CN102300631A - 新型三氰基硼酸盐 - Google Patents
新型三氰基硼酸盐 Download PDFInfo
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- CN102300631A CN102300631A CN2010800056581A CN201080005658A CN102300631A CN 102300631 A CN102300631 A CN 102300631A CN 2010800056581 A CN2010800056581 A CN 2010800056581A CN 201080005658 A CN201080005658 A CN 201080005658A CN 102300631 A CN102300631 A CN 102300631A
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- CN
- China
- Prior art keywords
- alkyl
- group
- tricyano
- cation
- aryl
- 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.)
- Granted
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002892 organic cations Chemical class 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 10
- 150000001767 cationic compounds Chemical class 0.000 claims abstract description 9
- 229910001411 inorganic cation Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- -1 organic cation cation Chemical class 0.000 claims description 42
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000005864 Sulphur Chemical group 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 17
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002891 organic anions Chemical group 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003235 pyrrolidines Chemical class 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical compound C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004880 oxines Chemical class 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 229910052717 sulfur Chemical group 0.000 abstract 1
- 239000011593 sulfur Chemical group 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ZZAPUBCMDORKBR-UHFFFAOYSA-N C(C)N1CN(C=C1)C.B(O)(O)O Chemical compound C(C)N1CN(C=C1)C.B(O)(O)O ZZAPUBCMDORKBR-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- KHVDKGBRIPYIAV-UHFFFAOYSA-N CCCCP.OB(O)O Chemical compound CCCCP.OB(O)O