WO2014037291A1 - Tricyanoborate alkyl ethers - Google Patents
Tricyanoborate alkyl ethers Download PDFInfo
- Publication number
- WO2014037291A1 WO2014037291A1 PCT/EP2013/068048 EP2013068048W WO2014037291A1 WO 2014037291 A1 WO2014037291 A1 WO 2014037291A1 EP 2013068048 W EP2013068048 W EP 2013068048W WO 2014037291 A1 WO2014037291 A1 WO 2014037291A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- formula
- group
- catorg
- cat
- Prior art date
Links
- 150000005215 alkyl ethers Chemical class 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 132
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 19
- -1 thiazolium Chemical compound 0.000 claims description 18
- 238000009472 formulation Methods 0.000 claims description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 12
- 150000001768 cations Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 230000005693 optoelectronics Effects 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229910052760 oxygen Chemical group 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 5
- 239000001301 oxygen Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Chemical group 0.000 claims description 5
- SCDKVHCGNOYKFK-OAHLLOKOSA-N (2r)-2-[4-chloro-3-[[3-(6-methoxy-1,2-benzoxazol-3-yl)-2-methyl-6-(trifluoromethoxy)indol-1-yl]methyl]phenoxy]propanoic acid Chemical compound N=1OC2=CC(OC)=CC=C2C=1C(C1=CC=C(OC(F)(F)F)C=C11)=C(C)N1CC1=CC(O[C@H](C)C(O)=O)=CC=C1Cl SCDKVHCGNOYKFK-OAHLLOKOSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 150000001336 alkenes Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002892 organic cations Chemical class 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000001767 cationic compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- DDODVIVTJJOSRF-UHFFFAOYSA-N (2,3-diphenylcyclopropen-1-yl)benzene Chemical compound C1=CC=CC=C1C([C+]1C=2C=CC=CC=2)=C1C1=CC=CC=C1 DDODVIVTJJOSRF-UHFFFAOYSA-N 0.000 claims description 2
- CRIGIOFPLSXFAD-UHFFFAOYSA-N 1,3,3-tritert-butylcyclopropene Chemical compound CC(C)(C)C1=[C+]C1(C(C)(C)C)C(C)(C)C CRIGIOFPLSXFAD-UHFFFAOYSA-N 0.000 claims description 2
- NRSYQLZFGDRLIX-UHFFFAOYSA-N 1,3-dioxol-1-ium Chemical compound C1=C[O+]=CO1 NRSYQLZFGDRLIX-UHFFFAOYSA-N 0.000 claims description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 claims description 2
- KEQTWHPMSVAFDA-UHFFFAOYSA-N 2,3-dihydro-1h-pyrazole Chemical compound C1NNC=C1 KEQTWHPMSVAFDA-UHFFFAOYSA-N 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KYDKPSWYYLPUCZ-UHFFFAOYSA-N C[Si](C)(C)c1c([c+]1[Si](C)(C)C)[Si](C)(C)C Chemical compound C[Si](C)(C)c1c([c+]1[Si](C)(C)C)[Si](C)(C)C KYDKPSWYYLPUCZ-UHFFFAOYSA-N 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 2
- XLFUIJHKQHIXCH-UHFFFAOYSA-N [2,3-bis(diethylamino)cycloprop-2-en-1-ylidene]-diethylazanium Chemical compound CCN(CC)c1c(N(CC)CC)[c+]1N(CC)CC XLFUIJHKQHIXCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 claims description 2
- MKKOVSZUIZAJEY-UHFFFAOYSA-N cyclopropene Chemical compound C1C=[C+]1 MKKOVSZUIZAJEY-UHFFFAOYSA-N 0.000 claims description 2
- 229960000878 docusate sodium Drugs 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-O hydron piperazine Chemical compound [H+].C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-O 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- LPAGFVYQRIESJQ-UHFFFAOYSA-N indoline Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 125000005498 phthalate group Chemical class 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-O quinoxalin-1-ium Chemical compound [NH+]1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-O 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical compound C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 25
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 0 *C(*(CC1)N=O)*1(C1CCCCCC1)N Chemical compound *C(*(CC1)N=O)*1(C1CCCCCC1)N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052756 noble gas Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- YBPOXFBOJBNBMC-UHFFFAOYSA-N 1,2,3,4,5,6,7-heptakis-phenylcyclohepta-1,3,5-triene Chemical compound c1ccc(cc1)-c1c(-c2ccccc2)c(-c2ccccc2)c(-c2ccccc2)[c+](-c2ccccc2)c(-c2ccccc2)c1-c1ccccc1 YBPOXFBOJBNBMC-UHFFFAOYSA-N 0.000 description 1
- NHCGQHAZAQDUDS-UHFFFAOYSA-N 1,2-dimethylimidazole;hydroiodide Chemical compound [I-].C[NH+]1C=CN=C1C NHCGQHAZAQDUDS-UHFFFAOYSA-N 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- HITWHALOZBMLHY-UHFFFAOYSA-N 2-Butyl-1H-benzimidazole Chemical compound C1=CC=C2NC(CCCC)=NC2=C1 HITWHALOZBMLHY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DHWRYSABLQBXLE-APQBBXBWSA-N CCC(C)/C=C/N(CC)/C=C\C Chemical compound CCC(C)/C=C/N(CC)/C=C\C DHWRYSABLQBXLE-APQBBXBWSA-N 0.000 description 1
- RRORJFSVLJEJHB-UHFFFAOYSA-N CCNN(N)[NH+]=[N-] Chemical compound CCNN(N)[NH+]=[N-] RRORJFSVLJEJHB-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005035 Surlyn® Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- GEWAYNSSSMLHQZ-UHFFFAOYSA-N bis(3,3-dimethylbutyl)phosphinic acid Chemical compound CC(C)(C)CCP(O)(=O)CCC(C)(C)C GEWAYNSSSMLHQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical compound [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DSQCNXSPLHDLED-UHFFFAOYSA-M methanesulfonate;tetrabutylphosphanium Chemical compound CS([O-])(=O)=O.CCCC[P+](CCCC)(CCCC)CCCC DSQCNXSPLHDLED-UHFFFAOYSA-M 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to tricyanoborate alkyl ethers, a method for their preparation and their use as ionic liquids.
Description
Tricyanoborate alkyl ethers
The invention relates to tricyanoborate alkyl ethers, a method for their preparation and their use as ionic liquids.
BACKGROUND OF THE INVENTION
The term "ionic liquid" (IL) is usually used to refer to a salt which is liquid at temperatures below 100°C, in particular at room temperature. Such liquid salts typically comprise organic cations and organic or inorganic anions, and are described inter alia in P. Wasserscheid et al., Angew. Chem., 2000, 1 12, 3926-3945.
Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a low vapour pressure. They show good solvability for numerous organic and inorganic substances. In addition, ionic liquids have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability.
These attributes give rise to many applications of ionic liquids: They can be used foremost as solvent in synthesis, as electrolyte, as lubricant and as hydraulic fluid. Moreover they serve as phase-transfer catalyst, as extraction medium, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte, as component in electrolyte formulations, wherein such electrolyte formulation comprising an ionic liquid is preferably used in electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, particularly preferred in a dye sensitized solar cell.
