleado en la literatura científica). Esta clase incluye (CF3SO2)2N- y (C2F5SO2)2N-como ejemplos ilustrativos pero no limitantes.. Bis (perfluoroalkanesulfonyl) imides (the term "amide" instead of "imide" is often used in the scientific literature). This class includes (CF 3 SO 2 ) 2 N- and (C 2 F 5 SO 2 ) 2 N-as illustrative but not limiting examples.
BF4-haluros, haluros de alquilo o haluros de alquilo perhalogenados de elementos del grupo 15. Esta clase incluye PF^, SbF^, P(C2F5^F 3-, P(C2F5^ 2-, AsF^, P(C2^ ) 3F3-como ejemplos ilustrativos pero no limitantes.BF4-halides, alkyl halides or perhalogenated alkyl halides of group 15 elements. This class includes PF ^, SbF ^, P (C 2 F 5 ^ F 3 -, P (C 2 F 5 ^ 2 -, AsF ^ , P (C 2 ^) 3 F 3 - as illustrative but not limiting examples.
CxY2x+1SO3- donde x tiene un valor entre 1 y 6 e Y es un grupo F o H. Esta clase incluye CH3SO3" y CF3SO3" como ejemplos ilustrativos pero no limitantes.CxY2x + 1SO3- where x has a value between 1 and 6 and Y is a group F or H. This class includes CH3SO3 "and CF3SO3" as illustrative but not limiting examples.
CxF2x+1COO- donde x tiene un valor entre 1 y 6, incluyendo CF3COO".CxF2x + 1COO- where x has a value between 1 and 6, including CF3COO ".
Cianamidas y aniones con grupos ciano, incluyendo CN", (CN)2N" y (CN)3C", como ejemplos ilustrativos pero no limitantes. Cyanoamides and anions with cyano groups, including CN ", (CN) 2N" and (CN) 3C ", as illustrative but not limiting examples.
. SCN".. SCN ".
Según realizaciones particulares, el líquido iónico de la presente invención tiene una conductividad iónica comprendida entre 8.10"4 y 3.10"3 S.cm-1.According to particular embodiments, the ionic liquid of the present invention has an ionic conductivity comprised between 8.10 "4 and 3.10" 3 S.cm-1.
Según realizaciones particulares adicionales, el líquido iónico es estable en atmósfera inerte y en atmósfera oxidante hasta 300oC.According to additional particular embodiments, the ionic liquid is stable under an inert atmosphere and in an oxidizing atmosphere up to 300 ° C.
Según realizaciones particulares concretas, el líquido iónico se selecciona entre:According to particular embodiments, the ionic liquid is selected from:
-Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2,5,8,11-tetraoxatri-decan-13-il)tiazolio, - Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio, -Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio, -Bis(trifluorometilsulfonil)amiduro de 5-[2-(hexiloxi)etil]-3,4-dimetiltiazolio, -Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio,-Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- (2,5,8,11-tetraoxatri-decan-13-yl) thiazolium, - Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- { 2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium, 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium bis (trifluoromethylsulfonyl) amide, -Bis (trifluoromethylsulfonyl) amide 5- [2- (Hexyloxy) ethyl] -3,4-dimethylthiazolium, -Bis (trifluoromethylsulfonyl) 4-methyl-3- [2- (2-methoxyethoxy) ethyl] -5- {2- [2- ( 2-methoxyethoxy) ethoxy] ethyl} thiazolium,
-Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-(2,5,8,11-tetraoxatri decan-13-il)tiazolio,-Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- [2- (2-methoxyethoxy) ethyl] -5- (2,5,8,11-tetraoxatri decan-13-yl) thiazolium,
-Bis(trifluorometilsulfonil)amiduro de 4-metil-3-{2-[2-(2-metoxietoxi)etoxi]etil}-5-(2,5,8,11-tetraoxatri decan-13-il)tiazolio,-Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} -5- (2,5,8,11-tetraoxatri decan-13-yl) thiazolium,
-Bis(trifluorometilsulfonil)amiduro de 4-metil-5-[2-(2-metoxietoxi)etil]-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio,-Bis (trifluoromethylsulfonyl) 4-methyl-5- [2- (2-methoxyethoxy) ethyl] -3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium amide,
-Bis(trifluorometilsulfonil)amiduro de 4-metil-3,5-bis{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio, -Bis(trifluorometilsulfonil)amiduro de 3-hexil-4-metil-5-(2-metoxietil)tiazolio, -Bis(trifluorometilsulfonil)amiduro de 4-metil-5-(2-metoxietil)-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio,-Bis (trifluoromethylsulfonyl) amide of 4-methyl-3,5-bis {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium, -Bis (trifluoromethylsulfonyl) amide of 3-hexyl-4-methyl-5- (2-methoxyethyl) thiazolium, 4-methyl-5- (2-methoxyethyl) -3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium bis (trifluoromethylsulfonyl) amide,
yY
- Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2-metoxietil)tiazolio.- Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- (2-methoxyethyl) thiazolium.
La síntesis de los compuestos de fórmula general I de la presente invención se ha llevado a cabo por métodos habituales de síntesis orgánica, los cuales son conocidos por los expertos de la técnica.The synthesis of the compounds of general formula I of the present invention has been carried out by customary methods of organic synthesis, which are known to those skilled in the art.
La presente invención se refiere por lo tanto, también a un procedimiento de preparación de líquidos iónicos tal como se han definido anteriormente, que comprende las siguientes etapas: The present invention therefore also relates to a process for the preparation of ionic liquids as defined above, which comprises the following steps:
1) O-alquilación entre el grupo hidroxilo presente en 4-metil-5-tiazoetanol como nucleófilo y un haluro como electrófilo:1) O-alkylation between the hydroxyl group present in 4-methyl-5-thiazoethanol as a nucleophile and a halide as an electrophile:
2) alquilación del derivado O-protegido resultante de la anterior etapa con un haluro como electrófilo:2) alkylation of the O-protected derivative resulting from the previous step with a halide as an electrophile:
3) Metátesis del haluro con un anión.3) Methothesis of the halide with an anion.
Así, un ejemplo ilustrativo pero no limitante, de la ruta empleada en la síntesis de los compuestos del tipo I se muestra en el Esquema 1:Thus, an illustrative but not limiting example of the route used in the synthesis of compounds of type I is shown in Scheme 1:
Esquema 1Scheme 1
Donde R1 y R2 tienen los significados que se han indicado para la formula I.Where R1 and R2 have the meanings indicated for formula I.
La primera etapa consiste en una reacción de O-alquilación (síntesis de éteres de Williamson) entre el grupo hidroxilo presente en 4-metil-5-tiazoetanol, como nucleófilo, y un haluro de alquilo, haluro de cicloalquilo, haluro del etilenglicol monometileter, haluro de dietilenglicol monometileter o haluro de trietilenglicol monometileter como electrófilo en presencia de una base. Según un modo de realización particular, la base se selecciona entre NaH (hidruro sódico), tBuOK (terc-butóxido potásico), LDA (diisopropil amiduro de litio) o KOH (hidróxido potásico) en dimetilsulfoxido.The first stage consists of an O-alkylation reaction (synthesis of Williamson ethers) between the hydroxyl group present in 4-methyl-5-thiazoethanol, as a nucleophile, and an alkyl halide, cycloalkyl halide, ethylene glycol monomethylether halide, diethylene glycol monomethylether halide or triethylene glycol monomethylether halide as an electrophile in the presence of a base. According to a particular embodiment, the base is selected between NaH (sodium hydride), tBuOK (potassium tert-butoxide), LDA (lithium diisopropyl amide) or KOH (potassium hydroxide) in dimethylsulfoxide.
La segunda etapa consiste en la alquilación del derivado O-protegido resultante de la anterior etapa con un haluro de alquilo, haluro del etilenglicol monometileter, haluro de dietilenglicol monometileter o haluro de trietilenglicol monometileter como electrófilo. La tercera etapa es una metátesis del haluro con el anión apropiado. La tercera etapa puede llevarse a cabo tanto con un ácido como se muestra en (3b), como con una sal metálica como se muestra en (3a).The second step consists of the alkylation of the O-protected derivative resulting from the above step with an alkyl halide, ethylene glycol monomethylether halide, diethylene glycol monomethylether halide or triethylene glycol monomethylether halide as an electrophile. The third stage is a metathesis of the halide with the appropriate anion. The third stage can be carried out either with an acid as shown in (3b), or with a metal salt as shown in (3a).
