EP1521745A1 - Method for producing imidazolium salts - Google Patents
Method for producing imidazolium saltsInfo
- Publication number
- EP1521745A1 EP1521745A1 EP03763595A EP03763595A EP1521745A1 EP 1521745 A1 EP1521745 A1 EP 1521745A1 EP 03763595 A EP03763595 A EP 03763595A EP 03763595 A EP03763595 A EP 03763595A EP 1521745 A1 EP1521745 A1 EP 1521745A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radicals
- imidazolium
- substituted
- triflate
- 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- Withdrawn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
- 150000004693 imidazolium salts Chemical class 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000002168 alkylating agent Substances 0.000 claims abstract description 17
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- -1 Metal complex ion Chemical class 0.000 claims description 56
- 150000003254 radicals Chemical class 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- GGRHYQCXXYLUTL-UHFFFAOYSA-N chloromethyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCCl GGRHYQCXXYLUTL-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 claims description 6
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
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- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 3
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- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
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- 239000003960 organic solvent Substances 0.000 claims description 3
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- BIAAQBNMRITRDV-UHFFFAOYSA-N 1-(chloromethoxy)-2-methoxyethane Chemical compound COCCOCCl BIAAQBNMRITRDV-UHFFFAOYSA-N 0.000 claims description 2
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000707 boryl group Chemical group B* 0.000 claims description 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
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- 239000003502 gasoline Substances 0.000 claims description 2
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- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
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- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
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- 150000003871 sulfonates Chemical class 0.000 claims description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 125000003172 aldehyde group Chemical group 0.000 claims 1
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- 229910052802 copper Inorganic materials 0.000 claims 1
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- 125000002993 cycloalkylene group Chemical group 0.000 claims 1
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- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- JNJFONBBNLVENC-UHFFFAOYSA-N 1h-imidazole;trifluoromethanesulfonic acid Chemical compound C1=CNC=N1.OS(=O)(=O)C(F)(F)F JNJFONBBNLVENC-UHFFFAOYSA-N 0.000 description 22
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- HERNGMUUVSRQRR-UHFFFAOYSA-M 1,3-bis(2,4,6-trimethylphenyl)imidazol-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)C=C1 HERNGMUUVSRQRR-UHFFFAOYSA-M 0.000 description 4
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- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 description 1
- BNNMDMGPZUOOOE-UHFFFAOYSA-N 4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1 BNNMDMGPZUOOOE-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000005620 boronic acid group Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005888 cyclopropanation reaction Methods 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZLUSCZLCHQSJRU-UHFFFAOYSA-N thallium(1+) Chemical compound [Tl+] ZLUSCZLCHQSJRU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
Definitions
- the invention relates to a process for the preparation of imidazolium salts by reacting bisimines or corresponding heterocycles with a combination of alkylating agent and a metal salt as a promoter of the reaction.
- This method allows a large number of imidazolium salts to be prepared under mild reaction conditions and in good yields.
- This synthetic process can be used to prepare novel imidazolium salts of the general formulas II, IV and XI (in particular chiral enantiomerically pure and highly substituted imidazolium salts) and to produce known imidazolium salts of the general formula VI in improved yield.
- the imidazolium salts can be converted into N-heterocyclic carbenes and their transition metal complexes by deprotonation. These complexes have high thermal and chemical stability, as well as very good catalyst properties in the homogeneous catalysis of various reactions.
- N-heterocyclic carbenes based on the imidazole backbone as ligands in homogeneous transition metal catalysis has developed into an important area of research. Methods for CC, CO and CN bond formation as well as applications in olefin metathesis have become particularly important.
- imidazolium salts The deprotonation of imidazolium salts to produce the corresponding N-heterocyclic carbenes and their transition metal complexes has been widely used as the method of choice. Synthetic methods for imidazolium salts that can be used in general are therefore of great interest. Numerous synthetic methods for imidazolium salts already exist. (Review: WA Herrmann, Angew. Chem. (2002) 114, 1342.) Starting from glyoxal, primary amines and formaldehyde, imidazolium salts can be formed under acidic reaction conditions (US Patent No. 5182405).
- Isolated bisimines obtained from glyoxal can also be reacted with acid and formaldehyde or with chloromethyl ethyl ether to give imidazolium salts (US Patent No. 5077414).
- Unbalanced 1.3 disubstituie 'rte imidazolium can be obtained by alkylation of mono-substituted imidazoles.
- the monosubstituted imidazoles required for this can be obtained analogously to the synthesis from glyoxal, formaldehyde and a mixture of a primary amine with ammonium chloride mentioned above.
- Saturated imidazolium salts can be obtained from substituted 1,2-bisamines by reaction with formaldehyde or trialkyl orthoformate.
- the invention relates to a process for the preparation of imidazolium salts of the general formulas II, IV and VI, comprising the reaction of the corresponding substrates I, IM and V,
- X represents O, S, a group NR 9 or CR 9a R 9b in which R 9 , R 9a and R 9 are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C- o-alkyl-, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 aralkyl or C 6-14 aryl radicals mean
- Y is O, S, a group NR 10 or NR 10a R 10b , in which R 10 , R 10a , R 10b are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1-0 -alkyl-, C 2-5 -alkenyl-, C 2 . 5 -alkynyl, C 7- ⁇ 9 aralkyl or C 6- ⁇ 4 aryl radicals mean, and
- A represents a mono- or polyvalent, organic or inorganic anion or a metal complex ion, with a combination of an alkylating agent of the general formula VII, VIII or IX
- MA in which M represents a mono- or polyvalent metal cation, a tetraorganoammonium compound or a triorganosilyl radical, and A has the meaning given above for A " , as a promoter of the reaction.
- the present invention further provides compounds of the general formulas II, IV and XI,
- I 1 and I 2 are the same or different imidazolium salts of the formulas II, IV and VI, which are linked to L at the position of the radicals R 1 , R 2 , R 7 , R 8 , R 12 or R 14 , with the proviso that not I 1 and I 2 are both an imidazolium salt of the formula VI, the imidazolium salt of the formula VI, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , X, Y, L and A "have the meaning given above.
- R 11 and R 12 are linked to one another to form a substituted or unsubstituted cycle, preferably to form a pyridyl ring.
- Preferred substituents are C 1-6 alkyl and C 6- ⁇ aryl. The substituents are preferably bonded to the carbon adjacent to the ring nitrogen.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 9a , R 9b , R 10a , R 10 , R 11 , R 2 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1- 6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 7-10 aralkyl or phenyl radicals.
- the C 1-6 alkyl radicals can be selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl , i-hexyl, t-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
- the C 2-4 alkenyl radicals can be selected from ethenyl, propenyl or butenyl, the C 2 .
- the C 7-10 aralkyl radicals can be selected from benzyl, phenylethyl, phenylpropyl and phenylbutyl.
- the radicals R 1 to R 19 can be halogenated, in particular by one or more, identical or different amine, nitro, nitrile, isonitrile, ether, alcohol, aldehyde or ketone groups, carboxylic acid derivatives, in particular esters or amides fluorinated or perfluorinated hydrocarbon residues, carbohydrate, phosphane, phosphine oxide, phosphine sulfide, phosphole residues, phosphite derivatives, aliphatic or aromatic sulfonic acid derivatives, their salts, esters or amides, silyl functions, boryl groups or heterocyclic substituents.
- radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 4 are CC 6 - alkyl, C 2 -C 4 alkenyl, or C 2 . 4 - alkynyl residues.
- one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 4 is substituted by an azolium salt or a pyridine ring.
- one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 is a linker L to a further imidazolium salt of the formula II, IV or VI.
- L can in particular be a C 1-4 - Alkylene radical (such as a methylene, ethylene, propylene or butylene radical), a C 5-12 cycloalkylene radical (such as a 1, 2- or 1, 4-cyclohexylene radical), a C 6 . 12 arylene residue (such as a 1,2-, 1,3- or 1,4-phenylene residue) or a C 6-12 heteroarylene residue (such as a 2,3-, 2,4- or 2,6-pyridinylene residue) his.
- a C 1-4 - Alkylene radical such as a methylene, ethylene, propylene or butylene radical
- a C 5-12 cycloalkylene radical such as a 1, 2- or 1, 4-cyclohexylene radical
- a C 6 . 12 arylene residue such as a 1,2-, 1,3- or 1,4-phenylene residue
- a C 6-12 heteroarylene residue such as a 2,3-, 2,4- or 2,6-pyri
- radicals can optionally be substituted (for example with C 1-4 -alkyl radicals, d ⁇ -alkoxy radicals, halogen atoms, hydroxyl groups etc.) or by a hetero atom (for example O or NH) or a cyclic radical (for example a phenyl or cyclohexyl radical) be interrupted.
- An imidazolium salt which has the general formula X is particularly preferred
- the mono- or polyvalent organic anion A " in the general formulas II, IV, VI and XI is a sulfate, halide, pseudohalide, borate, phosphate or metal complex ion or an optionally halogenated sulfonate -, carboxylate or acetylacetonate ion and in particular A " for a triflate, mesylate, tosylate, nonaflate, tresylate, benzenesulfonate, brosylate, nosylate, fluorosulfonate, tetraphenylborate, tetrakis [3 , 5-bis (trifluoromethyl) phenyl] borate (BARF) -, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, perchlorate, tetracarbonyl cobaltate or hexa
- Process (1) comprises the use of an alkylating agent of the general formula VII, VIII or IX defined above.
- the leaving group Z in this alkylating agent preferably represents a halide, pseudohalide or (optionally halogenated) carboxylate, particularly preferably a halide, particularly preferably chloride.
- Preferred alkylating agents are those in which R 15 represents an unsubstituted or substituted phenyl, benzyl or C 1-4 alkyl radical, which can each contain one or more substituents, in particular ether, ester or silyl substituents.
- Preferred metal salts of the general formula MA which can be used in process (1) are those in which the mono- or polyvalent metal cation M is a silver (I), alkali and alkaline earth metal, lanthanide, lead (II) , Mercury (II), cadmium (II), thallium (I), copper (II), zinc (II) or aluminum (III) ion, and those in which the tetraorganoammonium compound is a tetraalkylammonium compound and finally those in which the triorganosilyl radical is a trialkylsilyl radical.
- Particularly preferred metal salts are those in which M is silver (I) and A is a sulfonate, sulfate, halide, pseudohalide, oxide, borate, phosphate, carboxylate, acetylacetonate or metal complex ion , preferably for a trifluoromethanesulfonate (triflate) -, methanesulfonate (mesylate), p-toluenesulfonate (tosylate) -, nonafluorobutanesulfonate (nonaflate) -, 2,2,2-trifluoroethanesulfonate (tresylate) -, benzenesulfonate, p-bromobenzenesulfonate Brosylate), p-nitrobenzenesulfonate (nosylate), fluorosulfonate, tetraphenyl borate, tetrakis [3,5-bis (triflu
- alkylating agents and metal salts are used in at least a stoichiometric amount, preferably in a 5 to 100% excess with respect to the substrate.
- the ratio of alkylating agent to metal salt can be varied within a wide range and is preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1.2.
- the imidazolium salts of the general formulas II, IV and VI are preferably synthesized with the exclusion of air and moisture. It has proven to be particularly advantageous to add the alkylating agent to a solution of the corresponding starting material of the general formula I, III or V and the metal salt in an organic solvent.
- Suitable solvents can be acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1, 2-dimethoxyethane, 1, 4-dioxane, petroleum ether, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 1, 3- Dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone, acetonitrile, propionitrile, ethyl acetate, benzene, toluene, xylene, gasoline, chloroform, 1, 2-dichloroethane and methylene chloride, preferably methylene chloride.
- the reaction solution is purified in a conventional manner according to the physical properties of the products, e.g. B. by column chromatography or crystallization.
- the imidazolium salts of the present invention are in particular those compounds in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , RR 18 , X, Y, L and A "have the preferred meaning given above.
- OTf means trifluoromethanesulfonate (triflate), Ph phenyl, TMS trimethylsilyl, TES triethylsilyl and Bn benzyl.
- OTf means trifluoromethanesulfonate (triflate), Ph phenyl, and Bn benzyl.
- the compounds specifically mentioned above may also have tetrafluoroborate, mesylate, tosylate, nonaflate or hexafluoroantimonate instead of triflate as the counter anion.
- the method according to the invention enables a large number of previously unknown, achiral and chiral imidazolium salts to be prepared in surprisingly good yield, high purity and, if appropriate, high optical purity. This is due, on the one hand, to the large constitutional diversity of the starting materials of the general formulas I, III and V and, on the other hand, to the mild alkylation conditions, which surprisingly become possible through the combined use of an alkylating agent and a metal salt as a promoter.
- the method according to the invention has proven particularly useful therefore for the production of imidazolium salts from acid-sensitive substrates and for the production of chiral imidazolium salts. Furthermore, the method can be used for the synthesis of milligram and multigram amounts of imidazolium salts. Because of the simple reaction procedure, the process is also suitable for industrial use.
- the imidazolium salts of the general formulas II, IV and VI which can be prepared by this process can be deprotonated in accordance with the literature and thus converted into N-heterocyclic carbenes or their transition metal complexes.
- These transition metal-carbene complexes can be used as catalysts in homogeneous catalysis , wherein chiral, enantiomerically pure imidazolium salts of the general formulas II, IV and VI lead to chiral transition metal complexes which can be used in particular in asymmetric catalysis.
- novel imidazolium salts of the general formulas II and IV in which the imidazolium nucleus is bridged by one (IV) or two (II) rings, are particularly promising.
- suitable substitution of these bridges with the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 chiral, enantiomerically pure imidazolium salts with rigid geometry can be obtained, the transition metal-carbene complexes of which asymmetric catalysis can be used.
- CDCI 3 ⁇ 141.5 (C), 137.9 (NCHN), 134.0 (C), 130.4 (C), 129.9 (CH ar ), 124.9 (NCHCHN),
Abstract
The invention relates to a method for producing imidazolium salts by reacting bisimines or corresponding heterocycles with a combination consisting of an alkylating agent and of a metal salt serving as promoters of the reaction. This method makes it possible to obtain a multitude of imidazolium salts under mild reaction conditions and in good yields. The imidazolium salts produced from heterocycles constitute novel compounds.
Description
Verfahren zur Herstellung von Imidazoliumsalzen Process for the preparation of imidazolium salts
Die Erfindung betrifft ein Verfahren zur Herstellung von Imidazoliumsalzen durch Umsetzung von Bisiminen oder entsprechender Heterozyklen mit einer Kombination von Alkylierungsmittel und einem Metallsalz als Promoter der Reaktion. Dieses Verfahren erlaubt die Darstellung einer Vielzahl von Imidazoliumsalzen unter milden Reaktionsbedingungen und in guten Ausbeuten. Durch dieses Syntheseverfahren können neuartige Imidazoliumsalze der allgemeinen Formeln II, IV und XI (insbesondere chirale enantiomerenreine sowie hochsubstituierte Imidazoliumsalze) hergestellt sowie bereits bekannte Imidazoliumsalze der allgemeinen Formel VI in verbesserter Ausbeute hergestellt werden. Die Imidazoliumsalze können durch Deprotonierung in N-heterozyklische Carbene und deren Übergangsmetallkomplexe überführt werden. Diese Komplexe besitzen eine hohe thermische und chemische Stabilität, sowie sehr gute Katalysatoreigenschaften in der Homogenkatalyse verschiedener Reaktionen.The invention relates to a process for the preparation of imidazolium salts by reacting bisimines or corresponding heterocycles with a combination of alkylating agent and a metal salt as a promoter of the reaction. This method allows a large number of imidazolium salts to be prepared under mild reaction conditions and in good yields. This synthetic process can be used to prepare novel imidazolium salts of the general formulas II, IV and XI (in particular chiral enantiomerically pure and highly substituted imidazolium salts) and to produce known imidazolium salts of the general formula VI in improved yield. The imidazolium salts can be converted into N-heterocyclic carbenes and their transition metal complexes by deprotonation. These complexes have high thermal and chemical stability, as well as very good catalyst properties in the homogeneous catalysis of various reactions.