KHVDKGBRIPYIAV-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229940094989 trimethylsilane Drugs 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AWYVOUGUSDCGAC-UHFFFAOYSA-N 1-butyl-2-methyl-2h-pyridine Chemical compound CCCCN1C=CC=CC1C AWYVOUGUSDCGAC-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZZQWYVKWJHBWRC-UHFFFAOYSA-N [O].C(CCCCCCCCCCC)OCCCCCCCCCCCCC Chemical compound [O].C(CCCCCCCCCCC)OCCCCCCCCCCCCC ZZQWYVKWJHBWRC-UHFFFAOYSA-N 0.000 description 1
- GTZOZDOTOWNSJH-UHFFFAOYSA-N [O].CCCCCCC Chemical compound [O].CCCCCCC GTZOZDOTOWNSJH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 229960003019 loprazolam Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- OTIVLGJBKUFOEX-UHFFFAOYSA-N n-tetradecoxyaniline Chemical compound CCCCCCCCCCCCCCONC1=CC=CC=C1 OTIVLGJBKUFOEX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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 Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本发明涉及通式Catn+[B(CN)3(XR1)]- n的新型三氰基硼酸盐,其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基;X为氧或硫;且Catn+为选自由无机阳离子及有机阳离子组成的群的阳离子,其中n为1或2;且还涉及其制备及用途。
Description
技术领域
本发明涉及新型三氰基硼酸盐、其用途及其制备方法。
背景技术
术语“离子液体”通常用于指在低于100℃的温度下、尤其在室温下为液体的盐。这些液体盐通常包含有机阳离子及有机阴离子或无机阴离子。
离子液体的有机阳离子通常为四级铵离子或四级鏻离子或芳族碱(通常为含氮碱)的阳离子,所述离子可经烷基、卤素原子或氰基取代且还可含有其它杂原子(诸如磷、硫或氧)。通常的有机阳离子的实例为咪唑鎓、噁唑鎓、吡嗪鎓、吡唑鎓、哒嗪鎓、吡咯烷鎓、吡啶鎓、噻唑鎓及三唑鎓阳离子。
离子液体中的典型阴离子为AlCl4 -、AsF6 -、BF4 -、Br-、CF3SO3 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、Cl-、CN-、SCN-、FeCl3 -、NO3 -、PF6 -、丙酮酸根、乙酸根、草酸根或EP-A-1634867中所述的三氰基甲烷阴离子。另外,WO 2004/072089及WO2007/093961公开通式[BFn(CN)4-n]-的氰基硼酸根阴离子,其中n为0、1、2或3。
离子液体具有一系列值得关注的特性:通常,其为热稳定的、相对不易燃,且具有极低蒸气压。另外,其对诸多有机物及无机物具有极佳溶剂特性。离子液体因其离子结构而亦具有值得关注的电化学特性,例如通常伴有高电化学稳定性的导电性。因此,对具有各种特性的新型离子液体存在基本需要,从而为其用途开辟其它机会。
发明内容
本发明的一目的在于提供可用作离子液体或离子液体的前体的新型稳定化合物以及其制备方法。这些化合物在使用之后应能够以对环境无害的方式处理。
此目的通过由如权利要求1所述的三氰基硼酸盐、如权利要求12所述的其用途及如权利要求13和14所述的其制备方法实现。其它优选具体实施方式为从属权利要求的主题。
本发明涉及以下通式的新型三氰基硼酸盐:
其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,
X为氧或硫,且
Catn+为阳离子(其中n为1或2),其选自由无机阳离子Mn+及有机阳离子Qn+(其中n为1或2)组成的群。
在此处及下文中,表述“C1-n烷基”指含有1至n个碳原子的任何直链或支链烷基。举例而言,表述“C1-6烷基”包含以下基团:诸如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基(3-甲基丁基)、新戊基(2,2-二甲基丙基)、己基及异己基(4-甲基戊基)。
在此处及下文中,表述“C2-n烯基”指由2至n个碳原子组成且含有至少一个双键的碳链,其中碳原子被氢原子饱和且所述碳链能够分支。举例而言,表述“C2-4烯基”包含以下基团:诸如乙烯基、1-甲基乙烯基、丙-1-烯基、丙-2-烯基、2-甲基丙-2-烯基及丁-1,3-二烯基。
在此处及下文中,表述“C6-10芳基”指具有6至10个碳原子且可经一个或一个以上C1-4烷基或C1-4烷氧基取代的芳基。举例而言,“C6-10芳基”包含苯基、苯甲基、甲基苯基、甲氧基苯基、二甲基苯基、乙基甲基苯基、二乙基苯基及萘基。
优选其中X为氧的式I的三氰基硼酸盐。
还优选其中R1为C1-6烷基(R1优选为甲基、乙基或丙基,且更优选为甲基)的式I的三氰基硼酸盐。
在另一优选具体实施方式中,阳离子Catn+为选自由Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+组成的群的无机阳离子Mn+(其中n为1或2)。
在一亦优选的具体实施方式中,阳离子Catn+为含有至少一个选自由氮、磷、硫及氧组成的群的杂原子的有机阳离子Qn+(其中n为1或2,优选为n为1)。
特别优选具有二价有机阳离子Q2+(诸如乙二铵)的式I三氰基硼酸盐。
进一步特别优选具有单价有机阳离子Q+的式I三氰基硼酸盐,所述单价有机阳离子Q+选自由下式阳离子组成的群:
(a)(WR2R3R4R5)+,其中W为氮或磷,且
(i)其中R2至R4独立地为C1-20烷基,且R5为C1-20烷基、C3-10环烷基或C6-10芳基,其中R2至R5独立地任选含有一个或一个以上卤素,或
(ii)其中R2及R3与W一起形成5元至7元环,且R4及R5独立地为C1-20烷基,其中R4及R5独立地任选含有一个或一个以上卤素,或
(iii)其中R2及R3或R4及R5在各种情况下与W一起形成5元至7元环,或
(b)(XR6R7R8)+,其中X为氮,且R6及R7与X一起形成环,其中X在形式上经由一个单键及一个双键键合至R6及R7,且R8为C1-20烷基、C3-10环烷基或C6-10芳基,其中R8任选含有一个或一个以上卤素,或
(c)(YR9R10R11)+,其中Y为硫,且
(i)其中R9及R10独立地为C1-20烷基,且R11为C1-20烷基、C3-10环烷基或C6-10芳基,其中R9至R11独立地任选含有一个或一个以上卤素,或
(ii)其中R9及R10与Y一起形成5元至7元环,且R11为C1-20烷基、C3-10环烷基或C6-10芳基,其中R11任选含有一个或一个以上卤素,或
(d)(ZR12R12)+,其中Z为氧或硫,且R12及R13与Z一起形成环,其中Z在形式上经由一个单键及一个双键键合至R12及R13,且
其中一个或一个以上选自由C1-20烷基、C1-20烷氧基、C3-10环烷基、C6-10芳基、卤素及氰基组成的群的取代基任选结合至由所述取代基R1至R13所形成的各环,其中所述C1-20烷基、所述C1-20烷氧基、所述C3-10环烷基及所述C6-10芳基独立地任选含有一个或一个以上卤素,且
其中由所述取代基R1至R13所形成的各环任选含有一或两个经进一步取代的或未经取代的选自由氮、硫及氧组成的群的杂原子,和/或与另一芳族或非芳族5元至7元环稠合。杂原子的适合取代基为例如C1-8烷基。
在此处及下文中,表述“C3-n环烷基”指具有3至n个碳原子的环烷基。“C3-10环烷基”代表例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基或环癸基。
在此处及下文中,表述“C1-n烷氧基”指具有1至n个碳原子的无支链或支链烷氧基。“C1-20烷氧基”代表例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、1,4-二甲基戊氧基、己氧基、庚氧基、辛氧基、1,5-二甲基己氧基、壬氧基、癸氧基、4-乙基-1,5-二甲基己氧基、十一烷氧基、十二烷氧基、十三烷氧基、十四烷氧基或二十烷氧基。
