CN1823044A - 离子型液体与路易斯酸的混合物 - Google Patents
离子型液体与路易斯酸的混合物 Download PDFInfo
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- CN1823044A CN1823044A CNA2004800206422A CN200480020642A CN1823044A CN 1823044 A CN1823044 A CN 1823044A CN A2004800206422 A CNA2004800206422 A CN A2004800206422A CN 200480020642 A CN200480020642 A CN 200480020642A CN 1823044 A CN1823044 A CN 1823044A
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 37
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 title abstract 2
- -1 bis(trifluoromethylsulfonyl)imide salt Chemical class 0.000 claims abstract description 44
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 59
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 54
- 150000002500 ions Chemical class 0.000 claims description 53
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000002460 imidazoles Chemical class 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006317 isomerization reaction Methods 0.000 claims description 5
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005810 carbonylation reaction Methods 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- PHTJYWLLDMGGKH-UHFFFAOYSA-N 4h-pyridin-4-ylium Chemical compound C1=CN=CC=[C+]1 PHTJYWLLDMGGKH-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims 1
- 238000006384 oligomerization reaction Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- 150000002466 imines Chemical class 0.000 description 39
- 239000002253 acid Substances 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000007848 Bronsted acid Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011831 acidic ionic liquid Substances 0.000 description 9
- VHAOCWDRQDRWOX-UHFFFAOYSA-N C(F)(F)F.[P] Chemical compound C(F)(F)F.[P] VHAOCWDRQDRWOX-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 238000005352 clarification Methods 0.000 description 6
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- 229910018286 SbF 6 Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- IOTJZPOUUUWDIX-UHFFFAOYSA-N 2-chloroethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCl)C1=CC=CC=C1 IOTJZPOUUUWDIX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 239000011828 neutral ionic liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYNROCNODWBDCM-UHFFFAOYSA-N 1,3-diethyl-2h-imidazole Chemical class CCN1CN(CC)C=C1 RYNROCNODWBDCM-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 