Die Anwendung von N-heterozyklischen Carbenen auf Grundlage des Imidazolgrundgerüsts als Liganden in der homogenen Übergangsmetallkatalyse hat sich zu einem bedeutenden Forschungsgebiet entwickelt. Besonders Verfahren zur C-C-, C-O- und C-N- Bindungsknüpfung sowie Anwendungen in der Olefinmetathese haben große Bedeutung erlangt. Zu nennen sind insbesondere erfolgreiche Anwendungen in Heck-, Suzuki-, Sonogashira-, Kumada- und Stille-Kupplungen, Arylaminierungen, α-Arylierung von Amiden, Hydrosilylierung, Hydrierung, 1 ,4-Addition, Hydroformylierung, Cyclopropanierung von Olefinen, Arylierung und Alkenylierung von Aldehyden, Reduktion von Halogenarenen, Radikalische Atomtransfer-Polymerisation, Olefinmetathese, Ethylen/Kohlenmonoxid- Copolymerisation, C-H-Aktivierung und Telomerisation von 1 ,3-Dienen mit Alkoholen. So werden z. B. in der DE 4447067 A1 Kobalt- und Rhodium-Komplexe mit heterozyklischen Mono- oder Dicarben-Liganden als Katalysatoren für die industriell wichtige Hydroformylierung beschrieben. Industrielles Interesse erregt weiterhin die radikalische Atomtransfer- Polymerisation, wobei ein Eisen(ll)-Carben-Kompiex die derzeit höchsten in Lösungsmitteln beobachteten Polymerisationsgeschwindigkeiten bei gleichzeitig geringer Polydispersität zeigt. Besonders bedeutend sind zudem die zahlreichen Anwendungen von Ruthenium- Komplexen N-heterozyklischer Carbene in der Olefinmetathese, wobei die Vorteile von N- heterozyklischen Carbenliganden gegenüber Phosphanliganden klar gezeigt wurden, z. B. in der DE 1981527.5.
Der Gesamtumsatz enantiomerenreiner Pharmaka wuchs im Jahr 2000 erstmals auf über 100 Milliarden Dollar an, so dass ein grosser Bedarf an enantiomerenreinen Substanzen besteht. Übergangsmetall-Komplexe chiraler, enantiomerenreiner N-heterozyklischer Carbene sind viel versprechende Katalysatoren in der asymmetrischen Katalyse. (Comprehensive Asymmetrie Catalysis; Hrsg.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto; Springer: Berlin, 1999.) Erste sehr erfolgreiche Anwendungen derartiger chiraler Komplexe in der Hydrierung von dreifach substituierten Alkenen sowie der Olefinmetathese bestätigen dieses Potential. Zur Zeit existieren nur relativ wenige chirale Imidazoliumsalze. (Siehe z. B. C. Bolm, M. Kesselgruber, G. Raabe, Organometallics (2002) 21 , 707; J. J. Van Veldhuizen S. B. Garber, J. S. Kingsbury, A. H. Hoveyda, J. Am. Chem. Soc. (2002) 124, 4954; T. J Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. (2001) 3, 3225; M. T. Powell, D.-R. Hou, M C. Perry, X. Cui, K. Burgess, J. Am. Chem. Soc. (2001) 123, 8878; S. Lee, J. F. Hartwig, J Org. Chem. (2001) 66, 3402; D. S. Clyne, J. Jin, E. Genest, J. C. Gallucci, T. V. RajanBabu Org. Lett. (2000) 2, 1125.) Die Synthese neuer, chiraler Imidazoliumsalze, insbesondere Imidazoliumsalze mit einem Stereozentrum in unmittelbarer Nachbarschaft, und die Anwendung ihrer Übergangsmetallkomplexe in der asymmetrischen Katalyse ist daher von großer Bedeutung.The use of N-heterocyclic carbenes based on the imidazole backbone as ligands in homogeneous transition metal catalysis has developed into an important area of research. Methods for CC, CO and CN bond formation as well as applications in olefin metathesis have become particularly important. Particularly noteworthy are successful applications in Heck, Suzuki, Sonogashira, Kumada and Stille couplings, arylaminations, α-arylation of amides, hydrosilylation, hydrogenation, 1, 4 addition, hydroformylation, cyclopropanation of olefins, arylation and alkenylation of aldehydes, reduction of halogen arenes, radical atom transfer polymerization, olefin metathesis, ethylene / carbon monoxide copolymerization, CH activation and telomerization of 1,3-dienes with alcohols. So z. B. described in DE 4447067 A1 cobalt and rhodium complexes with heterocyclic mono- or dicarbene ligands as catalysts for the industrially important hydroformylation. Radical atom transfer polymerization continues to attract industrial interest, with an iron (II) -carbene complex showing the highest polymerization rates currently observed in solvents with low polydispersity. In addition, the numerous applications of ruthenium complexes of N-heterocyclic carbenes in olefin metathesis are particularly significant. The advantages of N-heterocyclic carbene ligands over phosphine ligands have been clearly demonstrated. B. in DE 1981527.5. The total turnover of enantiomerically pure pharmaceuticals grew to over $ 100 billion for the first time in 2000, so that there is a great need for enantiomerically pure substances. Transition metal complexes of chiral, enantiomerically pure N-heterocyclic carbenes are promising catalysts in asymmetric catalysis. (Comprehensive Asymmetry Catalysis; Ed .: EN Jacobsen, A. Pfaltz, H. Yamamoto; Springer: Berlin, 1999.) First very successful applications of such chiral complexes in the hydrogenation of triple-substituted alkenes and olefin metathesis confirm this potential. There are currently relatively few chiral imidazolium salts. (See, e.g., BC Bolm, M. Kesselgruber, G. Raabe, Organometallics (2002) 21, 707; JJ Van Veldhuizen SB Garber, JS Kingsbury, AH Hoveyda, J. Am. Chem. Soc. (2002) 124, 4954; T. J Seiders, DW Ward, RH Grubbs, Org. Lett. (2001) 3, 3225; MT Powell, D.-R. Hou, M C. Perry, X. Cui, K. Burgess, J. Am. Chem Soc. (2001) 123, 8878; S. Lee, JF Hartwig, J Org. Chem. (2001) 66, 3402; DS Clyne, J. Jin, E. Genest, JC Gallucci, TV RajanBabu Org. Lett. ( 2000) 2, 1125.) The synthesis of new, chiral imidazolium salts, especially imidazolium salts with a stereocenter in the immediate vicinity, and the use of their transition metal complexes in asymmetric catalysis is therefore of great importance.
Die Deprotonierung von Imidazoliumsalzen zur Herstellung der entsprechenden N- heterozyklischen Carbene und ihrer Übergangsmetall-Komplexe hat dabei als Methode der Wahl breite Anwendung gefunden. Generell einsetzbare Synthesemethoden für Imidazoliumsalze sind daher von großem Interesse. Es existieren bereits zahlreiche Synthesemethoden für Imidazoliumsalze. (Übersicht: W. A. Herrmann, Angew. Chem. (2002) 114, 1342.) Ausgehend von Glyoxal, primären Aminen und Formaldehyd können Imidazoliumsalze unter sauren Reaktionsbedingungen gebildet werden (U. S. Patent No. 5182405). Aus Glyoxal erhaltene, isolierte Bisimine können ebenfalls mit Säure und Formaldehyd bzw. mit Chlormethylethylether zu Imidazoliumsalzen umgesetzt werden (U. S. Patent No. 5077414). Unsymmetrische 1,3-disubstituie'rte Imidazoliumsalze können durch Alkylierung von monosubstituierten Imidazolen erhalten werden. Die hierzu benötigten monosubstituierten Imidazole können dabei in Analogie zur oben erwähnten Synthese aus Glyoxal, Formaldehyd und einem Gemisch eines primären Amins mit Ammoniumchlorid erhalten werden. Gesättigte Imidazoliumsalze können aus substituierten 1 ,2-Bisaminen unter Umsetzung mit Formaldehyd oder Trialkylorthoformiat erhalten werden.The deprotonation of imidazolium salts to produce the corresponding N-heterocyclic carbenes and their transition metal complexes has been widely used as the method of choice. Synthetic methods for imidazolium salts that can be used in general are therefore of great interest. Numerous synthetic methods for imidazolium salts already exist. (Review: WA Herrmann, Angew. Chem. (2002) 114, 1342.) Starting from glyoxal, primary amines and formaldehyde, imidazolium salts can be formed under acidic reaction conditions (US Patent No. 5182405). Isolated bisimines obtained from glyoxal can also be reacted with acid and formaldehyde or with chloromethyl ethyl ether to give imidazolium salts (US Patent No. 5077414). Unbalanced 1.3 disubstituie 'rte imidazolium can be obtained by alkylation of mono-substituted imidazoles. The monosubstituted imidazoles required for this can be obtained analogously to the synthesis from glyoxal, formaldehyde and a mixture of a primary amine with ammonium chloride mentioned above. Saturated imidazolium salts can be obtained from substituted 1,2-bisamines by reaction with formaldehyde or trialkyl orthoformate.
Diese Synthesemethoden sind aufgrund ihrer Reaktionsbedingungen (zumeist im sauren Milieu, in Anwesenheit von Nucleophilen und bei relativ hoher Temperatur) in ihrer
Anwendungsbreite limitiert. Die Vielfalt der als Ausgangsmaterial in Betracht kommenden Stoffklassen ist daher eingeschränkt, so dass zahlreiche Substitutionsmuster mit den bekannten Methoden nicht erhalten werden können. Insbesondere viele chirale Imidazoliumsalze und Imidazoliumsalze mit säureempfindlichen Substituenten konnten bisher nicht dargestellt werden. Unter anderem sind in der Literatur keine Beispiele für Imidazoliumsalze der allgemeinen Formeln II und IV beschrieben. Weiterhin liefern die oben beschriebenen Syntheseverfahren häufig nur moderate Ausbeuten nach häufig langen Reaktionszeiten.These synthesis methods are in their due to their reaction conditions (mostly in an acidic environment, in the presence of nucleophiles and at a relatively high temperature) Limited range of applications. The variety of the material classes that can be considered as the starting material is therefore restricted, so that numerous substitution patterns cannot be obtained with the known methods. In particular, many chiral imidazolium salts and imidazolium salts with acid-sensitive substituents have not yet been shown. Among other things, no examples of imidazolium salts of the general formulas II and IV are described in the literature. Furthermore, the synthetic processes described above often only provide moderate yields after often long reaction times.
Überraschenderweise wurde gefunden, dass unter Verwendung einer Kombination aus Alkylierungsmittel und einem Metallsalz als Promoter der Reaktion unter milden Bedingungen die erstmalige Herstellung der nachfolgend gezeigten Imidazoliumsalze der allgemeinen Formeln II, IV und XI möglich, sowie die Herstellung der Imidazoliumsalze der allgemeinen Formel VI in verbesserter Ausbeute möglich ist.Surprisingly, it was found that using a combination of alkylating agent and a metal salt as a promoter of the reaction under mild conditions, it is possible for the first time to prepare the imidazolium salts of the general formulas II, IV and XI shown below, and to prepare the imidazolium salts of the general formula VI in improved yield is possible.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Imidazoliumsalzen der allgemeinen Formeln II, IV und VI umfassend die Umsetzung der entsprechenden Substrate I, IM und V,The invention relates to a process for the preparation of imidazolium salts of the general formulas II, IV and VI, comprising the reaction of the corresponding substrates I, IM and V,
AA
AA
IVIV
AA
V VI worin
R R2, R3, R4, R5, R6, R7, R8, R11, R12, R13 und R14 gleich oder verschieden sind und gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C-Mo-Alkyl-, C2-5-Alkenyl-, C2-5-Alkinyl-, C7-19-Aralkyl- oder C6-14-Arylreste bedeuten, R1, R2, R3, R4, R5, R6, R7, R8, R11, R12 und R13 auch für Wasserstoff stehen können oder gemeinsam anellierte, substituierte oder unsubstituierte Reste mit 3-7 Kohlenstoffatomen bilden, R11 und R13 auch -OR16, -SR17 oder -NR18R19 sein können, in denen R16, R17, R18 und R19 die für die Reste R1 bis R8 und R11 bis R 4 angegebene Bedeutung haben können, wobei R16, R17,R18 und R19, einer der Reste R1, R2, R7, R8, R 2 und R14 auch ein Linker L zu einer weiteren Imidazoliumsalz der Formel II, IV oder VI sein kann,V VI in which RR 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 and R 14 are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C M o-alkyl, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 -aralkyl or C 6-14 -aryl radicals, R 1, R 2, R 3, R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 and R 13 can also represent hydrogen or together form fused, substituted or unsubstituted radicals with 3-7 carbon atoms, R 11 and R 13 also -OR 16 , -SR 17 or -NR 18 R 19 , in which R 16 , R 17 , R 18 and R 19 can have the meaning given for the radicals R 1 to R8 and R 11 to R 4 , where R 16 , R 17 , R 18 and R 19 , one of the radicals R 1 , R 2 , R 7 , R 8 , R 2 and R 14 can also be a linker L to a further imidazolium salt of the formula II, IV or VI,
X für O, S, eine Gruppe NR9 oder CR9a R9b steht, in der R9, R9a und R9 Wasserstoff, gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C- o-Alkyl-, C2-5-Alkenyl-, C2-5-Alkinyl-, C7-19-Aralkyl- oder C6-14-Arylreste bedeuten, Y für O, S, eine Gruppe NR10 oder NR10a R10b steht, in der R10, R10a, R10b Wasserstoff, gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C1- 0-Alkyl-, C2-5-Alkenyl-, C2.5-Alkinyl-, C7-ι9-Aralkyl- oder C6-ι4-Arylreste bedeuten, undX represents O, S, a group NR 9 or CR 9a R 9b in which R 9 , R 9a and R 9 are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C- o-alkyl-, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 aralkyl or C 6-14 aryl radicals mean Y is O, S, a group NR 10 or NR 10a R 10b , in which R 10 , R 10a , R 10b are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1-0 -alkyl-, C 2-5 -alkenyl-, C 2 . 5 -alkynyl, C 7- ι 9 aralkyl or C 6- ι 4 aryl radicals mean, and
A für ein ein- oder mehrwertiges, organisches oder anorganisches Anion oder ein Metallkomplex-Ion steht, mit einer Kombination aus einem Alkylierungsmittel der allgemeinen Formel VII, VIII oder IXA represents a mono- or polyvalent, organic or inorganic anion or a metal complex ion, with a combination of an alkylating agent of the general formula VII, VIII or IX
VII VIII IX worin Z für eine Abgangsgruppe steht und R15 dieselbe Bedeutung wie R3 hat, und einemVII VIII IX wherein Z represents a leaving group and R 15 has the same meaning as R 3 , and one
Metallsalz der allgemeinen FormelMetal salt of the general formula
MA, worin M für ein ein- oder mehrwertiges Metallkation, eine Tetraorganoammoniumverbindung oder einen Triorganosilylrest steht, und A die vorstehend für A" angegebene Bedeutung hat, als Promoter der Reaktion.MA, in which M represents a mono- or polyvalent metal cation, a tetraorganoammonium compound or a triorganosilyl radical, and A has the meaning given above for A " , as a promoter of the reaction.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Verbindungen der allgemeinen Formeln II, IV und XI,The present invention further provides compounds of the general formulas II, IV and XI,
IV XI
worin IV XI wherein
I1 und I2 gleiche oder verschiedene Imidazoliumsalze der Formeln II, IV und VI sind, die an der Position der Reste R1, R2, R7, R8, R12 oder R14 mit L verknüpft sind, mit der Maßgabe dass nicht I1 und I2 beide ein Imidazoliumsalz der Formeln VI sind, das Imidazoliumsalz der Formel VI, R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, X, Y, L und A" die oben angegebene Bedeutung haben.I 1 and I 2 are the same or different imidazolium salts of the formulas II, IV and VI, which are linked to L at the position of the radicals R 1 , R 2 , R 7 , R 8 , R 12 or R 14 , with the proviso that not I 1 and I 2 are both an imidazolium salt of the formula VI, the imidazolium salt of the formula VI, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , X, Y, L and A "have the meaning given above.