在此处及下文中,表述“卤素”指氟、氯、溴或碘。
特别优选其中有机阳离子Q+选自由以下组成的群的式I的三氰基硼酸盐:有机铵、鏻、锍、吡咯烷鎓、吡咯啉鎓、吡咯鎓、吡唑鎓、咪唑鎓、三唑鎓、噁唑鎓、噻唑鎓、哌啶鎓、哌嗪鎓、吗啉鎓、吡啶鎓、哒嗪鎓、嘧啶鎓、吡嗪鎓、1,3-二氧杂环戊烯鎓、吡喃鎓及硫代吡喃鎓阳离子。
优选地,所述有机阳离子Q+选自由以下组成的群:
其中R及R′独立地为C1-20烷基,优选为C1-14烷基且更优选为C1-8烷基,且m为0与4的间的整数。取代基R及R′宜具有不同长度。
更优选地,所述有机阳离子Q+选自由以下组成的群:
在另一特别优选的具体实施方式中,所述有机阳离子Q+为咪唑鎓阳离子,尤其以下通式的咪唑鎓阳离子
其中R及R′独立地为C1-20烷基,优选为C1-14烷基。在一最优选的具体实施方式中,R为甲基且R′为乙基。
详言之,要求保护的是化合物三氰基甲氧基硼酸1-乙基-3-甲基咪唑鎓。
具有有机阳离子的三氰基硼酸盐通常在低于100℃的温度下,尤其在室温下为液体,且因此称作离子液体。离子液体因其特性而极其适合用作多种有机物及无机物的溶剂。
因此,要求保护的是式I的三氰基硼酸盐(其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,X为氧或硫,且Catn+为有机阳离子Qn+(其中n为1或2,优选n为1))用作极性非质子性溶剂的用途,所述三氰基硼酸盐任选与一种或一种以上其它离子液体、水或有机溶剂混合。
离子液体适用于诸多领域:其使用范围自用作无机及有机合成中的溶剂直至用作脱模剂的电解质及/或润滑剂及液压流体的添加剂。因此,离子液体必须满足以适用于特定应用的特定要求的范围相对较宽。本发明离子液体的特征尤其在于非配位阴离子。另外,其不含卤素,从而可以廉价且对环境无害的方式处理,例如焚化,且由于对金属的腐蚀性低而简化了其使用及储存。
本发明离子液体的特性可通过选择适合有机阳离子及硼酸盐阴离子的适合取代基-X-R1而改变。因此,例如,通过改变硼酸盐阴离子的取代基-X-R1以及改变有机阳离子及其取代基可强烈影响熔点、热稳定性及电化学稳定性、粘度、极性及在水或有机溶剂中的溶解性。
此外,本发明涉及制备式I的无机三氰基硼酸盐(其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,X为氧或硫,且Catn+为优选选自由Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+组成的群的无机阳离子Mn+(其中n为1或2))的方法,其特征在于
使B(XR1)3与氰基三-C1-6烷基硅烷(尤其氰基三甲基硅烷(TMSCN))在Mn+(CN-)n存在下反应,其中
R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,
X为氧或硫,且
Mn+为优选选自由Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+组成的群的无机阳离子(其中n为1或2)。
优选地B(XR1)3与Mn+(CN-)n以摩尔比0.8∶1.0至1.2∶1.0、尤其以摩尔摩尔比0.9∶1.0至1.1∶1.0施用。以B(XR1)3计,优选使用过量氰基三-C1-6烷基硅烷,例如摩尔比为1.5∶1至10∶1,尤其摩尔比为3∶1至5∶1。制备无机三氰基硼酸盐的方法优选在0℃至250℃的温度下、尤其在50℃至100℃的温度下进行。制备无机三氰基硼酸盐的方法优选在高于作为副产物形成的烷氧基三-C1-6烷基硅烷的沸点的温度下进行。
本发明还涉及制备式I的有机三氰基硼酸盐(其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,X为氧或硫,且Catn+为有机阳离子Qn+(其中n为1或2,优选n为1))的方法,其特征在于
使式I的无机三氰基硼酸盐(其中R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,X为氧或硫,且Catn+为优选选自由Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+组成的群的无机阳离子Mn+(其中n为1或2)),
与式(Qn+)p(Yp-)n的盐反应,其中