1,3-lutidine Natural products CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- IESVWESMDKFOBZ-UHFFFAOYSA-N 1-butyl-4-methyl-2H-pyridine fluoroform Chemical compound C(F)(F)F.C(CCC)N1CC=C(C=C1)C IESVWESMDKFOBZ-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- JMNFVQWMBCLWAS-UHFFFAOYSA-N C(F)(F)F.C(C)N1CN(C=C1)C Chemical compound C(F)(F)F.C(C)N1CN(C=C1)C JMNFVQWMBCLWAS-UHFFFAOYSA-N 0.000 description 2
- DYVIVMCAMDJZLM-UHFFFAOYSA-N C(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound C(F)(F)F.C(CCC)N1CN(C=C1)C DYVIVMCAMDJZLM-UHFFFAOYSA-N 0.000 description 2
- IPZVBXNQMFRYCS-UHFFFAOYSA-N CN(C)C.FC(F)F Chemical compound CN(C)C.FC(F)F IPZVBXNQMFRYCS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NVLVXCCCTMOXMO-UHFFFAOYSA-N FC(F)F.C(CCC)N1CC(=CC=C1)C Chemical compound FC(F)F.C(CCC)N1CC(=CC=C1)C NVLVXCCCTMOXMO-UHFFFAOYSA-N 0.000 description 2
- OHBNVTWVFWUQBM-UHFFFAOYSA-N FC(F)F.C(CCC)[N+]1=CC=CC=C1 Chemical compound FC(F)F.C(CCC)[N+]1=CC=CC=C1 OHBNVTWVFWUQBM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AJDVLMSYXRFQQL-UHFFFAOYSA-N fluoroform;tetramethylazanium Chemical compound FC(F)F.C[N+](C)(C)C AJDVLMSYXRFQQL-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical group CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- RNLLHJJKVFXQKX-UHFFFAOYSA-M scandium(3+);trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F RNLLHJJKVFXQKX-UHFFFAOYSA-M 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
- B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了可在路易斯酸催化的反应中用作催化剂的包含一种或多种三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐和一种或多种路易斯酸的离子型液体,其中混合物中路易斯酸的总摩尔含量为约0.01-98%。
Description
技术领域
本发明涉及新的离子型液体材料,其是咪唑鎓、吡啶鎓、铵或磷鎓离子的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐与路易斯酸(AlCl3、AlBr3、SnCl2、FeCl3和ZnCl2)的混合物。
背景技术
弗瑞德-克来福特反应(酰化和烷基化)是用于合成功能基化的芳族化合物的基本反应,而这些化合物是药品和精细化学品中十分重要的中间体。在现有技术中,采用液体和固体路易斯和布朗斯台德酸作为弗瑞德-克来福特反应的催化剂。
催化剂的酸性以许多方式影响弗瑞德-克来福特反应的反应动力学。例如,催化剂的酸性越强,则可以使用更容易被灭活的芳族化合物。更高的酸性还可以改善反应的选择性,例如可以改善弗利斯重排反应中的选择性。目前在化学工业中常用的酸是各种变型形式的硫酸和AlCl3。
一种已知的酸性反应物是酸性离子型液体,其是具有低于100℃的熔点的盐,也可被用于弗瑞德-克来福特反应中。目前所用的系统是通过向咪唑鎓、吡啶鎓、铵或磷鎓离子的卤化物盐中加入过量摩尔量的路易斯酸所形成的系统。一个实例是氯化咪唑鎓盐与过量摩尔量的AlCl3的混合物。用这些酸性氯代铝酸盐熔化物代替固体AlCl3来催化有机反应,从而将AlCl3在大多数有机溶剂中溶解度低的缺点最小化。文献中的实例包括苯和甲苯与各种烷基氯化物在氯化1-乙基-3-甲基咪唑鎓([EMIM]Cl)和AlCl3(4份[EMIM]Cl/6份AlCl3)的混合物中的反应;以及采用液体催化剂相用乙烯将苯烷基化从而形成乙基苯的反应,其中所说的液体催化剂相是具有过量摩尔量AlCl3或过量摩尔量GaCl3的氯化咪唑鎓盐混合物。