In einer möglichen Ausführungsform sind R11 und R12 unter Bildung eines substituierten oder unsubstituierten Cyclus miteinander verknüpft, vorzugsweise unter Bildung eines Pyridylringes. Bevorzugte Substituenten sind C1-6-Alkyl und C6-ι -Aryl. Bevorzugt sind die Substituenten an dem zum Ring-Stickstoff benachbarten Kohlenstoff gebunden.In a possible embodiment, R 11 and R 12 are linked to one another to form a substituted or unsubstituted cycle, preferably to form a pyridyl ring. Preferred substituents are C 1-6 alkyl and C 6- ι aryl. The substituents are preferably bonded to the carbon adjacent to the ring nitrogen.
In den vorstehend definierten Verbindungen ist es bevorzugt, dass R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 ,R9a, R9b, R10a, R10 , R11, R 2, R13, R14, R15, R16, R17, R18, R19, gleich oder verschieden sind und gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C1-6-Alkyl-, C2-4-Alkenyl-, C2-4-Alkinyl-, C7-10-Aralkyl- oder Phenylreste bedeuten.In the compounds defined above, it is preferred that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 9a , R 9b , R 10a , R 10 , R 11 , R 2 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1- 6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 7-10 aralkyl or phenyl radicals.
Die C1-6-Alkylreste können ausgewählt werden aus Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, t-Butyl, n-Pentyl, i-Pentyl, t-Pentyl, n-Hexyl, i-Hexyl, t-Hexyl, Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Die C2-4-Alkenylreste können ausgewählt werden aus Ethenyl, Propenyl oder Butenyl, die C2.4-Alkinylreste aus Ethinyl, Propinyl oder Butinyl. Die C7-10- Aralkylreste können ausgewählt werden aus Benzyl, Phenylethyl, Phenylpropyl und Phenylbutyl.The C 1-6 alkyl radicals can be selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl , i-hexyl, t-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The C 2-4 alkenyl radicals can be selected from ethenyl, propenyl or butenyl, the C 2 . 4 -alkynyl radicals from ethynyl, propynyl or butynyl. The C 7-10 aralkyl radicals can be selected from benzyl, phenylethyl, phenylpropyl and phenylbutyl.
Die Reste R1 bis R19 können durch einen oder mehrere, gleiche oder verschiedene Amin-, Nitro-, Nitril-, Isonitril-, Ether-, Alkohol-, Aldehyd-, oder Ketongruppen, Carbonsäurederivate, insbesondere Ester oder Amide, halogenierte, insbesondere fluorierte oder perfluorierte Kohlenwasserstoff-Reste, Kohlenhydrat-, Phosphan-, Phosphanoxid-, Phosphansulfid-, Phosphol-Reste, Phosphitderivate, aliphatische oder aromatische Sulfonsäurederivate, deren Salze, Ester oder Amide, Silylfunktionen, Borylgruppen oder heterozyklische Substituenten substituiert sein. Weitere geeignete Substituenten, insbesondere wenn die Reste aromatische Systeme sind, sind C C6- Alkyl-, C2-C4-Alkenyl-, oder C2.4- Alkinylreste. In einer besonders bevorzugten Ausführungsform ist einer der Reste R1, R2, R7, R8, R12 und R 4 durch ein Azoliumsalz oder einen Pyridinring substituiert.
In einer weiteren Ausführungsform stellt einer der Reste R1, R2, R7, R8, R12 und R14 ein Linker L zu einem weiteren Imidazoliumsalz der Formel II, IV oder VI dar. L kann insbesondere ein C1-4-Alkylenrest (wie z.B. ein Methylen-, Ethylen-, Propylen oder Butylenrest), ein C5-12-Cycloalkylenrest (wie z.B. ein 1 ,2- oder 1 ,4-Cyclohexylenrest), ein C6.12-Arylenrest (wie z.B. ein 1,2-, 1 ,3- oder 1 ,4-Phenylenrest) oder ein C6-12 Heteroarylenrest (wie z.B. ein 2,3-, 2,4- oder 2,6-Pyridinylenrest) sein. Die vorstehend genannten Reste können gegebenenfalls substituiert sein (z.B. mit C1-4-Alkylresten, d^-Alkoxyresten, Halogenatomen Hydroxygruppen usw.) oder durch ein Heteroatom (z.B. O oder NH) oder einen zyklischen Rest (z.B. einen Phenyl- oder Cyclohexylrest) unterbrochen sein. Besonders bevorzugt ist dabei ein Imidazoliumsalz, das die allgemeine Formel XThe radicals R 1 to R 19 can be halogenated, in particular by one or more, identical or different amine, nitro, nitrile, isonitrile, ether, alcohol, aldehyde or ketone groups, carboxylic acid derivatives, in particular esters or amides fluorinated or perfluorinated hydrocarbon residues, carbohydrate, phosphane, phosphine oxide, phosphine sulfide, phosphole residues, phosphite derivatives, aliphatic or aromatic sulfonic acid derivatives, their salts, esters or amides, silyl functions, boryl groups or heterocyclic substituents. Other suitable substituents, especially if the radicals are aromatic systems, are CC 6 - alkyl, C 2 -C 4 alkenyl, or C 2 . 4 - alkynyl residues. In a particularly preferred embodiment, one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 4 is substituted by an azolium salt or a pyridine ring. In a further embodiment, one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 is a linker L to a further imidazolium salt of the formula II, IV or VI. L can in particular be a C 1-4 - Alkylene radical (such as a methylene, ethylene, propylene or butylene radical), a C 5-12 cycloalkylene radical (such as a 1, 2- or 1, 4-cyclohexylene radical), a C 6 . 12 arylene residue (such as a 1,2-, 1,3- or 1,4-phenylene residue) or a C 6-12 heteroarylene residue (such as a 2,3-, 2,4- or 2,6-pyridinylene residue) his. The abovementioned radicals can optionally be substituted (for example with C 1-4 -alkyl radicals, d ^ -alkoxy radicals, halogen atoms, hydroxyl groups etc.) or by a hetero atom (for example O or NH) or a cyclic radical (for example a phenyl or cyclohexyl radical) be interrupted. An imidazolium salt which has the general formula X is particularly preferred
R4 x R11 R13 Y R5 R3 WVR6 R 4 x R 11 R 13 YR 5 R3 WV R6
R _R _
A AA A
X aufweist, worin die Variablen die vorstehend angegebene Bedeutung haben.X has, in which the variables have the meaning given above.
Es ist weiterhin bevorzugt, dass das ein- oder mehrwertige organische Anion A" in den allgemeinen Formeln II, IV, VI und XI ein Sulfat-, Halogenid-, Pseudohalogenid-, Borat-, Phosphat- oder Metallkomplex-Ion oder ein gegebenenfalls halogeniertes Sulfonat-, Carboxylat- oder Acetylacetonat-Ion ist und insbesondere A" für ein Triflat-, Mesylat-, Tosylat-, Nonaflat-, Tresylat-, Benzolsulfonat-, Brosylat-, Nosylat-, Fluorsulfonat-, Tetra- phenylborat-, Tetrakis[3,5-bis(trifluormethyl)phenyl]-borat(BARF)-, Tetrafluoroborat-, Hexa- fluorophosphat-, Hexafluoro-antimonat-, Acetat-, Trifluoracetat-, Perchlorat-, Tetracar- bonylcobaltat- oder Hexafluoroferrat(lll)-lon steht. Aus den genannten Anionen A" besonders bevorzugtes Anion ist das Triflat-Ion.It is further preferred that the mono- or polyvalent organic anion A " in the general formulas II, IV, VI and XI is a sulfate, halide, pseudohalide, borate, phosphate or metal complex ion or an optionally halogenated sulfonate -, carboxylate or acetylacetonate ion and in particular A " for a triflate, mesylate, tosylate, nonaflate, tresylate, benzenesulfonate, brosylate, nosylate, fluorosulfonate, tetraphenylborate, tetrakis [3 , 5-bis (trifluoromethyl) phenyl] borate (BARF) -, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, perchlorate, tetracarbonyl cobaltate or hexafluoroferrate (III) -lon , The triflate ion is a particularly preferred anion from the anions A " mentioned.
Das Verfahren (1) umfasst die Verwendung eines Alkylierungsmittels der vorstehend definierten allgemeinen Formel VII, VIII oder IX. Die Abgangsgruppe Z in diesem Alkylierungsmittel steht dabei vorzugsweise für ein Halogenid, Pseudohalogenid oder (ggf. halogeniertes) Carboxylat, besonders bevorzugt für ein Halogenid, besonders bevorzugt für Chlorid. Bevorzugte Alkylierungsmittel sind solche, in denen R15 einen unsubstituierten oder substituierten Phenyl-, Benzyl- oder C1-4-Alkylrest darstellt, der jeweils einen oder mehrere Substituenten, insbesondere Ether-, Ester- oder Silylsubstituenten enthalten kann. Besonders bevorzugt sind Chlormethylpivalat, Chlormethylbutyrat, Chlormethylethylether, (2-Methoxyethoxy)-methylchlohd und (2-Chlormethoxyethyl)-trimethylsilan.
Bevorzugte Metallsalze der allgemeinen Formel MA, die in dem Verfahren (1) eingesetzt werden können sind solche, in denen das ein- oder mehrwertige Metallkation M ein Silber(l)-, Alkali- und Erdalkalimetalle-, Lanthanid-, Blei(ll)-, Quecksilber(ll)-, Cadmium(II)-, Thallium(l)-, Kupfer(ll), Zink(ll)- oder Aluminium(lll)-lon ist, sowie solche, in denen die Tetraorganoammoniumverbindung eine Tetraalkylammoniumverbindung ist und schließlich solche, in der der Triorganosilylrest ein Trialkylsilylrest ist. Besonders bevorzugte Metallsalze sind solche, in denen M für Silber(l) steht und A für ein Sulfonat-, Sulfat-, Halogenid-, Pseudohalogenid-, Oxid, Borat-, Phosphat-, Carboxylat-, Acetylacetonat- oder Metallkom- plex-lon, bevorzugt für ein Trifluormethansulfonat (Triflat)-, Methansulfonat (Mesylat), p-Toluolsulfonat (Tosylat)-, Nonafluorbutansulfonat (Nonaflat)-, 2,2,2-Tri-fluorethansulfonat (Tresylat)-, Benzolsulfonat-, p-Brombenzolsulfonat (Brosylat)-, p-Nitrobenzolsulfonat- (Nosylat)-, Fluorsulfonat-, Tetraphenyl-borat-, Tetrakis[3,5-bis(trifluormethyl)phenyl]borat (BARF)-, Tetrafluoro-borat-, Hexafluorophosphat-, Hexafluoroantimonat-, Acetat-, Trifluoracetat, Perchlorat-, Tetracarbonylcobaltat- oder Hexafluoroferrat(lll)-lon, und besonders bevorzugt für ein Triflat-Ion steht.Process (1) comprises the use of an alkylating agent of the general formula VII, VIII or IX defined above. The leaving group Z in this alkylating agent preferably represents a halide, pseudohalide or (optionally halogenated) carboxylate, particularly preferably a halide, particularly preferably chloride. Preferred alkylating agents are those in which R 15 represents an unsubstituted or substituted phenyl, benzyl or C 1-4 alkyl radical, which can each contain one or more substituents, in particular ether, ester or silyl substituents. Chloromethyl pivalate, chloromethyl butyrate, chloromethyl ethyl ether, (2-methoxyethoxy) methylchloride and (2-chloromethoxyethyl) trimethylsilane are particularly preferred. Preferred metal salts of the general formula MA which can be used in process (1) are those in which the mono- or polyvalent metal cation M is a silver (I), alkali and alkaline earth metal, lanthanide, lead (II) , Mercury (II), cadmium (II), thallium (I), copper (II), zinc (II) or aluminum (III) ion, and those in which the tetraorganoammonium compound is a tetraalkylammonium compound and finally those in which the triorganosilyl radical is a trialkylsilyl radical. Particularly preferred metal salts are those in which M is silver (I) and A is a sulfonate, sulfate, halide, pseudohalide, oxide, borate, phosphate, carboxylate, acetylacetonate or metal complex ion , preferably for a trifluoromethanesulfonate (triflate) -, methanesulfonate (mesylate), p-toluenesulfonate (tosylate) -, nonafluorobutanesulfonate (nonaflate) -, 2,2,2-trifluoroethanesulfonate (tresylate) -, benzenesulfonate, p-bromobenzenesulfonate Brosylate), p-nitrobenzenesulfonate (nosylate), fluorosulfonate, tetraphenyl borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (BARF), tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, Acetate, trifluoroacetate, perchlorate, tetracarbonyl cobaltate or hexafluoroferrate (III) ion, and particularly preferably represents a triflate ion.
Üblicherweise werden Alkylierungsmittel und Metallsalz in mindestens stöchiometrischer Menge, bevorzugt in einem 5 bis 100%igem Überschuß in Bezug auf das Substrat eingesetzt. Das Verhältnis von Alkylierungsmittel zu Metallsalz kann in einem weiten Bereich variiert werden und beträgt bevorzugt 2:1 bis 1 :2, besonders bevorzugt 1.2:1 bis 1 :1.2.Usually, alkylating agents and metal salts are used in at least a stoichiometric amount, preferably in a 5 to 100% excess with respect to the substrate. The ratio of alkylating agent to metal salt can be varied within a wide range and is preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1.2.
Die Synthese der Imidazoliumsalze der allgemeinen Formeln II, IV und VI erfolgt vorzugsweise unter Luft-, und Feuchtigkeitsausschluss. Es hat sich als besonders vorteilhaft erwiesen, das Alkylierungsmittel zu einer Lösung des entsprechenden Ausgangsmaterials der allgemeinen Formel I, III oder V und des Metallsalzes in einem organischen Lösungsmittel zuzugeben. Geeignete Lösungsmittel können sein Aceton, Tetrahydrofuran, Di- ethylether, Methyltertbutylether, 1 ,2-Dimethoxyethan, 1 ,4-Dioxan, Petrolether, Dimethylsulf- oxid, N,N-Dimethylformamid, 1-Methyl-2-pyrrolidon, 1 ,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)- pyrimidon, Acetonitril, Propionitril, Ethylacetat, Benzol, Toluol, Xylol, Benzin, Chloroform, 1 ,2-Dichlorethan und Methylenchlorid, bevorzugt Methylenchlorid. Nach einigen Stunden Rühren bei -78 bis 120°C, bevorzugt bei 0 bis 70°C, insbesondere bei 20 bis 50°C wird die Reaktionslösung auf herkömmliche Weise entsprechend der physikalischen Eigenschaften der Produkte gereinigt, z. B. durch Säulenchromatographie oder Kristallisation.
