TWI310768B - New ruthenium complexes as (pre)catalysts for the metathesis reaction, 2-alkoxy-5-nitrostyrene derivatives as intermediates and the method of their manufacturing - Google Patents
New ruthenium complexes as (pre)catalysts for the metathesis reaction, 2-alkoxy-5-nitrostyrene derivatives as intermediates and the method of their manufacturing Download PDFInfo
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- TWI310768B TWI310768B TW092128427A TW92128427A TWI310768B TW I310768 B TWI310768 B TW I310768B TW 092128427 A TW092128427 A TW 092128427A TW 92128427 A TW92128427 A TW 92128427A TW I310768 B TWI310768 B TW I310768B
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- alkyl
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- aryl
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- 239000003054 catalyst Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 10
- 238000005649 metathesis reaction Methods 0.000 title claims description 7
- 239000000543 intermediate Substances 0.000 title description 6
- 150000003303 ruthenium Chemical class 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 239000003446 ligand Substances 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- -1 2,6-didecylphenyl Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000006772 olefination reaction Methods 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000005686 cross metathesis reaction Methods 0.000 claims description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 230000002152 alkylating effect Effects 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 11
- 101150041968 CDC13 gene Proteins 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 102000001708 Protein Isoforms Human genes 0.000 description 2
- 108010029485 Protein Isoforms Proteins 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000005865 alkene metathesis reaction Methods 0.000 description 2
- 125000005282 allenyl group Chemical group 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000002739 cryptand Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229920006250 telechelic polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Chemical group 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical class OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 1