一个较早的在离子型液体中进行的弗瑞德-克来福特酰化反应的实例使用氯化咪唑鎓盐与过量摩尔量AlCl3的混合物作为催化活性相,还描述了反应速率随着该混合物中路易斯酸AlCl3百分比的增加而增加。
还描述了通过在[EMIM]Cl-AlCl3(X(AlCl3)=0.67)的酸性混合物中进行的弗瑞德-克来福特酰化反应来合成一些工业上很重要的芳香化合物(例如:Traseolid)。当在该混合物中进一步增加AlCl3的百分比时再一次观察到了反应的加快。但是,在[EMIM]Cl-AlCl3中,AlCl3的摩尔百分比不能增加至超过67%摩尔,这是因为在更高的AlCl3含量下,该混合物的熔点攀升至超过100℃。
所研究的其它反应包括萘和蒽的酰化;聚乙烯的裂化;脂肪酸的异构化;所有这些反应都是在酸性氯代铝酸盐熔化物中进行的。
还描述了使用路易斯酸FeCl3在[EMIM]Cl-FeCl3系统中形成酸性离子型液体。其中也使用过量的路易斯酸,但是仅FeCl3摩尔含量低于62%的混合物在低于100℃的温度下是液体。其中描述了用酰氯对苯进行酰化,其中当催化活性混合物中FeCl3的摩尔含量为51至55mol%时,通过萃取将所形成的酮从催化剂相中分离出来。
除了将过量的路易斯酸与有机氯化物盐相结合形成所说的催化活性的离子型液体外,还描述了少量的其它例子,在这些例子中,将路易斯酸如三氟甲磺酸钪(III)和其它镧系元素盐与包含[PF6]-、[BF4]-、[SbF6]-或三氟甲磺酸根离子的中性离子型液体进行混合从而得到一种催化活性系统。但是,在所有该类系统中,相对于所说的离子型液体而言,所用路易斯酸的浓度都很低。通常,这些混合物具有1份路易斯酸:27份中性离子型液体的摩尔比。所得的系统被用于用1-己烯来烷基化苯。
还记载了镧系元素三氟甲磺酸盐和包含[PF6]-、[BF4]-、[SbF6]-或三氟甲磺酸根离子的中性离子型液体的混合物,其中使用相对于离子型液体而言摩尔比很低的镧系元素作为路易斯酸。镧系元素三氟甲磺酸盐和离子型液体的摩尔比典型地为1∶200。这些混合物被用来完成α-氨基膦酸盐的三组分合成。其在工业应用中的一个重要限制是在强路易斯酸的存在下不稳定的络合物阴离子(如[PF6]-、[SbF6]-))会发生分解。
已经研制了在本质上不同的有催化活性的酸性离子型液体,并且将其用于例如用癸烯进行的苯的弗瑞德-克来福特烷基化。其实例包括基本没有路易斯酸酸度的离子型液体,其是[BMIM][HSO4]和布朗斯台德酸硫酸的混合物;这些混合物不能用来获得超过纯硫酸的酸度。
基于相似概念的其它酸性离子型液体包括酸催化的环化反应中的三丁基己基铵-二(三氟甲磺酰基)亚胺([NBu3(C6H13)][(CF3SO2)2N])和布朗斯台德酸的混合物。曾使用磷酸和甲苯磺酸作为布朗斯台德酸。但是,所存在的问题是,如果向二(三氟甲磺酰基)胺熔化物中加入更强的布朗斯台德酸,则会形成在低温下易于升华的阴离子的游离酸。
一般而言,由前面所公开的酸性离子型液体在各种酸催化反应中的应用可以看出,从工业观点来看,用酸性液体盐作为催化剂是很有前景的。现有技术中的酸性离子型液体具有在一定范围内可变的酸性和可以通过阳离子的性质来改变的令人感兴趣的溶解度特性。这些溶解度特性使得可以将一些新方法用于酸催化反应的工业实践,例如采用多相反应方案。
本发明的描述
本发明涉及新的意想不到的离子型液体材料的生产,其中所说的离子型液体材料是咪唑鎓、吡啶鎓、铵或磷鎓离子的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐与路易斯酸(AlCl3、AlBr3、SnCl2、FeCl3和ZnCl2)的混合物,并且其中路易斯酸和咪唑鎓、吡啶鎓、铵或磷鎓离子的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合摩尔比高于1∶1。这些材料在低于100℃的温度下是液体。
在本发明的一个实施方案中,该材料在低于100℃的温度下,在液体混合物中具有高至4.5/1的路易斯酸/咪唑鎓、吡啶鎓、铵或磷鎓离子的三氟甲磺酸盐或路易斯酸/咪唑鎓、吡啶鎓、铵或磷鎓离子的二(三氟甲磺酰基)亚胺盐的摩尔比。
本发明还涉及多种不同的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐与选自AlCl3、AlBr3、SnCl2、FeCl3和ZnCl2的各种路易斯酸的混合物混合的混合物。所用路易斯酸组分的摩尔含量可以超过整个混合物的50mol%,其优选可以超过整个混合物的67mol%。
本发明的新型酸性离子型液体是通过将咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐或多种咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合物与过量摩尔量的选自AlCl3、AlBr3、SnCl2、FeCl3和ZnCl2的路易斯酸进行混合或者与过量摩尔量的上述路易斯酸的混合物进行混合来制备的。优选将咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐或多种咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合物与选自AlCl3、AlBr3、SnCl2、FeCl3和ZnCl2的路易斯酸混合从而获得一种其中路易斯酸的含量高于67mol%的混合物。
用这种方法获得的材料的熔点一般低于25℃;本发明所有实例的熔点都低于100℃。
与现有技术中所述的已知的酸性离子型液体的差异涉及本发明新的酸性离子型液体工业应用的下述相关优点:
与通过向咪唑鎓、吡啶鎓、铵或磷鎓离子的卤化物盐中加入过量摩尔量的路易斯酸形成的现有技术的系统相比,本发明的新型酸性离子型液体的特征为具有下面的优点:
I)本发明的新型离子型液体是由比例>2∶1的选自AlCl3、SnCl2、FeCl3和ZnCl2的路易斯酸与咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合物形成的,而现有技术中由路易斯酸与卤化物盐的混合物获得的系统中没有任何系统可以使用>2∶1的比例,这是因为在后一种情况中该混合物将具有高于100℃的熔点。由于可获得的混合比例与该系统的总酸度直接相关,而总酸度又与该系统在酸催化的反应中的活性和选择性有关,所以在本发明的系统中使用更高百分比的路易斯酸消除了之前存在的对现有技术的酸性离子型液体应用范围的许多限制因素。
II)在必须对产物混合物进行水解处理的反应中(例如,弗瑞德-克来福特酰化反应或其中分子包含氧或其中在该分子中存在氮官能团的其它反应),本发明的新型酸性离子型液体首次使得可以将昂贵的阳离子组分循环使用。在水解后,可以通过萃取将所用的咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐或咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐与产物的混合物与水相分离开并在将反应产物蒸馏或结晶后将其重新使用。因此,本发明的新型离子型液体首次提供了用于对离子型液体中所用的相对昂贵的阳离子进行分离和回收的有效方法。离子型液体中相对昂贵的阳离子的损失是现有技术中所用方法的一个很重要的成本因素。
与之前通过将镧系元素三氟甲磺酸盐与包含[PF6]-、[BF4]-、[SbF6]-或三氟甲磺酸根离子的中性有机液体进行混合所形成的已知系统相比,当使用本发明的新型酸性离子型液体时可以产生以下优点:
III)相对于中性熔化物而言,现有技术中没有任何系统可以以化学计量比或甚至超化学计量比的比例使用路易斯酸(镧系元素三氟甲磺酸盐),这严重限制了可以获得的酸度。相反,本发明的新型离子型液体是由摩尔比>2∶1的一种或多种选自AlCl3、SnCl2、FeCl3和ZnCl2的路易斯酸与一种或多种咪唑鎓、吡啶鎓、铵或磷鎓三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合物形成的。
IV)虽然已知在存在强路易斯酸的情况下,现有技术以及本发明所用的离子型液体中的阴离子[PF6]-、[BF4]-、[SbF6]-是不稳定的,但本发明的新型酸性离子型液体的特征为其稳定性大大提高,既使在使用更高摩尔含量的路易斯酸或酸的情况下也具有很高的稳定性。
与通过将布朗斯台德酸与包含[HSO4]或[(CF3SO2)2N]离子的离子型液体混合所形成的现有技术的系统相比,当使用本发明的新型酸性离子型液体时具有如下优点:
V)本发明的新系统是路易斯酸系统,而布朗斯台德酸系统是通过将布朗斯台德酸与现有技术中的包含[HSO4]或[(CF3SO2)2N]离子的离子型液体混合获得的。但是,许多应用仅能通过使用路易斯酸系统来完成。
VI)在现有技术的系统中,离子型液体的阴离子(例如[(CF3SO2)2N])在存在强酸的情况下形成挥发性酸H[(CF3SO2)2N]的事实严格限制了反应系统中可获得的活性酸性组分的酸度和百分比以及一般性的应用容易性。该挥发性酸易于从反应混合物中升华,这大大限制了现有技术中的离子型液体的应用范围。当使用本发明的新型酸性离子型液体时则不会发生该类问题。
本发明新型酸性离子型液体的应用范围包括其中用强路易斯酸作为催化剂或其中在存在强路易斯酸的情况下在反应条件下形成强布朗斯台德酸的所有反应。本发明的新型酸性离子型液体特别适用于与之前所用的现有技术的系统相比,增加酸度将会改善催化活性组分的活性、选择性或寿命的情况。可以成功使用本发明的新型酸性离子型液体的具体应用的实例包括弗瑞德-克来福特反应(烷基化和酰化反应)、弗利斯重排、芳族化合物的羰基化、氯甲苯的异构化、二氯苯的异构化、甲苯的烷基转移反应、链烷烃的骨架异构化、以及所谓的炼油烷基化(将异丁烯与丙烷或丁烷反应来制备烷基化汽油),但这种列举并不是穷尽列举或排他性列举。
本发明的新型酸性离子型液体的一种特别令人感兴趣的实施方案是基于如下出人意料的发现:即,当以某些混合比例将所用的路易斯酸或多种路易斯酸的混合物与三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐或多种三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的混合物混合时,本发明的新型酸性离子型液体是以液-液多相系统的形式存在的。其开辟了用提取法对反应混合物和产物混合物进行处理的新的可能性。
本发明的新型酸性离子型液体尤其优选的实施方案包括下面的混合物:
·1-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-乙基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-丁基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1,4-二甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1,3-二甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-乙基-4-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-乙基-3-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-丁基-4-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-丁基-3-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1,3-二甲基咪唑鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-乙基-3-甲基咪唑鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1,3-二乙基咪唑鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-丁基-3-甲基咪唑鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-丁基-3-乙基咪唑鎓-二(三氟甲磺酰基)亚胺与AlCl3
·三甲基铵-二(三氟甲磺酰基)亚胺与AlCl3
·四甲基铵-二(三氟甲磺酰基)亚胺与AlCl3
·四丁基铵-二(三氟甲磺酰基)亚胺与AlCl3
·四丁基磷鎓-二(三氟甲磺酰基)亚胺与AlCl3
·1-甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1-乙基吡啶鎓三氟甲磺酸盐与AlCl3
·1-丁基吡啶鎓三氟甲磺酸盐与AlCl3
·1,4-二甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1,3-二甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1-乙基-4-甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1-乙基-3-甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1-丁基-4-甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1-丁基-3-甲基吡啶鎓三氟甲磺酸盐与AlCl3
·1,3-二甲基咪唑鎓三氟甲磺酸盐与AlCl3
·1-乙基-3-甲基咪唑鎓三氟甲磺酸盐与AlCl3
·1,3-二乙基咪唑鎓三氟甲磺酸盐与AlCl3
·1-丁基-3-甲基咪唑鎓三氟甲磺酸盐与AlCl3
·1-丁基-3-乙基咪唑鎓三氟甲磺酸盐与AlCl3
·三甲基铵三氟甲磺酸盐与AlCl3
·四甲基铵三氟甲磺酸盐与AlCl3
·四丁基铵三氟甲磺酸盐与AlCl3
·四丁基磷鎓三氟甲磺酸盐与AlCl3
·1-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-乙基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-丁基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1,4-二甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1,3-二甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-乙基-4-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-乙基-3-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-丁基-4-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-丁基-3-甲基吡啶鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1,3-二甲基咪唑鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-乙基-3-甲基咪唑鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1,3-二乙基咪唑鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-丁基-3-甲基咪唑鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-丁基-3-乙基咪唑鎓-二(三氟甲磺酰基)亚胺与FeCl3
·三甲基铵-二(三氟甲磺酰基)亚胺与FeCl3
·四甲基铵-二(三氟甲磺酰基)亚胺与FeCl3
·四丁基铵-二(三氟甲磺酰基)亚胺与FeCl3
·四丁基磷鎓-二(三氟甲磺酰基)亚胺与FeCl3
·1-甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1-乙基吡啶鎓三氟甲磺酸盐与FeCl3
·1-丁基吡啶鎓三氟甲磺酸盐与FeCl3