Los haluros de alquilo y haluros de éteres monometílicos de etilenglicol, dietilenglicol y trietilenglicol usados en la síntesis de los compuestos de formula I son comerciales o se preparan por métodos habituales en síntesis orgánica a partir de los alcoholes correspondientes.The alkyl halides and monomethyl ether halides of ethylene glycol, diethylene glycol and triethylene glycol used in the synthesis of the compounds of formula I are commercially available or are prepared by customary methods in organic synthesis from the corresponding alcohols.
Los ácidos (HX) y las sales metálicas (MX) empleadas en la síntesis de los compuestos de formula I son comerciales o se preparan por métodos habituales en síntesis orgánica.The acids (HX) and the metal salts (MX) used in the synthesis of the compounds of formula I are commercial or are prepared by customary methods in organic synthesis.
Una característica esencial de los compuestos de la presente invención es la posibilidad que presentan los compuestos de coordinarse, a través de los oxígenos de las cadenas de oxietileno de los sustituyentes del anillo de tiazol con los iones litio, lo que proporcionará una contribución adicional al proceso de conducción iónica, lo que sumado a la buena estabilidad térmica y electroquímica y su carácter líquido en un amplio intervalo de temperaturas permitirá su empleo con éxito como electrolito conductor iónico en dispositivos de almacenamiento de energía.An essential characteristic of the compounds of the present invention is the possibility that the compounds have to coordinate, through the oxygens of the oxyethylene chains of the thiazole ring substituents with the lithium ions, which will provide an additional contribution to the process of ionic conduction, which added to the good thermal and electrochemical stability and its liquid character in a wide range of temperatures will allow its successful use as an electrically conductive ionic electrolyte in energy storage devices.
La presente invención se refiere también al uso de los líquidos iónicos definidos anteriormente como electrolitos para dispositivos electroquímicos de almacenamiento de energía. Según realizaciones particulares, estos electrolitos son estables en atmósfera inerte y en atmósfera oxidante hasta 300oC.The present invention also relates to the use of the ionic liquids defined above as electrolytes for electrochemical energy storage devices. According to particular embodiments, these electrolytes are stable in an inert atmosphere and in an oxidizing atmosphere up to 300 ° C.
BREVE DESCRIPCION DE LAS FIGURASBRIEF DESCRIPTION OF THE FIGURES
La figura 1 muestra la variación de la conductividad iónica del líquido iónico Bis(trifluorometilsulfonil)amiduro de 4-metil-3-{2-[2-(2-metoxietoxi)etoxi]etil}-5-(2,5,8,11-tetraoxatridecan-13-il)tiazolio Figure 1 shows the variation of the ionic conductivity of the ionic liquid Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} -5- (2,5,8, 11-tetraoxatridecan-13-yl) thiazolium
.La figura 2 muestra la estabilidad térmica (curvas termogravimétricas de descomposición), en atmósfera inerte y oxidante del líquido iónico Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio. Figure 2 shows the thermal stability (thermogravimetric decomposition curves), in an inert atmosphere and oxidant of the ionic liquid Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium.
MODO DE REALIZACIÓN DE LA INVENCIÓNMODE FOR CARRYING OUT THE INVENTION
Como ejemplos ilustrativos, aunque no limitantes, se indican los procedimientos experimentales y datos espectroscópicos de algunos líquidos iónicos a temperatura ambiente de fórmula I.Illustrative but not limiting examples are the experimental procedures and spectroscopic data of some ionic liquids at room temperature of formula I.
Los datos espectroscópicos se obtuvieron empleando los siguientes equipos:The spectroscopic data were obtained using the following equipment:
Resonancia Magnética NuclearNuclear magnetic resonance
Los espectros de resonancia magnética nuclear fueron realizados en un equipo Varian-INOVA-300. Los desplazamientos químicos se describen en partes por millón (5) y las constantes de acoplamiento (J) se indican en hertzios (Hz). Los espectros de 1H-RMN están referenciados respecto a la señal residual de protón del cloroformo deuterado (CDCl3) empleado como disolvente. Los espectros de 13C-RMN, desacoplados de protón en todos los casos, están referenciados respecto a la señal residual de carbono del cloroformo deuterado (CDCl3) empleado como disolvente. Si no se indica de otro modo, todos los espectros se registraron a temperatura ambiente.The nuclear magnetic resonance spectra were performed on a Varian-INOVA-300 device. The chemical shifts are described in parts per million (5) and the coupling constants (J) are indicated in hertz (Hz). The 1 H-NMR spectra are referenced to the residual proton signal of the deuterated chloroform (CDCl 3) used as the solvent. The 13 C-NMR spectra, which are uncoupled from the proton in all cases, are referenced with respect to the residual carbon signal of the deuterated chloroform (CDCl 3 ) used as solvent. If not stated otherwise, all spectra were recorded at room temperature.
InfrarrojoInfrared
Los espectros de infrarrojo (IR) se registraron en un espectrofotómetro modelo Perkin-Elmer-Spectrum One FT-IR. Las frecuencias del espectro se indican en cm-1.The infrared (IR) spectra were recorded on a Perkin-Elmer-Spectrum One FT-IR spectrophotometer. Spectrum frequencies are indicated in cm-1.
Espectros de masasMass spectra
Los espectros de masa exacta de los compuestos fueron obtenidos con un espectrómetro de masas modelo Agilent 6520-Accurate-Mass LC/MS Q-TOF.The exact mass spectra of the compounds were obtained with a mass spectrometer model Agilent 6520-Accurate-Mass LC / MS Q-TOF.
Ejemplo 1.Example 1.
4-Metil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazol (1).4-Methyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazole (1).
Sobre una disolución de NaH (dispersión al 60% en aceite mineral, 978 mg, 24.4 mmol) en DMF anhidra (50 ml) se añade lentamente 4-metil-5-tiazoletanol (1.0 g, 6.98 mmol) disuelto en DMF (15 ml) a temperatura ambiente. La mezcla se agitó durante 90 minutos tras los cuales se añadió gota a gota una disolución de 1-bromo-2-(2-metoxietoxi)etano (5.108 g, 27.92 mmol) en DMF anhidra (20 ml) a 0oC. La mezcla se agita toda la noche dejando que alcance la temperatura ambiente y a continuación se añade H2O (15 ml) gota a gota. Se elimina el disolvente a presión reducida y a continuación se añade H2O (50 ml) y se extrae con AcOEt (3 x 75 ml). Las fases orgánicas se juntan, se secan (MgSO4) y se filtran. Se elimina el disolvente a presión reducida y el residuo se purifica por cromatografía en columna, obteniéndose 4-Metil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazol (1) (1.42 g, 83%).To a solution of NaH (60% dispersion in mineral oil, 978 mg, 24.4 mmol) in anhydrous DMF (50 ml) is slowly added 4-methyl-5-thiazoletanol (1.0 g, 6.98 mmol) dissolved in DMF (15 ml) at room temperature. The mixture was stirred for 90 minutes after which a solution of 1-bromo-2- (2-methoxyethoxy) ethane (5.108 g, 27.92 mmol) in anhydrous DMF (20 ml) at 0 ° C was added dropwise. The mixture is stirred overnight allowing it to reach room temperature and then H2O (15 ml) is added dropwise. The solvent is removed under reduced pressure and then H 2 O (50 ml) is added and extracted with AcOEt (3 x 75 ml). The organic phases are combined, dried (MgSO 4) and filtered. The solvent is removed under reduced pressure and the residue is purified by column chromatography, obtaining 4-Methyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazole ( 1 ) (1.42 g, 83%). .
1H NMR (300 MHz, CDCl3) 58.56 (s, 1H), 3.68-3.60 (m, 8H), 3.54 (m, 2H), 3.37 (s, 3H), 3.02 (t, 2H, J = 6.7 Hz), 2.39 (s, 3H). 1 H NMR (300 MHz, CDCl 3) 58.56 (s, 1 H), 3.68-3.60 (m, 8 H), 3.54 (m, 2 H), 3.37 (s, 3 H), 3.02 (t, 2 H, J = 6.7 Hz), 2.39 (s, 3H).