- 125000004080 3-carboxypropanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C(O[H])=O 0.000 description 1
- TZPVPJUHWLYGSL-UHFFFAOYSA-N 5-nitro-2-propan-2-yloxybenzaldehyde Chemical compound CC(C)OC1=CC=C([N+]([O-])=O)C=C1C=O TZPVPJUHWLYGSL-UHFFFAOYSA-N 0.000 description 1
- 125000001960 7 membered carbocyclic group Chemical group 0.000 description 1
- 125000003627 8 membered carbocyclic group Chemical group 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- ONYZSGHNTNWBRJ-UHFFFAOYSA-N C(CC(=O)O)(=O)O.C(C)C(=CC)CC Chemical compound C(CC(=O)O)(=O)O.C(C)C(=CC)CC ONYZSGHNTNWBRJ-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006952 Enyne metathesis reaction Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Chemical group 0.000 description 1
- XKVYZLLWKHGKMT-BEJOYRPXSA-N Gemin D Natural products O([C@@H]([C@@H](O)C=O)[C@@H]1[C@@H](O)COC(=O)c2c(c(O)c(O)c(O)c2)-c2c(O)c(O)c(O)cc2C(=O)O1)C(=O)c1cc(O)c(O)c(O)c1 XKVYZLLWKHGKMT-BEJOYRPXSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JGFFTJDJHXLDNJ-UHFFFAOYSA-L [O-]OOO[O-].[K+].[K+] Chemical compound [O-]OOO[O-].[K+].[K+] JGFFTJDJHXLDNJ-UHFFFAOYSA-L 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003046 allene group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 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
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229930192479 gemin Natural products 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002198 insoluble material Substances 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
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- VCCPBPXMXHHRLN-UHFFFAOYSA-N methylsulfinylmethane;propan-2-one Chemical compound CC(C)=O.CS(C)=O VCCPBPXMXHHRLN-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004081 narcotic agent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
Description
1310768 玖、發明說明: 【發明所屬之技術領域】 本發明係關於式1之釕碳烯複合物,其合成及其作爲不a 類型複分解反應之觸媒之實際用途。