Therefore, there is a fundamental need for ionic liquids having a variety of properties which open up additional opportunities for their use.
WO2012/041434 discloses the use of specific ionic liquids as component in electrolyte formulations, in particular in electrolyte formulations for electrochemical or optoelectronic devices such as dye sensitized solar cells.
WO 2010/086131 A discloses tricyanoborates of the general formula Catn+[B(CN)3(XRl)]n", wherein Rl is inter alia Ci_6 alkyl; X is inter alia oxygen; and Catn is a cation, which is
selected from the group consisting of an inorganic cation and an organic cation; with n being 1 or 2.
There was a need for stable compounds which can be used as ionic liquids or as precursors of ionic liquids. These compounds should be able to be disposed of in an environmentally friendly manner after use. They should show good performance in applications for ionic liquids, e.g. such as dye sensitized solar cells.
This task object is achieved by tricyanoborates with a fourth substituent, the fourth substituent being an alkyloxy-alkoxy residue.
Unexpectedly, the compounds of instant invention show good efficiency in dye sensitized solar cells. In this text, the following meanings are used, if not otherwise stated:
alkyl linear or branched alkyl;
Ci_q alkyl refers to any alkyl residue which contains from 1 to q carbon atoms; for example Ci_6 alkyl encompasses inter alia methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), n-hexyl and isohexyl (4-methylpentyl);
C2-q alkenyl refers to an alkenyl residue which contains from 2 to q carbon atoms and
contains at least one double bond, the carbon chain can be linear or branched; for example C2_4 alkenyl encompasses inter alia ethenyl, 1-methylethenyl, prop-l-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-l ,3-dienyl;
C2_q alkynyl refers to an alkynyl residue which contains from 2 to q carbon atoms and
contains at least one triple bond, the carbon chain can be linear or branched; for example C2_4 alkynyl encompasses inter alia ethynyl, prop-l-ynyl and prop-2-ynyl;
C6-io aryl refers to an aryl residue which has from 6 to 10 carbon atoms and is
unsubstituted or substituted by 1 , 2, 3 or 4 identical or different substituents
independently from each other selected from the group consisting of Ci_4 alkyl and
Ci_4 alkoxy; for example C6-io aryl encompasses inter alia phenyl, methylphenyl, methoxyphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl and naphthyl;
cyclic alkyl or cycloalkyl include cyclo and polycyclo, such as bicyclo or tricyclo,
aliphatic residues;
C3_q cycloalkyl refers to a cycloalkyl group having from 3 to q carbon atoms; for example C3_io cycloalkyl encompasses inter alia cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
Ci_q alkoxy refers to an linear or branched alkoxy group having from 1 to q carbon
atoms; for example Ci_2o alkoxy encompasses inter alia methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy,
1 ,4-dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1 ,5-dimethylhexyloxy, nonyloxy, decyloxy, 4-ethyl- 1 ,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy and eicosyloxy;
alkylene means a linear or branched alkylene group; e.g. propylene, and e.g. propylene can be connected via its CI and C2 carbon atoms (branched alkylene group), or via its CI and C3 carbon atoms (linear alkylene group);
DCM dichloromethane;
eq. molar equivalent;
halide F , CI , Br or I , preferably F , CI or Br , more preferably CI ;
halogen F, CI, Br or I; preferably F, CI or Br;
IL ionic liquid;
"linear" and "n-" are used synonymously with respect to the respective isomers of alkanes; RT room temperature, it is used synonymously with the expression ambient
temperature;
TMSCN (CH3)3SiCN, i.e. trimethylsilylcyanide;
"wt%", "% by weight" and "weight-%" are used synonymously and mean percent by weight.
SUMMARY OF THE INVENTION
Subject of the invention is a compound of formula (I);
R101 is Ci_6 alkyl;
R102 is a linear or branched C1-12 alkylene;
Catn+ is a cation, which is selected from the group consisting of inorganic cation
CatINORGn+ and organic cation CatORGn ;
n is 1 or 2;
m is 1, 2, 3 or 4.
DETAILED DESCRIPTION OF THE INVENTION
Preferably,
R101 is Ci_2 alkyl;
m is 1, 2 or 3;
R102 is a linear or branched C2_i2 alkylene. More preferably,
R101 is Ci_2 alkyl;
m is 1 or 2;
R102 is selected from the group consisting of ethylene, propylene, butylene, pentylene, hexylen.
Even more preferably,
R101 is Ci_2 alkyl;
m is 1 or 2;
R102 is selected from the group consisting of ethylene and propylene.
Especially,
R101 is Ci_2 alkyl;
m is 1 or 2;
R102 is ethylene.
Preferably, CatINORGn+ is selected from the group consisting of Li+, Na+, K+, Rb+, Cs+, NH4 +, Ag+, Be2+, Mg2+, Ca2+, Sr2+ and Ba2+;
more preferably, CatlNORG is selected from the group consisting of Li , Na , K , NH4 ,
Ag+, Mg2+, and Ca2+;
even more preferably, CatINORGn+ is selected from the group consisting of Li+, Na+, K+, NH4 + and Ag+;
especially, CatINORGn+ is Li+, Na+, K+ or Ag+; more especially, CatINORGn is Li+ or K+.
Preferably, CatORG contains a heteroatom selected from the group consisting of nitrogi phosphorus, sulfur and oxygen;
more preferably, CatORGn contains a heteroatom selected from the group consisting of nitrogen and phosphorus.
When n is 2, then CatORG is preferably (H3N-CH2-CH2-NH3)2+.
Preferably, n in CatORG is 1.
When n is 1, then CatORG is preferably selected from the group consisting of cation CatORG-A+, CatORG-B+, CatORG-C+, CatOrg-D+ and CatORG-E+;
CatOrg-A+ is (WR2R3R4R5)+,
wherein
W is a nitrogen or phosphorus;
(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_2o alkyl, Ci_2o
perfluoroalkyl, C3-10 cycloalkyl and C6-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or
(ii) R2 and R3 together with W form a 5- to 7-membered saturated or unsaturated ring, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_2o alkyl, Ci_2o perfluoroalkyl, C3-10 cycloalkyl and C6-io aryl; or
(iii) R2 and R3 together with W and R4 and R5 together with W form, independently from each other, a 5- to 7-membered saturated or unsaturated ring;
CatOrg-B+ is (XR6R7R8)+,
wherein
X is nitrogen,
R6 and R7 together with X form a 5- to 7-membered unsaturated ring in which X formally has one single bond and one double bond to R6 and R7 respectively,
R8 is selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl,
C3-10 cycloalkyl or C6-io aryl;
CatOrg-C+ is (YR9R10R11)+,
wherein
Y is sulphur;
(i) R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl, C3-10 cycloalkyl and C6-io aryl; or
(ii) R9 and RIO together with Y form a 5- to 7-membered saturated or unsaturated ring, Rl 1 is selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl,
C3-10 cycloalkyl and C6-io aryl;
CatOrg-D+ is (ZR12R13)+,
wherein
Z is oxygen or sulphur;
R12 and R13 together with Z form a 5- to 7-membered ring in which Z formally has one single bond and one double bond to R12 and R13 respectively;
CatORG-E+ is a cyclic C3_9 alkane or a cyclic C3_9 alkene bearing a positive charge;
in case of a cyclic C3-9 alkene, CatORG-E+ has 1, 2 or 3 double bonds; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2 or 3 substituents selected from the group consisting of halogen, cyano and Ci_4 alkoxy;
the rings formed by R2 and R3 together with W, R4 and R5 together with W, R6 and R7 together with X, R9 and RIO together with Y and R12 and R13 together with Z contain no, 1 or 2 further heteroatoms, the heteroatoms being selected from the group consisting of O, N and S; and wherein any further heteroatom N can be substituted by Ci_s alkyl or Ci_8 perfluoroalkyl.
