EP1636173A2 - Liquides ioniques contenant des cations de guanidine - Google Patents
Liquides ioniques contenant des cations de guanidineInfo
- Publication number
- EP1636173A2 EP1636173A2 EP04724995A EP04724995A EP1636173A2 EP 1636173 A2 EP1636173 A2 EP 1636173A2 EP 04724995 A EP04724995 A EP 04724995A EP 04724995 A EP04724995 A EP 04724995A EP 1636173 A2 EP1636173 A2 EP 1636173A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- atoms
- perfluorinated
- substituted
- guanidinium
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- -1 guanidinium cations Chemical class 0.000 title claims abstract description 96
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910004013 NO 2 Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005490 tosylate group Chemical group 0.000 claims description 3
- VQNVZLDDLJBKNS-UHFFFAOYSA-N carbamimidoylazanium;bromide Chemical compound Br.NC(N)=N VQNVZLDDLJBKNS-UHFFFAOYSA-N 0.000 claims description 2
- ZPQINZAVTLGLIW-UHFFFAOYSA-N guanidine;hydrofluoride Chemical compound F.NC(N)=N ZPQINZAVTLGLIW-UHFFFAOYSA-N 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 claims 4
- 239000012454 non-polar solvent Substances 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 238000005481 NMR spectroscopy Methods 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 35
- 239000011541 reaction mixture Substances 0.000 description 28
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007983 Tris buffer Substances 0.000 description 19
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- WKHWMSFGRUVCNP-UHFFFAOYSA-M bis(dimethylamino)methylidene-dimethylazanium;chloride Chemical compound [Cl-].CN(C)C(N(C)C)=[N+](C)C WKHWMSFGRUVCNP-UHFFFAOYSA-M 0.000 description 8
- JLLAPHQHRKWOPI-UHFFFAOYSA-N n,n-diethyl-1,3-dimethylimidazolidin-1-ium-2-amine;chloride Chemical compound [Cl-].CCN(CC)C1N(C)CC[NH+]1C JLLAPHQHRKWOPI-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LNHDPPLSOBXLPC-UHFFFAOYSA-N O.O.O.O.O.FP(F)(F)=O Chemical compound O.O.O.O.O.FP(F)(F)=O LNHDPPLSOBXLPC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- KDMVSQGSGFMHKJ-UHFFFAOYSA-N [dimethylamino(ethylamino)methylidene]-dimethylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCNC(N(C)C)=[N+](C)C KDMVSQGSGFMHKJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- FCPMOQKUPRKDAN-UHFFFAOYSA-N bis(dimethylamino)methylidene-dimethylazanium Chemical compound CN(C)C(N(C)C)=[N+](C)C FCPMOQKUPRKDAN-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 4
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 4
- LJNQGWIMQCKPSH-UHFFFAOYSA-N 2-ethyl-1,1,3,3-tetramethylguanidine Chemical compound CCN=C(N(C)C)N(C)C LJNQGWIMQCKPSH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NWRUYZFPTCHVRF-UHFFFAOYSA-N n,n-diethyl-1,3-dimethylimidazolidin-1-ium-2-amine;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCN(CC)C1N(C)CC[NH+]1C NWRUYZFPTCHVRF-UHFFFAOYSA-N 0.000 description 3
- MTKINKFHQHAGNP-UHFFFAOYSA-N n,n-diethyl-1,3-dimethylimidazolidin-2-amine Chemical compound CCN(CC)C1N(C)CCN1C MTKINKFHQHAGNP-UHFFFAOYSA-N 0.000 description 3
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 2
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 2
- BNGPVKSKKYIJCR-UHFFFAOYSA-N 2-chloro-1,3-dimethylimidazolidine;hydrochloride Chemical compound [Cl-].CN1CC[NH+](C)C1Cl BNGPVKSKKYIJCR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 2