【先前技術】 近年來,烯類複分解在有機合成中之應用已取得了巨大 進步。已研製出作爲(預)觸媒之一些釕碳烯複合物,其在各 種複分解反應中具有高活性,且對若干官能基團具有廣泛 的耐爻性(tolerance)。該多種特徵之組合係可將該等(預)觸 媒用於有機合成之基礎。 此外,爲實際應用’尤其是於工業規模中,其極需要該 等釕複合物在熱負荷(thermaI 】〇ad)條件下於一較長時期内 保持安定,且需要彼等可在無保護氣體的環境_被儲存、 純化及使用。 具有上述特徵之釕複合物在文獻中爲人所知。參見j. Am. m- Soc· 2000,122,8168-8179 或 Tetrahedron Lett. 2000, 41,9973-9976。然而,吾人已發現,較佳的安定性與較低 的觸媒活性相關。該局限性發現於,例如式A之(預)觸媒( 參見 Angew. Chemie Int. Ed. 2002,1 14, 832)。 88125 1310768
Μθ8—Mes
c
接下來’描述式B及式C(預)觸媒,該等(預)觸媒展示了比 式A(預)觸媒更高之觸媒活性。式A、❹及式c之觸媒包含 整合(chelate)金屬廣子之異丙m起系統肢C具有更 同活性之原因係由於在異丙氧基之鄰位存在之苯基或(經 取代之)萘基而造成之位阻(Angew Chemie Int. Ed 2〇〇2, 114, 832-834; Angew. Chemie Int, Ed. 2002, 114, 2509-2511)。 已人地电現,包含芳族硝基之通式1之釕複合物(預)觸 媒,也明比習知之釘複合物具更高之觸媒活性,且彼等複 合物係熱安定的,且同時在空氣十係安定的。 【發明内容】
本發明係關於式1之新穎釕複合物,其合成,及所有中間 體之合成,及式1複合物作爲觸媒或預觸媒之應用,
其中, L係中性配位體; X及X'爲陰離子配位體; 88125 1310768 R1係-c丨-5_烷基或_C56dt烷基; R係Η、_Cl-2Q-烷基、-C2-20-烯基、-C2_2Q-炔基或芳基; R3係-C,·6-烷基、_Ci-6_烷氧基或芳基,其中芳基可經_C| 烷基或-ci-6_烷氧基取代; η係 0、1、2或 3。 本發明之式1之化合物可被用於催化烯類複分解反應,包 括(但不限於)開環複分解(ROMP)、閉環複分解(RCM)、不 飽和聚合物體之解聚合作用、遠螯聚合體(telechelic polymer)之合成、烯炔複分解及烯類合成。 本發明之另—實施例係關於式2之新穎2-烷氧基-5-硝基 苯乙烯衍生物,其係用於製備複合物1之中間體,
其中’ R1、R2、R3及η之定義如上,且 R4係-ci-2〇-:^ 基; 該部分式
代表伸炫>基’其中该伸甲基(methylene)之 一個或兩個氫原子可被基團R4替代。因此,其包含下列伸 烧基: 88125
本發明之另一態樣係式2之新穎2_烷氧基_5_硝基苯乙烯 1310768 衍生物之製備,其中: --經取代之2-羥基-5-硝基苯甲醛3經R!Z烷基化,其中 R1具有式1之定義,且Z係選自下列物質之離去基團:齒素 原子、CV6-烷基-S(0)-0-、C丨-6-氟烷基-S(0)-0-、芳基· s(o)-o-或芳基-S(0)2-0-;
經取代之式4之2 -烧氧基-5 -石肖基苯曱輕接著柄式 略 、、’ H_CtW 一 之烯化試劑處理以生成式2,其中R4及m具有其用 於式2之定義,且W係適合於稀化反應之離去基團;
NO, R2
4 烯化 ——化合物2接著可與式5之釕複合物反應’生成式1 <句 複合物’其中L1及L2係中性配位體;R5係Η、-CU2〇-燒基、 -C2-2<r烯基、-Cwo-炔基或芳基;R6係芳基、乙烯基或内_ 烯基(allenyl) ’且X及X'係陰離子配位體。 88125 1310768 R1
2
視情況’所獲得的式1之化合物可接著與不同的中性配位 體L!反應,以取代存在於式丨化合物中的中性配位體^,並 精此獲得不同的式1化合物。
本文所述之該等化合物可具有不對稱中心。本發明之包 含經不對稱取代之原子之化合物’可以旋光形態或外消旋 形態而被單離。熟悉此項技術者即知如何製備旋光形能, 例如藉由外《形態之解析或藉由自旋光性初始材料之合 成。烯類之許多幾何異構體可亦存在於本文所述之該等化 ,物中’ i本發明涵蓋所有該等安《異構豸。本發明之該 等化合物之”順”及"反”幾何異構體被描述,且彼等可作爲異 構體之混合物或作爲分離之異構體形態而被單離。意欲涵
-構之所有對掌性、非對映性、外消旋形態及其所有 成何”構體开/恶’除非特定指明特定的立體化學或異構體 形態。 【實施方式] 本文中未特定界定之術語應被理解爲具有由熟悉此項技 術者依據本揭不及其内容而給予之含義。然而,如於本說 月曰中所使用的(除非被特定爲具有相反含義),下述之術語 具有所指示之含義且下列常規遵守該含義。 88125 -10- 1310768