13C NMR (75 MHz, CDCl3) 5 149.7, 149.3, 128.1, 72.1, 71.3, 70.7 (2C), 70.6, 59.2, 27.1, 15.0. 13 C NMR (75 MHz, CDCl 3) 5 149.7, 149.3, 128.1, 72.1, 71.3, 70.7 (2C), 70.6, 59.2, 27.1, 15.0.
HRMS-ESI (m/z): Calculado para C11H20NO3S [M+H]+: 246.1157, encontrado: 246.1158 FTIR (entre cristales) vmax: 2872, 1543, 1452, 1415, 1351, 1243, 1199, 1110, 846 cm-1. HRMS-ESI (m / z): Calculated for C11H20NO3S [M + H] +: 246.1157, found: 246.1158 FTIR (between crystals) v max: 2872, 1543, 1452, 1415, 1351, 1243, 1199, 1110, 846 cm -one.
Ejemplo 2.Example 2
4-Metil-5-[2-(2-metoxietoxi)etil]tiazol (2).4-Methyl-5- [2- (2-methoxyethoxy) ethyl] thiazole (2).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 1 utilizando 882 mg de NaH (22.05 mmol) en dispersión al 60% en aceite mineral, 4-metil-5-tiazoletanol (900 mg, 6.10 mmol) y 1-bromo-2-metoxietano (3.5 g, 25.2 mmol). La purificación del crudo de reacción mediante cromatografía en columna, permite obtener 4-Metil-5-[2-(2-metoxietoxi)etil]tiazol (2) (949 mg, 75%).It is prepared according to the procedure described in Example 1 using 882 mg of NaH (22.05 mmol) in 60% dispersion in mineral oil, 4-methyl-5-thiazoletanol (900 mg, 6.10 mmol) and 1-bromo-2. -methoxyethane (3.5 g, 25.2 mmol). Purification of the reaction crude by column chromatography affords 4-Methyl-5- [2- (2-methoxyethoxy) ethyl] thiazole ( 2 ) (949 mg, 75%).
1H NMR (300 MHz, CDCU) 58.56 (s, 1H), 3.67-3.59 (m, 4H), 3.55 (m, 2H), 3.38 (s, 3H), 3.04 (t, 2H, J = 6.7 Hz), 2.40 (s, 3H). 1 H NMR (300 MHz, CDC U ) 58.56 (s, 1H), 3.67-3.59 (m, 4H), 3.55 (m, 2H), 3.38 (s, 3H), 3.04 (t, 2H, J = 6.7 Hz ), 2.40 (s, 3H).
13C NMR (75 MHz, CDCl3) 5149.9, 149.4, 128.0, 72.1, 71.4, 70.5, 59.3, 27.1, 15.1. 13 C NMR (75 MHz, CDCl 3 ) 5149.9, 149.4, 128.0, 72.1, 71.4, 70.5, 59.3, 27.1, 15.1.
FTIR (entre cristales) v max: 2922, 2873, 1677, 1542, 1452, 1415, 1378, 1356, 1242, 1198, 1116, 848 cm-1. FTIR (between crystals) v max : 2922, 2873, 1677, 1542, 1452, 1415, 1378, 1356, 1242, 1198, 1116, 848 cm-1.
Ejemplo 3.Example 3
4-Metil-5-(2,5,8,11-tetraoxatridecan-13-il)tiazol (3).4-Methyl-5- (2,5,8,11-tetraoxatridecan-13-yl) thiazole (3).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 1 utilizando 980 mg de NaH (24.4 mmol) en dispersión al 60% en aceite mineral, 4-metil-5-tiazoletanol (1.0 g, 6.98 mmol) y 1-bromo-2-[2-(2-metoxietoxi)etoxi]etano (6.31 g, 27.92 mmol). La purificación del crudo de reacción mediante cromatografía en columna, permite obtener 4-Metil-5-(2,5,8,11-tetraoxatridecan-13-il)tiazol (3) (1.57g, 78%).It is prepared according to the procedure described in Example 1 using 980 mg of NaH (24.4 mmol) in 60% dispersion in mineral oil, 4-methyl-5-thiazoletanol (1.0 g, 6.98 mmol) and 1-bromo-2 - [2- (2-methoxyethoxy) ethoxy] ethane (6.31 g, 27.92 mmol). Purification of the reaction crude by column chromatography allows to obtain 4-Methyl-5- (2,5,8,11-tetraoxatridecan-13-yl) thiazole ( 3 ) (1.57g, 78%).
1H NMR (300 MHz, CDCl3) 1 H NMR (300 MHz, CDCl 3 )
5 8.56 (s, 1H), 3.67-3.59 (m, 12H), 3.36 (s, 3H), 3.02 (t, 3H, J = 6.7 Hz), 2.39 (s, 3H).5 8.56 (s, 1H), 3.67-3.59 (m, 12H), 3.36 (s, 3H), 3.02 (t, 3H, J = 6.7 Hz), 2.39 (s, 3H).
HRMS-ESI (m/z): calcd for C13H14NO4S [M+H]+: 290.1434, found: 290.1434 HRMS-ESI (m / z): calcd for C13H14NO4S [M + H] +: 290.1434, found: 290.1434
FTIR (entre cristales) Vmax: 2871, 1543, 1453, 1415, 1377, 1350, 1244, 1199, 1114, 846 cm-1 FTIR (between crystals) Vmax : 2871, 1543, 1453, 1415, 1377, 1350, 1244, 1199, 1114, 846 cm-1
Ejemplo 4.Example 4
5-[2-(hexiloxi)etil]-4-metiltiazol (4).5- [2- (Hexyloxy) ethyl] -4-methylthiazole (4).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 1 utilizando 980 mg de NaH (24.4 mmol) en dispersión al 60% en aceite mineral, 4-metil-5-tiazoletanol (1.0 g, 6.98 mmol) y 1-bromohexano (4.58 g, 27.9 mmol). La purificación del crudo de reacción mediante cromatografía en columna, permite obtener 5-(2-(hexiloxi)etil)-4-metiltiazol (4) (1.39 g, 88%).It is prepared according to the procedure described in Example 1 using 980 mg of NaH (24.4 mmol) in 60% dispersion in mineral oil, 4-methyl-5-thiazoletanol (1.0 g, 6.98 mmol) and 1-bromohexane (4.58). g, 27.9 mmol). Purification of the reaction crude by column chromatography affords 5- (2- (hexyloxy) ethyl) -4-methylthiazole ( 4 ) (1.39 g, 88%).
1H NMR (300 MHz, CDCl3) 58.54 (s, 1H), 3.56 (t, 2H, J = 6.6 Hz), 3.41 (t, 2H, J = 6.6 Hz), 2.98 (t, 2H, J = 6.6 Hz), 2.38 (s, 3H), 1.54 (m, 2H), 1.36-1.21 (m, 6H), 0.86 (t, 3H, J = 6.8 Hz). 1 H NMR (300 MHz, CDCl 3 ) 58.54 (s, 1H), 3.56 (t, 2H, J = 6.6 Hz), 3.41 (t, 2H, J = 6.6 Hz), 2.98 (t, 2H, J = 6.6 Hz), 2.38 (s, 3H), 1.54 (m, 2H), 1.36-1.21 (m, 6H), 0.86 (t, 3H, J = 6.8 Hz).
5 HRMS-ESI (m/z): calc. para C12H22NOS [M+H]+: 228.1417, real: 228.14335 HRMS-ESI (m / z): calc. for C12H22NOS [M + H] +: 228.1417, actual: 228.1433
FTIR (entre cristales) Vmax: 29554, 2930, 2858, 1542, 1466, 1416, 1376, 1115, 913, 856, 842, 787 cm-1. FTIR (between crystals) Vmax : 29554, 2930, 2858, 1542, 1466, 1416, 1376, 1115, 913, 856, 842, 787 cm-1.
Ejemplo 5.Example 5
4-Metil-5-(2-metoxietil)tiazol (5).4-Methyl-5- (2-methoxyethyl) thiazole (5).