- CMHNVHICMZPDGB-UHFFFAOYSA-N [dimethylamino-[methyl(propyl)amino]methylidene]-dimethylazanium Chemical compound CCCN(C)C(N(C)C)=[N+](C)C CMHNVHICMZPDGB-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- DIDJYKBXJRWYSX-UHFFFAOYSA-M bis(dimethylamino)methylidene-dimethylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CN(C)C(N(C)C)=[N+](C)C DIDJYKBXJRWYSX-UHFFFAOYSA-M 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- OPUWQXMXNREWKC-UHFFFAOYSA-N diaminomethylideneazanium;trifluoromethanesulfonate Chemical compound NC(N)=[NH2+].[O-]S(=O)(=O)C(F)(F)F OPUWQXMXNREWKC-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 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 2
- 125000005980 hexynyl group Chemical group 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- ONZXWZBWSBWVTJ-UHFFFAOYSA-N 1,1,3,3-tetramethyl-2-propylguanidine Chemical compound CCCN=C(N(C)C)N(C)C ONZXWZBWSBWVTJ-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UOAYJWKOLSAHLL-UHFFFAOYSA-N 2-(1,3-dimethylimidazolidin-1-ium-2-yl)oxy-1,3-dimethylimidazolidin-1-ium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.CN1CC[NH+](C)C1OC1[NH+](C)CCN1C UOAYJWKOLSAHLL-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000006305 3-iodophenyl group Chemical group [H]C1=C([H])C(I)=C([H])C(*)=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- 125000004539 5-benzimidazolyl group Chemical group N1=CNC2=C1C=CC(=C2)* 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- TZCCKCLHNUSAMQ-DUGSHLAESA-N NC(=O)C[C@H](NC(=O)[C@H](CCCNC(=N)N)NC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCNC(=N)N)NC(=O)[C@H](Cc2ccc(F)cc2)NC(=O)[C@H](Cc3c[nH]c4ccccc34)NC(=O)Cc5cccs5)C(=O)N Chemical compound NC(=O)C[C@H](NC(=O)[C@H](CCCNC(=N)N)NC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCNC(=N)N)NC(=O)[C@H](Cc2ccc(F)cc2)NC(=O)[C@H](Cc3c[nH]c4ccccc34)NC(=O)Cc5cccs5)C(=O)N TZCCKCLHNUSAMQ-DUGSHLAESA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- LYWKAJZTPLXHEM-UHFFFAOYSA-M bis(diethylamino)methylidene-diethylazanium;chloride Chemical class [Cl-].CCN(CC)C(N(CC)CC)=[N+](CC)CC LYWKAJZTPLXHEM-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000002100 cyclohexa-1,3-dienyl group Chemical group [H]C1([*])C([H])=C([H])C([H])=C([H])C1([H])[H] 0.000 description 1
- 125000002150 cyclohexa-1,4-dienyl group Chemical group [H]C1=C([H])C([H])(*)C([H])=C([H])C1([H])[H] 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 125000004943 pyrimidin-6-yl group Chemical group N1=CN=CC=C1* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/44—Nitrogen atoms not forming part of a nitro radical
- C07D233/48—Nitrogen atoms not forming part of a nitro radical with acyclic hydrocarbon or substituted acyclic hydrocarbon radicals, attached to said nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/02—Guanidine; Salts, complexes or addition compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- 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
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
Definitions
- the present invention relates to salts containing guanidinium cations and various anions, processes for the preparation of these salts and their use as ionic liquids.
- Ionic liquids or liquid salts are ionic species that consist of an organic cation and a generally inorganic anion. They contain no neutral molecules and mostly have melting points below 373 K. A large number of compounds which are used as ionic liquids are known in the prior art. In particular, they are also the subject of a number of patents and patent applications. For example, solvent-free ionic liquids were first disclosed by Hurley and Wier in a number of US patents (US 2,446,331, US 2,446,339 and US 2,446,350).
- ionic liquids e.g. melting point, thermal and electrochemical stability, viscosity
- properties of ionic liquids are strongly influenced by the nature of the Anions influenced.