在下面之該等基團、殘基或部分中,通常在該基團之前 說明碳原+ > t Q ’、 数目,例如,-烷基係指該烷基或殘基具 有1至6個石叹原子。除非下文另外說明,應認爲在所有式或 基團中沿用習知對術語之界定以及習知之安定的原子價。 一本文所使用之術語"經取代之”,意指指定原子上之任何 θ $或多個氫被所指示之基團之選集(selection)所替代,但 而不超過所指定之原子的正常原子價,且該取代可產生 安定的化合物。 單獨地或與另外取代基組合使用之術語”芳基"音指 芳族單碳環系統或芳族多麵、统。例如,芳基包括;基 或萘基環系統。 本文所使用之術語1素„,意指選自氟、氯、漠或蛾之 虐素取代基。 ^文單獨地或與另外取代基組合使用之術語,,々2〇_烧基” :旨包含1至2G個碳原子之非環狀 '直鏈或分支鏈烧基取代 ^本文所使用之術語^基,,或',_^基,,,具有與 蝴吾相同之含義,但是包含更少碳原子,特定言之, =最多五個或六個碳原子。該等術語、CN2Q-絲”、,,_C_ ^或”-C"_院基"可包括(意即)甲基、乙基、丙基、丁基 其已基、丨甲基乙基、"基丙基、2_甲基丙基或二甲
乙基D 單獨也或與另外取代基組合使用之術語”_Cw〇_稀基” 包含2至2°個碳原子且具有至少-個雙鍵之非環狀、直 鍵或分支鏈烯基取代基。本文所使用之術語,,々6_稀基” 88125 1310768 ,具有與上述術語相同之含羞 —一 π 義仁疋包含更少碳原子,特 定言之’具有最多六個碳屌 丁 特 „r 反原子。该等術語”-C丨…-烯基”、或 1-6_烯基可包括(意即)乙烯基或丙二烯基。 一 本文單獨地或與另外取代基组合制之術語 思丸包含2至20個碳原子且呈古 、土 于且具有至少一個三鍵之非環狀、吉 鏈或分支鏈炔基取代基。太々 直 本文所使用之術語"-(:2·6-炔基", 具有與上述術語相同之含義 土 _ J < 3我,但疋包含更少碳原子,特 言之,具有最多六個碳原子。 本立文單獨地或與另外取代基組合使用之術語"Ί燒 m包含5或6個碳原子之環院基取代基,且其包括= 即)環戊基或環己基。 & 本文單獨地或與另外取代基組合使用之術語烷氧 基思指-Cy烷基-0_取代基,其中烷基如上所述包含多至 、個妷原子。烷氧基包括曱氧基、乙氧基、丙氧基、1-甲 基-乙氧基、丁氧基或u-二曱基乙.氧基。 其他實施例 車乂仏係式1 a化合物,其中L1、 X、 X,、 R1、R2、R3芬 a及η 之疋義如上。
更佳係通式1或式la之化合物,其中 L係P(R")3,且Rll各自獨立的爲_C|_6_烷基、_Cw_環烷 88125 •12- !310768 基或方基;或 L係式6a、6b、6c或6d之配位體:
V γ,7 W
6c nn^n~R8
其中 R7與R8各自獨立的爲H、-Cl-2G-烷基、-hi烯基或苯基 ,其中苯基視情況可經獨立選自-C,·6·烷基、-(^ ^烷氧基或 i素之多至三個基團所取代;特定言之, R9與R1G各自獨立的爲H、-Cl.2〇-烷基、烯基或苯基 ,其中笨基視情況可經獨立選自_C1_6-烷基、_C16_烷氧基或 _素之多至三個基團所取代,或 R與R1Q與彼等所附著之碳原子一起組合以形成一 3至8 員碳環。 γ及Y1爲鹵素。 尤其較佳之化合物係其中: R7與R8各自獨立的爲h、-Cl·6-烷基、_c26_烯基或苯基, 其中苯基視情況可經獨立選自mCi6道氧基或函 素之多至三個基團所取代; R9與R1G各自獨立的爲H、_Ci·6·烷基、_C26·烯基或苯基, 其中苯基視情況可經獨立選自-Gw —烷基、_Ci 6_烷氧基或虐 素之多.至三個基團所取代,或 R與R與彼等所附著之碳原子一起組合以形成一 5至7 員碳環。 88125 -13 - 1310768 最佳係通式1或la之化合物,其中: • R1係異丙基;及/或 • R2係Η、-(^_6-烷基或芳基,特定言之,R2具有氫原子之 含義;及/或 • X及V係鹵素、尤其係氯;及/或 • L1係Ρ(環己基)3 ;或 •L1係式6a、6b、6c或6d之基團;及/或 • R7與R8係2-曱基苯基、2,6-二曱基苯基或2,4,6-三曱基苯 基;及/或 • η 爲 0。 其他實施例係式1或1 a化合物,其中 • R1係異丙基; • R2 爲 Η ; • η 爲 0 ; • X及X'均爲氯;及 • L1係式6 a之配位體:
其中R7與R8各爲2,4,6-三甲基苯基;及 • R9與R1G各爲Η。 較佳係式2a化合物,其中R1、R2、R3、R4、m及η之定義 如上。 88125 -14 - 1310768 (A〆
更·^•係通式2或式2 a化合物,其中: • R1係異丙基;及/或 •R2爲Η、-CN6-烷基或芳基’特定言之,R2具有氫原子么 含義;及/或 • R4爲-1.6-烷基,特定言之爲曱基或乙基;及/或 • η爲〇 ;及/或 • m爲 〇 〇 其他實施例係式2或2a之化合物,其中: • R1係異丙基; • R2 爲 Η ; • m爲0 ;及 • η爲 0。 此外較佳係製備式1或la複合物之方法,其中通式2或2a 化合物與式5釕複合物在視情況之不同的中性配位體l 1存 在下反應:
其中 L1及L2爲中性配位體; R5爲H、-CuQ-烷基、-C2.2(r烯基、_C22q_炔基或芳基;及 88125 -15 - 1310768 R6爲芳基、乙烯基或丙二烯基;及 X及X’爲陰離子配位體。 更佳係在以下條件下進行而合成上述之式丨釕複合物的 •存在一種銅鹽’特定言之爲CuCi;及/或 •於鹵化之溶液或芳族溶液中,尤其係選自二氣甲烷、氯 仿、苯、甲苯、二曱苯、 均三甲苯或其混合物;及/或 •於〇至iooc之溫度,特定言之於10至80艺,更特定言之 於20至60°c ;及/或 - •反應時間爲1至24小時,尤其爲i至10小時,更尤其為i 至4小時。 更it爲上述之釕複合物的合成,其中於一容器中如下執 亍該反應.藉由將式6a、6b、6c或6d之配位體與式5(其中 配位體L1及L2均爲式P(Rn)3之膦,其中Rll具有上述之定義) 之固體複合物混合,且隨後添加式2或2a之配位體。 上述之釕複合物之合成之一較佳變體係:就地自式7a、
7d 生成通式6a、6b、6e或6d之配位體,纟中陰離子係選自甲
88125 •16- 1310768 自鹼孟屬氫化物或鹼土金屬氫化物或醇化物,尤其是第三 戊S子卸、第三戊氧化卸或第三丁醇化鉀。隨後添加式5(其 令配位體L及L2均爲式P(Rll)3之膦)之固體複合物,且隨後 ''式2或2a配位體而繼續進行反應,以生成通式1或I 3之 化合物。 此外較佳係製備中間體之方法,其包含以下步驟:a)利 用式RlZ(9)之試劑來烧化通式3化合物,以生成式4之中間 體,及b)使4與式10之烯烴化試劑反應,以生成通式^之化
2
其中式2a、 m及n之定義如 4、9及 10之 Rl、R2、R3、R4、 上,及 W爲適合於烯烴化反應之離去基團;及 Z爲 _ 素、'Ci-6-烷基-S(〇)-〇-、-Cw 氟烷基-S(〇)-〇-、芳 基'S⑼-0_或芳基-S(0)2-0-。 更佳之方法為其中上述步驟a)於以下條件中進行: •於非質子性溶劑中,特定言之,其選自DMF、DMSO 丙酮乙腈、乙酸乙醋、乙二醇醚、曱醇、乙醇或其混 合物’更特定言之該溶劑爲DMF ;或 •於具有相轉移觸媒之雙相溶劑系統中;或 •存在觸媒’特定言之’該觸媒係選自Cs2C02、CsF、四 88125 •17· 1310768 級銨鹽、冠㈣或穴狀配體(cryptand),更肖定言之係Cs2c〇 ;或 屬氫氧化物,特定言之係 Cs2C03、NaOH、KOH、 •存在鹼土金屬碳酸鹽或鹼金 選自 Na2C〇3 ' K2C03 ' Li2C〇3 >
LiOH、CsOH ;或 •反應時間爲!至24小時,特定言之8至24小時,更特定 a之16至24小時。 •於0至150 C之溫度,特定言之於1〇至1〇(Γ(:之溫度更 特定言之於20至80°C之溫度;或 自化合物4開始,可在特彼(Tebbe)、威帝(Wiuig)、威帝 (wiuig)-奥奈(H〇rner)、威帝(Wittig)_奥奈(H〇rner)_伊孟斯 (Emmons)或彼得森(Peters〇n)條件下獲得化合物2,但較佳 之方法為其中上述步驟b)在以下條件中進行: •於選自醇類、乙二醇醚或環喊之溶劑中,較佳係THf 中;或 • w係適合於烯烴化反應之離去基團:根據特彼(τ^&) ,利用特彼(Tebbe)氏鈦試劑;或根據威帝(Wittig),利两威 帝氏鱗鍚鹽試劑,更特定言之,係選自pph34TiCp2之離去 基團;其中Ph係經取代或未經取代之苯基且以係經取代或 未經取代之锿戊二浠基陰離子,其可在反應之後以氧化態 出現。 本發明之另一較佳貫施例係一用於所有類型之複分解反 應之方法,包含使烯烴與通式丨或13之觸媒接觸;特定言之 ,其中該複分解反應爲閉環複分解或交叉複分解反應。 88125 -18· 1310768 ^ $貫例欲例示本發明之各種實施例,且不應將其理解 爲以任何方式來限制本發明。 實例1
4.1 ·在粉末狀無水碳酸鉀(1 · i g,8 mm〇1)、觸媒量的碳酸 絶(521 mg,40 rnol%)、及 3.1 (668 mg, 4 mmol)之無水 DMF(25 ml)攪拌懸浮液中,添加純2_碘丙烷(〇8 d,8爪爪“) 。在室溫下將反應混合物攪拌24小時,接著真空蒸發溶劑 。殘留物倒入水(50 ml)中,且利用tBu〇Me (4x25 ml)進行萃 取。將組合的有機層用鹽水沖洗,並藉由Mg2S〇4乾燥且蒸 發至乾。利用矽膠管柱層析法(環己烷/Et〇Ac 8:2)純化粗産 物’以産生低熔點固體2-異丙氧基_5_硝基苯曱醛4.mg, 産率86%)。 