The term "where applicable" means e.g., that any of the 1 , 2 or 3 substituents of the residues R2 to R13 requires a respective site, and e.g. in case of R2 being a perfluorinated side chain no respective site is available any more a substituents.
More preferably, CatORGn is selected from the group consisting of ammonium,
phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium, imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1 ,3-dioxolium, pyrylium and thiopyrylium, quinoxalinium, indolinium, indolium, cyclopropenylium, 1 ,2,3-triphenylcyclopropenylium, tri-tert- butylcyclopropenylium, 1 ,2,3-tris(diethylamino)cyclopropenylium, 1 ,2,3- tris(trimethylsilyl)cyclopropenylium and tropylium, 1 ,2,3,4,5,6,7- heptaphenylcyclohepta-2,4,6-trien- 1 -ylium.
Even more preferably, CatORG is selected from the group consisting of
R20 is Ci_2o alkyl;
R21 , R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_2o alkyl; preferably,
R20 is Ci-14 alkyl;
R21 , R22 and R23 are identical or different and independently selected from the group consisting of H and C1 -14 alkyl; more preferably,
R20 is Ci_8 alkyl;
R21 , R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_s alkyl.
[NH(C2H5)3]+, [NH(C4H9)3]+, [N(C2H5)4]+, [N(C4H9)4]+, [P(C2H5)4]+, [P(C4H9)4]+ and [P(C6H13)3(C14H29)]+;
more especially, CatORG is selected from the group consisting of C¾
[N(C4H9)4]+, [P(C2H5)4]+, and [P(C4H9)4]
In another more preferable embodiment, CatORGn is
1 wherein
R20 is Ci_20 alkyl;
R21 is H and Ci_2o alkyl;
preferably,
R20 is Ci-14 alkyl;
R21 is H and C i_i 4 alkyl;
more preferably,
R20 is Ci_8 alkyl;
R21 is H and Ci_8 alkyl;
even more preferably,
R20 is methyl and R21 is ethyl.
In particular,
R101 is Ci_2 alkyl;
m is 1 or 2;
R102 is ethylene;
CatINORGn+ is Li+ or K+;
CatORG is
R20 is methyl and R21 is ethyl.
More in particular, compound of formula (I) is selected from the group consisting of compound of formula (1), compound of formula (2), compound of formula (3), compound of formula (4), compound of formula (5), compound of formula (6) and compound of formula (V).
Further subject of the invention is a method for the preparation of compound of formula (I), the method comprises a step (Stl) or a step (St2);
step (Stl) comprises a reaction (Real), wherein compound of formula (X) is reacted with trimethylsilylcyanide in the presence of cation Catn ;
(Catn )(AnINORGq )t (I-Cat-n) q is 1 or 2;
r is 1 or 2;
when n and q are identical, then t is 1 ;
when n is 2 and q is 1 , then t is 2;
when n is 1 and q is 2, then t is 0.5;
AnINORGq is an anion selected from the group consisting of halide, OH", CN , OCN , SCN~, N3 ", sulfate, hydrogensulfate, nitrate, C03 2", HC03 ", BF4 ~, PF6 ", SbF6 ", CF3S03
(CF3S02)2N , (FS02)2N , Ci_6 alkylsulfonate, Ci_6 alkylsulfate, dioctylsulfosuccinate, anions of Ci_2o monocarboxylic aliphatic acids, anions of C2-6 dicarboxylic aliphatic
acids, benzoate, phthalates, N(CN)2 ", C(CN)3 ", B(CN)4 ", P(CN)6 ",Sb(CN)6 ", and mixtures thereof;
Cat-/ has the same definition as Catn and is different from Catn ;
Catn , n, m, RlOl and R102 are as defined above, also with all their preferred embodiments.
Preferably, in reaction (Real) cation Cat is present in form a compound (CYAN SALT) and compound (CYANS ALT) is [Catn+][CN]n, with Catn+ and n as defined above, also with all its preferred embodiments;
more preferably, compound (CYANS ALT) is [CatINORGn+][CN]„, with CatINORGn+ and n as defined above, also with all its preferred embodiments;
even more preferably, compound (CYANS ALT) is [CatINORGn+][CN]„, and CatINORGn+
I
is selected from the group consisting of Li , Na , K , NH4 , Mg , and Ca , n is 1 or 2 respectively in this case;
especially, compound (CYANSALT) is [CatINORGn+][CN]„, and CatINORGn+ is selected from the group consisting of Li+, Na+, K+ and NH4 +, n is in this case;
more especially, compound (CYANSALT) is [CatINORGn+][CN]„, and CatINORGn+ is Na+ or K+, n is 1 in this case.
Preferably, from 1.5 to 10 mol equivalents, more preferably from 3 to 5 mol equivalents, of trimethylsilylcyanide are used in reaction (Real), the mol equivalents being based on the mol of compound of formula (X).
Preferably, from 0.8 to 5 mol equivalents, more preferably from 0.9 to 3 mol equivalents, even more preferably from 0.9 to 2 mol equivalents, of Catn+, preferably in form of compound (CYANSALT), are used in reaction (Real), the mol equivalents being based on the mol of compound of formula (Al).
The reaction temperatures of reaction (Real) is preferably from 0 to 250 °C, more preferably from 50 to 200 °C, even more preferably from 50 to 150 °C.
Preferably, reaction (Real) is done at a reaction temperature which is above the boiling point of compound of formula (XX), which is formed during the reaction.
Reaction (Real) can be done in a closed system and at the pressure caused by the chosen temperature.
The reaction time of reaction (Real) is preferably from 30 min to 96 h, more preferably from 1 h to 72 h, even more preferably from 2 h to 48 h. Preferably, reaction (Real) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
The lower boiling alkane is preferably a Ci_3 alkane, i.e. methane, ethane or propane. After the reaction, compound of formula (I) can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration,
crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.
For example, when the reaction product of reaction (Real) is a solid, it is preferably suspended in a solvent (SUSP),
solvent (SUSP) is selected from the group consisting of heptane, DCM, acetonitrile and
mixtures thereof;
then the obtained suspension is filtered and preferably washed. This extraction can be repeated with a different solvent (SUSP). Evaporation, preferably under vacuum, provides compound of formula (I).