Qn+为有机阳离子,尤其含有至少一个选自由氮、磷、硫及氧组成的群的杂原子的有机阳离子,
n为1或2,
Yp-为选自由卤离子、拟卤离子(pseudohalide)、硫酸根及有机酸阴离子组成的群的阴离子,且
p为1或2。
在一优选具体实施方式中,所用无机三氰基硼酸盐是根据上文所主张的其制备方法预先制备。
作为式(Qn+)(Y-)n盐的阴离子Y-的卤离子可选自由氟离子、氯离子、溴离子及碘离子组成的群。特别优选为氯离子。
对于盐(Qn+)(Y-)n中的拟卤阴离子Y-,可使用由至少两个负电性原子组成且化学上类似于卤素的阴离子。拟卤阴离子优选选自由CN-、OCN-、SCN-及N3 -组成的群。拟卤阴离子更优选为CN-。
有机酸阴离子的适合实例为一元及二元非芳族酸及芳族酸的阴离子,诸如乙酸根、油酸根、反丁烯二酸根、顺丁烯二酸根、丙酮酸根、草酸根及苯甲酸根。更优选为乙酸根及丙酮酸根阴离子。
当n及p为1时,且当n及p为2时,如上所定义的无机三氰基硼酸盐及式QY的盐优选以0.8∶1.0至1.2∶1.0的摩尔比、尤其以0.9∶1.0至1.1∶1.0的摩尔比使用。
所述反应优选在溶剂或溶剂混合物中(例如在包含水及至少一种有机溶剂的两相溶剂混合物中、例如在水与二氯甲烷的混合物中)进行。或者,所述反应亦可在无溶剂的情况下进行或在有机溶剂中进行,其中作为副产物形成的无机盐难溶或不溶于所述有机溶剂。或者,亦可在水溶液中使用预先装载的离子交换剂进行反应。
制备有机三氰基硼酸盐的方法优选在10℃至250℃的温度下、尤其在室温至100℃范围内的温度下进行。
具体实施方式
缩写:
TMSCN=氰基三甲基硅烷
TMSOMe=甲氧基三甲基硅烷
EA=元素分析
CP-OES=感应耦合等离子体光学发射光谱测定法
br=宽峰
实施例1:合成三氰基甲氧基硼酸钾K[B(CN)
3
(OCH
3
)]
将B(OCH3)3(20.0g,0.19mol)及KCN(12.5g,0.19mol)溶解于TMSCN(66.8g,0.67mol)中,且在70℃的回流温度下在保护气体下加热18小时。冷却之后,蒸馏出所有挥发性组份(未反应的TMSCN,形成的TMSOMe),得到粉末状K[B(CN)3(OCH3)],产量为27.8g(92%)。
1H-NMR(400MHz,CD3CN,TMS):δ[ppm]=3.22(q,JH/B=3.5Hz,3H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=53.26(s);128.7(q(80%)+七重峰(20%),q:J=69.9Hz,七重峰:J=23.0Hz)。
11B-NMR(160.3MHz,CD3CN,BF3·Et2O(外标)):δ[ppm]=-18.5(s)。
IR(液体石蜡(Nujol)):v[cm-1]=2228,2163,1201,1221br,965,926,866。
熔点:>240℃(分解)。
分析:
元素 | C | H | N | B | K |
方法 | EA | EA | EA | CP-OES | CP-OES |
理论值,% | 30.22 | 1.90 | 26.43 | 6.80 | 24.29 |
实测值,% | 30.50 | 2.20 | 25.70 | 6.90 | 21.13 |
实施例2:合成三氰基甲氧基硼酸1-乙基-3-甲基咪唑鎓(离子
液体)
将氯化1-乙基-3-甲基咪唑鎓(5.0g,34mmol)、K[B(CN)3(OCH3)](5.4g,34mmol)及水(25.1g)的水溶液与二氯甲烷(67g)混合,且在室温下搅拌1小时。分离水相及有机相之后,用10ml水洗涤有机相且在旋转蒸发仪上蒸发,得到5.81g(74%)呈无色低粘度液体状的三氰基甲氧基硼酸1-乙基-3-甲基咪唑鎓,其即使在-10℃的温度下亦不凝固。
1H-NMR(400MHz,CD3CN,TMS):δ[ppm]=1.62(br t,J=7.0Hz,3H),3.33(q,JH/B=3.5Hz,3H),4.01(s,3H),4.30(br q,J=7,0Hz,2H),7.36(s,1H),7.39(s,1H),8.67(s,1H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=15.1(s),36.8(br),45.7(s),53.3(s),122.3(br),124.0(br),128.3(q(80%)+七重峰(20%),q:J=69.9Hz,七重峰:J=23.0Hz)。