Die erfindungsgemäßen Imidazoliumsalze der vorliegenden Erfindung sind insbesondere solche Verbindungen, in denen R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, R15, R16, R R18, X, Y, L und A" die vorstehend angegebene bevorzugte Bedeutung haben.The imidazolium salts of the general formulas II, IV and VI are preferably synthesized with the exclusion of air and moisture. It has proven to be particularly advantageous to add the alkylating agent to a solution of the corresponding starting material of the general formula I, III or V and the metal salt in an organic solvent. Suitable solvents can be acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1, 2-dimethoxyethane, 1, 4-dioxane, petroleum ether, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 1, 3- Dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone, acetonitrile, propionitrile, ethyl acetate, benzene, toluene, xylene, gasoline, chloroform, 1, 2-dichloroethane and methylene chloride, preferably methylene chloride. After stirring for a few hours at -78 to 120 ° C, preferably at 0 to 70 ° C, especially at 20 to 50 ° C, the reaction solution is purified in a conventional manner according to the physical properties of the products, e.g. B. by column chromatography or crystallization. The imidazolium salts of the present invention are in particular those compounds in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , RR 18 , X, Y, L and A "have the preferred meaning given above.
Besonders bevorzugt sind dabei Verbindungen mit den folgenden Strukturformeln:Compounds with the following structural formulas are particularly preferred:
wobei OTf Trifluormethansulfonat (Triflat), Ph Phenyl, TMS Trimethylsilyl, TES Triethylsilyl und Bn Benzyl bedeuten.
Weiterhin bevorzugt sind die folgenden Verbindungen der Formel X where OTf means trifluoromethanesulfonate (triflate), Ph phenyl, TMS trimethylsilyl, TES triethylsilyl and Bn benzyl. The following compounds of the formula X are further preferred
A AA A
X wobei alle Variablen die vorstehend angegebene Bedeutung haben. Hieraus sind besonders Verbindungen mit den folgenden Strukturformeln bevorzugt:X where all variables have the meaning given above. From this, compounds with the following structural formulas are particularly preferred:
wobei OTf Trifluormethansulfonat (Triflat), Ph Phenyl, und Bn Benzyl bedeuten.where OTf means trifluoromethanesulfonate (triflate), Ph phenyl, and Bn benzyl.
Die vorstehend spezifisch genannten Verbindungen können ebenfalls Tetrafluoroborat, Mesylat, Tosylat, Nonaflat oder Hexafluoroantimonat anstatt Triflat als Gegenanion aufweisen.The compounds specifically mentioned above may also have tetrafluoroborate, mesylate, tosylate, nonaflate or hexafluoroantimonate instead of triflate as the counter anion.
Das erfindungsgemäße Verfahren ermöglicht die Darstellung einer Vielzahl bisher unbekannter, achiraler und chiraler Imidazoliumsalze in überraschend guter Ausbeute, hoher Reinheit und gegebenenfalls hoher optischer Reinheit. Dies ist zum einen auf die große konstitutionelle Vielfalt der Ausgangsmaterialien der allgemeinen Formeln I, III und V zurückzuführen und zum anderen auf die milden Alkylierungsbedingungen, welche überraschend durch die gemeinsame Verwendung von einem Alkylierungsmittel und einem Metallsalz als Promoter möglich werden. Besonders bewährt hat sich das erfindungsgemäße Verfahren
daher zur Herstellung von Imidazoliumsalzen aus säureempfindlichen Substraten und zur Herstellung von chiralen Imidazoliumsalzen. Des Weiteren kann das Verfahren sowohl zur Synthese von Milligramm- als auch Multigramm-Mengen von Imidazoliumsalzen dienen. Aufgrund der einfachen Reaktionsführung eignet sich das Verfahren auch für eine technische Anwendung.The method according to the invention enables a large number of previously unknown, achiral and chiral imidazolium salts to be prepared in surprisingly good yield, high purity and, if appropriate, high optical purity. This is due, on the one hand, to the large constitutional diversity of the starting materials of the general formulas I, III and V and, on the other hand, to the mild alkylation conditions, which surprisingly become possible through the combined use of an alkylating agent and a metal salt as a promoter. The method according to the invention has proven particularly useful therefore for the production of imidazolium salts from acid-sensitive substrates and for the production of chiral imidazolium salts. Furthermore, the method can be used for the synthesis of milligram and multigram amounts of imidazolium salts. Because of the simple reaction procedure, the process is also suitable for industrial use.
Die nach diesem Verfahren herstellbaren Imidazoliumsalze der allgemeinen Formeln II, IV und VI können gemäß der Literatur deprotoniert und damit in N-heterozyklische Carbene bzw. deren Übergangsmetall-Komplexe überführt werden. (Übersicht: W. A. Herrmann, Angew. Chem. (2002) 114, 1342; A. J. Arduengo, III, Acc. Chem. Res. (1999) 32, 913.) Diese Übergangsmetall-Carben-Komplexe können als Katalysatoren in der Homogenkatalyse eingesetzt werden, wobei chirale, enantiomerenreine Imidazoliumsalze der allgemeinen Formeln II, IV und VI zu chiralen Übergangsmetall-Komplexen führen, die insbesondere in der asymmetrischen Katalyse eingesetzt werden können. Insbesondere die neuartigen Imidazoliumsalze der allgemeinen Formeln II und IV, in denen der Imida- zoliumkern mit einem (IV) oder zwei (II) Ringen überbrückt ist, sind hierbei viel versprechend. Durch geeignete Substitution dieser Brücken mit den Substituenten R1, R2, R3, R4, R5, R6, R7 und R8 können chirale, enantiomerenreine Imidazoliumsalze mit starrer Geometrie erhalten werden, deren Übergangsmetall-Carben-Komplexe in der asymmetrischen Katalyse Anwendung finden können.The imidazolium salts of the general formulas II, IV and VI which can be prepared by this process can be deprotonated in accordance with the literature and thus converted into N-heterocyclic carbenes or their transition metal complexes. (Overview: WA Herrmann, Angew. Chem. (2002) 114, 1342; AJ Arduengo, III, Acc. Chem. Res. (1999) 32, 913.) These transition metal-carbene complexes can be used as catalysts in homogeneous catalysis , wherein chiral, enantiomerically pure imidazolium salts of the general formulas II, IV and VI lead to chiral transition metal complexes which can be used in particular in asymmetric catalysis. The novel imidazolium salts of the general formulas II and IV, in which the imidazolium nucleus is bridged by one (IV) or two (II) rings, are particularly promising. By suitable substitution of these bridges with the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , chiral, enantiomerically pure imidazolium salts with rigid geometry can be obtained, the transition metal-carbene complexes of which asymmetric catalysis can be used.
Ausführungsbeispieleembodiments
Umsetzung von Bioxazolinen 1 in die entsprechenden Imidazolium Triflate 2 gemäß der nachfolgenden Gleichung.Conversion of Bioxazolinen 1 into the corresponding Imidazolium Triflate 2 according to the following equation.
e
e
1a: R16 = iPr 2a: R16 = iPr1a: R 16 = iPr 2a: R 16 = iPr
1b: R16 = tBu 2b: R16 = tBu1b: R 16 = tBu 2b: R 16 = tBu
1c: R16 = Ph 2c: R16 = Ph1c: R 16 = Ph 2c: R 16 = Ph
Beispiel 1example 1
Darstellung von Imidazolium Triflat 2aPresentation of imidazolium triflate 2a
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- undIn a heated and argonized Schlenk vessel under light, air and
Feuchtigkeitsausschluß zu einer Lösung von Bioxazolin 1a (5.0 g, 22.2 mmol) undExclusion of moisture to a solution of Bioxazolin 1a (5.0 g, 22.2 mmol) and
Silbertriflat (6.8 g, 26.6 mmol) in Methylenchlorid (75 ml) Chlormethylpivalat (4.6 ml, 31.2
AJδS Ul - 12 -Silver triflate (6.8 g, 26.6 mmol) in methylene chloride (75 ml) chloromethyl pivalate (4.6 ml, 31.2 AJδS Ul - 12 -
mmoi) gegeben und das Reaktionsgefäß verschlossen. Nach 24 Stunden Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (25 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch Säulenchromatographie (4x10 cm, CH2CI2/MeOH 20:1) und anschließende Umkristallisation aus THF (30 ml), Toluol (150 ml) und Pentan (50 ml) ergab das Imidazolium Triflat 2a (6.85 g, 80%). [a]20 D = +55.0 (c 1.0, CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 8.73 (s, 1 H, NCHN), 5.07 (dd, J = 7.9, 9.0 Hz, 2H, CH2), 4.98-4.93 (m, 2H, CHCH2), 4.83 (dd, = 4.1 , 9.0 Hz, 2H, CH2), 2.33 (m, 2H, Cr/CH3), 1.03 (d, J = 6.9 Hz, 6H, CH3), 0.99 (d, J = 6.9 Hz, 6H, CH3); 13C-NMR (100 MHz, CDCI3) δ 125.6 (NCO), 120.6 (q, J = 320 Hz, CF3), 116.3 (NCHN), 79.1 (CH2), 63.9 (CHCH2), 31.1 (CHCH3), 17.6 (CH3), 16.7 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.7 (CF3).mmoi) and closed the reaction vessel. After stirring for 24 hours with the exclusion of light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (25 ml) and the filtrate was concentrated. Purification of the residue by column chromatography (4x10 cm, CH 2 CI 2 / MeOH 20: 1) and subsequent recrystallization from THF (30 ml), toluene (150 ml) and pentane (50 ml) gave the imidazolium triflate 2a (6.85 g, 80 %). [a] 20 D = +55.0 (c 1.0, CH 2 CI 2 ); 1 H NMR (400 MHz, CDCI 3 ) δ 8.73 (s, 1 H, NCHN), 5.07 (dd, J = 7.9, 9.0 Hz, 2H, CH 2 ), 4.98-4.93 (m, 2H, CHCH 2 ) , 4.83 (dd, = 4.1, 9.0 Hz, 2H, CH 2 ), 2.33 (m, 2H, Cr / CH 3 ), 1.03 (d, J = 6.9 Hz, 6H, CH 3 ), 0.99 (d, J = 6.9 Hz, 6H, CH 3 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 125.6 (NCO), 120.6 (q, J = 320 Hz, CF 3 ), 116.3 (NCHN), 79.1 (CH 2 ), 63.9 (CHCH 2 ), 31.1 (CHCH 3 ), 17.6 (CH 3 ), 16.7 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.7 (CF 3 ).
Beispiel 2Example 2
Darstellung von Imidazolium Triflat 2bPresentation of imidazolium triflate 2b
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Lösung von Bioxazolin 1b (425 mg, 1.7 mmol) und Silbertriflat (518 mg, 2.0 mmol) in Methylenchlorid (15 ml) Chlormethylpivalat (0.35 ml, 2.4 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 8 Stunden Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (10 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch Säulenchromatographie (2.5x10 cm, CH2CI2/MeOH 20:1) und anschließende Umkristallisation aus THF (5 ml), Toluol (20 ml) und Pentan (5 ml) ergab das Imidazolium Triflat 2b (521 mg, 75%). [a]20 D = +69.5 (c 1.0, CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 8.61 (s, 1 H, NCHN), 5.07 (dd, J = 7.9, 9.3 Hz, 2H, CH2), 4.92 (dd, J = 3.3, 9.4 Hz, 2H, CH2), 4.83 (dd, J = 3.2, 7.8 Hz, 2H, CH), 1.08 (s, 18H, CH3); 13C-NMR (75 MHz, CDCI3) δ 125.9 (NCO), 120.6 (q, J = 320 Hz, CF3), 117.0 (NCH), 78.8 (CH2), 68.2 (CH), 34.1 (CCH3), 25.3 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.6 (CF3).In a heated and argonized Schlenk flask with the exclusion of light, air and moisture to a solution of Bioxazolin 1b (425 mg, 1.7 mmol) and silver triflate (518 mg, 2.0 mmol) in methylene chloride (15 ml) chloromethyl pivalate (0.35 ml, 2.4 mmol ) and closed the reaction vessel. After stirring for 8 hours with the exclusion of light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (10 ml) and the filtrate was concentrated. Purification of the residue by column chromatography (2.5x10 cm, CH 2 CI 2 / MeOH 20: 1) and subsequent recrystallization from THF (5 ml), toluene (20 ml) and pentane (5 ml) gave the imidazolium triflate 2b (521 mg, 75%). [a] 20 D = +69.5 (c 1.0, CH 2 CI 2 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 8.61 (s, 1 H, NCHN), 5.07 (dd, J = 7.9, 9.3 Hz, 2H, CH 2 ), 4.92 (dd, J = 3.3, 9.4 Hz, 2H, CH 2 ), 4.83 (dd, J = 3.2, 7.8 Hz, 2H, CH), 1.08 (s, 18H, CH 3 ); 13 C-NMR (75 MHz, CDCI 3 ) δ 125.9 (NCO), 120.6 (q, J = 320 Hz, CF 3 ), 117.0 (NCH), 78.8 (CH 2 ), 68.2 (CH), 34.1 (CCH 3 ), 25.3 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.6 (CF 3 ).
Beispiel 3Example 3
Darstellung von Imidazolium Triflat 2cPresentation of imidazolium triflate 2c
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- undIn a heated and argonized Schlenk vessel under light, air and
Feuchtigkeitsausschluß zu einer Lösung von Bioxazolin 1c (1.2 g, 4.1 mmol) und SilbertriflatExclusion of moisture to a solution of Bioxazolin 1c (1.2 g, 4.1 mmol) and silver triflate
(2.6 g, 10.3 mmol) in Methylenchlorid (20 ml) Chlormethylpivalat (0.85 ml, 5.8 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 15 Stunden Rühren unter(2.6 g, 10.3 mmol) in methylene chloride (20 ml) chloromethyl pivalate (0.85 ml, 5.8 mmol) and the reaction vessel closed. After stirring for 15 hours
Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch
durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (10 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch zweimalige Säulenchromatographie (3x10 cm, CH2CI2/MeOH 20:1) ergab das Imidazolium Triflat 2c (430 mg, 23%).Exclusion of light at 40 ° C was the reaction mixture cooled to room temperature filtered through a glass frit, the filter residue washed with methylene chloride (10 ml) and the filtrate concentrated. Purification of the residue by two column chromatography (3x10 cm, CH 2 Cl 2 / MeOH 20: 1) gave the imidazolium triflate 2c (430 mg, 23%).
[a]20 D = +226.3 (c 0.8, CH2CI2); H-NMR (400 MHz, CDCI3) δ 7.72 (s, 1 H, NCHN), 7.42-7.31 (m, 10H, CHar), 6.05 (t, J = 7.2 Hz, 2H, CHPh), 5.41 (dd, J = 7.9, 8.9 Hz, 2H, CH2), 4.90 (dd, J = 6.6, 9.0 Hz, 2H, CH2); 13C-NMR (100 MHz, CDCI3) δ 133.4(C), 130.3 (CH), 129.8 (CH), 127.1 (CH), 126,6 (NCO), 120.6 (q, J = 320 Hz, CF3), 114.9 (NCHN), 84.1 (CH2), 62.2 (CHPh); 19F-NMR (300 MHz, CDCI3) δ -78.6 (CF3).[a] 20 D = +226.3 (c 0.8, CH 2 CI 2 ); H-NMR (400 MHz, CDCI 3 ) δ 7.72 (s, 1 H, NCHN), 7.42-7.31 (m, 10H, CH ar ), 6.05 (t, J = 7.2 Hz, 2H, CHPh), 5.41 (dd , J = 7.9, 8.9 Hz, 2H, CH 2 ), 4.90 (dd, J = 6.6, 9.0 Hz, 2H, CH 2 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 133.4 (C), 130.3 (CH), 129.8 (CH), 127.1 (CH), 126.6 (NCO), 120.6 (q, J = 320 Hz, CF 3 ), 114.9 (NCHN), 84.1 (CH 2 ), 62.2 (CHPh); 19 F NMR (300 MHz, CDCI 3 ) δ -78.6 (CF 3 ).