Este compuesto se preparó siguiendo el procedimiento descrito para el mismo (J. Med. Chem. 2005, 48, 3639-3643). Los datos espectroscópicos y analíticos, concuerdan con los descritos para este compuesto. This compound was prepared following the procedure described therefor (J. Med. Chem. 2005, 48, 3639-3643). The spectroscopic and analytical data agree with those described for this compound.
Ejemplo 6.Example 6
Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2,5,8,11-tetraoxatri-decan-13-il)tiazolio (6).Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- (2,5,8,11-tetraoxatri-decan-13-yl) thiazolium (6).
En un tubo sellado, sobre una disolución de 4-Metil-5-(2,5,8,11-tetraoxatridecan-13-il)tiazol (3) (1.35 g, 4.67 mmol) en acetonitrilo anhidro (10 ml) se añade MeI (0.88 ml, 14.1 mmol) y la mezcla se calienta a 100oC durante 5 horas. Una vez alcanzada la temperatura ambiente se elimina el disolvente a presión reducida. Sobre el residuo se añade una mezcla metanol/agua (1:1, 20 ml) y a continuación bistrifluorometanosulfonimida de litio (1.54 g, 5.37 mmol). La mezcla se agita vigorosamente durante 3 horas, tras las cuales se elimina el metanol a presión reducida y posteriormente la fase acuosa se extrae con CH2Cl2 (2 x 20 ml). La fase orgánica se concentra y el residuo se purifica mediante cromatografía en columna (gel de sílice), obteniéndose Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2,5,8,11-tetraoxatri-decan-13-il)tiazolio (6) (2.43 g, 89%).In a sealed tube, on a solution of 4-Methyl-5- (2,5,8,11-tetraoxatridecan-13-yl) thiazole ( 3 ) (1.35 g, 4.67 mmol) in anhydrous acetonitrile (10 ml) is added Me (0.88 ml, 14.1 mmol) and the mixture is heated at 100 ° C for 5 hours. Once the room temperature is reached, the solvent is removed under reduced pressure. A methanol / water mixture (1: 1, 20 ml) and then lithium bistrifluoromethanesulfonimide (1.54 g, 5.37 mmol) are added to the residue. The mixture is stirred vigorously for 3 hours, after which the methanol is removed under reduced pressure and subsequently the aqueous phase is extracted with CH2Cl2 (2 x 20 ml). The organic phase is concentrated and the residue is purified by column chromatography (silica gel), obtaining Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- (2,5,8,11-tetraoxatri-decan-13- il) thiazolium ( 6 ) (2.43 g, 89%).
1H NMR (300 MHz, CDCl3) 59.59 (s, 1H), 4.08 (s, 3H), 3.72 (t, 2H, J = 5.5 Hz), 3.64 (m, 10H), 3.55 (m, 2H), 3.36 (s, 3H), 3.08 (t, 2H, J = 5.4 Hz), 2.47 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.59 (s, 1H), 4.08 (s, 3H), 3.72 (t, 2H, J = 5.5 Hz), 3.64 (m, 10H), 3.55 (m, 2H), 3.36 (s, 3H), 3.08 (t, 2H, J = 5.4 Hz), 2.47 (s, 3H).
13C NMR (75 MHz, CDCl3) 5 156.0, 141.9, 136.0, 119.9 (q, J = 321 Hz), 71.9, 70.7, 70.5 (3C), 70.2, 68.5, 58.9, 40.8, 27.8, 11.8. 13 C NMR (75 MHz, CDCl 3 ) 5 156.0, 141.9, 136.0, 119.9 (q, J = 321 Hz), 71.9, 70.7, 70.5 (3C), 70.2, 68.5, 58.9, 40.8, 27.8, 11.8.
HRMS-ESI (m/z): Calculado para C14H26NO4S [M]+: 304.1577, encontrado: 304.1563 FTIR (entre cristales) Vmax: 3098, 2879, 1595, 1454, 1352, 1191, 1136, 1058, 788, 740, 653, 617570, 514 cm'1. HRMS-ESI (m / z): Calculated for C14H26NO4S [M] +: 304.1577, found: 304.1563 FTIR (between crystals) Vmax : 3098, 2879, 1595, 1454, 1352, 1191, 1136, 1058, 788, 740, 653 , 617570, 514 cm'1.
Ejemplo 7.Example 7
Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (7).Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium (7).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 6, utilizando 4-Metil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazol (1) (1.0 g, 4.08 mmol), MeI (0.75 ml, 12.24 mmol) y bistrifluorometanosulfonimida de litio (1.34 g, 4.69 mmol) para dar lugar a bis(trifluorometilsulfonil)amiduro de Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (7) (2.02 g, 92%).It is prepared according to the procedure described in Example 6, using 4-Methyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazole ( 1 ) (1.0 g, 4.08 mmol), MeI (0.75 g). ml, 12.24 mmol) and lithium bistrifluoromethanesulfonimide (1.34 g, 4.69 mmol) to give bis (trifluoromethylsulfonyl) bis (3,4-dimethyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium bis (trifluoromethylsulfonyl) amide ( 7 ) (2.02 g, 92%).
1H NMR (300 MHz, CDCI3) 59.54 (s, 1H), 4.10 (s, 3H), 3.73 (t, 2H, J = 5.5 Hz), 3.68-3.61 (m, 6H), 3.54 (m, 2H), 3.37 (s, 3H), 3.09 (t, 2H, J = 5.4 Hz), 2.47 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.54 (s, 1H), 4.10 (s, 3H), 3.73 (t, 2H, J = 5.5 Hz), 3.68-3.61 (m, 6H), 3.54 (m, 2H ), 3.37 (s, 3H), 3.09 (t, 2H, J = 5.4 Hz), 2.47 (s, 3H).
13C NMR (75 MHz, CDCI3) 5 155.8, 142.0, 136.0, 119.9 (q, J = 321 Hz), 72.0, 70.6, 70.5, 70.4, 68.6, 59.1,40.8, 27.8, 11.8 13 C NMR (75 MHz, CDCI 3 ) 5 155.8, 142.0, 136.0, 119.9 (q, J = 321 Hz), 72.0, 70.6, 70.5, 70.4, 68.6, 59.1,40.8, 27.8, 11.8
HRMS-ESI (m/z): Calculado para C12H22NO3S [M]+: 260.1315, encontrado: 260.1295 FTIR (entre cristales) Vmax: 3099, 2881, 1595, 1455, 1351, 1191, 1135, 1056, 924, 852, 788, 740, 653, 617, 570, 514 cm-1. HRMS-ESI (m / z): Calculated for C12H22NO3S [M] +: 260.1315, found: 260.1295 FTIR (between crystals) Vmax : 3099, 2881, 1595, 1455, 1351, 1191, 1135, 1056, 924, 852, 788 , 740, 653, 617, 570, 514 cm-1.
Ejemplo 8.Example 8
Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio (8).Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium (8).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 6, utilizando 4-Metil-5-[2-(2-metoxietoxi)etil]tiazol (2) (1.0 g, 4.97 mmol), MeI (0.93 ml, 14.92 mmol) y bistrifluorometanosulfonimida de litio (1.63 g, 5.71 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio (8). (2.21 g, 90%).It is prepared according to the procedure described in Example 6, using 4-Methyl-5- [2- (2-methoxyethoxy) ethyl] thiazole ( 2 ) (1.0 g, 4.97 mmol), MeI (0.93 mL, 14.92 mmol) and lithium bistrifluoromethanesulfonimide (1.63 g, 5.71 mmol) to give Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium ( 8 ). (2.21 g, 90%).
1H NMR (300 MHz, CDCU) 59.57 (s, 1H), 4.10 (s, 3H), 3.73 (t, 2H, J = 5.5 Hz), 3.65 (m, 2H), 3.56 (m, 2H), 3.38 (s, 3H), 3.11 (t, 2H, J = 5.5 Hz), 2.47 (s, 3H).1 H NMR (300 MHz, CDC U ) 59.57 (s, 1H), 4.10 (s, 3H), 3.73 (t, 2H, J = 5.5 Hz), 3.65 (m, 2H), 3.56 (m, 2H), 3.38 (s, 3H), 3.11 (t, 2H, J = 5.5 Hz), 2.47 (s, 3H).