·1,4-二甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1,3-二甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1-乙基-4-甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1-乙基-3-甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1-丁基-4-甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1-丁基-3-甲基吡啶鎓三氟甲磺酸盐与FeCl3
·1,3-二甲基咪唑鎓三氟甲磺酸盐与FeCl3
·1-乙基-3-甲基咪唑鎓三氟甲磺酸盐与FeCl3
·1,3-二乙基咪唑鎓三氟甲磺酸盐与FeCl3
·1-丁基-3-甲基咪唑鎓三氟甲磺酸盐与FeCl3
·1-丁基-3-乙基咪唑鎓三氟甲磺酸盐与FeCl3
·三甲基铵三氟甲磺酸盐与FeCl3
·四甲基铵三氟甲磺酸盐与FeCl3
·四丁基铵三氟甲磺酸盐与FeCl3
·四丁基磷鎓三氟甲磺酸盐与FeCl3
用下面的实施例来对本发明进行说明。
实施例1:1-乙基-3-甲基吡啶鎓([3-MEP])二(三氟甲磺酰基)亚胺/氯化铝(III)([3-MEP][(CF3SO2)2N]/AlCl3)混合物:
A.1∶1的混合物
在室温下,在搅拌的同时缓慢将21.7mmol AlCl3加入到21.7mmol([3-MEP][(CF3SO2)2N]中。在轻微放热的同时,AlCl3溶解于熔化物中从而形成一种两相系统,其中所说的两相具有大致相等的体积,但是下层的相比上层的相粘得多。该混合物在70℃下仍保持两相形式,但是在100℃下则产生一种单相系统。
B.1∶2的混合物
在搅拌的同时,将43.1mmol AlCl3缓慢加入到21.7mmol([3-MEP][(CF3SO2)2N])中。在冷却至室温时,加入的全部AlCl3仍溶解于反应系统中,而反应系统本身以两相形式存在。
C.1∶3的混合物
在搅拌的同时,将64.2mmol AlCl3缓慢加入到21.7mmol([3-MEP][(CF3SO2)2N])中。得到一种澄清、均匀的单相溶液,在冷却至室温后,其仍然保持澄清并且是单相的。
D.1∶4.5的混合物
在搅拌的同时,在130℃下,将99.1mmol AlCl3缓慢加入到21.7mmol([3-MEP][(CF3SO2)2N])中。形成一种澄清、均匀的单相溶液,并且既使在冷却至室温后其仍然保持澄清和单相。
实施例2:1-乙基-4-甲基吡啶鎓([4-MEP])二(三氟甲磺酰基)亚胺/氯化铝(III)([4-MEP][(CF3SO2)2N]/AlCl3)混合物:
A.1∶1的混合物
在90℃下,在搅拌的同时将11.7mmol AlCl3加入到11.7mmol([4-MEP][(CF3SO2)2N])中。形成一种两相系统,其中所说的两相具有大致相同的体积。在冷却时,AlCl3在低于70℃的温度下从该系统中沉淀出来。
B.1∶2的混合物
在70℃下,在搅拌的同时将23.2mmol AlCl3加入到11.7mmol([4-MEP][(CF3SO2)2N])中。形成一种两相混合物,其中下层相的体积比上层相的体积小得多。既使在冷却至室温时也没有固体从该系统中沉淀出来。
C.1∶3的混合物
在105℃下,在搅拌的同时将34.3mmol AlCl3加入到11.7mmol([4-MEP][(CF3SO2)2N])中。形成一种澄清的相,其在冷却至室温后仍然是单相并且是澄清的。
D.1∶4的混合物
在130℃下,在搅拌的同时将46.6mmol AlCl3加入到11.7mmol([4-MEP][(CF3SO2)2N])中。形成一种澄清的相,其在冷却至室温后仍然是单相并且是澄清的。
实施例3:使用离子型液体([3-MEP][(CF3SO2)2N]/AlCl3)(摩尔比为1∶3)作为催化活性组分的辛酰氯与1-氯-2-苯基乙烷的反应
在惰性气氛下,在105℃下进行搅拌的同时,将40mmol AlCl3缓慢加入到13.3mmol([3-MEP][(CF3SO2)2N])中。形成一种澄清、均匀的单相溶液并且其在冷却至室温后仍然是澄清和单相的。在室温下,将所得的离子型液体与20mmol辛酰氯进行混合。在室温下向其中滴加20mmol 1-氯-2-苯基乙烷。将反应混合物在室温下搅拌6小时。用过量的水小心将该反应混合物水解;将水相用CH2Cl2萃取。在高真空下除去CH2Cl2,并用戊烷对残余物进行提取。反应产物溶解于戊烷中,以残余物形式回收了11mmol离子型液体([3-MEP][(CF3SO2)2N])。根据GC分析,该戊烷相包含:70.2%对位酰化的产物、12.6%间位酰化的产物、5.5%的辛酸(辛酸的水解产物)和4.6%的1-氯-2-苯基乙烷。通过对物料衡算进行计算来对所用的方法进行校验。
起始材料:包含咪唑鎓、吡啶鎓、铵或磷鎓离子的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐是已知的。
Claims (11)
1.一种包含一种或多种三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐和一种或多种路易斯酸的混合物的离子型液体,其中所说混合物中路易斯酸的总摩尔含量为约0.01-98%。
2.如权利要求1所述的离子型液体,其中所说混合物中路易斯酸的总摩尔含量为约50-85%。
3.如权利要求2所述的离子型液体,其中所说混合物中路易斯酸的总摩尔含量为约67-80%。
4.如权利要求1-3中任意一项所述的离子型液体,其中所用的三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐是
(1)铵盐,
(2)磷鎓盐,
(3)咪唑鎓盐,或
(4)吡啶鎓盐。