Reaction (Rea2) is a metathesis reaction, also called a salt-exchange reaction, in which a first cation is replaced by a second cation. Preferably, AnINORGq is an anion selected from the group consisting of halide, OH", CN~, sulfate, hydrogensulfate, nitrate, C03 2", HC03 ", BF4 ", PF6 ", CF3S03 ", (CF3S02)2N~,
(FS02)2N , methyl sulfonate, ethyl sulfonate, methyl sulfate, ethyl sulfate, acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)2 , and mixtures thereof; more preferably, AnlNORG^ is an anion selected from the group consisting of CI , OH", GST, sulfate, hydrogensulfate, CO3 2", HCO3 , acetate, and mixtures thereof.
Preferably in case of reaction (Rea2), a compound of formula (I) with Catn being CatORGn is prepared in step (St2) by a reaction (Rea2), wherein a compound of formula (I-Cat-r), wherein Cat-/ has the definition of CatINORGn , is reacted with a compound of formula (I-CatORG)
(CatORGn+)q(AnINORGq")n (I-CatORG) wherein
Catn+, n, CatORGn+, CatINORGn+, q and AnINORGq are as defined above, also with all their preferred embodiments.
Preferably, when n and r are identical, then from 1 to 1.5 mol equivalents, more preferably from 1 to 1.2 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r).
Preferably, when n is 2 and r is 1, then from 0.5 to 0.75 mol equivalents, more preferably from 0.5 to 0.6 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r). Preferably, when n is 1 and r is 2, then from 2 to 3 mol equivalents, more preferably from 2 to 2.4 mol equivalents, of compound of formula (I-Cat-n) are used in reaction (Rea2), the mol equivalents being based on the mol of compound of formula (I-Cat-r).
The reaction temperatures of reaction (Rea2) is preferably from 0 to 250 °C, more preferably from 10 to 200 °C, even more preferably from 10 to 150 °C.
The reaction (Rea2) is preferably carried out in a solvent (Sol2), solvent (Sol2) is preferably selected from the group consisting of water, DCM, ethyl acetate, C5-10 alkane, and mixtures thereof.
C5_io alkane is preferably pentane, hexane or heptane.
In a more preferred embodiment, reaction (Rea2) is done in a biphasic solvent system of water and DCM.
As an alternative, the reaction can also be carried out in the absence of a solvent or in a solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble. As a further alternative, it is also possible to carry out the reaction in an aqueous solution using an ion exchanger loaded with the desired cation Catn .
The amount of solvent is preferably from 2 to 40 fold, more preferably from 3 to 20 fold, of the weight of compound of formula (I-Cat-r).
Reaction (Rea2) can be done in a closed system and at the pressure caused by the chosen temperature.
The reaction time of reaction (Rea2) is preferably from 15 or from 30 min to 48 h, more preferably from 15 min, from 30 min or from 1 h to 24 h, even more preferably from 15 min, from 30 min or from 1 h to 12 h.
Preferably, reaction (Rea2) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
The lower boiling alkane is preferably a Ci_3 alkane, i.e. methane, ethane or propane.
Subsequent to reaction (Rea2) there can be a further metathesis reaction or further metathesis reactions.
After reaction (Rea2), compound of formula (I) can be isolated from the reaction mixture by standard methods such as filtration, evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.
For example, when reaction (Rea2) was done in a biphasic solvent system of water and DCM, the aqueous and organic phases are separated, the organic phase is preferably washed, preferably with water, then preferably dried, preferably with Na2S04, K2C03, CaCl2 or MgS04, and finally evaporated.
Preferably, compound of formula (X) is prepared in a step (StO);
step (StO) is done before step (Stl);
step (StO) comprises a reaction (ReaO), wherein boric acid is reacted with a compound of formula (X-0);
m, R101 and R102 are as defined above, also with all their preferred embodiments.
Preferably, from 3 to 6 mol equivalents, more preferably from 3 to 5 mol equivalents, of compound of formula (X-0) are used in reaction (ReaO), the mol equivalents being based on the mol of boric acid.
The reaction temperatures of reaction (ReaO) is preferably from 0 to 250 °C, more preferably from 50 to 200 °C, even more preferably from 50 to 150 °C.
Preferably, reaction (ReaO) is done is a solvent (SolO), solvent (SolO) is preferably selected from the group consisting of toluene, xylene and C5-10 alkane.
C5_io alkane is preferably pentane, hexane or heptane.
Reaction (ReaO) can be done in a closed system and at the pressure caused by the chosen temperature.
The reaction time of reaction (ReaO) is preferably from 30 min to 48 h, more preferably from 1 h to 24 h.
Preferably, reaction (ReaO) is done under inert atmosphere. Preferably, the inert atmosphere is achieved by the use if an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
The lower boiling alkane is preferably a Ci_3 alkane, i.e. methane, ethane or propane.
Compound of formula (X) can be isolated after reaction (ReaO), preferably by distillation.
Further subject of the invention is the use of compound of formula (I), with compound of formula (I) as defined above, also with all its preferred embodiments,
preferably of compound of formula (I) with Catn being CatORGn ,
as solvent, preferably as solvent in inorganic and organic synthesis; as phase-transfer catalyst, as extractant, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte; as lubricant and as hydraulic fluid, as component in electrolyte formulations, wherein such electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catn being CatORGn , are preferably used in electrochemical and/or optoelectronic devices, wherein the electrochemical and/or optoelectronic devices are preferably selected from the group consisting of photovoltaic cell, light emitting device, electrochromic or photo- electrochromic device, electrochemical sensor and/or biosensor, and dye sensitized solar cell, particularly preferred in a dye sensitized solar cell.
In the case of the use of compounds of formula (I) as solvents, these are suitable in any type of reaction known to the person skilled in the art, for example for transition-metal- or enzyme-catalysed reactions, such as, for example, hydroformylation reactions,
oligomerisation reactions, esterifications or isomerisations, where the said list is not exhaustive.
When used as extractant, compound of formula (I) can be employed to separate off reaction products, but also to separate off impurities, depending on the solubility of the respective component in the ionic liquid. In addition, the ionic liquids may also serve as separation media in the separation of a plurality of components, for example in the distillative separation of a plurality of components of a mixture.
Further possible applications for compounds of formula (I) are the use as plasticiser in polymer materials and as conductive salt or additive in various electrochemical cells and applications, for example in galvanic cells, in capacitors or in fuel cells.
Further fields of applications of compounds of formula (I), according to this invention, are their use as solvents for carbohydrate containing solids, in particular biopolymers and derivatives or degradation products thereof. In addition, compound of formula (I) can be used as lubricants, working fluids for machines, such as compressors, pumps or hydraulic devices. A further field of application is the field of particle or nanomaterial synthesis where these ionic liquids can act as medium or additive.
Further subject of the invention is the use of compounds of formula (I), with compound of formula (I) as defined above, also with all its preferred embodiments, preferably of compounds of formula (I) with Catn being CatORGn , in electrochemical and/or optoelectronic devices, especially in electrolyte formulations in such electrochemical and/or optoelectronic devices, preferably as electrolyte in such electrochemical and/or optoelectronic devices. Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catn being CatORGn , can be preferably used in batteries, preferably in primary batteries and secondary batteries, in capacitors, in supercapacitors or in
electrochemical cells, optionally also in combination with further conductive salts, additives and/or solvents. Preferred batteries are lithium batteries or lithium-ion batteries. A preferred capacitor is a lithium-ion capacitor.
Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catn being CatORGn , can be preferably used in electrochemical and/or optoelectronic devices such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, and a dye sensitized solar cell, particularly preferred in a dye sensitized solar cell.
Electrolyte formulations comprising a compound of formula (I), preferably a compound of formula (I) with Catn being CatORGn , are alternatives to already known electrolyte formulations. They show especially in the field of electrolyte formulations of dye sensitized solar cells increased power conversion efficiency particularly under low temperature. The advantage of the use of compounds of formula (I) is their low viscosity, and subsequently the smaller Nernst diffusion resistance of the oxidant species, especially at lower temperature.
Compound of formula (I) exhibit interesting melting points, thermal and electrochemical stability, viscosity, polarity and solubility in water or in organic solvents.
Compounds of formula (I) are halogen- free, which makes inexpensive and environmentally friendly disposal possible, for example by incineration, and they have low corrosivity towards metals, which simplifies their use and storage.
EXAMPLES
Methods
LCMS:
Agilent Instruments 1100 Series
Some mg of the compound were dissolved in MeCN, filtered over a 0.45 μιη Nylon filter and injected (1 μΐ) on a Waters XBridge (C18, 30 x 2.1mm, 3.5 μ) column.
Flow: 1 ml/min Column temp: 35°C
Eluent A: 0.1% formic acid in acetonitrile
Eluent B : 0.1% formic acid in water
Lin. Gradient: t = 0 min 2% A, t = 1.6 min 98% A, t = 3 min 98% A
Detection: DAD (220 to 320 nm)
Detection: MSD (ESI pos/neg) mass range: 100 to 800
Detection: NQAD (Quant QT-500) filter 1.3 sec; evaporation temperature: 35°C
Example 1: Synthesis of compound of formula (A)
13C-NMR (100.6 MHz, CDC13, TMS): delta [ppm] = 59.09 (s); 63.26 (s); 72.23 (s)
"B-NMR (160.5 MHz, CDC13, TMS): delta [ppm] = 17.97 (s)
Example 2: Synthesis of compound of formula (1)
A suspension of compound of formula (A) (45 g, 0.19 mol, 1 eq., prepared according to example 1) and KCN (12.4 g, 0.19 mol, 1 eq.) in TMSCN (66.2 g, 0.67 mol, 3.5 eq.) was stirred at 70°C for 24 hours and then at 130°C for 20 hours. The crude reaction product was solid and was suspended in heptane (200 ml) and DCM (50 ml) and stirred for 15 minutes. After filtration over a glass filter (pore size P3), 35.44 g (92%) of a solid was obtained. 34.4 g of the solid was suspended in CH3CN (650 ml), stirred for 30 minutes, filtered over celite and washed with CH3CN (500 ml). The filtrate was concentrated under vacuum to provide 32.23 g (94%>) of a reddish orange solid. 30.5 g of the solid was suspended in CH3CN (80 ml), stirred for 60 minutes, filtered over a glass filter (pore size P4) to afford after drying under vacuum 22.96 g (59%o) of compound of formula (1) as a solid, with a melting point (DSC) of ca.
238°C
1H-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 3.30 ( s, 3H); 3.43 to 3.46 (m, 2H); 3.49 (m, 2H)
13C-NMPv (100.6 MHz, CD3CN, TMS): delta [ppm] = 59.13 (s); 65.79 (s); 74.27 (q: J = 4 Hz); 129.06 (q: J = 70 Hz)
"B-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.08 (t: J = 1.6 Hz)
LCMS [B(CN)3(OCH2CH2OCH3)]": 164 Elementary Analysis:
Example 3: Synthesis of compound of formula (B)
1H-NMR (400 MHz, CDC13, TMS): delta [ppm] = 1.15 ( br t, J = 8Hz, 3H); 3.45 to 3.54 (m,
8H); 3.89 ( br t, JH/B = 4Hz, 2H)
13C-NMR (100.6 MHz, CDC13, TMS): delta [ppm] = 15.29 (s); 62.81 (s); 66.76 (s); 70.02
(s); 70.68 (s); 71.76 (s)
"B-NMR (160.5 MHz, CDC13, TMS): delta [ppm] = -18.00 (s)
Example 4: Synthesis of compound of formula (2)
A suspension of compound of formula (B) (15 g, 36.6 mmol, 1 eq., prepared according to example 3) and KCN (2.38 g, 36.6 mmol, 1.0 eq.) in TMSCN (12.69 g, 128 mmol, 3.5 eq.) was stirred at 90°C for 19 hours in an autoclave under nitrogen atmosphere. To the suspension was added heptane (66 ml) and DCM (15 ml) and the suspension was filtered over a glass filter (pore size P4). The obtained solid was washed three times with heptane (60 ml) and DCM (15 ml) and dried under vacuum resulting in 7.9 g yield (83%). The dried product was suspended in CH3CN (19 ml), filtered over a glass filter (pore size P4) and dried under vacuum to yield 5.5 g (57%) of compound of formula (2) as a white solid with a melting point (DSC) of ca. 208°C
1H-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 1.15 ( br t, J = 8Hz, 3H); 3.47 to 3.55 (m, 10H)
13C-NMR (100.6 MHz, CD3CN, TMS): delta [ppm] = 15.41 (s); 65.57 (s); 67.10 (s); 70.31
(s); 70.86 (s); 72.27 (q: J = 4 Hz); 128.57 (q: J = 70 Hz)
"B-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.12 (s)
LCMS [B(CN)3(OCH2CH2OCH2CH2OCH3)]-: 222
Elementary Analysis:
Example 5: Synthesis of compound of formula (3)
A solution of l-Ethyl-3 -methyl- IH-imidazo Hum chloride (2.89 g, 19.7 mmol), compound of formula (1) (4.0 g, 19.7 mmol, prepared according to example 2) in water (14.5 ml) was mixed with DCM (29 ml) and stirred at room temperature for 3 hours. After separation of the aqueous from the organic phase, the organic phase was washed with water (5.8 ml), dried over K2CO3 and evaporated on a rotary evaporator yielding 4.33 g (80%) of compound of formula (3) as a slightly yellow solid with a melting point (DSC) of ca. 62°C
1H-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 1.46 ( t, J = 8Hz, 3H); 3.29 (s, 3H); 3.43 to 3.48 (m, 4H); 3.82 (s, 3H); 4.11 (q, J = 8Hz, 3H); 7.33 (s, 1H); 7.38 (s, 1H); 8.42 (s, 1H)
13C-NMR (100.6 MHz, CD3CN, TMS): delta [ppm] = 15.5 (s); 36.8 (s); 45.8 (s); 58.8 (s);
65.5 (s); 74.0 (q: J = 4 Hz); 123.0 (s); 124.7 (s); 128.8 (q: J = 70 Hz)
"B-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.07 (t, 1.6 Hz)
Elementary Analy
Example 6: Synthesis of compound of formula (4)