- the polarity and the hydrophilicity or lipophilicity can be varied by the suitable choice of the cation / anion pair.
- the object of the present invention is to provide new, stable, low viscosity, salt-like compounds which can be used as ionic liquids, and to provide a process for their preparation.
- Nitrogen atoms are delocalized in combination with selected anions according to claim 1.
- EP 1 363 345 explicitly discloses the compound tetramethylguanidinium bis (trifluoromethanesulfonyl) imide and its use as an electrolyte.
- EP 1 363 345 was published after the priority application DE 10325051 was submitted.
- Guanidinium cations are understood in the sense that not all three nitrogen atoms may be substituted identically. However, alicyclic and aromatic groups can also be substituents of a proton or some protons of guanidinium, in particular which form a mono-, bi- or tricyclic ring. 1-methyl-7-n-propyl-1,5,7-triazabicysclo [4.4.0] dec-5-enium is given as an example of this.
- Suitable anions include not only bis (trifluoromethanesulfonyl) imide also hexafluorophosphate, tetrafluoroborate and trifluoromethanesulfonate (triflate) or Trifluormethansulfonyltrifluoracetylimid, Trifluormethansulfonylpentafluorethansulfonylimid or Closocarborate as B 9 H 9 CH “B- ⁇ H 22 CH ', Closoborate such as B 10 H 10 2" and B ⁇ 2 H ⁇ 2 2 " and their halogenated derivatives, AsF 6 " , SbF 6 " , CIO4 “ , O 2 " , AICI 4 " , GaCI 4 " , C (SO 2 CF 3 ) 3 " , SCN-, C 6 F 5 S0 3 " , O2CCF3 “ , SO 6 F and B (C 6 H 5 ) 4 " .
- the object is to obtain stable, low viscosity, salt-like compounds which can be used as ionic liquids from salts with guanidinium cations, in which the positive charge is delocalized over several nitrogen atoms, according to the general formula (1)
- the groups R have the meaning of
- R can be partially or completely substituted with halogens, in particular -F and / or -Cl, or partially with -CN or -N0 2l
- a ⁇ is selected from the group consisting of: [(FSO 2 ) 2 N] ⁇ [R F CF 2 SO 3 ] ⁇ , [(R p SO 2 ) 2 N] -, [(R p SO 2 ) 3 C] ⁇ [(FS0 2 ) 3 C] - [R F CF 2 C (O) O] - [P (C n F 2n + 1-rn H m ) y F 6 - y ] " [P (C 6 F 5 ) y F 6-y ] " [R F 2 P (O) O] ⁇
- R F perfluorinated and straight-chain or branched alkyl
- R F can each be the same or different
- R F can be connected in pairs by single or double bond
- R F perfluorinated straight-chain or branched alkyl with 2-20 C atoms, perfluorinated and straight-chain or branched alkenyl with 2-20 C-atoms and one or more double bonds perfluorinated and straight-chain or branched alkynyl with 2-20 C-atoms and one or more triple bonds perfluorinated and saturated, partially or completely unsaturated cycloalkyl with 3-7 C Atoms, especially phenyl, which can be substituted with perfluoroalkyl groups,
- R F can each be the same or different
- R F can be connected in pairs by single or double bond
- the compounds according to the invention are distinguished in particular by very stable cations.
- the compounds according to the invention are accordingly salts which have an optionally substituted guanidinium cation.
- the substituents R of the guanidinium cation which can be used according to the invention are: C 1 -C 2 -o, in particular C to C1.2-alkyl groups, and saturated or unsaturated, ie also aromatic, C 3 -C -cycloalkyl groups, which can be substituted with Cr to C 6 alkyl groups, especially phenyl.
- the six substituents R of the guanidinium cation according to the invention can be the same or different.