IR (KBr) : v [cm-丨]=3 1 15, 2991,2942, 1679, 1609, 1526, 1348, 1284, 1111, 950, 832, 748, 667 ; H-NMR (500 MHz, CDC13) · 6[ppm]= 1.48 (d, 6H, J = 6.1 Hz), 4.85 (q, 1H, J = 6.1 Hz), 7.10 (d, 1H, J = 9.2 Hz), 8.39 (dd, 1H, J = 2.9, 9.2 Hz), 8.69 (d, 1H, J = 2.9 Hz), 10.41 (s,lH); ljC-NMR (125 MHz, CDC13) ; 5[ppm] = 21.8, 72.6, 113.6, 124.7, 125.12, 130.4, 141.1,164.3, 187.8 ; MS (El) : m/z 209 (10, [M] + .), 167 (100), 137 (18), 120 88125 -19- 1310768 (11),93 (7),75 (3),65 (10),53 (4); HRMS (El) : [M]+ (C10HnO4N)之計算值爲 209.0688 ;實 驗值爲:209.0686。 2,1 :於-78°C 下在 Ph3PCH3Br (932 mg,2.53 mmol)之無水 THF(20 ml)授拌懸浮液中,慢慢連續地添加BuLi之己院溶 液(1_8 ml,2.7 mmol,1.5 M)及 4.1之無水 THF(2 ml)溶液。此 後,使反應混合物溫至室溫’並攪拌1 〇小時。在這段時間 以後,添加NH4C1 (2 ml)及tBuOMe (1.00 ml)的飽和溶液 。濾除不可溶物質,並在真空中蒸發所得之溶液。藉由矽 膠管柱層析法(利用環己烷/EtOAc 8:2)純化粗産物,以生成 淺黃色油狀2-異丙氧基-5-硝基苯乙烯2.1(236 mg,産率63%)。 IR(膜):v [cm·1] = 3088,2982,2967,1627, 1607,1583, 1516, 1341,1271,1107, 950, 742 cm-1 ; 'H-NMR (5 00 MHz, CDC13): 5[ppm] = 1.41 (d, 6H, J = 6.0 Hz), 4.71 (q, 1H, J = 6.0 Hz), 5.40 (dd, 1H, J = 0.5, 11.2 Hz), 5.87 (dd, 1H, J = 0.5, 17.7 Hz), 6.91 (d, 1H, J = 9.1 Hz), 7.〇〇 (dd, 1H, J = 11.2, 17.7 Hz), 8.12 (dd, 1H, J = 2.8, 9.1 Hz), 8.36 (d, 1H, J = 2.8 Hz); 13C-NMR (125 MHz, CDC13) : 5[ppm] = 21.9,71.5, 112.2, 1 16.8, 122.4, 124.5, 128.1, 130.1, 141.0, 159.9 ; MS (El) : m/z 207 (4, [M] + .), 165 (59), 148 (100), 135 (4), 1 18 (96), 104 (2), 90 (15), 65 (8), 63 (7), 5 1 (4); MS (ESI) : m/z 230 ([M+Na] + ); HRMS (ESI): [M+Na]+ (CUH丨303NNa)之 m/z計算值爲 88125 -20 - 1310768 230.0788;實驗值爲:23〇.〇776。 實例2
於氬大氣中,將式511(其中L2代表式6a ii之nhc配位體)
之碳稀複合物(153 mg, 0.18 mmol)^ m 7xcuC1(18 mg,0.18 mmol) £ ^ - Schlenckt^ 管中。接著添加無水、去氧iCH2Cl2(1〇ml),隨後添加化 合物2.1(38 mg,().18 mmGl)之CH2Cl2 (4叫溶液。將所得之 懸浮液在坑下㈣1小時,隨後在真空中濃縮,並藉由石夕 膠管柱層析法(環己旧⑽Ae 5 : 2)進行純化。移除溶劑, 並藉由少里的無水n_戊烧進行沖洗之後,獲得綠色微晶固 體複合物⑶(其中Mes表示三f基苯基)(⑽叫,纟率83%) 。Rf = 0.30 (己烷/EtOAc 8 : 2)。 ,Η-Ν· (500 MHz,CD2Cl2) : s[ppm]= 16 42 (s,叫,8 4< (dd, 1H, J = 9.1,2.5Hz), 7.80 (d, 1H, J ^ 2.5 Hz), 7.1 〇 (s 4H), 6.94 (d, 1H> J = 9.1 Hz), 5.01 (-t^, 1H, j = 6-1 Hz) 4.22 (s,4H),2.47 (2s,18H),1.30 (d,6H,】=61 Hz); 88125 -21 - 1310768 13C-NMR (125 MHz, CD2C12) : 5[ppm]= 289.1, 208.2, 156.8, 150.3, 145.0, 143.5, 139.6, 139.3, 129.8, 124.5, 117.2, 113.3, 78.2, 52.0, 21.3, 21.2,19.4 ; IR (KBr) : v [cm'1] = 2924, 2850, 1606, 1521,1480, 1262, 1093, 918, 745 ; MS (ESI) : m/z 636 [M-CI]+ ; HRMS(EI) : C31H37N303Ru之 m/z計算值爲[m+.]671.1255 ; 實驗值爲:671.1229 ; C31H37N303Ru (671.63)之元素分析計算值(〇/。)爲:c 55.44,Η5_55,Ν6·26;實驗值爲:C 55.35 ; H5.70,N6.09。 實例3