熔点:低于0℃。
实施例3:合成三氰基甲氧基硼酸1-乙基-3-甲基咪唑鎓(离子
液体)
将氯化1-乙基-3-甲基咪唑鎓(5.0g,34mmol)在水(25ml)中的溶液和K[B(CN)3(OCH3)](5.4g,34mmol)与二氯甲烷(67g)混合,且在室温下搅拌3小时。分离水相及有机相之后,用10ml水洗涤后者,经碳酸钾干燥且最后在旋转蒸发仪上蒸发,得到3.78g(48%)呈低粘度液体状的三氰基甲氧基硼酸1-乙基-3-甲基咪唑鎓。
1H-NMR(400MHz,CD3CN,TMS):δ[ppm]=1.62(br t,J=7.0Hz,3H),3.33(q,JH/B=3.5Hz,3H),4.01(s,3H),4.30(br q,J=7,0Hz,2H),7.36(s,1H),7.39(s,1H),8.67(s,1H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=15.1(q),36.8(br),45.7(br),53.3(q),122.3(br),124.0(br),128.3(q(80%)+七重峰(20%),q:J=69.9Hz,七重峰:J=23.2Hz),135.7(d)。
熔点:低于0℃。
实施例4:合成三氰基甲氧基硼酸N-正丁基-2-甲基吡啶鎓(离
子液体)
将氯化N-正丁基-2-甲基吡啶鎓(5.0g,27mmol)在水(20ml)中的溶液和K[B(CN)3(OCH3)](4.3g,27mmol)与二氯甲烷(53g)混合,且在室温下搅拌5小时。分离水相及有机相之后,用10ml水洗涤后者,经碳酸钾干燥且最后在旋转蒸发仪上蒸发,得到4.0g(55%)呈低粘度液体状的三氰基甲氧基硼酸N-正丁基-2-甲基吡啶鎓。
1H-NMR(500MHz,CD3CN,TMS):δ[ppm]=0.92(t,J=7.3Hz,3H),1.35-1.43(m,2H),1.79-1.83(m,2H),2.74(s,3H),3.15(q,JH/B=3.9Hz,3H),4.39(br t,J=8Hz,2H),7.76-7.82(m,2H),8.26-8.30(m,1H),8.52-8.54(m,1H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=12.9(q),19.4(q),19.7(t),31.7(t),52.5(q),58.0(t),126.0(d),128.0(q(80%)+七重峰(20%),q:J=69.9Hz,七重峰:J=20.7Hz),130.5(d),145.1(d),145.3(d),155.61(s)。
熔点:低于0℃。
实施例5:合成三氰基甲氧基硼酸四乙铵(离子液体)
将氯化四乙铵(5.0g,30mmol)在水(22ml)中的溶液和K[B(CN)3(OCH3)](4.8g,30mmol)与二氯甲烷(59g)混合,且在室温下搅拌5小时。分离水相及有机相之后,用10ml水洗涤后者,经碳酸钾干燥且最后在旋转蒸发仪上蒸发,得到4.0g(53%)呈低粘度液体状的三氰基甲氧基硼酸四乙铵。
1H-NMR(500MHz,CD3CN,TMS):δ[ppm]=1.16(tt,J=7.3,JH/N=1.9Hz,12H),3.12(q,J=7.3Hz,8H),3.16(JH/B=3.4Hz,3H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=6.8(q),52.3(dt,Jc/N=3.2Hz),54.5(q),128.0(q(80%)+七重峰(20%),q:J=70Hz,七重峰:J=23.5Hz)。
熔化范围(DSC):1℃与26℃之间。
实施例6:合成三氰基甲氧基硼酸四丁基鏻(离子液体)
将甲烷磺酸四丁基鏻(5.0g,14mmol)在水(10.4ml)中的溶液和K[B(CN)3(OCH3)](2.2g,14mmol)与二氯甲烷(27.6g)混合,且在室温下搅拌5小时。分离水相及有机相之后,用10ml水洗涤后者,经碳酸钾干燥且最后在旋转蒸发仪上蒸发,得到3.4g(64%)呈低粘度液体状的三氰基甲氧基硼酸四丁基鏻。
1H-NMR(500MHz,CD3CN,TMS):δ[ppm]=0.95(t,J=7.3Hz,12H),1.44-1.53(m,16H),2.04-2.10(m,8H),3.21(JH/B=3.4Hz,3H)。