- the CrCe alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl or hexyl. If necessary, difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
- Unsubstituted saturated or partially or completely unsaturated cycloalkyl groups with 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1, 3-dienyl, cyclohexenyl, cyclohexa-1, 3-dienyl, cyclohexa-1 , 4-dienyl, phenyl, cycloheptenyl, cyclohepta-1, 3-dienyl, cyclohepta-1, 4-dienyl or cyclohepta-1, 5-dienyl, which can be substituted by C to C 6 alkyl groups, again the cycloalkyl group or the cycloalkyl group substituted by C to C 6 alkyl groups can also be substituted by halogen atoms such as F, Cl, Br or I, in particular F or Cl,
- the substituents R can be partially or completely substituted with halogen atoms, in particular with F and / or Cl, or partially with CN or NO 2 .
- R ' is C 3 - to C 7 -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
- R 'substituted phenyl means by C to C 6 alkyl, d to C 6 alkenyl, NO 2 , F, Cl, Br, I, OH, CrC 6 alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C (O) 0-CrC 6 alkyl, NH 2 , CrC 6 alkylamino or CrC 6 dialkylamino, COOH, C (O) NR " 2 , SO 2 OR", S0 2 X ', SO 2 NR " 2 , SO 3 H or NHC (O) R" substituted phenyl, where X 'F, Cl or Br and R "is a non, partially or perfluorinated Cr to C 6 alkyl or C
- the heterocycle is understood to mean a saturated or unsaturated mono- or bicyclic heterocyclic radical with 5 to 13 ring members, where 1, 2 or 3 N and / or 1 or 2 S or O atoms can be present and the heterocyclic radical is one - or several times by Cr to Cö-alkyl, Cr to Ce-alkenyl, NO 2 , F, Cl, Br, I, OH, -C-C 6 alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C ( O) O-Cr Ce alkyl, NH 2 , CrC 6 alkylamino or CrC 6 dialkylamino, COOH, C (O) NR " 2 , SO 2 OR", SO 2 X ', SO 2 NR " 2 , SO 3 H or NHC (0) R "can be substituted, where X 'and R" have a meaning given above.
- the heterocyclic radical is preferably substituted or unsubstituted.
- Benzopyrazolyl 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzthiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1, 3-oxadiazolyl, 1-, 2-, 3-, 4-, 5 -, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl or 1-, 2- or 3-pyrrolidinyl.
- substituents R can also be linked in pairs in such a way that mono-, bi- or polycyclic cations are formed.
- the substituents R can have a previously specified or particularly preferred meaning.
- the carbocycles or heterocycles of the guanidinium cations given above can also be substituted by C to Ce alkyl, Cr to Ce alkenyl, NO 2 , F, Cl, Br, I, OH, CrC 6 alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 ,
- the anion A of the salts according to the invention is selected from [(FSO 2 ) 2 N] ⁇ [R F CF 2 SO 3 ] -, [(R P SO 2 ) 2 N] - [(R F SO 2 ) 3 C] " , [(FSO 2 ) 3 C] -, [R F CF 2 C (O) O] -, [P (C n F 2n + 1.
- the organic groups R F and and R F of the anion which can be used according to the invention are: Cr or C 2 - to C 2 o-, in particular Cr or C 2 - to C 2 -alkyl groups, C 2 - to C 2 o -, In particular C 2 - to C ⁇ . 2 -, alkenyl or alkynyl groups and saturated or unsaturated, ie also aromatic, C 3 - to C 7 -cycloalkyl groups, which can be substituted by Cr to C 6 -alkyl groups 0, in particular phenyl, with all the groups listed being perfluorinated.
- a straight-chain or branched alkenyl with 2 to 20 C atoms it also being possible for several double bonds to be present, for example allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, Heptenyl, octenyl, -C 9 H 17 , -C 10 H - ⁇ to -C 2 oH 3 g; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, further preferred is 4-pentenyl, isopentyl or hexenyl.
- R F or R F are present in one anion, these can also be connected in pairs by single or double bonds in such a way that bi- or polycyclic anions are formed.