於氬大氣中,將式5_m碳稀複合物(164_6mg,〇2〇mm〇j 置放於—SehleneUf中。接著添加無水、去氧之ch2C1 ⑴ml),隨後添加化合物2 1(5()叫,q 24麵。丨)之呵〇 ( _溶液。將所得之懸浮液機下授拌丨小日寺’隨後μ 空中濃縮,並藉由石夕踢管柱層析法(環己烧/Et〇Ac 5 : 2)i| 行純化。移除溶劑,並藉由少量的無水η·戊烧進行沖洗之 後,獲得褐色微晶固體複合物1Jn(其中心表示三甲美笨 88125 •22 · 1310768 基)(95 mg,産率 70%)。 'H-NMR (500 MHz, CDC13) '· δ [ppm] = 1.26 - 2.35 (m, 39 H), 5.33 - 5.40 (m 1H), 7.18 (d, J = 5 Hz, 1H), 8.54 (d, J = 5 Hz, 1H), 8.60 (s, 1H), 17.38 (d, J = 5.0 Hz, 1H); nC-NMR (125 MHz, CDC13) : δ [ppm] = 22.1, 26.2, 27.7 (d, J= 24 Hz), 30.1, 35.8 (d, J = 10 Hz), 78.2, 113.2, 117.6, 124.2, 143.3, 157.0, 273.2 ; IR (CH2C12,薄膜)·· v [cm.1] = 2930 (s),2852 (s), 1604 (m), 1 575 (m), 1521 (s), 1476 (m), 1447 (m), 1379 (w), 1342 (s), 1275 (s), 1241 (m), 1205 (w), 1181 (w), 1136 (m), 1095 (s),1049 (w),1005 (w), 951 (m),918 (s), 851 (m),830 (m), 789 (m), 745 (s), 656 (m), 606 (m), 518 (m); HRMS (El) : C28H4403N(35)Cl2P(i°2)Ru(M+)之 m/z計算值爲 645.14794;實驗值爲 645.14706。 實例4 在氬大氣下,於一Schlenck試管中,鹽7.IV(152 mg, 0.3 8 8 mmol)懸浮於η-己炫(7 ml)中。
隨後,添加第三戊氧化鉀Ch3CH2C(CH3)2〇-k+(〇.22如 0·372 mmol,1.7 Μ的甲笨溶液),並在室溫下將所得之淺黃 88125 -23- 1310768 色昆濁液攪拌30分鐘。
Mgs—Μ •Ο
r Η 7,1V N—Mes
Mes 一
Ns^N—Mes
Mes—N^^N—Mes 6JV 鬌 接著添加式5.III之釕複合物(25 5 mg, 0.310 mmol),並使 所得之懸浮液回流(reflux)30分鐘。於室溫下,於所得之褐 色懸浮液中添加化合物2.1(83.5 mg, 0.403 mmol)之 H2Cl2(7ml)>谷液’及固體CuCl (33.8 mg, 0.341 mmol)。 fcy3 u I Ph PCy3
Ck
Mes-N^N-Mes 6.1V 5JI!
Mes-N^N-Mes Cl^: ~ Ph — PCy3 中間體 *
將所彳寸之混合物在40°c下加熱1小時。在真空中濃縮所得 之此口物,並藉由矽膠管柱層析法(環己烷/Et〇Ac 5 : 2)進 盯純化。移除溶劑’並藉由少量的無水n_戊烧進行沖洗之 後’獲得綠色微晶固體複合HI(149mg,産率72%)。分析 資料與先前獲得之資料-致(參見實例2)。 實例5
類似於實例2,生成綠色微晶固體(産率
/
Me 2.1 複合物1_V之製備 40%) ° 88125 -24- 1310768 IR (KBr) : v [cm·1] = 2924 (s), 2853 (s), l6〇8 (m), 1523 (m), 1483 (s), 1343 (s), 1267,1010 (w), 905 (s),826 (m), 745 (m)。 MS(El):m/z 643 (3), 322 (4), 304 (l〇〇), 289 (1 1), 246 (5), 181 (12),159 (12),158 (12),105 (8),77 (15),43 (58)。 MS (LSIMS) m/z 644 (M+H+)。 使用通式1之化合物作爲複分解反應(分別爲包含雙鍵 c=c及/或其他官能基團之化合物的合成)之觸媒,會出現驚 人高的成功率。因此下述之式丨新穎(預)觸媒似乎較已知的 其他具有可比性的高活性釕觸媒更佳,特別是若考慮到其 活性。 其結果是與通常所用的既定複合物相較,產生更好的産 率之下,本發明需要更少數量的觸媒、更低之反應溫度及 更知'之反應時間。下列實例6-10顯示式1觸媒之此優越性。 實例6 藉由式1 · 11之化合物(參見實例2)催化之閉環複分解反應。