13C-NMR(125MHz,CD3CN,TMS):δ[ppm]=13.76(br q),19.2(td,JP/C=48.3Hz),24.1(td,JP/C=4.6Hz),24.7(td,JP/C=15.6),53.4(q),128.0(q+m,q:J=70Hz)。
熔点:低于0℃。
Claims (15)
2.根据权利要求1所述的三氰基硼酸盐,其中X为氧。
3.根据权利要求1或2所述的三氰基硼酸盐,其中R1为甲基、乙基或丙基。
4.根据权利要求3所述的三氰基硼酸盐,其中R1为甲基。
5.根据权利要求1至4任一项所述的三氰基硼酸盐,其中Catn+为选自由以下组成的群的无机阳离子:Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+。
6.根据权利要求1至4任一项所述的三氰基硼酸盐,其中Catn+为含有至少一个选自由氮、磷、硫及氧组成的群的杂原子的有机阳离子。
7.根据权利要求6所述的三氰基硼酸盐,其中该有机阳离子选自由下式阳离子组成的群:
(a)(WR2R3R4R5)+,其中W为氮或磷,且
(i)其中R2至R4独立地为C1-20烷基,且R5为C1-20烷基、C3-10环烷基或C6-10芳基,其中R2至R5独立地任选含有一个或一个以上卤素,或
(ii)其中R2及R3与W一起形成5元至7元环,且R4及R5独立地为C1-20烷基,其中R4及R5独立地任选含有一个或一个以上卤素,或
(iii)其中R2及R3或R4及R5在各种情况下与W一起形成5元至7元环,或
(b)(XR6R7R8)+,其中X为氮,且R6及R7与X一起形成环,其中X在形式上经由一个单键及一个双键键合至R6及R7,且R8为C1-20烷基、C3-10环烷基或C6-10芳基,其中R8任选含有一个或一个以上卤素,或
(c)(YR9R10R11)+,其中Y为硫,且
(i)其中R9及R10独立地为C1-20烷基,且R11为C1-20烷基、C3-10环烷基或C6-10芳基,其中R9至R11独立地任选含有一个或一个以上卤素,或
(ii)其中R9及R10与Y一起形成5元至7元环,且R11为C1-20烷基、C3-10环烷基或C6-10芳基,其中R11任选含有一个或一个以上卤素,或
(d)(ZR12R13)+,其中Z为氧或硫,且R12及R13与Z一起形成环,其中Z在形式上经由一个单键及一个双键键合至R12及R13,且
其中一个或一个以上选自由C1-20烷基、C1-20烷氧基、C3-10环烷基、C6-10芳基、卤素及氰基组成的群的取代基任选结合至由取代基R2至R13所形成的各环,其中所述C1-20烷基、所述C1-20烷氧基、所述C3-10环烷基及所述C6-10芳基独立地任选含有一个或一个以上卤素,且
其中由取代基R2至R13所形成的各环任选含有一或两个经进一步取代的或未经取代的选自由氮、硫及氧组成的群的杂原子,和/或与另一芳族或非芳族的5元至7元环稠合。
8.根据权利要求6或7所述的三氰基硼酸盐,其中所述有机阳离子选自由以下组成的群:有机铵、鏻、锍、吡咯烷鎓、吡咯啉鎓、吡咯鎓、吡唑鎓、咪唑鎓、三唑鎓、噁唑鎓、噻唑鎓、哌啶鎓、哌嗪鎓、吗啉鎓、吡啶鎓、哒嗪鎓、嘧啶鎓、吡嗪鎓、1,3-二氧杂环戊烯鎓、吡喃鎓及硫代吡喃鎓阳离子。
11.根据权利要求10所述的三氰基硼酸盐,其中R为甲基且R′为乙基。
12.根据权利要求6至11任一项所定义的三氰基硼酸盐用作极性非质子性溶剂的用途,所述三氰基硼酸盐任选与一种或一种以上其它离子液体、水或有机溶剂混合。
13.制备根据权利要求5所定义的三氰基硼酸盐的方法,其特征在于使B(XR1)3与氰基三-C1-6烷基硅烷在Mn+(CN-)n存在下反应,
其中
R1为C1-6烷基、C2-6烯基、C6-10芳基或苯甲基,
X为氧或硫,且
Mn+为选自由Li+、Na+、K+、Rb+、Cs+、NH4 +、Be2+、Mg2+、Ca2+、Sr2+及Ba2+组成的群的无机阳离子,其中n为1或2。
14.制备根据权利要求6至11任一项所定义的三氰基硼酸盐的方法,其特征在于使根据权利要求5所定义的三氰基硼酸盐与式
(Qn+)p(Yp-)n盐反应,
其中
Qn+为根据权利要求6至11任一项中所定义的有机阳离子,
n为1或2,
Yp-为选自由卤离子、拟卤离子、硫酸根及有机酸阴离子组成的群的阴离子,且
p为1或2。
15.根据权利要求14所述的方法,其中所述采用的三氰基硼酸盐根据如权利要求13所定义的方法预先制备。
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