Umsetzung von Imin-oxazolinen 3 in die entsprechenden Imidazolium Triflate 4 gemäß der nachfolgenden Gleichung.Conversion of imine oxazolines 3 into the corresponding imidazolium triflates 4 according to the following equation.
3a: R17 = Me, R18 = Me 4a: R17 = Me, R18 = Me3a: R 17 = Me, R 18 = Me 4a: R 17 = Me, R 18 = Me
3b: R17 = iPr, R18 = H 4b: R17 = iPr, R18 = H3b: R 17 = iPr, R 18 = H 4b: R 17 = iPr, R 18 = H
Beispiel 4Example 4
Darstellung von Imidazolium Triflat 4aPresentation of imidazolium triflate 4a
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Lösung von Iminoxazolin 3a (330 mg, 1.3 mmol) und Silbertriflat (395 mg, 1.5 mmol) in Methylenchlorid (10 ml) Chlormethylpivalat (0.27 ml, 1.8 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 16 Stunden Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (10 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch zweimalige Säulenchromatographie (2x10 cm, CH2CI2 bis CH2CI2/MeOH 15:1) ergab das Imidazolium Triflat 4a (432 mg, 80%).In a heated and argonized Schlenk flask with the exclusion of light, air and moisture, a solution of iminoxazoline 3a (330 mg, 1.3 mmol) and silver triflate (395 mg, 1.5 mmol) in methylene chloride (10 ml) chloromethyl pivalate (0.27 ml, 1.8 mmol ) and closed the reaction vessel. After stirring for 16 hours with the exclusion of light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (10 ml) and the filtrate was concentrated. Purification of the residue by two column chromatography (2x10 cm, CH 2 CI 2 to CH 2 CI 2 / MeOH 15: 1) gave the imidazolium triflate 4a (432 mg, 80%).
[a]20 D = +19.5 (c 0.9, CHCI3); H-NMR (400 MHz, CDCI3) δ 8.81 (d, J = 1.4 Hz, 1 H, NCHN), 7.02 (s, 1 H, CHar), 7.00 (s, 1 H, CHar), 6.29 (d, J = 1.4 Hz, NCHC), 5.42-5.39 (m, 1 H, CHCH2), 5.29 (t, = 8.7 Hz, 1 H, CH2), 4.99 (dd, J = 3.7, 9.2 Hz, 1 H, CH2), 2.54-2.47 (m, 1 H, CHCH3), 2.35 (s, 3H, CH3), 2.16 (s, 3H, CH3), 2.07 (s, 3H, CH3), 1.04 (d, J = 6.9 Hz, 3H, CHCH3), 0.98 (d, J = 6.9 Hz, 3H, CHCH3); 13C-NMR (100 MHz, CDCI3) δ 151.3 (C), 141.4
(C), 135.0 (C), 133.8 (C), 131.5 (C), 130.0 (CHar), 129.5 (CHar), 127.8 (NCHN), 120.6 (q, J = 320 Hz, CF3), 95.4 (NCHC), 79.6 (CH2), 63.1 (CHCH2), 31.1 (CHCH3), 21.1 (CH3), 17.4 (CH3), 17.2 (CH3), 17.0 (CH3), 16.2 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.7 (CF3).[a] 20 D = +19.5 (c 0.9, CHCI 3 ); H-NMR (400 MHz, CDCI 3 ) δ 8.81 (d, J = 1.4 Hz, 1 H, NCHN), 7.02 (s, 1 H, CH ar ), 7.00 (s, 1 H, CH ar ), 6.29 ( d, J = 1.4 Hz, NCHC), 5.42-5.39 (m, 1 H, CHCH 2 ), 5.29 (t, = 8.7 Hz, 1 H, CH 2 ), 4.99 (dd, J = 3.7, 9.2 Hz, 1 H, CH 2 ), 2.54-2.47 (m, 1 H, CHCH 3 ), 2.35 (s, 3H, CH 3 ), 2.16 (s, 3H, CH 3 ), 2.07 (s, 3H, CH 3 ), 1.04 (d, J = 6.9 Hz, 3H, CHCH 3 ), 0.98 (d, J = 6.9 Hz, 3H, CHCH 3 ); 13 C NMR (100 MHz, CDCI 3 ) δ 151.3 (C), 141.4 (C), 135.0 (C), 133.8 (C), 131.5 (C), 130.0 (CH ar ), 129.5 (CH ar ), 127.8 (NCHN), 120.6 (q, J = 320 Hz, CF 3 ), 95.4 (NCHC), 79.6 (CH 2 ), 63.1 (CHCH 2 ), 31.1 (CHCH 3 ), 21.1 (CH 3 ), 17.4 (CH 3 ), 17.2 (CH 3 ), 17.0 (CH 3 ), 16.2 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.7 (CF 3 ).
Beispiel 5Example 5
Darstellung von Imidazolium Triflat 4bPresentation of imidazolium triflate 4b
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Lösung von Imin-oxazolin 3b (600 mg, 2.0 mmol) und Silbertriflat (617 mg, 2.4 mmol) in Methylenchlorid (17 ml) Chlormethylpivalat (0.42 ml, 2.8 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 16 Stunden Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (10 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch zweimalige Säulenchromatographie (2.5x10 cm, CH2CI2 bis CH2CI2/MeOH 15:1) ergab das Imidazolium Triflat 4b (771 mg, 83%).In a heated and argonized Schlenk vessel, with the exclusion of light, air and moisture, a solution of imine oxazoline 3b (600 mg, 2.0 mmol) and silver triflate (617 mg, 2.4 mmol) in methylene chloride (17 ml) was chloromethyl pivalate (0.42 ml, 2.8 mmol) and the reaction vessel is closed. After stirring for 16 hours with the exclusion of light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (10 ml) and the filtrate was concentrated. Purification of the residue by two column chromatography (2.5x10 cm, CH 2 Cl 2 to CH 2 Cl 2 / MeOH 15: 1) gave the imidazolium triflate 4b (771 mg, 83%).
[a]20 D = +23.8 (c 0.9, CHCI3); 1H-NMR (400 MHz, CDCI3) δ 8.86 (d, J = 1.5 Hz, 1 H, NCHN), 7.55-7.51 (m, 1H, CHar), 7.33-7.27 (m, 2H, CHar), 6.33 (d, J = 1.5 Hz, NCHC), 5.47-5.43 (m, 1 H, CHCH2), 5.33 (t, J = 8.7 Hz, 1 H, CH2), 5.02 (dd, J = 3.6, 9.2 Hz, 1 H, CH2), 2.58-2.51 (m, 2H, CHCH3), 2.32 (sept, J = 6.9 Hz, 1 H, CHCH3), 1.26 (d, J = 6.8 Hz, 3H, CH3), 1.21 (d, J = 7.0 Hz, 3H, CH3), 1.19 (d, J = 7.0 Hz, 3H, CH3), 1.17 (d, J = 6.8 Hz, 3H, CH3), 1.04 (d, J = 6.9 Hz, 3H, CH3), 0.98 (d, J = 6.9 Hz, 3H, CH3); 13C-NMR (100 MHz, CDCI3) δ 151.2 (C), 146.1 (C), 145.0 (C), 132.0 (CHar), 130.9 (C), 128.4 (NCHN), 125.0 (CHar), 124.3 (CHar), 120.6 (q, J = 320 Hz, CF3), 96.7 (NCHC), 79.7 (CH2), 63.2 (CHCH2), 31.2 (CH), 28.8 (CH), 28.5 (CH), 24.5 (CH3), 24.5 (CH3), 23.9 (CH3), 23.8 (CH3), 17.3 (CH3), 16.1 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.7 (CF3).[a] 20 D = +23.8 (c 0.9, CHCI 3 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 8.86 (d, J = 1.5 Hz, 1 H, NCHN), 7.55-7.51 (m, 1H, CH ar ), 7.33-7.27 (m, 2H, CH ar ) , 6.33 (d, J = 1.5 Hz, NCHC), 5.47-5.43 (m, 1 H, CHCH 2 ), 5.33 (t, J = 8.7 Hz, 1 H, CH 2 ), 5.02 (dd, J = 3.6, 9.2 Hz, 1 H, CH 2 ), 2.58-2.51 (m, 2H, CHCH 3 ), 2.32 (sept, J = 6.9 Hz, 1 H, CHCH 3 ), 1.26 (d, J = 6.8 Hz, 3H, CH 3 ), 1.21 (d, J = 7.0 Hz, 3H, CH 3 ), 1.19 (d, J = 7.0 Hz, 3H, CH 3 ), 1.17 (d, J = 6.8 Hz, 3H, CH 3 ), 1.04 ( d, J = 6.9 Hz, 3H, CH 3 ), 0.98 (d, J = 6.9 Hz, 3H, CH 3 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 151.2 (C), 146.1 (C), 145.0 (C), 132.0 (CH ar ), 130.9 (C), 128.4 (NCHN), 125.0 (CH ar ), 124.3 (CH ar ), 120.6 (q, J = 320 Hz, CF 3 ), 96.7 (NCHC), 79.7 (CH 2 ), 63.2 (CHCH 2 ), 31.2 (CH), 28.8 (CH), 28.5 (CH), 24.5 (CH 3 ), 24.5 (CH 3 ), 23.9 (CH 3 ), 23.8 (CH 3 ), 17.3 (CH 3 ), 16.1 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.7 (CF 3 ).
Umsetzung von Bisiminen 5 in die entsprechenden Imidazolium Triflate 6 gemäß der nachfolgenden Gleichungen.Implementation of bisimines 5 in the corresponding imidazolium triflate 6 according to the following equations.
5a: R17 = Me, R18 = Me 6a: R17 = Me, R 8 = Me5a: R 17 = Me, R 18 = Me 6a: R 17 = Me, R 8 = Me
5b: R 7 = iPr, R18 = H 6b: R17 = iPr, R18 = H
5b: R 7 = iPr, R 18 = H 6b: R 17 = iPr, R 18 = H
5c 6c5c 6c
Beispiel 6Example 6
Darstellung von 1 ,3-Bis-(2,4,6-trimethyl-phenyl)-imidazolium Triflat (6a)Preparation of 1,3-bis (2,4,6-trimethylphenyl) imidazolium triflate (6a)
In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- undIn a heated and argonized Schlenk vessel under light, air and
Feuchtigkeitsausschluß zu einer Lösung von Bisimin 5a (100 mg, 0.34 mmol) undExclusion of moisture to a solution of bisimin 5a (100 mg, 0.34 mmol) and
Silbertriflat (105 mg, 0.41 mmol) in Methylenchlorid (2 ml) Chlormethylethylether (0.047 ml,Silver triflate (105 mg, 0.41 mmol) in methylene chloride (2 ml) chloromethyl ethyl ether (0.047 ml,
0.48 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 16 Stunden Rühren unter0.48 mmol) and the reaction vessel is closed. After stirring for 16 hours
Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (2 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstands durch Umkristallisation aus Toluol ergab das Imidazolium Triflat 6a (129 mg, 83%).Excluding light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (2 ml) and the filtrate was concentrated. Purification of the residue by recrystallization from toluene gave the imidazolium triflate 6a (129 mg, 83%).
1H-NMR (400 MHz, CDCI3) δ 9.20 (t, J = 1.4 Hz, 1 H, NCHN), 7.56 (d, J = 1.4 Hz, 2H, 1 H-NMR (400 MHz, CDCI 3 ) δ 9.20 (t, J = 1.4 Hz, 1 H, NCHN), 7.56 (d, J = 1.4 Hz, 2H,
NCHCHN), 7.03 (s, 4H, CHar), 2.35 (s, 6H, p-CH3), 2.11 (s, 12H, o-CH3; 13C-NMR (100 MHz,NCHCHN), 7.03 (s, 4H, CH ar ), 2.35 (s, 6H, p-CH 3 ), 2.11 (s, 12H, o-CH 3 ; 13 C-NMR (100 MHz,
CDCI3) δ 141.5 (C), 137.9 (NCHN), 134.0 (C), 130.4 (C), 129.9 (CHar), 124.9 (NCHCHN),CDCI 3 ) δ 141.5 (C), 137.9 (NCHN), 134.0 (C), 130.4 (C), 129.9 (CH ar ), 124.9 (NCHCHN),
120.4 (q, J = 321 Hz, CF3), 21.1 (p-CH3), 17.2 (o-CH3); 19F-NMR (300 MHz, CDCI3) δ -78.9120.4 (q, J = 321 Hz, CF 3 ), 21.1 (p-CH 3 ), 17.2 (o-CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.9
(CF3).(CF 3 ).
Beispiel 7Example 7
Darstellung von 1 ,3-Bis-(2,6-diisopropyl-phenyl)-imidazolium Triflat (6b) In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Lösung von Bisimin 5b (100 mg, 0.27 mmol) und Silbertriflat (82 mg, 0.32 mmol) in Methylenchlorid (1.5 ml) Chlormethylethylether (0.036 ml, 0.37 mmol) gegeben und das Reaktionsgefäß verschlossen. Nach 1 Stunde Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (2 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstands durch Umkristallisation aus Toluol ergab das Imidazolium Triflat 6b (116 mg, 81%).Preparation of 1,3-bis (2,6-diisopropylphenyl) imidazolium triflate (6b) In a heated and argonized Schlenk vessel, a solution of bisimin 5b (100 mg, 0.27 mmol ) and silver triflate (82 mg, 0.32 mmol) in methylene chloride (1.5 ml) chloromethyl ethyl ether (0.036 ml, 0.37 mmol) and the reaction vessel was closed. After stirring for 1 hour with the exclusion of light at 40 ° C., the reaction mixture, cooled to room temperature, was filtered through a glass frit, the filter residue was washed with methylene chloride (2 ml) and the filtrate was concentrated. Purification of the residue by recrystallization from toluene gave the imidazolium triflate 6b (116 mg, 81%).
1H-NMR (400 MHz, CDCI3) δ 9.13 (t, J = 1.6 Hz, 1 H, NCHN), 7.79 (d, J = 1.6 Hz, 2H, NCHCHN), 7.57 (t, J = 7.9 Hz, 2H, CHar), 7.34 (d, J = 7.9 Hz, 4H, CHar), 2.40 (sept, J = 6.8 Hz, 2H, CH), 1.26 (d, J = 6.8 Hz, 6H, CH3), 1.20 (d, J = 6.8 Hz, 6H, CH3); 13C-NMR (100 MHz, CDCI3) δ 144.9 (C), 138.2 (NCHN), 132.1 (CHar), 129.7 (C), 126.3 (NCHCHN), 124.7 (CHar), 120.5 (q, J = 321 Hz, CF3), 29.1 (CH), 24.2 (CH3), 23.8 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.9 (CF3).