13C NMR (75 MHz, CDCU) 5 155.8, 142.0, 135.9, 119.9 (q, J = 321 Hz), 71.8, 79.6, 68.7, 59.1, 40.8, 27.8, 11.9.13 C NMR (75 MHz, CDC U ) 5 155.8, 142.0, 135.9, 119.9 (q, J = 321 Hz), 71.8, 79.6, 68.7, 59.1, 40.8, 27.8, 11.9.
HRMS-ESI (m/z): Calculado para C10H18NO2S [M]+: 216.1053, encontrado: 216.1067 FTIR (entre cristales) vmax: 3102, 1930, 1882, 1595, 1486, 1453, 1352, 1199, 1137, 1057, 789, 740, 654, 617, 571, 514 cm'1. HRMS-ESI (m / z): Calculated for C10H18NO2S [M] +: 216.1053, found: 216.1067 FTIR (between crystals) vmax : 3102, 1930, 1882, 1595, 1486, 1453, 1352, 1199, 1137, 1057, 789 , 740, 654, 617, 571, 514 cm'1.
Ejemplo 9.Example 9
Bis(trifluorometilsulfonil)amiduro de 5-[2-(hexiloxi)etil]-3,4-dimetiltiazolio (9).5- (2- (Hexyloxy) ethyl] -3,4-dimethylthiazolium bis (trifluoromethylsulfonyl) amide (9).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 6, utilizando 5-[2-(hexiloxi)etil]-4-metiltiazol (4), MeI (0.82 ml, 13.20 mmol) y bistrifluorometanosulfonimida de litio (1.44 g, 5.06 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 5-[2-(hexiloxi)etil]-3,4-dimetiltiazolio (9) (1.93 g, 84%).It is prepared according to the procedure described in Example 6, using 5- [2- (hexyloxy) ethyl] -4-methylthiazole ( 4 ), MeI (0.82 ml, 13.20 mmol) and lithium bistrifluoromethanesulfonimide (1.44 g, 5.06 mmol). ) to give 5- [2- (hexyloxy) ethyl] -3,4-dimethylthiazolium bis (trifluoromethylsulfonyl) amide (9) (1.93 g, 84%).
1H NMR (300 MHz, CDCl3) 59.56 (s, 1H), 4.10 (s, 3H), 3.65 (t, 2H, J = 5.5 Hz), 3.47 (t, 2H, J = 6.7 Hz), 3.08 (t, 2H, J = 5.4 Hz), 2.47 (s, 3H), 1.59 (m, 2H), 1.39-1.24 (m, 6H), 0.88 (t, 3H, J = 5.7 Hz). 1 H NMR (300 MHz, CDCl 3 ) 59.56 (s, 1H), 4.10 (s, 3H), 3.65 (t, 2H, J = 5.5 Hz), 3.47 (t, 2H, J = 6.7 Hz), 3.08 ( t, 2H, J = 5.4 Hz), 2.47 (s, 3H), 1.59 (m, 2H), 1.39-1.24 (m, 6H), 0.88 (t, 3H, J = 5.7 Hz).
13C NMR (75 MHz, CDCl3) 5 155.8, 141.9, 136.0, 119.9 (q, J = 321 Hz), 71.7, 68.1, 40.8, 31.7, 29.6, 27.9, 25.9, 22.7, 14.1, 11.8. 13 C NMR (75 MHz, CDCl 3 ) 5 155.8, 141.9, 136.0, 119.9 (q, J = 321 Hz), 71.7, 68.1, 40.8, 31.7, 29.6, 27.9, 25.9, 22.7, 14.1, 11.8.
5 HRMS-ESI (m/z): Calculado para C13H24NOS [M]+: 242.1573, encontrado: 242.1569 FTIR (entre cristales) Vmax: 3550, 3106, 2958, 2935, 2864, 1636, 1595, 1487, 1469, 1455, 1350, 1199, 1137, 1061, 793, 742, 655, 618, 573, 515 cm-1. HRMS-ESI (m / z): Calculated for C13H24NOS [M] +: 242.1573, found: 242.1569 FTIR (between crystals) Vmax : 3550, 3106, 2958, 2935, 2864, 1636, 1595, 1487, 1469, 1455, 1350, 1199, 1137, 1061, 793, 742, 655, 618, 573, 515 cm-1.
Ejemplo 10.Example 10
Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (10).4-Methyl-3- [2- (2-methoxyethoxy) ethyl] -5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium bis (trifluoromethylsulfonyl) amide (10).
En un tubo sellado, sobre una disolucion de 4-Metil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazol (1) (1.0 g, 4.08 mmol) en acetonitrilo anhidro (10 ml) se añade 1-yodo-2-(2-metoxietoxi)etano (1.31 g, 5.7 mmol) y la mezcla se calienta a 120oC durante 72 horas. Transcurrido ese tiempo se elimina el disolvente a presión reducida y sobre el residuo se añade una mezcla metanol/agua (1:1, 20 ml) y a continuación bistrifluorometanosulfonimida de litio (1.34 g, 4.69 mmol). La mezcla se agita vigorosamente durante 3 horas, tras las cuales se elimina el metanol a presión reducida y posteriormente la fase acuosa se extrae con CH2Cl2 (2 x 20 ml). La fase orgánica se concentra y el residuo se purifica mediante cromatografía en columna (gel de sílice), obteniéndose Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (10) (2.07 g, 81%).In a sealed tube, over a solution of 4-Methyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazole ( 1 ) (1.0 g, 4.08 mmol) in anhydrous acetonitrile (10 ml) is added 1-iodo-2- (2-methoxyethoxy) ethane (1.31 g, 5.7 mmol) and the mixture is heated at 120 ° C for 72 hours. After that time, the solvent was removed under reduced pressure and a mixture of methanol / water (1: 1, 20 ml) and then lithium bistrifluoromethanesulfonimide (1.34 g, 4.69 mmol) was added to the residue. The mixture is stirred vigorously for 3 hours, after which the methanol is removed under reduced pressure and subsequently the aqueous phase is extracted with CH2Cl2 (2 x 20 ml). The organic phase is concentrated and the residue is purified by column chromatography (silica gel) to obtain Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- [2- (2-methoxyethoxy) ethyl] -5- {2- [ 2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium ( 10 ) (2.07 g, 81%).
1H NMR (300 MHz, CDCU) 59.65 (s, 1H), 4.57 (t, J = 4.5 Hz, 2H), 3.94 (t, J = 4.5 Hz, 2H), 3.74 (t, J = 5.4 Hz, 2H), 3.69-3.58 (m, 8H), 3.55 (m, 2H), 3.48 (m, 2H), 3.37 (s, 3H), 3.32 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H), 2.50 (s, 3H). 1 H NMR (300 MHz, CDC U ) 59.65 (s, 1 H), 4.57 (t, J = 4.5 Hz, 2 H), 3.94 (t, J = 4.5 Hz, 2 H), 3.74 (t, J = 5.4 Hz, 2 H ), 3.69-3.58 (m, 8H), 3.55 (m, 2H), 3.48 (m, 2H), 3.37 (s, 3H), 3.32 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H) 2.50 (s, 3H).
13C NMR (75 MHz, CDCU) 5 155.8, 141.9, 135.1, 119.8 (q, CF3, J = 321 Hz), 71.9, 71.4, 70.42, 70.38, 70.30, 70.26, 68.5, 67.8, 58.9, 58.8, 53.1,27.7, 12.0. 13C NMR (75 MHz, CDC U ) 5 155.8, 141.9, 135.1, 119.8 (q, CF3, J = 321 Hz), 71.9, 71.4, 70.42, 70.38, 70.30, 70.26, 68.5, 67.8, 58.9, 58.8, 53.1, 27.7, 12.0.
HRMS-ESI (m/z): Calculado para C16H30NO5S [M]+: 348.1839, encontrado: 348.1853. HRMS-ESI (m / z): Calculated for C 16 H 30 NO 5 S [M] +: 348.1839, found: 348.1853.
FTIR (entre cristales) vmax: 3513, 3099, 2882, 1650, 1594, 1455, 1352, 1227, 1194, 1137, 1058, 924, 850, 789, 762, 740 cm'1. FTIR (between crystals) vmax : 3513, 3099, 2882, 1650, 1594, 1455, 1352, 1227, 1194, 1137, 1058, 924, 850, 789, 762, 740 cm'1.