A solution of tetraethylammonium chloride (3.26 g, 19.7 mmol) and compound of formula (1) (4.0 g, 19.7 mmol, prepared according to example 2) in water (14.5 ml) was mixed with DCM (29 ml) and stirred at room temperature for 5 hours. After separation of the aqueous from the organic phase, the organic phase was washed with water (5.8 ml), dried over K2C03 and evaporated on a rotary evaporator yielding 5.02 g (87%) of compound of formula (4) as a viscous liquid. After standing some days at RT, it solidified into a glassy colorless substance. 1H-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 1.21 ( t, J = 8Hz, 12H); 3.16 (q, J = 8Hz,
8H); 3.29 (s, 3H); 3.42 to 3.45 (m, 2H); 3.48 (m, 2H)
13C-NMR (100 MHz, CD3CN, TMS): delta [ppm] = 7.7 (s); 53.12 (dt, Jc/N = 3Hz); 58.8 (s);
65.5 (s); 74.0 (q: J = 4 Hz); 128.9 (q: J = 70 Hz)
nB-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.04 (t, 1.6 Hz )
Elementary Analysis:
Element C H N
% expected 57.15 9.25 19.04
% found 47.77 8.00 20.6
Example 7: Synthesis of compound of formula (5)
A solution of tetrabutylphosphonium methanesulfonate (5.02 g, 14.16 mmol), and compound of formula (1) (2.88 g, 14.16 mmol, prepared according to example 2) in water (14.5 ml) was mixed with DCM (29 ml) and stirred at room temperature for 5 hours. After separation of the aqueous from the organic phase, the organic phase was washed with water (5.8 ml), dried over K2C03 and evaporated on a rotary evaporator yielding 5.53 g (92%) of compound of formula (5) as a viscous liquid. 1H-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 0.95 ( t, J = 8Hz, 12H); 1.41 to 1.52 (m, 16H); 2.03 to 2.09 (m, 8H); 3.30 (s, 3H); 3.42 to 3.45 (m, 2H); 3.48 to 3.49 (m, 2H) 13C-NMR (100.6 MHz, CD3CN, TMS): delta [ppm] = 13.6 (s); 18.9 (d, JP/C = 48Hz); 23.9 (d, Jp/c = 5Hz); 24.5 (d, JP/C = 15Hz); 58.8 (s); 65.5 (s); 74.1 (q: J = 4 Hz); 128.9 (q: J = 69 Hz)
"B-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.03 (t, 1.6 Hz )
Elementary Analysis:
Example 8: Synthesis of compound of formula (6)
A solution of l-butyl-2-methylpyridin-l-ium bromide (4.53 g, 19.7 mmol) and compound of formula (1) (4 g, 19.7 mmol, prepared according to example 2) in water (14.5 ml) was mixed with DCM (29 ml) and stirred at room temperature for 5 hours. After separation of the aqueous from the organic phase, the organic phase was washed with water (5.8 ml), dried over K2CO3 and evaporated on a rotary evaporator yielding 5.34 g (86%) of compound of formula (1) as a viscous liquid.
Ή-NMR (400 MHz, CD3CN, TMS): delta [ppm] = 1.05 ( t, J = 8Hz, 3H); 1.47 to 1.54 (m, 2H); 1.90 to 1.94 (m, 2H); 2.87 (s, 3H); 3.36 (s, 3H); 3.49 to 3.54 (m, 4H); 4.52 (br t, J = 8Hz, 3H); 7.88 to 7.95 (m, 2H); 8.39 (m, 1H); 8.65 to 8.66 (m, 1H)
13C-NMR (100.6 MHz, CD3CN, TMS): delta [ppm] = 13.8 (s); 20.2 (s); 20.5 (S); 32.5 (s);
58.85 (s); 58.87 (s); 65.5 (s); 74.1 (q: J = 4 Hz); 126.8 (s); 128.8 (q: J = 70 Hz); 146.1 (d);
155.4 (s)
"B-NMR (160.5 MHz, CD3CN, TMS): delta [ppm] = -19.06 (t, 1.6 Hz )
Elementary Analysis:
Example 9: Synthesis of compound of formula (7)
To compound of formula (2) (5.17 g, 19.8 mmol), prepared according to example 4, were added dichloromethane (40 ml) and l-ethyl-3 -methylimidazolium chloride (2.95 g, 20.1 mmol). The mixture was stirred at room temperature for 26 h. The mixture was then filtered and concentrated under reduced pressure, to yield 6.49 g (98%) of compound of formula (7) as a colorless oil.
1H NMR (400 MHz, CDC13) delta [ppm] = 1.05 (t, J = 7 Hz, 3H), 1.60 (t, J = 7 Hz, 3H), 3.44 (quart, J = 7 Hz, 2H), 3.57 (m, 2H), 3.66 (m, 6H), 3.98 (s, 3H), 4.28 (quart, J = 7 Hz, 2H), 7.32 (s, 2H), 9.01 (s, 1H).
Application example
Compound were tested in dye sensitized solar cells and compared to the compound l-ethyl-3- methylimidazolium tricyanomethoxyborate, called COMP-W0131-Ex2, prepared according to example 2 of WO 2010/086131 Al.
DMII dimethylimidazoliumiodide
EMU ethylmethylimidazo liumiodide
EMI ethylmethylimidazo Hum
NBB n-butylbenzimidazol
GNCS guanidiniumthiocyanid
The compound tested is called compound(TEST), compound(TEST) is selected from the group consisting of was compound of formula (7), compound of formula (5) and COMP- W0131-Ex2.
Device fabrication: Photoanodes used to make the devices consisted of a screen-printed nanoparticulate mesoporous Ti02 layers. A 8 μιη thick transparent layer of 20 nm sized Ti02 particles was first printed on the fluorine doped Sn02 (FTO) conducting glass (purchased from NSG with ΙΟΩ/cm2, 4 mm thick) and subsequently coated with a 5 μιη thick second layer of 400 nm light-scattering anatase particles (CCIC, Japan). Detailed procedures for the preparation of Ti02 nanoparticles and pastes are reported in Ito, S. et al, Prog. Photovolt. Res. AppL, 2007, 15, 603. A standard C106 dye with CAS 1165943-93-0 was used as the sensitizer with the addition of dineohexyl bis-(3,3-dimethyl-butyl)-phosphinic acid
(DINHOP) as a co-adsorbent (4: 1 ratio) in a solvent mixture of 10% DMSO and tert-butanol and acetonitrile (1 :1) v/v ratio. The above-described double-layered Ti02 films were sintererd for 30 min at 500° C and immersed in the dye solution for 16 h. After sensitization they were rinsed in pure MeCN and assembled with platinized counter electrodes. The counter electrodes were prepared using conducting glass TEC 15 (purchased from NSG, resistance 15Ω/αη2, 2 mm thick) on which the drop of a solution of hexachloroplatinate acid in n- propanol was cast. Thermal platinization occured during heating the electrodes twice for 15 min at 425 °C in air. Electrodes were then sealed with a 25 micrometer thick hot-melt film (Surlyn®, Dupont) by heating the system at 100°C.
The composition of the electrolyte B which was used:
electrolyte A = DMII/EMII/compound(TEST) /I2/NBB/GNCS (12/12/16/1.67/3.33/0.67) electrolyte B = electrolyte A + sulfolane (50:50 v/v).