- R F is preferably pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
- R F is preferably trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
- [P (C ⁇ F 5 ) 2F 4 ] " [(CF 3 ) 2 P (O) O] -, [(C 4 F ⁇ ) 2 P (0) 0] -, [CF 3 P (O) ⁇ 2J ⁇ 2 ⁇ - ⁇ , [BF 3 (CF 3 )], [BF 2 (C 2 F 5 ) 2 ] - [BF 3 (C 2 F 5 )] -, [BF 2 (CF 3 ) 2 j-, [B ( C 2 F 5 ) 4 ] ⁇ [BF 3 (CN)] - [BF 2 (CN) 2 ] -, [B (CN) 4 ] - [B (CF 3 ) 4 ] - [N (CF 3 ) 2 ] -, [N (CN 2 ) 2 ] -, [C (CN) 3 r,
- Very preferred anions of this group are [P (CnF 2n + 1-m Hm) y F 6-y ] " , [BF Z R F 4-Z ] ⁇ or [BF Z (CN) 4 -Z ] ⁇ , where n , m, y and z have one of the abovementioned meanings, for example [B (CN) 4 ] " , [(C 2 F 5 ) 3 PF 3 j ⁇ , [(C 2 F 5 ) 2 PF 4 ] ⁇ , [( C 4 F 9 ) 3 PF 3 ] " , [(C 3 F 7 ) 3 PF 3 ] - [B (C 2 F 5 ) F 3 ] ' or [B (CF 3 ) 4 ] " .
- Very particularly preferred anions of this group are [B (CN) 4 ] " , [(C 2 F 5 ) 3 PF 3 ] ⁇ or
- a group of salts of the formula (1) is preferred, the substituents R of the guanidinium cation being hydrogen or a straight-chain or branched alkyl group having 1-12 C atoms, in particular having 1-4 C atoms, and A " a Formula (1) or has a meaning given as preferred or particularly preferred.
- a group of salts of the formula (1) is preferred, the substituents R of the guanidinium cation from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, phenyl and Cyclohexyl are selected and A "has a meaning given in formula (1) or a preferred or particularly preferred meaning.
- a group of salts of the formula (1) is preferred in which at least two substituents R are bonded to one another by single or double bonds, so that a monocyclic cation is formed and A "is a preferred or particularly preferred formula (1) Has meaning.
- a group of salts is particularly preferred, the substituents R each independently signifying hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or i-butyl or two substituents R being linked to one another in such a way that an imidazolidinium cation arises and A "has a meaning given in formula (1) or a preferred or particularly preferred meaning.
- the present invention also relates to a process for the preparation of the salts according to the invention with guanidinium cations according to the general formula (1).
- the anion X ⁇ of the reacting guanidinium salt is selected from the group F “ , Cl “ Br “ I " [HF 2 ] “ , [CN] ⁇ , [SCN] “ , [CH 3 COO] “ , [CF 3 COO] -, [CF3SO3] -, [CH3OSO 3 ] - [SiFe] 2 " , [BF 4 ] -, [SO 4 ] 2 ' [N0 3 ] " , [C 2 H 5 OSO3] " , tosylates, malonates Malonates and [CO 3 ] ⁇ .
- the groups or substituents A and R are defined like those of the general formula (1) and Kt is an alkali or alkaline earth metal, it being the case for the esters AR that for the meaning of the substituents R perhalogenated alkyl groups with 1-20 C- Atoms, cycloalkyl groups with 3- 7 C atoms, alkenyl groups with 2-20 C atoms and alkynyl groups with 2- 20 C atoms are excluded.
- the reaction is preferably carried out at a temperature at which at least one of the components is liquid. Particularly preferred the reaction is carried out in a temperature range at which the reaction mixture is liquid.
- reaction of the guanidine or the guanidinium salt with an acid AH or a salt Kt + A " can be carried out in polar inorganic or organic solvents, for example water, acetonitrile, dimethoxyethane, methanol, dimethylformamide, propionitrile or dichloromethane.