Ejemplo 11.Example 11
Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-(2,5,8,11-tetraoxatridecan-13-il)tiazolio (11).4-Methyl-3- [2- (2-methoxyethoxy) ethyl] -5- (2,5,8,11-tetraoxatridecan-13-yl) thiazolium bis (trifluoromethylsulfonyl) amide (11).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-(2,5,8,11-tetraoxatridecan-13-il)tiazol (3) (1.0 g, 3.46 mmol), 1-yodo-2-(2-metoxietoxi)etano (1.11 g, 4.83 mmol) y bistrifluorometanosulfonimida de litio (883 mg, 3.98 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 4-metil-3-[2-(2-metoxietoxi)etil]-5-(2,5,8,11-tetraoxatridecan-13-il)tiazolio (11) (1.86 g, 80%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- (2,5,8,11-tetraoxatridecan-13-yl) thiazole ( 3 ) (1.0 g, 3.46 mmol), 1-iodine -2- (2-methoxyethoxy) ethane (1.11 g, 4.83 mmol) and lithium bistrifluoromethanesulfonimide (883 mg, 3.98 mmol) to give bis (trifluoromethylsulfonyl) 4-methyl-3- [2- (2-methoxyethoxy) amide ) ethyl] -5- (2,5,8,11-tetraoxatridecan-13-yl) thiazolium ( 11 ) (1.86 g, 80%).
1H NMR (300 MHz, CDCl3) 59.69 (s, 1H), 4.57 (t, J = 4.5 Hz, 2H), 3.94 (t, J = 4.5 Hz, 2H), 3.74 (t, J = 5.4 Hz, 2H), 3.69-3.58 (m, 10H), 3.55 (m, 2H), 3.48 (m, 2H), 3.36 (s, 3H), 3.32 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H), 2.50 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.69 (s, 1H), 4.57 (t, J = 4.5 Hz, 2H), 3.94 (t, J = 4.5 Hz, 2H), 3.74 (t, J = 5.4 Hz, 2H), 3.69-3.58 (m, 10H), 3.55 (m, 2H), 3.48 (m, 2H), 3.36 (s, 3H), 3.32 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H ), 2.50 (s, 3H).
13C NMR (75 MHz, CDCU) 5 156.0, 141.8, 135.1, 119.8 (q, CF3, J = 321 Hz), 71.8, 71.5, 70.6, 70.4 (3C), 70.3, 70.2, 68.4, 67.8, 58.8 (2C), 53.1, 27.7, 12.0. 13 C NMR (75 MHz, CDC U ) 5 156.0, 141.8, 135.1, 119.8 (q, CF3, J = 321 Hz), 71.8, 71.5, 70.6, 70.4 (3C), 70.3, 70.2, 68.4, 67.8, 58.8 ( 2C), 53.1, 27.7, 12.0.
HRMS-ESI (m/z): Calculado para C18H34NO6S [M]+: 392.2101, encontrado: 392.2105. HRMS-ESI (m / z): Calculated for C18H34NO6S [M] +: 392.2101, found: 392.2105.
FTIR (entre cristales) v max: 3468, 3097, 2880, 1592, 1455, 1353, 1333, 1227, 1194, 1136, 1058, 927, 850, 788, 739 cm’1. FTIR (between crystals) v max : 3468, 3097, 2880, 1592, 1455, 1353, 1333, 1227, 1194, 1136, 1058, 927, 850, 788, 739 cm'1.
Ejemplo 12.Example 12
Bis(trifluorometilsulfonil)amiduro de 4-metil-3-{2-[2-(2-metoxietoxi)etoxi]etil}-5-(2,5,8,11 -tetraoxatridecan-13-il)tiazolio (12).4-Methyl-3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} -5- (2,5,8,11-tetraoxatridecan-13-yl) thiazolium bis (trifluoromethylsulfonyl) amide (12).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-(2,5,8,11-tetraoxatridecan-13-il)tiazol (3) (1.0 g, 3.46 mmol), 1-yodo-2-[2-(2-metoxietoxi)etoxi]etano (1.32 g, 4.83 mmol) y bistrifluorometanosulfonimida de litio (883 mg, 3.98 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 4-metil-3-{2-[2-(2-metoxietoxi)etoxi]etil}-5-(2,5,8,11-tetraoxatridecan-13-il)tiazolio (12) (2.05 g, 83%). It is prepared according to the procedure described in Example 10, using 4-Methyl-5- (2,5,8,11-tetraoxatridecan-13-yl) thiazole ( 3 ) (1.0 g, 3.46 mmol), 1-iodine -2- [2- (2-methoxyethoxy) ethoxy] ethane (1.32 g, 4.83 mmol) and lithium bistrifluoromethanesulfonimide (883 mg, 3.98 mmol) to give Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- {2} - [2- (2-methoxyethoxy) ethoxy] ethyl} -5- (2,5,8,11-tetraoxatridecan-13-yl) thiazolium (12) (2.05 g, 83%).
1H NMR (300 MHz, CDCI3) 59.87 (s, 1H), 4.53 (t, J = 4.5 Hz, 2H), 3.94 (t, J = 4.5 Hz, 2H), 3.72 (t, J = 5.4 Hz, 2H), 3.69-3.50 (m, 20H), 3.36 (s, 3H), 3.35 (s, 3H), 3.09 (t, J = 5.4 Hz, 2H), 2.48 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.87 (s, 1H), 4.53 (t, J = 4.5 Hz, 2H), 3.94 (t, J = 4.5 Hz, 2H), 3.72 (t, J = 5.4 Hz, 2H), 3.69-3.50 (m, 20H), 3.36 (s, 3H), 3.35 (s, 3H), 3.09 (t, J = 5.4 Hz, 2H), 2.48 (s, 3H).
13C NMR (75 MHz, CDCI3) 5 157.2, 142.1, 135.4, 112.2 (q, CF3, J = 321 Hz), 72.3, 72.2, 71.0, 70.9, 70.8 (2C), 70.7, 70.6, 70.4 (2C), 69.0, 67.7, 59.3, 59.2, 53.2, 28.0, 12.3. 13 C NMR (75 MHz, CDCI 3 ) 5 157.2, 142.1, 135.4, 112.2 (q, CF3, J = 321 Hz), 72.3, 72.2, 71.0, 70.9, 70.8 (2C), 70.7, 70.6, 70.4 (2C) , 69.0, 67.7, 59.3, 59.2, 53.2, 28.0, 12.3.
FTIR (entre cristales) v max: 3496, 3078, 2879, 1651, 1589, 1455, 1353, 1333, 1227, 1194, 1136, 1058, 935, 850, 788 cm-1. FTIR (between crystals) v max : 3496, 3078, 2879, 1651, 1589, 1455, 1353, 1333, 1227, 1194, 1136, 1058, 935, 850, 788 cm-1.
Ejemplo 13.Example 13
Bis(trifluorometilsulfonil)amiduro de 4-metil-5-[2-(2-metoxietoxi)etil]-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (13).4-Methyl-5- [2- (2-methoxyethoxy) ethyl] -3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium bis (trifluoromethylsulfonyl) amide (13).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-[2-(2-metoxietoxi)etil]tiazol (2) (1.0 g, 4.97 mmol), 1-yodo-2-[2-(2-metoxietoxi)etoxi]etano (1.90 g, 6.95 mmol) y bistrifluorometanosulfonimida de litio (1.27 g, 5.71 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 4-metil-5-[2-(2-metoxietoxi)etil]-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (13) (2.46 g, 79%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- [2- (2-methoxyethoxy) ethyl] thiazole ( 2 ) (1.0 g, 4.97 mmol), 1-iodo-2- [2 - (2-methoxyethoxy) ethoxy] ethane (1.90 g, 6.95 mmol) and lithium bistrifluoromethanesulfonimide (1.27 g, 5.71 mmol) to give bis (trifluoromethylsulfonyl) 4-methyl-5- [2- (2-methoxyethoxy) amide. ) ethyl] -3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium ( 13 ) (2.46 g, 79%).