Beispiel 8 1 H-NMR (400 MHz, CDCI 3 ) δ 9.13 (t, J = 1.6 Hz, 1 H, NCHN), 7.79 (d, J = 1.6 Hz, 2H, NCHCHN), 7.57 (t, J = 7.9 Hz, 2H, CH ar ), 7.34 (d, J = 7.9 Hz, 4H, CH ar ), 2.40 (sept, J = 6.8 Hz, 2H, CH), 1.26 (d, J = 6.8 Hz, 6H, CH 3 ), 1.20 (d, J = 6.8 Hz, 6H, CH 3 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 144.9 (C), 138.2 (NCHN), 132.1 (CH ar ), 129.7 (C), 126.3 (NCHCHN), 124.7 (CH ar ), 120.5 (q, J = 321 Hz, CF 3 ), 29.1 (CH), 24.2 (CH 3 ), 23.8 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.9 (CF 3 ). Example 8
Darstellung von (S,S)-1 ,3-Bis-(1-phenyl-ethyl)-imidazolium Triflat (6c) In einem ausgeheizten und argonierten Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Lösung von Bisimin 5c (2.6 g, 10.0 mmol) und Silbertriflat (3.1 g, 12.0 mmol) in Methylenchlorid (20 ml) Chlormethylethylether (1.4 ml, 14.0 mmol) bei 0°C gegeben und das Reaktionsgefäß verschlossen. Nach 1 Stunde Rühren unter Lichtausschluß bei 40°C wurde das auf Raumtemperatur abgekühlte Reaktionsgemisch durch eine Glasfritte filtriert, der Filterrückstand mit Methylenchlorid (20 ml) nachgewaschen und das Filtrat aufkonzentriert. Reinigung des Rückstandes durch Säulenchromatographie (3.5x12 cm, CH2CI2 bis CH2CI2/MeOH 15:1) ergab das Imidazolium Triflat 6c (3.5 g, 81%). [a]20 D = -21.5 (c 1.1 , CHCI3); 1H-NMR (400 MHz, CDCI3) δ 9.51 (t, J = 1.7 Hz, 1 H, NCHN), 7.41-7.35 (m, 10H, CHar), 7.20 (d, J = 1.7 Hz, 2H, NCHCHN), 5.77 (q, J = 7.0 Hz, 2H, CH), 1.95 (d, J = 7.0 Hz, 6H, CH3); 13C-NMR (100 MHz, CDCI3) δ 137.6 (C), 134.6 (NCHN), 129.4 (CHar,CHar), 126.9 (CHar), 120.8 (NCHCHN), 120.7 (q, J = 320 Hz, CF3), 60.2 (CH), 20.8 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.5 (CF3).Preparation of (S, S) -1, 3-bis- (1-phenyl-ethyl) -imidazolium triflate (6c) In a heated and argonized Schlenk vessel, a solution of bisimin 5c (2.6 g, 10.0 mmol) and silver triflate (3.1 g, 12.0 mmol) in methylene chloride (20 ml) chloromethyl ethyl ether (1.4 ml, 14.0 mmol) at 0 ° C. and the reaction vessel closed. After stirring for 1 hour with the exclusion of light at 40 ° C., the reaction mixture cooled to room temperature was filtered through a glass frit, the filter residue was washed with methylene chloride (20 ml) and the filtrate was concentrated. Purification of the residue by column chromatography (3.5x12 cm, CH 2 Cl 2 to CH 2 Cl 2 / MeOH 15: 1) gave the imidazolium triflate 6c (3.5 g, 81%). [a] 20 D = -21.5 (c 1.1, CHCI 3 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 9.51 (t, J = 1.7 Hz, 1 H, NCHN), 7.41-7.35 (m, 10H, CH ar ), 7.20 (d, J = 1.7 Hz, 2H, NCHCHN), 5.77 (q, J = 7.0 Hz, 2H, CH), 1.95 (d, J = 7.0 Hz, 6H, CH 3 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 137.6 (C), 134.6 (NCHN), 129.4 (CH ar , CH ar ), 126.9 (CH ar ), 120.8 (NCHCHN), 120.7 (q, J = 320 Hz , CF 3 ), 60.2 (CH), 20.8 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.5 (CF 3 ).
Beispiel 9Example 9
Darstellung von Imidazolium Triflat 8Preparation of imidazolium triflate 8
In einem Schlenkgefäß wurde unter Licht-, Luft- und Feuchtigkeitsausschluß zu einer Suspension von Silbertriflat (2.2 g, 8.4 mmol) in Methylenchlorid (30 ml) Chlormethylpivalat (1.25 ml, 8.4 mmol) gegeben und die Reaktionslösung für 45 Minuten gerührt. Nach Absetzen des gebildeten Feststoffs wurde die Lösung mit einer Spritze in ein zweites Reaktionsgefäß gegeben, in dem sich das Bioxazolin 7 (1.6 g, 5.8 mmol) befand. Die Lösung wurde für 20 Stunden bei 40°C gerührt und anschließend das auf Raumtemperatur abgekühlte Reaktionsgemisch im Vakuum eingeengt. Reinigung des Rückstandes durch Säulenchromatographie (2.5x10 cm, CH2CI2/MeOH 20:1 bis 10:1) und folgende Umkristallisation aus einem Gemisch aus THF (10 ml), Toluol (40 ml) und Pentan (40 ml) ergab das Imidazolium Triflat 8 (2.2 g, 85%) in Form farbloser Kristalle.A suspension of silver triflate (2.2 g, 8.4 mmol) in methylene chloride (30 ml), chloromethyl pivalate (1.25 ml, 8.4 mmol) was added in a Schlenk vessel with the exclusion of light, air and moisture and the reaction solution was stirred for 45 minutes. After the solid formed had settled, the solution was transferred with a syringe into a second reaction vessel in which the Bioxazolin 7 (1.6 g, 5.8 mmol) was. The solution was stirred at 40 ° C. for 20 hours and then the reaction mixture, cooled to room temperature, was concentrated in vacuo. Purification of the residue by column chromatography (2.5x10 cm, CH 2 Cl 2 / MeOH 20: 1 to 10: 1) and subsequent recrystallization from a mixture of THF (10 ml), toluene (40 ml) and pentane (40 ml) gave this Imidazolium triflate 8 (2.2 g, 85%) in the form of colorless crystals.
1H-NMR (400 MHz, CDCI3) δ 9.12 (s, 1 H, NCHN), 4.80 (s, 4H, OCH2), 2.32 (td, J = 3.8, 12.5 Hz, 4H, CH2), 2.10-1.98 (m, 8H, CH2), 1.74-1.58 (m, 4H, CH2), 1.46-1.37 (m, 4H, CH2); 13C- NMR (100 MHz, CDCI3) δ 124.6 (NCO), 120.8 (q, J = 319 Hz, CF3), 113.9 (NCHN), 85.6
(OCH2), 67.5 (CCH2), 34.7 (CH2), 23.5 (CH2), 23.1 (CH2); 19F-NMR (300 MHz, CDCI3) δ-78.5 (CF3). 1 H-NMR (400 MHz, CDCI 3 ) δ 9.12 (s, 1 H, NCHN), 4.80 (s, 4H, OCH 2 ), 2.32 (td, J = 3.8, 12.5 Hz, 4H, CH 2 ), 2.10 -1.98 (m, 8H, CH 2 ), 1.74-1.58 (m, 4H, CH 2 ), 1.46-1.37 (m, 4H, CH 2 ); 13 C-NMR (100 MHz, CDCI 3 ) δ 124.6 (NCO), 120.8 (q, J = 319 Hz, CF 3 ), 113.9 (NCHN), 85.6 (OCH 2 ), 67.5 (CCH 2 ), 34.7 (CH 2 ), 23.5 (CH 2 ), 23.1 (CH 2 ); 19 F NMR (300 MHz, CDCI 3 ) δ-78.5 (CF 3 ).
Die Beispiele 10 bis 13 wurden in weitgehender Analogie zu der für Beispiel 9 angegebenen Vorschrift durchgeführt:Examples 10 to 13 were carried out largely in analogy to the instructions given for example 9:
9 109 10
Beispiel 10: Darstellung von Imidazolium Triflat 10.Example 10: Preparation of Imidazolium Triflat 10.
3.4 g, 70%, farblose Kristalle; [a]20 D = +184.8 (c 0.9, CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 9.48 (s, 1H, NCHN), 7.83 (d, J = 7.2 Hz, 2H, CHar), 7.40-7.28 (m, 6H, CHar), 6.32 (d, J = 6.4 Hz, 2H, CHN), 6.11-6.09 (m, 2H, CHO), 3.56-3.44 (m, 4H, CH2); 13C-NMR (100 MHz, CDCI3) .δ139.6 (C), 134.8 (C), 130.8 (CH), 129.0 (CH), 126.1 (CH), 125.3 (CH), 124.9 (C), 120.7 (q, J = 320 Hz, CF3), 114.4 (NCHN), 95.1 (OCH), 66.9 (NCHC), 38.3 (CH2); 19F-NMR (300 MHz, CDCI3) δ -78.6 (CF3).3.4 g, 70%, colorless crystals; [a] 20 D = +184.8 (c 0.9, CH 2 CI 2 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 9.48 (s, 1H, NCHN), 7.83 (d, J = 7.2 Hz, 2H, CH ar ), 7.40-7.28 (m, 6H, CH ar ), 6.32 ( d, J = 6.4 Hz, 2H, CHN), 6.11-6.09 (m, 2H, CHO), 3.56-3.44 (m, 4H, CH 2 ); 13 C-NMR (100 MHz, CDCI 3 ) .δ139.6 (C), 134.8 (C), 130.8 (CH), 129.0 (CH), 126.1 (CH), 125.3 (CH), 124.9 (C), 120.7 (q, J = 320 Hz, CF 3 ), 114.4 (NCHN), 95.1 (OCH), 66.9 (NCHC), 38.3 (CH 2 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.6 (CF 3 ).
11 1211 12
Beispiel 11 : Darstellung von Imidazolium Triflat 12.Example 11: Preparation of imidazolium triflate 12.
1.2 g, 56%, weißer Schaum; [a]20 D = +25.9 (c 1.1 , CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 8.94 (d, J = 1.7 Hz, NCHN), 6.49 (d, J = 1.7 Hz, CH), 5.15-5.08 (m, 2H, CH & CH2), 4.92- 4.86 (m, 1H, CH2), 2.47-2.38 (m, 1H, CH), 2.30 (s, 3H, CH), 2.13 (d, = 2.9 Hz, 6H, CH2), 1.78-1.76 (m, 6H, CH2), 1.02 (d, J = 6.9 Hz, 3H, CH3), 0.91 (d, J = 6.8 Hz, 3H, CH3); 13C- NMR (100 MHz, CDCI3) 5151.1 (C), 124.5 (CH), 120.7 (q, J = 322 Hz, CF3), 90.6 (CH), 79.2 (CH2), 62.9 (CH), 61.3 (C), 42.6 (CH2), 35.3 (CH2), 30.9 (CH), 29.4 (CH), 17.8 (CH3), 16.2 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.6 (CF3).1.2 g, 56%, white foam; [a] 20 D = +25.9 (c 1.1, CH 2 CI 2 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 8.94 (d, J = 1.7 Hz, NCHN), 6.49 (d, J = 1.7 Hz, CH), 5.15-5.08 (m, 2H, CH & CH 2 ), 4.92- 4.86 (m, 1H, CH 2 ), 2.47-2.38 (m, 1H, CH), 2.30 (s, 3H, CH), 2.13 (d, = 2.9 Hz, 6H, CH 2 ), 1.78-1.76 ( m, 6H, CH 2 ), 1.02 (d, J = 6.9 Hz, 3H, CH 3 ), 0.91 (d, J = 6.8 Hz, 3H, CH 3 ); 13 C-NMR (100 MHz, CDCI 3 ) 5151.1 (C), 124.5 (CH), 120.7 (q, J = 322 Hz, CF 3 ), 90.6 (CH), 79.2 (CH 2 ), 62.9 (CH), 61.3 (C), 42.6 (CH 2 ), 35.3 (CH 2 ), 30.9 (CH), 29.4 (CH), 17.8 (CH 3 ), 16.2 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.6 (CF 3 ).
AiSSFC l - 18 - AiSSFC l - 18 -
Beispiel 12: Darstellung von Imidazolium Triflat 14.Example 12: Preparation of imidazolium triflate 14.
0.7 g, 56%, farbloses Öl; [a]20 D = -21.3 (c 1.1 , CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 9.09 (d, J = 1.6 Hz, 1 H, NCHN), 6.46 (d, J = 1.6 Hz, 1 H, CH), 5.17-5.13 ( , 2H), 4.94-4.90 (m, 1 H), 4.36 (dd, J = 8.6, 9.7 Hz, 1H), 4.06 (t, J = 8.2 Hz, 1H), 3.98-3.92 (m, 1H), 2.47-2.43 (m, 1H), 1.96 (s, 3H), 1.90 (s, 3H), 1.78-1.71 (m, 1 H), 1.03 (d, J = 6.9 Hz, 3H), 0.92 (d, J = 6.8 Hz, 3H), 0.91 (d, J = 6.7 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H); 13C-NMR (100 MHz, CDCI3) δ165.4 (C), 150.8 (C), 126.4 (CH), 120.6 (q, J = 320 Hz, CF3), 92.7 (CH), 79.3 (CH2O), 72.2 (CHN), 71.8 (CH2O), 63.0 (CHN), 61.5 (CMe2), 32.4 (CH), 31.0 (CH), 26.0 (2 x CH3), 18.5 (CH3), 18.1 (CH3), 17.6 (CH3), 16.1 (CH3); 19F-NMR (300 MHz, CDCI3) δ -78.6 (CF3).0.7 g, 56%, colorless oil; [a] 20 D = -21.3 (c 1.1, CH 2 CI 2 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 9.09 (d, J = 1.6 Hz, 1 H, NCHN), 6.46 (d, J = 1.6 Hz, 1 H, CH), 5.17-5.13 (, 2H), 4.94-4.90 (m, 1 H), 4.36 (dd, J = 8.6, 9.7 Hz, 1H), 4.06 (t, J = 8.2 Hz, 1H), 3.98-3.92 (m, 1H), 2.47-2.43 (m , 1H), 1.96 (s, 3H), 1.90 (s, 3H), 1.78-1.71 (m, 1 H), 1.03 (d, J = 6.9 Hz, 3H), 0.92 (d, J = 6.8 Hz, 3H ), 0.91 (d, J = 6.7 Hz, 3H), 0.85 (d, J = 6.8 Hz, 3H); 13 C-NMR (100 MHz, CDCI 3 ) δ165.4 (C), 150.8 (C), 126.4 (CH), 120.6 (q, J = 320 Hz, CF 3 ), 92.7 (CH), 79.3 (CH 2 O), 72.2 (CHN), 71.8 (CH 2 O), 63.0 (CHN), 61.5 (CMe 2 ), 32.4 (CH), 31.0 (CH), 26.0 (2 x CH 3 ), 18.5 (CH 3 ), 18.1 (CH 3 ), 17.6 (CH 3 ), 16.1 (CH 3 ); 19 F NMR (300 MHz, CDCI 3 ) δ -78.6 (CF 3 ).
1d 2d1d 2d
Beispiel 13: Darstellung von Imidazolium Triflat 2d.Example 13: Preparation of imidazolium triflate 2d.