Devices were completed by filling the space between the electrodes with electrolyte through pre-drilled holes in the counter electrodes and the holes were sealed with a Surlyn sheet and a thin glass cover by heating. Finally, metal contacts were placed on both electrodes. Photovoltaic measurements: Photovoltaic measurements were performed under simulated sun irradiance (100 mW cm"1, equivalent of 1 sun at air mass global, AM 1.5G, at the surface of the device) provided by a 450 W Xenon light source (Oriel, USA). A Schott Kl 13 Tempax sunlight filter (Prazisions Glas & Optik GmbH, Germany) was used to correct the spectral output of the lamp in the region 350 to 750 nm. Current to voltage characteristics (in the dark
and under illumination) were obtained by applying a forward potential bias and measuring resulting current with a Keithley 2400 digital sourcemeter (Keithley, USA). A metal mask was used to precisely define the irradiated surface area (0.159 cm2). Quantum efficiencies of the cells were measured by using a SR830 lockin amplifier, however the incident light (300 W xenon lamp, ILC Technology) was focused through a Gemini- 180 double monochromator (Jobin-Yvon Ltd.). The cells were measured with an external light bias (10% Sun) provided by LED array. A black metal mask defined the cell active area to be 0.159 cm2.
Results
The photovoltaic parameters of devices containing electrolyte B @ 60 °C using Pt as a counter electrode are shown in the tables 1 to 3 at 0.1 sunlight and in table 4 at 1 sunlight. The tables show the photovoltaic parameters of CI 06 dye based devices measured under irradiation of 10 mW cm-2 AM 1.5G Sunlight.
The higher the efficiency the better.
Table 1 : results of COMP-W0131-Ex2
Table 2: results of compound of formula (5)
Table 3: results of compound of formula (7)
Jsc short circuit photo current
Voc open circuit voltage
FF fill factor
η efficiency
nd not determined
Table 4 shows better fill factors of compound of formula (7) compared to COMP-W0131- Ex2 in a suntest at 60°C with 100% sun.
Table 4 COMP-W0131-Ex2 compound of formula (7)
Time FF FF
[h] [%] [%]
0 69 69
117 67 71
283 56 69
Claims
1. A compound of formula (I);
R101 is Ci_6 alkyl;
R102 is a linear or branched Ci
Cat is a cation, which is selected from the group consisting of inorganic cation CatINORGn+ and organic cation CatORGn+;
n is 1 or 2;
m is 1, 2, 3 or 4.
2. Compound of formula (I) according to claim 1, wherein
R101 is Ci_2 alkyl;
m is 1, 2 or 3;
R102 is a linear or branched C2_i2 alkylene.
3. Compound of formula (I) according to claim 1 or 2, wherein
CatlNORG is selected from the group consisting of Li , Na , K , Rb , Cs , NH4 , Ag
Be2+, Mg2+, Ca2+, Sr2+ and Ba2+.
4. Compound of formula (I) according to claim 1 to 2, wherein
CatORGn+ contains a heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
5. Compound of formula (I) according to one or more of claims 1, 2 and 4, wherein,
when n is 2, then CatORGn+ is (H3N-CH2-CH2-NH3)2+.
6. Compound of formula (I) according to one or more of claims 1 , 2 and 4, wherein, when n is 1 , then CatORG+ is selected from the group consisting of cation CatORG-A+, CatORG-B+, CatORG-C+, CatOrg-D+ and CatORG-E+;
CatOrg-A+ is (WR2R3R4R5)+,
wherein
W is a nitrogen or phosphorus;
(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_2o alkyl, Ci_2o perfluoroalkyl, C3_io cycloalkyl and C6-io aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or
(ii) R2 and R3 together with W form a 5- to 7-membered saturated or unsaturated ring, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, Ci_2o alkyl, Ci_2o perfluoroalkyl, C3_io cycloalkyl and C6-io aryl; or
(iii) R2 and R3 together with W and R4 and R5 together with W form, independently from each other, a 5- to 7-membered saturated or unsaturated ring;
CatOrg-B+ is (XR6R7R8)+,
wherein
X is nitrogen,
R6 and R7 together with X form a 5- to 7-membered unsaturated ring in which X formally has one single bond and one double bond to R6 and R7 respectively,
R8 is selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl, C3_io cycloalkyl or C6-io aryl;
CatOrg-C+ is (YR9R10R1 1)+,
wherein
Y is sulphur;
(i) R9, RIO and Rl 1 are identical or different and independently from each other selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl, C3_io cycloalkyl and C6-io aryl; or
(ii) R9 and RIO together with Y form a 5- to 7-membered saturated or unsaturated ring, Rl 1 is selected from the group consisting of Ci_2o alkyl, Ci_2o perfluoroalkyl,
C3-10 cycloalkyl and C6-io aryl; CatOrg-D+ is (ZR12R13)+,
wherein
Z is oxygen or sulphur;
R12 and R13 together with Z form a 5- to 7-membered ring in which Z formally has one single bond and one double bond to R12 and R13 respectively;
CatORG-E+ is a cyclic C3_9 alkane or a cyclic C3_9 alkene bearing a positive charge;
in case of a cyclic C3_9 alkene, CatORG-E+ has 1, 2 or 3 double bonds; the residues R2, R3, R4, R5, R6, R7, R8, R9, RIO, Rl 1, R12 and R13 are, independently from each other, unsubstituted or, where applicable, substituted by 1 , 2 or 3 substituents selected from the group consisting of halogen, cyano and Ci_4 alkoxy; rings formed by R2 and R3 together with W, R4 and R5 together with W, R6 and R7 together with X, R9 and RIO together with Y and R12 and R13 together with Z contain no, 1 or 2 further heteroatoms, the heteroatoms being selected from the group consisting of O, N and S; and wherein any further heteroatom N can be substituted by Ci_s alkyl or Ci_2o perfluoroalkyl.
7. Compound of formula (I) according to one or more of claims 1, 2 and 4, wherein, CatORGn+ is selected from the group consisting of ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium,
imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium,
morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium and thiopyrylium, quinoxalinium, indolinium, indolium, cyclopropenylium, 1,2,3-triphenylcyclopropenylium, tri-tert-butylcyclopropenylium, 1,2,3- tris(diethylamino)cyclopropenylium, 1 ,2,3-tris(trimethylsilyl)cyclopropenylium and tropylium, l,2,3,4,5,6,7-heptaphenylcyclohepta-2,4,6-trien-l-ylium.
8. Compound of formula (I) according to one or more of claims 1, 2, 4 and 6, wherein
CatORG is selected from the group consisting of
R20 is Ci_2o alkyl;
R21 , R22 and R23 are identical or different and independently selected from the group consisting of H and Ci_2o alkyl.
9. Compound of formula (I) according to claim 1 , wherein,
compound of formula (I) is selected from the group consisting of compound of formula (1), compound of formula (2), compound of formula (3), compound of formula (4), compound of formula (5), compound of formula (6) and compound of formula (7).