1H NMR (300 MHz, CDCU) 59.88 (s, 1H), 4.52 (t, J = 4.5 Hz, 2H), 3.93 (t, J = 4.5 Hz, 2H), 3.72 (t, J = 5.4 Hz, 2H), 3.67-3.50 (m, 12H), 3.37 (s, 3H), 3.36 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H), 2.47 (s, 3H).1 H NMR (300 MHz, CDC U ) 59.88 (s, 1H), 4.52 (t, J = 4.5 Hz, 2H), 3.93 (t, J = 4.5 Hz, 2H), 3.72 (t, J = 5.4 Hz, 2H), 3.67-3.50 (m, 12H), 3.37 (s, 3H), 3.36 (s, 3H), 3.10 (t, J = 5.4 Hz, 2H), 2.47 (s, 3H).
13C NMR (75 MHz, CDCl3) 5 156.7, 141.7, 134.9, 119.7 (q, CF3, J = 321 Hz), 71.7, 71.6, 70.3, 70.1, 69.8 (2C), 68.6, 67.1, 58.9, 58.8, 52.7, 27.5, 11.8.13 C NMR (75 MHz, CDCl 3) 5 156.7, 141.7, 134.9, 119.7 (q, CF3, J = 321 Hz), 71.7, 71.6, 70.3, 70.1, 69.8 (2C), 68.6, 67.1, 58.9, 58.8, 52.7 , 27.5, 11.8.
HRMS-ESI (m/z): Calculado para C16H30NO5S [M]+: 348.1839, encontrado: 348.1852. HRMS-ESI (m / z): Calculated for C 16 H 30 NO 5 S [M] +: 348.1839, found: 348.1852.
FTIR (entre cristales) vmax: 3469, 3085, 2881, 1653, 1589, 1455, 1353, 1333, 1194, 1136, 1103, 1058, 922, 849, 788, 739 cm'1. FTIR (between crystals) v max : 3469, 3085, 2881, 1653, 1589, 1455, 1353, 1333, 1194, 1136, 1103, 1058, 922, 849, 788, 739 cm'1.
Ejemplo 14.Example 14
Bis(trifluorometilsulfonil)amiduro de 4-metil-3,5-bis{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (14).Bis (trifluoromethylsulfonyl) amide of 4-methyl-3,5-bis {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium (14).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-{2-[2-(2-metoxietoxi)etoxi]etil}tiazol (1) (1.0 g, 4.08 mmol), 1-iodo-2-[2-(2-metoxietoxi)etoxi]etano (1.56 g, 5.71 mmol) y bistrifluorometanosulfonimida de litio (1.04 g, 4.69 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 4-metil-3,5-bis{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (14) (2.35 g, 86%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazole ( 1 ) (1.0 g, 4.08 mmol), 1-iodine -2- [2- (2-methoxyethoxy) ethoxy] ethane (1.56 g, 5.71 mmol) and lithium bistrifluoromethanesulfonimide (1.04 g, 4.69 mmol) to give Bis (trifluoromethylsulfonyl) amide of 4-methyl-3,5- bis {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium ( 14 ) (2.35 g, 86%).
1H NMR (300 MHz, CDCl3) 59.86 (s, 1H), 4.52 (t, J = 4.4 Hz, 2H), 3.94 (t, J = 4.4 Hz, 2H), 3.73 (t, J = 5.3 Hz, 2H), 3.70-3.51 (m, 16H), 3.37 (s, 3H), 3.36 (s, 3H), 3.09 (t, J = 5.3 Hz, 2H), 2.48 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.86 (s, 1H), 4.52 (t, J = 4.4 Hz, 2H), 3.94 (t, J = 4.4 Hz, 2H), 3.73 (t, J = 5.3 Hz, 2H), 3.70-3.51 (m, 16H), 3.37 (s, 3H), 3.36 (s, 3H), 3.09 (t, J = 5.3 Hz, 2H), 2.48 (s, 3H).
13C NMR (75 MHz, CDCl3) 5 157.1, 142.2, 135.4, 120.2 (q, CF3, J = 321 Hz), 72.3, 72.2, 70.9 (2C), 70.7, 70.6, 70.4 (2C), 69.1, 67.6, 59.4, 59.3, 53.3, 28.1, 12.4. 13 C NMR (75 MHz, CDCl 3 ) 5 157.1, 142.2, 135.4, 120.2 (q, CF3, J = 321 Hz), 72.3, 72.2, 70.9 (2C), 70.7, 70.6, 70.4 (2C), 69.1, 67.6 , 59.4, 59.3, 53.3, 28.1, 12.4.
HRMS-ESI (m/z): Calculado para C18H34NO6S [M]+: 392.2101, encontrado: 392.2107. HRMS-ESI (m / z): Calculated for C18H34NO6S [M] +: 392.2101, found: 392.2107.
FTIR (entre cristales) Vmax: 3081, 2880, 1454, 1353, 1333, 1227, 1194, 1136, 1058, 925, 850, 788 cm-1. FTIR (between crystals) Vmax : 3081, 2880, 1454, 1353, 1333, 1227, 1194, 1136, 1058, 925, 850, 788 cm-1.
Ejemplo 15.Example 15
Bis(trifluorometilsulfonil)amiduro de 3-hexil-4-metil-5-(2-metoxietil)tiazolio (15).Bis (trifluoromethylsulfonyl) -3-hexyl-4-methyl-5- (2-methoxyethyl) thiazolium amide (15).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-(2-metoxietil)tiazol (5) (1.0 g, 6.37 mmol), 1-yodohexano (1.51 g, 7.64 mmol) y bistrifluorometanosulfonimida de litio (1.62 g, 7.32 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 3-hexil-4-metil-5-(2-metoxietil)tiazolio (15) (3.02 g, 91%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- (2-methoxyethyl) thiazole ( 5 ) (1.0 g, 6.37 mmol), 1-iodohexane (1.51 g, 7.64 mmol) and bistrifluoromethanesulfonimide lithium (1.62 g, 7.32 mmol) to give 3-hexyl-4-methyl-5- (2-methoxyethyl) thiazolium bis (trifluoromethylsulfonyl) amide ( 15 ) (3.02 g, 91%).
1H NMR (300 MHz, CDCU) 59.68 (s, 1H), 4.41 (t, J = 7.7 Hz, 2H), 3.68 (t, J = 5.3 Hz, 2H), 3.44 (s, 3H), 3.13 (t, J = 5.3 Hz, 2H), 2.53 (s, 3H), 1.93 (m, 2H), 1.38 (m, 6H), 0.93 (m, 3H).1 H NMR (300 MHz, CDC U ) 59.68 (s, 1H), 4.41 (t, J = 7.7 Hz, 2H), 3.68 (t, J = 5.3 Hz, 2H), 3.44 (s, 3H), 3.13 ( t, J = 5.3 Hz, 2H), 2.53 (s, 3H), 1.93 (m, 2H), 1.38 (m, 6H), 0.93 (m, 3H).
13C NMR (75 MHz, CDCU) 5 155.6, 141.6, 136.7, 118.2 (q, CF3, J = 321 Hz), 70.3, 59.2, 54.4, 31.4, 30.0, 28.1, 26.2, 22.7, 14.2, 12.2.13 C NMR (75 MHz, CDC U ) 5 155.6, 141.6, 136.7, 118.2 (q, CF3, J = 321 Hz), 70.3, 59.2, 54.4, 31.4, 30.0, 28.1, 26.2, 22.7, 14.2, 12.2.
FTIR (entre cristales) vmax: 3095, 2935, 2873, 1651, 1587, 1482, 1458, 1352, 1226, 1193, 1137, 1117, 1057, 788, 739 cm'1. FTIR (between crystals) vmax : 3095, 2935, 2873, 1651, 1587, 1482, 1458, 1352, 1226, 1193, 1137, 1117, 1057, 788, 739 cm'1.
Ejemplo 16.Example 16
Bis(trifluorometilsulfonil)amiduro de 4-metil-5-(2-metoxietil)-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (16).4-Methyl-5- (2-methoxyethyl) -3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium bis (trifluoromethylsulfonyl) amide (16).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-(2-metoxietil)tiazol (5) (1.0 g, 6.37 mmol), 1-iodo-2-[2-(2-metoxietoxi)etoxi]etano (1.51 g, 7.64 mmol) y bistrifluorometanosulfonimida de litio (1.62 g, 7.32 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 4-metil-5-(2-metoxietil)-3-{2-[2-(2-metoxietoxi)etoxi]etil}tiazolio (16) (3.34 g, 90%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- (2-methoxyethyl) thiazole (5) (1.0 g, 6.37 mmol), 1-iodo-2- [2- (2-methoxyethoxy ) ethoxy] ethane (1.51 g, 7.64 mmol) and lithium bistrifluoromethanesulfonimide (1.62 g, 7.32 mmol) to give Bis (trifluoromethylsulfonyl) amide of 4-methyl-5- (2-methoxyethyl) -3- {2- [ 2- (2-methoxyethoxy) ethoxy] ethyl} thiazolium (16) (3.34 g, 90%).