1.7 g, 36%, weißer Schaum; [a]20 D = +38.1 (c 1.4, CH2CI2); 1H-NMR (400 MHz, CDCI3) δ 8.04 (s, 1 H, NCHN), 7.31-7.20 (m, 10H, CHar), 5.27-5.20 (m, 2H, CH), 5.00 (dd, J = 7.5, 9.1 Hz, 2H, CH2), 4.75 (dd, J = 5.8, 9.0 Hz, 2H, CH2), 3.40 (dd, J = 6.2, 13.9 Hz, 2H, CH2Ph), 3.10 (dd, J = 8.1 , 13.9 Hz, 2H, CH2Ph); 13C-NMR (100 MHz, CDCI3) δ 133.8 (C), 129.2 (CH), 129.2 (CH), 127.9 (CHar), 125.8 (C), 120.6 (q, J = 321 Hz, CF3), 115.2 (NCHN), 81.0 (OCH2), 59.7 (NCH), 38.5 (CH2) δ19F-NMR (300 MHz, CDCI3) δ -78.5 (CF3).1.7 g, 36%, white foam; [a] 20 D = +38.1 (c 1.4, CH 2 CI 2 ); 1 H-NMR (400 MHz, CDCI 3 ) δ 8.04 (s, 1 H, NCHN), 7.31-7.20 (m, 10H, CH ar ), 5.27-5.20 (m, 2H, CH), 5.00 (dd, J = 7.5, 9.1 Hz, 2H, CH 2 ), 4.75 (dd, J = 5.8, 9.0 Hz, 2H, CH 2 ), 3.40 (dd, J = 6.2, 13.9 Hz, 2H, CH 2 Ph), 3.10 (dd , J = 8.1, 13.9 Hz, 2H, CH 2 Ph); 13 C-NMR (100 MHz, CDCI 3 ) δ 133.8 (C), 129.2 (CH), 129.2 (CH), 127.9 (CH ar ), 125.8 (C), 120.6 (q, J = 321 Hz, CF 3 ) , 115.2 (NCHN), 81.0 (OCH 2 ), 59.7 (NCH), 38.5 (CH 2 ) δ 19 F-NMR (300 MHz, CDCI 3 ) δ -78.5 (CF 3 ).
Ausführungsbeispiel für Anspruch 22:Exemplary embodiment for claim 22:
Die Suzuki-Kreuzkupplung ist im akademischen und industriellen Umfeld zu einer Standardsynthesemethode für Biaryle geworden. (N. Miyaura, A. Suzuki, Chem. Rev. (1995) 95, 2457; S. Kotha, K. Lahiri, D. Kashinath, Tetrahedron (2002) 58, 9633.) Während normalerweise Aryliodide und -bromide als Substrate dienen, wurde kürzlich durch die Entwicklung neuer Katalysatorsysteme auch die effiziente Kupplung der billigeren und besser verfügbaren Arylchloride möglich. (Übersichtsartikel: A. F. Littke, G. C. Fu, Angew. Chem. (2002) 114, 4350.) Trotz einiger Anstrengung gelang bisher die Kupplung von Arylchloriden zu Biarylen mit mehr als einem ortho-Substituenten nicht bei Raumtemperatur. (Synthese von sterisch gehinderten Biarylen durch Suzuki-Kreuzkupplung bei höheren Temperaturen: J. P. Wolfe, R. A. Singer, B. H. Yang, S. L. Buchwald, J. Am. Chem. Soc.
(1999) 121, 9550; A. F. Littke, C. Dai, G. C. Fu, J. Am. Chem. Soc. (2000) 122, 4020; J. Yin, M. P. Rainka, X.-X. Zhang, S. L Buchwald, J. Am. Chem. Soc. (2002) 124, 1162.)The Suzuki cross-coupling has become a standard synthetic method for biaryls in academic and industrial settings. (N. Miyaura, A. Suzuki, Chem. Rev. (1995) 95, 2457; S. Kotha, K. Lahiri, D. Kashinath, Tetrahedron (2002) 58, 9633.) While normally aryl iodides and bromides serve as substrates , recently the development of new catalyst systems also made it possible to efficiently couple the cheaper and more readily available aryl chlorides. (Review article: AF Littke, GC Fu, Angew. Chem. (2002) 114, 4350.) Despite some efforts, the coupling of aryl chlorides to biaryls with more than one ortho-substituent has so far failed at room temperature. (Synthesis of sterically hindered biarylene by Suzuki cross-coupling at higher temperatures: JP Wolfe, RA Singer, BH Yang, SL Buchwald, J. Am. Chem. Soc. (1999) 121, 9550; AF Littke, C. Dai, GC Fu, J. Am. Chem. Soc. (2000) 122, 4020; J. Yin, MP Rainka, X.-X. Zhang, S. L Buchwald, J. Am. Chem. Soc. (2002) 124, 1162.)
Durch die Verwendung eines aus Pd(OAc)2 und einem Äquiv. Imidazoliumsalz 8 hergestellten Katalysators gelingt die Synthese zahlreicher Biaryle aus verschiedenen Arylchloriden und Arylboronsäuren bei Raumtemperatur. Wie in Tabelle 1 gezeigt, können unsubstituierte, monoortho- und diortho-substituierte Arylchloride in guten bis sehr guten Ausbeuten mit einer Vielzahl an Arylboronsäuren verknüpft werden, mit Umsatzzahlen von bis zu 1730 bei Raumtemperatur. Weiterhin gelingt die Kupplung der sterisch gehinderten 2,6-Dimethyl- benzolboronsäure mit unsubstituierten, ortho-substituierten, elektronenarmen und -reichen Arylchloriden (Tabelle 2). Diese Ergebnisse stellen die ersten Suzuki-Kreuzkupplungen von Arylchloriden und Arylboronsäuren zur Herstellung von di- und triortho-substituierten Biarylen bei Raumtemperatur dar.By using one of Pd (OAc) 2 and an equiv. Imidazolium salt 8 catalyst successfully synthesizes numerous biaryls from various aryl chlorides and aryl boronic acids at room temperature. As shown in Table 1, unsubstituted, monoortho- and diortho-substituted aryl chlorides can be linked in good to very good yields with a large number of arylboronic acids, with turnover numbers of up to 1730 at room temperature. Coupling of the sterically hindered 2,6-dimethylbenzeneboronic acid with unsubstituted, ortho-substituted, electron-deficient and electron-rich aryl chlorides is also possible (Table 2). These results represent the first Suzuki cross-coupling of aryl chlorides and aryl boronic acids for the preparation of di- and triortho-substituted biarylene at room temperature.
Tabelle 1 : Suzuki-Kupplung sterisch gehinderter Arylchloride.[a] Table 1: Suzuki coupling of sterically hindered aryl chlorides. [a]
Nr. Arylchlorid Boronsäure Produkt Ausbeute IBΓNo. aryl chloride boronic acid product yield IBΓ
[a] Reaktionsbedingungen: 3 ol-% Pd(OAc)2, 1 (hergestellt aus 3.1 Mol-% 2, 6.25 Mol-% KH, 0.67 ol-% KOffiu in THF); 1.0 Äquiv. Arylchlorid (1 mmol), 1.1 Äquiv. Boronsäure, 2.0 Äquiv. CsF, THF [0.3 M], RT, 24 h (Reaktionszeiten wurden nicht optimiert).[a] Reaction conditions: 3 ol% Pd (OAc) 2 , 1 (made from 3.1 mol% 2, 6.25 mol% KH, 0.67 ol% KOffiu in THF); 1.0 equiv. Aryl chloride (1 mmol), 1.1 equiv. Boronic acid, 2.0 equiv. CsF, THF [0.3 M], RT, 24 h (reaction times were not optimized).
[b] Isolierte Ausbeute.[b] Isolated yield.
[c] <5% Produkt wurde unter Verwendung von 5 als Katalysator erhalten.[c] <5% product was obtained using 5 as a catalyst.
[d] 0.03 Mol-% Katalysator, [e] 0.03 Mol-% Katalysator, bei 60 °C.
Table 2: Suzuki-Kupplung sterisch gehinderter Boronsäuren. [a][d] 0.03 mol% catalyst, [e] 0.03 mol% catalyst, at 60 ° C. Table 2: Suzuki coupling of sterically hindered boronic acids. [A]
[a] Reaktionsbedingungen: 3 Mol-% Pd(OAc)2l 1 (hergestellt aus 3.1 Wlol-% 2, 6.25 Mol-% KH, 0.67 Mol-% KOfBu in THF); 1.0 Äquiv. Arylchlorid (1 mmol), 1.1 Äquiv. Boronsäure,[a] Reaction conditions: 3 mol% Pd (OAc) 2l 1 (made from 3.1 vol% 2, 6.25 mol% KH, 0.67 mol% KOfBu in THF); 1.0 equiv. Aryl chloride (1 mmol), 1.1 equiv. Boronic acid,
2.0 Äquiv. KOrBu; THF/H20 [10:1, 0.3 ], RT, 24 h (Reaktionszeiten wurden nicht optimiert).2.0 equiv. Korbu; THF / H 2 0 [10: 1, 0.3], RT, 24 h (reaction times were not optimized).
[b] Isolierte Ausbeute.[b] Isolated yield.
Vergleichsbeispiel 1Comparative Example 1
Die Synthese des Chlorids von Imidazoliumsalz 6a wurde in der Literatur mit einer Ausbeute von 40% nach einer Reaktionsdauer von fünf Tagen beschrieben. (A. J. Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.)The synthesis of the chloride of imidazolium salt 6a has been described in the literature with a yield of 40% after a reaction period of five days. (A.J. Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.)
Vergleichsbeispiel 2Comparative Example 2
Die Synthese des Chlorids von Imidazoliumsalz 6b wurde in der Literatur mit einer Ausbeute von 47% nach einer Reaktionsdauer von 16 Stunden beschrieben. (A. J. Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.)The synthesis of the chloride of imidazolium salt 6b has been described in the literature with a yield of 47% after a reaction time of 16 hours. (A.J. Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.)
Vergleichsbeispiel 3Comparative Example 3
Die angestrebte Synthese des Chlorids von Imidazoliumsalz 2a, 2b und 2c nach der in der Literatur (A. J. Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.) für Bisimine beschriebenen Vorschrift ergab ein komplexes Gemisch von mehreren Produkten.
The desired synthesis of the chloride of imidazolium salt 2a, 2b and 2c according to the procedure described in the literature (AJ Arduengo, III, R. Krafczyk, R. Schmutzler, Tetrahedron (1999) 55, 14523.) for a bisimine resulted in a complex mixture of several products.
Claims
1. Verfahren zur Herstellung von Imidazoliumsalzen der allgemeinen Formeln II, IV und VI umfassend die Umsetzung der entsprechenden Substrate I, III und V,1. Process for the preparation of imidazolium salts of the general formulas II, IV and VI, comprising the reaction of the corresponding substrates I, III and V,
AA
A IVA IV
A V VIA V VI
worinwherein
R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 und R 4 gleich oder verschieden sind und gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C^o-Alky!-, C2-5-Alkenyl-, C2-5-Alkinyl-, C7-19-Aralkyl- oder C6-14-Arylreste bedeuten, R1, R2, R3, R4, R5, R6, R7, R8, R1 und R13 auch für Wasserstoff stehen können oder gemeinsam anellierte, substituierte oder unsubstituierte Reste mit 3-7 Kohlenstoffatomen bilden, R11 und R13 auch -OR16, .-SR17 oder -NR18 R19 sein können, in denen R16, R17, R18 und R19 die für die Reste R1 bis R8 und R11 bis R 4 angegebene Bedeutung haben können, wobei R16, R17, R18, R19, einer der Reste R1, R2, R7, R8, R12 und R14 auch ein Linker L zu einer weiteren Imidazoliumsalz der Formel II, IV oder VI sein kann,R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 4 are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1 -C 4 -alky!, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 aralkyl or C 6-14 aryl radicals, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 1 and R 13 can also represent hydrogen or together form fused, substituted or unsubstituted radicals having 3-7 carbon atoms, R 11 and R 13 can also be -OR 16 ,.-SR 17 or -NR 18 R 19 , in which R 16 , R 17 , R 18 and R 19 are those given for the radicals R 1 to R 8 and R 11 to R 4 May have meaning, where R 16 , R 17 , R 18 , R 19 , one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 also a linker L to a further imidazolium salt of the formula II, IV or can be VI
X für O, S, eine Gruppe NR9 oder CR9a R9b steht, in der R9, R9a und R9b Wasserstoff, gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C1-10-Alkyl-, C2-5-Alkenyl-, C2-5-Alkinyl-, C7-19-Aralkyl- oder C6-ι4- Arylreste bedeuten, Y für O, S, eine Gruppe NR10 oder NR10a R10b steht, in der R10, R10a, R10b Wasserstoff, gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C-Mo-Alkyl-, C2-5-Alkenyl-, C2.5-Alkinyl-, C7-19-Aralkyl- oder C6-ι4-X represents O, S, a group NR 9 or CR 9a R 9b in which R 9 , R 9a and R 9b are hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1-10 -alkyl-, C 2-5 alkenyl, C 2-5 alkynyl, C 7-19 aralkyl or C 6- ι 4 aryl radicals, Y represents O, S, a group NR 10 or NR 10a R 10b , in which R 10 , R 10a , R 10b is hydrogen, saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C- M o-alkyl-, C 2-5 alkenyl, C 2 . 5 -alkynyl, C 7-19 aralkyl or C 6- ι 4 -
Arylreste bedeuten, undAryl radicals mean, and
A für ein ein- oder mehrwertiges, organisches oder anorganisches Anion oder einA for a mono- or polyvalent, organic or inorganic anion or a
Metallkomplex-Ion steht, mit einer Kombination aus einem Alkylierungsmittel der allgemeinen Formel VII, VIII oder IXMetal complex ion is, with a combination of an alkylating agent of the general formula VII, VIII or IX
VII VIII IXVII VIII IX
worin Z für eine Abgangsgruppe steht und R15 dieselbe Bedeutung wie R3 hat, und einem Metallsalz der allgemeinen Formelwherein Z represents a leaving group and R 15 has the same meaning as R 3 , and a metal salt of the general formula
MA, worin M für ein ein- oder mehrwertiges Metallkation, eine Tetraorganoammoniumverbindung oder einen Triorganosilylrest steht, und A die vorstehend für A" angegebene Bedeutung hat, als Promoter der Reaktion.MA, in which M represents a mono- or polyvalent metal cation, a tetraorganoammonium compound or a triorganosilyl radical, and A has the meaning given above for A " , as a promoter of the reaction.
2. Verfahren nach Anspruch 1 , wobei R1, R2, R3, R4, R5, R6, R7, R8, R9, R9a, R9b, R10, R10a, R11, R 2, R13, R14 und R15 gleich oder verschieden sind und gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische, unsubstituierte oder substituierte C1-6-Alkyl-, C2-4-Alkenyl-, C2.4-Alkinyl-, C7-ι0-Aralkyl-, oder Phenylreste bedeuten.2. The method according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 9a , R 9b , R 10 , R 10a , R 11 , R 2 , R 13 , R 14 and R 15 are the same or different and are saturated or unsaturated, straight-chain, branched or cyclic, unsubstituted or substituted C 1-6 alkyl, C 2-4 alkenyl, C 2 . 4 -alkynyl, C 7- ι 0 aralkyl, or phenyl radicals.
3. Verfahren nach Anspruch 1 oder 2, wobei das ein- oder mehrwertige, organische oder anorganische Anion A~ in den allgemeinen Formeln II, IV und VI ein Sulfat-, Halogenid-, Pseudohalogenid-, Borat-, Phosphat- oder Metallkomplex-Ion oder ein ggf. halogeniertes Sulfonat-, Carboxylat- oder Acetylacetonat-Ion ist und insbesondere A~ für ein Triflat-, Mesylat-, Tosylat-, Nonaflat-, Tresylat-, Benzolsulfonat-, Brosylat-, Nosylat-, Fluorsulfonat-, Tetraphenyl-borat-, Tetrakis[3,5-bis(trifluormethyl)phenyl]- borat(BARF)-, Tetra-fluoroborat-, Hexafluorophosphat-, Hexafluoroantimonat-, Acetat-, Trifluoracetat-, Perchlorat-, Tetracarbonylcobaltat- oder Hexafluoroferrat(III)-lon steht.3. The method according to claim 1 or 2, wherein the mono- or polyvalent, organic or inorganic anion A ~ in the general formulas II, IV and VI is a sulfate, halide, pseudohalide, borate, phosphate or metal complex ion or an optionally halogenated sulfonate, carboxylate or acetylacetonate ion and in particular A ~ for a triflate, mesylate, tosylate, nonaflate, tresylate, benzenesulfonate, brosylate, nosylate, fluorosulfonate, tetraphenyl borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (BARF), tetra-fluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, perchlorate, tetracarbonyl cobaltate or hexafluoroferrate (III) lon stands.