- polar inorganic or organic solvents for example water, acetonitrile, dimethoxyethane, methanol, dimethylformamide, propionitrile or dichloromethane.
- nonpolar organic solvents as a diluent , for example hexane or pentane, or without a solvent, for example in the molten salt
- the reaction can be carried out with an ester, an acid or a salt
- the alkylation of the guanidine with an ester can be carried out in a non-basic solvent, preferably hexane, pentane or
- solvent mixtures can also be used instead of pure solvents.
- the reagents can be reacted in an amount of up to five times excess of one of the reactants, in particular the alkylating agent, in the alkylation.
- the reactants are preferably used in an equimolar amount.
- the salts according to the invention can be isolated in very good yields, generally over 80%, preferably over 90%.
- Another object of the present invention is a process for the preparation of a salt with a guanidinium cation according to the general formula (1) and a [BF 4 ] ⁇ anion, where R has a meaning given or preferred given in formula (1), which can further be used for the preparation of the guanidinium salts according to the invention.
- This is a guanidinium chloride
- guanidinium tetrafluoroborates with a reduced amount of chloride ions i.e. the proportion of chloride ions is ⁇ 100 ppm, preferably ⁇ 50 ppm.
- the anhydrous hydrofluoric acid acts both as a solvent and as a reagent.
- the reaction is preferably carried out at a temperature at which at least one of the components is liquid.
- the reaction is particularly preferably carried out in a temperature range at which the reaction mixture is liquid.
- the boron trifluoride etherate can be used in excess of up to 10% in relation to the guanidinium salt.
- the reactants are preferably used in an equimolar amount.
- All compounds according to the invention have a salt-like character, relatively low melting points (mostly below 100 ⁇ C) and can be used as ionic liquids. In particular, as described above, they have particularly low viscosities.
- the salts according to the invention can be used as solvents for many synthetic or catalytic reactions, for example Friedel-Crafts acylation and alkylation, Diels-Alder cycloadditions, hydrogenation and oxidation reactions or Heck reactions. It is also possible to use the compounds according to the invention as a non-aqueous electrolyte, optionally in combination with other electrolytes known to the person skilled in the art.
- salts according to the invention can be used as non-aqueous polar
- Substances can be used in suitable reactions as a phase transfer catalyst, as a manufacturer (surface active agent) or as a medium for the heterogenization of homogeneous catalysts.
- the NMR spectra were measured on solutions in deuterated solvents at 20 ° C. on a Bruker Avance 300 spectrometer with a 5 mm broadband head 1 H / BB with deuterium lock, unless stated in the examples.
- the measuring frequencies of the different cores are: 1 H: 300.13 MHz, 11 B: 96.92 MHz, 19 F: 282.41 MHz and 31 P: 121, 49 MHz.
- the referencing method is specified separately for each spectrum or for each data set.
- Example 1 Hexamethylguanidinium triflate
- the yield at N, N, N ' , N ' , N " -pentamethyl-N " - / - propylguanidinium tris (pentafluoroethyl) trifluorophosphate is 94.0% based on N, N, N ', N', N ' pentamethyl-N " - / - propylguanidinium triflate.
- Tris (pentafluoroethyl) trifluorophosphoric acid pentahydrate added at room temperature.
- the flask with the reaction mixture is cooled with ice, the lower phase is separated and washed twice with 30 cm 3 of ice water.
- the yield of guanidinium tris (pentafluoroethyl) trifluorophosphate is 89.0%.
- the material is characterized by 19 F and 1 H NMR spectroscopy, 5 which show the formation of two isomers of N, N, N ', N'-tetramethyl-N "-ethylguanidinium triflate.
- reaction mixture is then stirred at room temperature overnight.
- the solvent is removed in vacuo.
- the residue is washed twice with 30 cm 3 of hexane and in vacuo for one hour
- Tris (pentafluoroethyl) trifluorophosphate is 97.8% based on 1,3-dimethyl-2-diethylaminoimidazolidinium chloride.