10. A method for the preparation of compound of formula (I) as defined in claim 1, the method comprises a step (Stl) or a step (St2);
step (Stl) comprises a reaction (Real), wherein compound of formula (X) is reacted with trimethylsilylcyanide in the presence of cation Catn ;
(Cat )(AnINORG4")t (I-Cat-n) q is 1 or 2;
r is 1 or 2;
when n and q are identical, then t is 1 ;
when n is 2 and q is 1 , then t is 2;
when n is 1 and q is 2, then t is 0.5;
AnINORGq" is an anion selected from the group consisting of halide, OH", CN~, OCN", SC , N3 ~, sulfate, hydrogensulfate, nitrate, C03 2", HC03 ", BF4 ", PF6 ", SbF6 ", CF3S03
(CF3S02)2N , (FS02)2N , Ci_6 alkylsulfonate, Ci_6 alkylsulfate, dioctylsulfosuccinate, anions of Ci_2o monocarboxylic aliphatic acids, anions of C2-6 dicarboxylic aliphatic
acids, benzoate, phthalates, N(CN)2 ", C(CN)3 ", B(CN)4 ", P(CN)6 ", Sb(CN)6 ", and mixtures thereof;
Cat-rr+ has the same definition as Catn and is different from Catn ; Catn , n, m, R101 and R102 are as defined in claim 1.
11. Method according to claim 10, wherein
AnINORGq is an anion selected from the group consisting of halide, OH", CN~, sulfate, hydrogensulfate, nitrate, C03 2", HC03 ", BF4 ", PF6 ", CF3S03 ", (CF3S02)2N~, (FS02)2N~, methyl sulfonate, ethyl sulfonate, methyl sulfate, ethyl sulfate, acetate, oleate, fumarate, maleate, oxalate, benzoate, N(CN)2 , and mixtures thereof.
12. Method according to claim 10 or 11, wherein
compound of formula (X) is prepared in a step (StO);
step (StO) is done before step (Stl);
step (StO) comprises a reaction (ReaO), wherein boric acid is reacted with a compound of formula (X-0);
wherein
m, R101 and R102 are as defined in claim 10.
13. Use of compound of formula (I) as defined in claim 1 as solvent, as phase-transfer catalyst, as extractant, as heat-transfer medium, as surface-active substance, as plasticizer, as conductive salt, organic salt or additive in electrochemical cells, as electrolyte; as lubricant and as hydraulic fluid, as component in electrolyte formulations.
14. Use according to claim 13 of compound of formula (I) as component in electrolyte formulations, wherein
such electrolyte formulations comprising a compound of formula (I) are used in batteries, in capacitors, in supercapacitors or in electrochemical cells.
15. Use according to claim 13 of compound of formula (I) as component in electrolyte formulations, wherein
such electrolyte formulations comprising a compound of formula (I) are used in
electrochemical and/or optoelectronic devices.
16. Use according to claim 15 of compound of formula (I), wherein the electrochemical and/or optoelectronic devices are selected from the group consisting of photovoltaic cell, light emitting device, electrochromic or photo-electrochromic device, electrochemical sensor and/or biosensor, and dye sensitized solar cell.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261696563P | 2012-09-04 | 2012-09-04 | |
| EP12182880.0 | 2012-09-04 | ||
| US61/696,563 | 2012-09-04 | ||
| EP12182880 | 2012-09-04 | ||
| EP13150665.1 | 2013-01-09 | ||
| EP13150665 | 2013-01-09 | ||
| EP13160510 | 2013-03-21 | ||
| EP13160510.7 | 2013-03-21 | ||
| EP13176037.3 | 2013-07-11 | ||
| EP13176037 | 2013-07-11 | ||
| EP13177686 | 2013-07-23 | ||
| EP13177686.6 | 2013-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014037291A1 true WO2014037291A1 (en) | 2014-03-13 |
Family
ID=50236568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2013/068048 WO2014037291A1 (en) | 2012-09-04 | 2013-09-02 | Tricyanoborate alkyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2014037291A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086131A1 (en) * | 2009-02-02 | 2010-08-05 | Lonza Ltd | Novel tricyanoborates |
| WO2012041434A1 (en) * | 2010-09-28 | 2012-04-05 | Merck Patent Gmbh | Electrolyte formulations containing cyano-alkoxy-borate anions |
-
2013
- 2013-09-02 WO PCT/EP2013/068048 patent/WO2014037291A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086131A1 (en) * | 2009-02-02 | 2010-08-05 | Lonza Ltd | Novel tricyanoborates |
| WO2012041434A1 (en) * | 2010-09-28 | 2012-04-05 | Merck Patent Gmbh | Electrolyte formulations containing cyano-alkoxy-borate anions |
Non-Patent Citations (2)
| Title |
|---|
| E. ZYGADLO-MONIKOWSKA ET AL: "Synthesis and characterization of new trifluoroalkoxyborates lithium salts of ionic liquid properties", ELECTROCHIMICA ACTA, vol. 57, 2011, pages 66 - 73, XP028124243, ISSN: 0013-4686, [retrieved on 20110805], DOI: 10.1016/J.ELECTACTA.2011.07.120 * |
| MAKOTO MORIYA ET AL: "Plastic crystalline lithium salt with solid-state ionic conductivity and high lithium transport number", CHEMICAL COMMUNICATIONS, vol. 47, 2011, pages 6311 - 6313, XP055043731, ISSN: 1359-7345, DOI: 10.1039/c1cc00070e * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5980918B2 (en) | Compounds containing alkyl-cyano-borate or alkyl-cyano-fluoroborate anions | |
| JP5990262B2 (en) | Compounds containing hydrido-tricyano-borate anions | |
| JP5950916B2 (en) | Electrolyte formulation comprising cyano-alkoxy-borate anion | |
| JP5898629B2 (en) | Electrolyte compound | |
| JP6038796B2 (en) | Electrolyte compound | |
| WO2014167035A1 (en) | Method for preparation of fluoro and chloro cyano compounds of the 15th group | |
| JP2013131477A (en) | Cobalt electrolyte, electrolytic solution, dye sensitized solar cell, and method for producing cobalt electrolyte | |
| JP5793509B2 (en) | Compounds containing perfluoroalkyl-cyano-alkoxy-borate anions or perfluoroalkyl-cyano-alkoxy-fluoro-borate anions | |
| TW201311709A (en) | Electrolyte formulations | |
| WO2013026563A1 (en) | Additives for dye-sensitized solar cells | |
| WO2011085964A1 (en) | Electrolyte formulations | |
| KR101352904B1 (en) | Electrolyte composition for dyesensitized solar cell having the same | |
| WO2014037291A1 (en) | Tricyanoborate alkyl ethers | |
| KR101158767B1 (en) | New imidazolium salts and electrolyte composition for dye-sensitized sollar cells containing the salt | |
| WO2014147162A1 (en) | Tricyano(fluorophenyl)borates | |
| US8859800B2 (en) | Compounds containing alkyl-alkoxy-cyano-borate anions | |
| JP2017008194A (en) | Sensitized dye, semiconductor electrode, photoelectric conversion element and dye sensitized solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13758827 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 13758827 Country of ref document: EP Kind code of ref document: A1 |