4. Verfahren nach Anspruch 1 oder 2, wobei A~ in den allgemeinen Formeln II, IV und VI für ein Triflat-Ion steht. 4. The method according to claim 1 or 2, wherein A ~ in the general formulas II, IV and VI represents a triflate ion.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, wobei R1, R2, R3, R4, R5, R6, R7, R8, R9, R9a, R9b, R10, R10a, R10b R11, R12, R13, R14 und R 5 Reste darstellen, die durch einen oder mehrere, gleiche oder verschiedene Amin-, Nitro-, Nitril-, Isonitril-, Ether-, Alkohol-, Aldehyd-, oder Ketongruppen, Carbonsäurederivate, insbesondere Ester oder Amide, halogenierte, insbesondere fluorierte oder perfluorierte Kohlenwasserstoff-Reste, Kohlenhydrat-, Phosphan-, Phosphanoxid-, Phosphansulfid-, Phosphol-Reste, Phosphitderivate, aliphatische oder aromatische Sulfonsäure- derivate, deren Salze, Ester oder Amide, Silylfunktionen, Borylgruppen oder heterozyklische Substituenten substituiert sein können.5. The method according to one or more of claims 1 to 4, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 9a , R 9b , R 10 , R 10a , R 10b R 11 , R 12 , R 13 , R 14 and R 5 represent radicals which are replaced by one or more, identical or different amine, nitro, nitrile, isonitrile, ether, alcohol, aldehyde -, or ketone groups, carboxylic acid derivatives, in particular esters or amides, halogenated, in particular fluorinated or perfluorinated hydrocarbon radicals, carbohydrate, phosphine, phosphine oxide, phosphine sulfide, phosphole radicals, phosphite derivatives, aliphatic or aromatic sulfonic acid derivatives, their salts, Esters or amides, silyl functions, boryl groups or heterocyclic substituents can be substituted.
6. Verfahren nach Anspruch 5, wobei einer der Reste R1, R2, R7, R8, R12 und R14 durch ein Azoliumsalz oder einen Pyridinring substituiert ist.6. The method according to claim 5, wherein one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 is substituted by an azolium salt or a pyridine ring.
7. Verfahren nach einem oder mehreren der Ansprüche 1-6, wobei die Abgangsgruppe Z ein Halogenid, Pseudohalogenid oder Carboxylat ist und insbesondere ein Alkylierungsmittel der allgemeinen Formel VII, VIII oder IX eingesetzt wird, worin Z für ein Halogenid steht, und R15 einen unsubstituierten oder substituierten Phenyl-, Benzyl- oder C C4-Aikylrest darstellt, der jeweils einen oder mehrere Substituenten, insbesondere Ether-, Ester- oder Silylsubstituenten enthalten kann.7. The method according to one or more of claims 1-6, wherein the leaving group Z is a halide, pseudohalide or carboxylate and in particular an alkylating agent of the general formula VII, VIII or IX is used, in which Z represents a halide, and R 15 one represents unsubstituted or substituted phenyl, benzyl or CC 4 -alkyl radical, which may each contain one or more substituents, in particular ether, ester or silyl substituents.
8. Verfahren nach Anspruch 7, wobei als Alkylierungsmittel Chlormethylpivalat, Chlormethylbutyrat, Chlormethylethylether, (2-Methoxyethoxy)-methylchlorid oder (2- Chlormethoxyethy!)-trimethylsilan und insbesondere Chlormethylpivalat verwendet wird.8. The method according to claim 7, wherein the alkylating agent used is chloromethyl pivalate, chloromethyl butyrate, chloromethyl ethyl ether, (2-methoxyethoxy) methyl chloride or (2-chloromethoxyethy!) Trimethylsilane and in particular chloromethyl pivalate.
9. Verfahren nach einem oder mehreren der Ansprüche 1-8, wobei das ein- oder mehrwertige Metallkation M ein Silber(l), Alkali- und Erdalkalimetall-, Lanthanid-, Blei(ll)-, Quecksilber(ll)-, Cadmium(ll)-, Thallium(l)-, Kupfer(ll)-, Zink(ll)- oder Aluminium(lll)-lon ist, die Tetraorganoammoniumverbindung Tetraalkylammoniumverbindung ist und der Triorganosilylrest ein T alkylsilylrest ist.9. The method according to one or more of claims 1-8, wherein the mono- or polyvalent metal cation M is a silver (l), alkali and alkaline earth metal, lanthanide, lead (ll) -, mercury (ll) -, cadmium ( ll) -, thallium (l) -, copper (ll) -, zinc (ll) - or aluminum (III) -lon, the tetraorganoammonium compound is tetraalkylammonium compound and the triorganosilyl radical is a T alkylsilyl radical.
10. Verfahren nach einem oder mehreren der Ansprüche 1-9, wobei ein Metallsalz der allgemeinen Formel MA verwendet wird, worin M für Silber(l) steht und A die in Anspruch 3 oder 4 angegebene Bedeutung hat. A38S.fC l - 24 -10. The method according to one or more of claims 1-9, wherein a metal salt of the general formula MA is used, wherein M is silver (I) and A has the meaning given in claim 3 or 4. A38S.fC l - 24 -
1 1. Verfahren nach einem oder mehreren der Ansprüche 1-10, wobei einer der Reste R1, R2, R7, R8, R12 und R14 ein Linker L zu einem weiteren Imidazoliumsalz der Formel II, IV oder VI darstellt, L insbesondere ein C1- Alkylen-, C5-12 Cycloalkylen-, C6-ι2 Arylen- oder C6-12 Heteroarylenrest ist, der gegebenenfalls substituiert oder durch ein Heteroatom oder einen zyklischen Rest unterbrochen sein kann, und besonders bevorzugt das Imidazoliumsalz die allgemeine Formel X1 1. The method according to one or more of claims 1-10, wherein one of the radicals R 1 , R 2 , R 7 , R 8 , R 12 and R 14 is a linker L to another imidazolium salt of the formula II, IV or VI , L is in particular a C 1- alkylene, C 5-12 cycloalkylene, C 6- ι 2 arylene or C 6-12 heteroarylene radical, which may be substituted or interrupted by a hetero atom or a cyclic radical, and is particularly preferred the imidazolium salt has the general formula X
A AA A
XX
aufweist, worin die Variablen die in Ansprüchen 1-5 angegebene Bedeutung haben.wherein the variables have the meaning given in claims 1-5.
12. Verfahren nach einem oder mehreren der Ansprüche 1-11 , dadurch gekennzeichnet, dass Alkylierungsmittel und Metallsalz in mindestens stöchiometrischer Menge bezogen auf das jeweilige Substrat eingesetzt werden.12. The method according to one or more of claims 1-11, characterized in that the alkylating agent and metal salt are used in at least stoichiometric amount based on the respective substrate.
13. Verfahren nach einem oder mehreren der Ansprüche 1-12, dadurch gekennzeichnet, dass ein vorab hergestelltes Reagenz aus Metallsalz und Alkylierungsmittel wie in Anspruch 1 definiert, insbesondere ein Reagenz aus einem Alkylierungsmittel wie in Anspruch 7 oder 8 definiert und einem Metallsalz wie in Anspruch 9 oder 10 definiert, eingesetzt wird.13. The method according to one or more of claims 1-12, characterized in that a previously prepared reagent of metal salt and alkylating agent as defined in claim 1, in particular a reagent of an alkylating agent as defined in claim 7 or 8 and a metal salt as in claim 9 or 10 defined, is used.
14. Verfahren nach einem oder mehreren der Ansprüche 1-13, dadurch gekennzeichnet, dass die Umsetzung der Substrate in einem organischen Lösungsmittel erfolgt.14. The method according to one or more of claims 1-13, characterized in that the reaction of the substrates is carried out in an organic solvent.
15. Verfahren nach Anspruch 14, wobei das organische Lösungsmittel Aceton, Diethylether, Methyltertbutylether, Petrolether, Acetonitril, Propionitril, Ethylacetat, Benzol, Toluol, Xylol, Benzin, 1 ,2-Dichlorethan, Chloroform oder Methylenchlorid und insbesondere Methylenchlorid ist.15. The method according to claim 14, wherein the organic solvent is acetone, diethyl ether, methyl tert-butyl ether, petroleum ether, acetonitrile, propionitrile, ethyl acetate, benzene, toluene, xylene, gasoline, 1, 2-dichloroethane, chloroform or methylene chloride and especially methylene chloride.
16. Verbindungen der allgemeinen Formeln II, IV und XI 16. Compounds of the general formulas II, IV and XI
A AA A
IV XIIV XI
worinwherein
I1 und I2 gleiche oder verschiedene Imidazoliumsalze der Formeln II, IV und VI sind, die an der Position der Reste R1, R2, R7, R8, R12 oder R14 mit L verknüpft sind, mit derI 1 and I 2 are the same or different imidazolium salts of the formulas II, IV and VI, which are linked to L at the position of the radicals R 1 , R 2 , R 7 , R 8 , R 12 or R 14 , with which
Massgabe dass nicht I1 und I2 beide ein Imidazoliumsalz der Formeln VI sind, das Imidazoliumsalz der Formel VI, R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, X,Provided that I 1 and I 2 are not both an imidazolium salt of the formula VI, the imidazolium salt of the formula VI, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , X,
Y, L und A" die in Anspruch 1 angegebene Bedeutung haben.Y, L and A "have the meaning given in claim 1.
17. Verbindungen nach Anspruch 16, wobei R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R13, R14, X, Y, L und A" die in den Ansprüchen 2 bis 6 und 11 angegebene Bedeutung haben.17. Compounds according to claim 16, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , X, Y, L and A "have the meaning given in claims 2 to 6 and 11.
18. Verbindungen nach den Ansprüchen 16 bis 17 mit den folgenden Strukturformeln:18. Compounds according to claims 16 to 17 with the following structural formulas:
wobei OTf Trifluormethansulfonat (Triflat), Ph Phenyl, TMS Trimethylsilyl, TES Triethylsilyl und Bn Benzyl bedeutet. where OTf means trifluoromethanesulfonate (triflate), Ph phenyl, TMS trimethylsilyl, TES triethylsilyl and Bn benzyl.
19. Verbindungen nach Anspruch 16 oder 17, die eine Verbindung der Formel X19. Compounds according to claim 16 or 17, which is a compound of formula X
XX
ist, wobei alle Variablen die in Anspruch 16 oder 17 angegebene Bedeutung haben.is, with all variables having the meaning given in claim 16 or 17.
20. Verbindungen nach Anspruch 19 mit den folgenden Strukturformeln:20. Compounds according to claim 19 with the following structural formulas:
wobei OTf Trifluormethansulfonat (Triflat), Ph Phenyl, und Bn Benzyl bedeutet. where OTf means trifluoromethanesulfonate (triflate), Ph phenyl, and Bn benzyl.
21. Verbindungen nach Anspruch 18 oder 20 mit Tetrafluoroborat, Mesylat, Tosylat, Nonaflat oder Hexafluoroantimonat anstatt Triflat als Gegenanion.21. Compounds according to claim 18 or 20 with tetrafluoroborate, mesylate, tosylate, nonaflate or hexafluoroantimonate instead of triflate as the counter anion.
22. Verwendung von Verbindungen gemäss der Ansprüche 16 bis 21 zur Herstellung von Katalysatoren in Form von Metallkomplexen N-heterozyklischer Carbene. 22. Use of compounds according to claims 16 to 21 for the preparation of catalysts in the form of metal complexes of N-heterocyclic carbenes.
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DE10231368 | 2002-07-11 | ||
DE10231368A DE10231368A1 (en) | 2002-07-11 | 2002-07-11 | Process for the preparation of imidazolium salts |
PCT/DE2003/002285 WO2004007465A1 (en) | 2002-07-11 | 2003-07-08 | Method for producing imidazolium salts |
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EP (1) | EP1521745A1 (en) |
JP (1) | JP2005538071A (en) |
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DE102008014028A1 (en) | 2008-03-13 | 2009-09-17 | Doris Dr. Kunz | Preparing imidazolium salts, preferably 1,3-disubstiuted imidazolium salts, useful e.g. as precursors of N-heterocyclic carbenes, comprises reducing 1,3-disubstituted-2-alkoxyimidazolium salts with hydrides and/or hydride donors |
WO2011064376A1 (en) | 2009-11-30 | 2011-06-03 | Novartis Ag | Imidazole derivatives as aldosterone synthase inhibitors |
JP2011178709A (en) * | 2010-02-28 | 2011-09-15 | Chiba Univ | Imidazolium salt, asymmetric synthesis catalyst using the same, and method for producing imidazolium salt |
DE102010040822B4 (en) * | 2010-09-15 | 2013-09-12 | Ernst-Moritz-Arndt-Universität | New imidazolium salts and carbene metal complexes based thereon for use as bioanalytical markers for biomolecules |
DE102011106849A1 (en) | 2010-12-15 | 2012-06-21 | Merck Patent Gmbh | Process for the synthesis of N-N linked and around the N-N bond of rotation-inhibited bis-N-heterocyclic carbenes and their use as ligands for metal complexes |
WO2012149523A1 (en) * | 2011-04-29 | 2012-11-01 | The University Of Akron | Azolium and purinium salt anticancer and antimicrobial agents |
DE102011054477A1 (en) * | 2011-10-13 | 2013-04-18 | Westfälische Wilhelms-Universität Münster | Process for the catalytic heteroaromatic hydrogenation |
JP2015061834A (en) * | 2014-09-22 | 2015-04-02 | 国立大学法人 千葉大学 | Imidazolium salt, asymmetric synthesis catalyst using the same, and method for producing imidazolium salt |
CN105503763B (en) * | 2014-10-17 | 2020-11-03 | 上海中科康润新材料科技有限公司 | Polyolefin oil catalyst and application thereof |
JP2016074729A (en) * | 2015-12-31 | 2016-05-12 | 国立大学法人 千葉大学 | Imidazolium salt and asymmetric synthesis catalyst prepared therewith, and method for producing imidazolium salt |
CN110407753B (en) * | 2019-07-21 | 2022-08-09 | 桂林理工大学 | Method for synthesizing pentaarylimidazolium salt from diaryl iodonium salt and imidazole |
CN110305171B (en) * | 2019-07-28 | 2021-09-28 | 苏州大学 | Preparation and application of mixed nickel (II) complex containing bisoxazoline-derived nitrogen heterocyclic carbene ligand and phosphite ligand |
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US5182405A (en) * | 1990-03-29 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Preparation of 1,3-disubstituted imidazolium salts |
US5077414A (en) * | 1990-03-29 | 1991-12-31 | E. I. Du Pont De Nemours And Company | Preparation of 1,3-disubstituted imidazolium salts |
DE4447067A1 (en) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Process for the preparation of aldehydes |
DE19815275B4 (en) * | 1998-04-06 | 2009-06-25 | Evonik Degussa Gmbh | Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis |
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