- Hexamethylguanidinium pentafluoroethyl trifluoroborate is 93.5% based on hexamethylguanidinium chloride.
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Abstract
La présente invention concerne des sels comprenant des cations de guanidine, un procédé pour les préparer et leur utilisation en tant que liquides ioniques.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10325051A DE10325051A1 (de) | 2003-06-02 | 2003-06-02 | Ionische Flüssigkeiten mit Guanidinium-Kationen |
PCT/EP2004/003459 WO2004106288A2 (fr) | 2003-06-02 | 2004-04-01 | Liquides ioniques contenant des cations de guanidine |
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EP1636173A2 true EP1636173A2 (fr) | 2006-03-22 |
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EP04724995A Withdrawn EP1636173A2 (fr) | 2003-06-02 | 2004-04-01 | Liquides ioniques contenant des cations de guanidine |
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US (1) | US7709656B2 (fr) |
EP (1) | EP1636173A2 (fr) |
DE (1) | DE10325051A1 (fr) |
WO (1) | WO2004106288A2 (fr) |
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DE10325051A1 (de) | 2003-06-02 | 2004-12-23 | Merck Patent Gmbh | Ionische Flüssigkeiten mit Guanidinium-Kationen |
DE102004060075A1 (de) * | 2004-12-14 | 2006-07-06 | Merck Patent Gmbh | Verfahren zur Herstellung von Onium-Salzen mit Dialkylphosphat-, Dialkylphosphinat oder (O-Alkyl)-alkyl- oder Alkyl-phosphonat-Anionen mit geringem Halogenid-Gehalt |
DE102004060076A1 (de) * | 2004-12-14 | 2006-07-06 | Merck Patent Gmbh | Verfahren zur Herstellung von Onium-Salzen mit Alkyl- oder Arylsulfonat-Anionen oder Alkyl- oder Arylcarboxylat-Anionen mit geringem Halogenid-Gehalt |
JP4706067B2 (ja) | 2004-12-27 | 2011-06-22 | 独立行政法人産業技術総合研究所 | イオン液体 |
DE102005025315A1 (de) * | 2005-06-02 | 2006-12-14 | Merck Patent Gmbh | Ionische Flüssigkeiten mit niedriger Viskosität |
DE102005032838A1 (de) * | 2005-07-14 | 2007-02-08 | Merck Patent Gmbh | Mischung von Onium-Alkylsulfonaten und Onium-Alkylsulfiten |
TW200710070A (en) * | 2005-07-27 | 2007-03-16 | Nippon Catalytic Chem Ind | Solvent for reaction and production method using the same |
CA2527144C (fr) * | 2005-11-15 | 2014-04-29 | Queen's University At Kingston | Surfactants reversibles, et methodes d'utilisation |
EP1819005A1 (fr) | 2006-02-13 | 2007-08-15 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Electrolyte composé d'un liquide ionique |
WO2009152902A2 (fr) * | 2008-05-28 | 2009-12-23 | Merck Patent Gmbh, | Liquides ioniques |
DE102009003466A1 (de) * | 2009-02-11 | 2010-08-19 | Karlsruher Institut für Technologie | Hexaalkylguanidiniumsalze |
CA2683660C (fr) | 2009-10-28 | 2017-07-04 | Queen's University At Kingston | Solvants a hydrophilicite modifiable et methodes d'utilisation |
US20130105377A1 (en) | 2010-02-10 | 2013-05-02 | Queen's University At Kingston | Water with Switchable Ionic Strength |
DE102010048614B4 (de) * | 2010-10-15 | 2015-01-15 | Bayer Intellectual Property Gmbh | Verfahren zur Gewinnung von Lignin, Tannin, Cellulose und Hemicellulose aus biogenem Material |