1H NMR (300 MHz, CDCl3) 59.96 (s, 1H), 4.58 (dd, J = 4.6 Hz, J = 4.4 Hz, 2H), 4.00 (dd, J = 4.7 Hz, J = 4.5 Hz, 2H), 3.73 (m, 2H), 3.70-3.55 (m, 8H), 3.44 (s, 3H), 3.43 (s, 3H), 3.12 ( t, J = 5.4 Hz, 2H), 2.53 (s, 3H). 1 H NMR (300 MHz, CDCl 3 ) 59.96 (s, 1H), 4.58 (dd, J = 4.6 Hz, J = 4.4 Hz, 2H), 4.00 (dd, J = 4.7 Hz, J = 4.5 Hz, 2H) , 3.73 (m, 2H), 3.70-3.55 (m, 8H), 3.44 (s, 3H), 3.43 (s, 3H), 3.12 (t, J = 5.4 Hz, 2H), 2.53 (s, 3H).
13C NMR (75 MHz, CDCl3) 5 157.3, 142.2, 135.3, 118.2 (q, CF3, J = 321 Hz), 72.2, 70.6, 70.4, 70.3 (2C), 67.5, 59.3, 59.1, 53.2, 28.0, 12.4. 13 C NMR (75 MHz, CDCl 3 ) 5 157.3, 142.2, 135.3, 118.2 (q, CF3, J = 321 Hz), 72.2, 70.6, 70.4, 70.3 (2C), 67.5, 59.3, 59.1, 53.2, 28.0, 12.4.
FTIR (entre cristales) Vmax: 3082, 2883, 1650, 1589, 1453, 1353, 1333, 1227, 1194, 1137, 1057, 936, 850, 788, 739 cm'1. FTIR (between crystals) Vmax : 3082, 2883, 1650, 1589, 1453, 1353, 1333, 1227, 1194, 1137, 1057, 936, 850, 788, 739 cm'1.
Ejemplo 17.Example 17
Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2-metoxietil)tiazolio (17).3,4-Dimethyl-5- (2-methoxyethyl) thiazolium bis (trifluoromethylsulfonyl) amide (17).
Se prepara de acuerdo con el procedimiento descrito en el Ejemplo 10, utilizando 4-Metil-5-(2-metoxietil)tiazol (5) (1.0 g, 6.37 mmol), CH3I (0.48 g, 7.64 mmol) y bistrifluorometanosulfonimida de litio (1.62 g, 7.32 mmol) para dar lugar a Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-(2-metoxietil)tiazolio (17) (2.70 g, 94%).It is prepared according to the procedure described in Example 10, using 4-Methyl-5- (2-methoxyethyl) thiazole (5) (1.0 g, 6.37 mmol), CH3I (0.48 g, 7.64 mmol) and lithium bistrifluoromethanesulfonimide ( 1.62 g, 7.32 mmol) to give Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- (2-methoxyethyl) thiazolium ( 17 ) (2.70 g, 94%).
1H NMR (300 MHz, CDCl3) 59.57 (s, 1H), 4.12 (s, 3H), 3.66 (t, J = 5.4 Hz, 2H), 3.43 (s, 3H), 3.11 (t, J = 5.4 Hz, 2H), 2.51 (s, 3H). 1 H NMR (300 MHz, CDCl 3) 59.57 (s, 1 H), 4.12 (s, 3 H), 3.66 (t, J = 5.4 Hz, 2 H), 3.43 (s, 3 H), 3.11 (t, J = 5.4 Hz, 2H), 2.51 (s, 3H).
13C NMR (75 MHz, CDCU) 5 156.0, 142.3, 136.2, 118.2 (q, CF3, J = 321 Hz), 70.3, 59.1, 41.1, 28.1, 12.1. 13C NMR (75 MHz, CDC U ) 5 156.0, 142.3, 136.2, 118.2 (q, CF3, J = 321 Hz), 70.3, 59.1, 41.1, 28.1, 12.1.
FTIR (entre cristales) vmax: 3103, 2936, 1596, 1486, 1454, 1352, 1191, 1138, 1057, 789, 740 cm"1. FTIR (between crystals) vmax : 3103, 2936, 1596, 1486, 1454, 1352, 1191, 1138, 1057, 789, 740 cm "1.
Ejemplo 18Example 18
Evaluación de la conductividad iónica de un líquido iónico comprendido en la fórmula (I)Evaluation of the ionic conductivity of an ionic liquid included in the formula (I)
Se ha evaluado la conductividad iónica de Bis(trifluorometilsulfonil)amiduro de 4-metil-3-{2-[2-(2-metoxietoxi)etoxi]etil}-5-(2,5,8,11-tetraoxatridecan-13-il)tiazolio (12), evaluada mediante espectroscopía de impedancia, en el intervalo de temperaturas comprendido entre -40 y 100 grados centígrados. El valor de la conductividad a cada temperatura se obtuvo a partir del diagrama de Nyquist, en el intervalo de frecuencias comprendido entre 0,1 y 107 Hz, empleando el programa de ajuste ZPlot.The ionic conductivity of Bis (trifluoromethylsulfonyl) amide of 4-methyl-3- {2- [2- (2-methoxyethoxy) ethoxy] ethyl} -5- (2,5,8,11-tetraoxatridecan-13-) has been evaluated. il) thiazolium (12) , evaluated by impedance spectroscopy, in the temperature range between -40 and 100 degrees centigrade. The conductivity value at each temperature was obtained from the Nyquist diagram, in the frequency range between 0.1 and 107 Hz, using the ZPlot adjustment program.
Se observa (ver Figura1) una variación continua de la conductividad iónica frente a la temperatura, típica de los compuestos líquidos. A temperatura ambiente (30°C), el valor de la conductividad iónica obtenido es de 9,2.10"4 S.cm"1. El resto de los líquidos iónicos presentan comportamiento similar, con valores de conductividad a temperatura ambiente comprendidos entre 8.10"4 y 3.10"3 S.cm"1 dependiendo de la naturaleza de los sustituyentes.A continuous variation of the ionic conductivity versus temperature, typical of liquid compounds, is observed (see Figure 1). At room temperature (30 ° C), the ionic conductivity value obtained is 9.2.10 "4 S.cm" 1. The rest of the ionic liquids exhibit similar behavior, with conductivity values at room temperature between 8.10 "4 and 3.10" 3 S.cm "1 depending on the nature of the substituents.
Ejemplo 19Example 19
Estabilidad térmica de Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio (8).Thermal stability of Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium (8).
Se ha determinado la estabilidad térmica (curvas termogravimétricas de descomposición), en atmósfera inerte y oxidante de Bis(trifluorometilsulfonil)amiduro de 3,4-dimetil-5-[2-(2-metoxietoxi)etil]tiazolio (8). Los resultados obtenidos (ver Figura 2) indican que el líquido iónico es estable, en ambos tipos de atmósferas, hasta temperaturas próximas a 300 grados centígrados. El resto de los líquidos iónicos sintetizados poseen un comportamiento similar, presentando una alta estabilidad térmica en todos los casos, observándose únicamente diferencias entre ellos debidas a las descomposición de los diferentes sustituyentes unidos al anillo de tiazolio. The thermal stability (thermogravimetric decomposition curves), in an inert atmosphere and oxidant of Bis (trifluoromethylsulfonyl) amide of 3,4-dimethyl-5- [2- (2-methoxyethoxy) ethyl] thiazolium ( 8 ) was determined. The results obtained (see Figure 2) indicate that the ionic liquid is stable, in both types of atmospheres, up to temperatures close to 300 degrees Celsius. The rest of the ionic liquids synthesized have a similar behavior, presenting a high thermal stability in all cases, observing only differences among them due to the decomposition of the different substituents attached to the thiazolium ring.
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