5.如权利要求4所述的离子型液体,其中所说三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐的阳离子是(1)具有通式[NR1R2R3R]+的季铵阳离子;(2)具有通式[PR1R2R3R]+的磷鎓阳离子;(3)具有式I的通式的咪唑鎓阳离子:
其中式I的咪唑环可以被一个或多个选自C1-C8烷基、C6-C12-芳基或C5-C12-芳基-C1-C6烷基的基团所取代;
(4)式II通式的吡啶鎓阳离子
其中式II的吡啶环可以被一个或多个选自C1-C8烷基或C6-C12-芳基或C5-C12-芳基-C1-C6烷基的基团所取代;
取代基R、R′、R1、R2、R3彼此独立地选自氢;直链或支链、饱和或不饱和的具有1至20个碳原子的脂族或脂环族烷基;和在芳基部分具有6至12个碳原子的芳基、芳基-C1-C6烷基,其可任选地被至少一个C1-C6烷基所取代。
6.如权利要求1-5中任意一项所述的离子型液体,其中所说的路易斯酸是AlCl3、AlBr3、SnCl2、FeCl3或ZnCl2。
7.如权利要求6所述的离子型液体,其中所说的路易斯酸是AlCl3。
8.如权利要求6所述的离子型液体,其中所说的路易斯酸是FeCl3。
9.制备如权利要求1-8中任意一项所述的离子型液体的方法,其包括在0至300℃,优选20至180℃,更优选50至150℃的温度下,在搅拌的同时按比例将路易斯酸加入到三氟甲磺酸盐或二(三氟甲磺酰基)亚胺盐中,从而形成液-液多相系统形式的离子型液体。
10.如权利要求1-8中任意一项所述的离子型液体作为催化剂或催化活性反应介质的应用,其中所说的反应是路易斯酸催化的反应。
11.如权利要求10所述的应用,其中所说的路易斯酸催化的反应包括弗瑞德-克来福特烷基化反应、弗瑞德-克来福特酰化反应、烷基化反应、羰基化反应、异构化反应和低聚反应。
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CN102671709A (zh) * | 2012-04-28 | 2012-09-19 | 温州大学 | 一种负载型酸性离子液体催化剂及其应用 |
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KR100914229B1 (ko) * | 2005-03-08 | 2009-08-27 | 가부시끼가이샤 도꾸야마 | 자기 헤드 고정 지립 연마용의 윤활제 조성물 |
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WO2007106943A1 (en) | 2006-03-22 | 2007-09-27 | Ultraclean Fuel Pty Ltd | Process for removing sulphur from liquid hydrocarbons |
US7488860B2 (en) * | 2006-09-13 | 2009-02-10 | Chinese Petroleum Corp. | Method for producing exo-tetrahydrodicyclopentadiene using ionic liquid catalyst |
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EP3490705B1 (en) * | 2016-07-29 | 2023-08-30 | The Procter & Gamble Company | Catalysts for making acrylic acid from lactic acid or its derivatives in liquid phase |
US10307744B2 (en) * | 2016-07-29 | 2019-06-04 | The Procter & Gamble Company | Catalysts for making acrylic acid from lactic acid or its derivatives in liquid phase |
US11420916B2 (en) | 2018-06-08 | 2022-08-23 | Board Of Regents, The University Of Texas System | Systems and methods for separation of olefins from mixtures that contain reducing agents |
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CN102671709A (zh) * | 2012-04-28 | 2012-09-19 | 温州大学 | 一种负载型酸性离子液体催化剂及其应用 |
CN109574815A (zh) * | 2018-11-27 | 2019-04-05 | 江苏师范大学 | 一种中间体5-溴茚酮的制备方法 |
CN110590497A (zh) * | 2019-09-30 | 2019-12-20 | 江苏七洲绿色化工股份有限公司 | 一种间二氯苯的合成方法 |
CN110590497B (zh) * | 2019-09-30 | 2022-04-05 | 江苏七洲绿色化工股份有限公司 | 一种间二氯苯的合成方法 |
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