US10377647B2 (en) | 2010-12-15 | 2019-08-13 | Queen's University at Kingson | Systems and methods for use of water with switchable ionic strength |
DE102013202254A1 (de) * | 2013-02-12 | 2014-08-14 | Siemens Aktiengesellschaft | Verfahren zur Herstellung von Hochenergiemagneten |
US9944593B2 (en) | 2013-10-04 | 2018-04-17 | Solvay Specialty Polymers Italy S.P.A. | Process for the synthesis of fluoralkyl sulfonate salts |
CN104447418B (zh) * | 2014-12-16 | 2016-07-20 | 四川大学 | 一种胍类磁性离子液体及其去除非极性溶液中含硫有机物的用途 |
JP6576656B2 (ja) * | 2015-03-13 | 2019-09-18 | デクセリアルズ株式会社 | イオン液体、潤滑剤及び磁気記録媒体 |
DE102015006926B4 (de) | 2015-05-29 | 2022-09-22 | Willi Kantlehner | Neuartiges durch RIBIL' s katalysiertes Verfahren zur Fraktionierung von Lignocellulose-haltiger Biomasse |
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US2446331A (en) | 1944-02-14 | 1948-08-03 | William Marsh Rice Inst For Th | Electrodeposition of aluminum |
US2446350A (en) | 1944-02-29 | 1948-08-03 | William Marsh Rice Inst For Th | Electrodeposition of aluminum |
US2446339A (en) | 1946-02-09 | 1948-08-03 | George M Holley | Speed density carburetor |
JP3194780B2 (ja) * | 1992-04-09 | 2001-08-06 | 森田化学工業株式会社 | 4級アルキルアンモニウムテトラフルオロボレート類の製造法 |
US5827602A (en) * | 1995-06-30 | 1998-10-27 | Covalent Associates Incorporated | Hydrophobic ionic liquids |
WO1998050153A1 (fr) * | 1997-05-01 | 1998-11-12 | Akzo Nobel N.V. | Formation in-situ de catalyseur liquide ionique pour une reaction chimique catalysee liquide ionique |
JPH11310555A (ja) * | 1998-04-30 | 1999-11-09 | Mitsui Chem Inc | 4級アルキルアンモニウムテトラフルオロボレート類の製造方法 |
GB9928290D0 (en) * | 1999-12-01 | 2000-01-26 | Univ Belfast | Process for preparing ambient temperature ionic liquids |
DE10027995A1 (de) | 2000-06-09 | 2001-12-13 | Merck Patent Gmbh | Ionische Flüssigkeiten II |
DE10038858A1 (de) * | 2000-08-04 | 2002-02-14 | Merck Patent Gmbh | Fluoralkylphosphate zur Anwendung in elektrochemischen Zellen |
JP4240263B2 (ja) * | 2000-12-22 | 2009-03-18 | 富士フイルム株式会社 | 電解質組成物及び非水電解質二次電池 |
CN100545133C (zh) | 2001-05-17 | 2009-09-30 | 罗狄亚化学公司 | 离子性质的组合物作为取代试剂的用途,由氟化试剂构成的组合物及其使用方法 |
JP2004253357A (ja) | 2002-05-09 | 2004-09-09 | Wilson Greatbatch Technologies Inc | 電気化学電源における常温溶融塩のためのカチオンとしてのグアニジン誘導体 |
DE10325051A1 (de) | 2003-06-02 | 2004-12-23 | Merck Patent Gmbh | Ionische Flüssigkeiten mit Guanidinium-Kationen |
-
2003
- 2003-06-02 DE DE10325051A patent/DE10325051A1/de not_active Withdrawn
-
2004
- 2004-04-01 US US10/559,183 patent/US7709656B2/en not_active Expired - Fee Related
- 2004-04-01 WO PCT/EP2004/003459 patent/WO2004106288A2/fr active Application Filing
- 2004-04-01 EP EP04724995A patent/EP1636173A2/fr not_active Withdrawn
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WO2004106288A3 (fr) | 2005-03-17 |
WO2004106288A2 (fr) | 2004-12-09 |
DE10325051A1 (de) | 2004-12-23 |
US7709656B2 (en) | 2010-05-04 |
US20070265453A1 (en) | 2007-11-15 |
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