TsM
S1
1.»[1 Mo)%] ---^ CH2CI2, 1h, 0°C
P1 (99%) 在 〇C 下’於二烯 S1 (21〇mg,0.75 mmol)之 CH2Cl2 (3 5 mi) ,合液中,添加觸媒1JI (5 mg,1 mol%)之CH2C12 (2 ml)溶液 於〇 C下額外攪拌一小時之後,於真空中將溶劑移除,並 U ^膠官柱層析法(環己览/ EtOAc 8 : 2)對殘留物進行純 化’以生成無色固體P1 (186 mg,産率99%)。 88125 •25 · 1310768 IR (KBr) : v [cm'1] = 3030, 2942, 2899, 2855, 1657,1596, 1450, 1332, 1286, 1162, 910, 816, 712 ; Ή-NMR (200MHz, CDC13) : δ [ppm] = 2.28 (m, 4H), 2.39 (s, 3H), 3.25 (m, 4H), 5.72 (m, 2H), 7.25 (d, 2H, J = 8.2 Hz), 7.64 (d, 2H, J = 8.2 Hz); l3C-NMR (50MHz, CDC13) : δ [ppm] = 21.5, 29.9, 48.2, 126.9, 129.5, 130.1, 136.2, 142.9 ; MS (El) : m/z 251 (5, [M]+) 223 (2), 184 (6), 155 (4), 105 (2), 91 (19), 96 (16), 77 (1), 65 (13), 42 (100); HRMS (El) : [M]+ (C丨3H1702NS)之m/z計算值爲 251.0980 ; 實驗值爲:251.0979。 實例7 藉由式1.II之化合物(參見實例2)催化之交叉複分解反應
广 COOMe S2
CH2C(2l 2h, 25qC
{£)-P2(91%) -^ss^COOMe 1.11 [1 Mol%] /~~ + ϋ ^ 'uuuwe -
0,NJ S2b
於吲哚 S2 (77.8 mg,0.36 mol)及丙稀酸曱酯 S2b (92.9 mg, 1.1 mmol)之無水CH2C12 (15 ml)攪拌溶液中,添加i.n觸媒 (12.1 mg,5 mol%)之CH2C12 (5 ml)溶液。於室溫下將所得之 此合物擾拌2小時。於真空中移除溶劑’並藉由石夕膠管柱層 析法(環己烷/EtOAc 8 : 2)對殘留物進行純化,以生成黃色 結晶固體(E)-P2(186mg,産率99%)。 IR (KBr) : v [cm.1] = 3364, 2953, 2904, 1707, 1655, 1504, 1324, 1215, 750 cm-1 ; 88125 -26- 1310768 Ή-NMR (500 MHz, CDC13) : δ [ppra]= 2.42 (s, 3H), 3.61 (dd, 2H, J = 1.7, 6.0 Hz), 3.70 (s, 3H), 5.74 (dt, 1H, J = 1.7,15.7 Hz), 7.09 (dt, 1H, J = 6.0, 15.7 Hz), 7.42 (d, 1H, J = 8.8 Hz), 7.98 (dd, 1H, J = 2.0, 8.8 Hz), 8.24 (d, 1H, J = 2.0 Hz), 8.51 (br. s, 1H); "C-NMR (125 MHz, CDC13) : δ [ppm]= 12.0, 26.7, 51.5, 1 07.2, 1 08.8, 1 15.4, 1 1 7.5, 121.4, 133.2, 133.6, 138.9, 142.6, 146.7, 167.0 ; MS (El) : m/z 274 (100, [M] + .), 259 (75), 242 (63), 215 (38),199 (11),1 89 (1 5), 1 75 (15),168 (53),154 (18), 143 (31), 127 (12), 115 (12), 84 (17); HRMS (El) : [M]+ (C14H1404N2)之m/z計算值爲 247.0954 ; 實驗值爲:274.0959。 (C14Hl404N2)之元素分析計算值爲:C,61.31 ; H,5.14 ; Ν, 10·21 ;實驗值爲:C,61.05 ; H, 5.22 ; N,10.09。 實例8 當使用1 .II觸媒時,檢測受質S3 (丙二酸2-烯丙基-2-(2-曱基烯丙基)二乙酯)之環化速度。
於一 Schlenk 試管中,添加二烯 S3 (100 mg,0.4 mmol)之 1310768 CH2C12 (20 ml)溶液,在25。。下,添加 1.II觸媒(2.6 mg,0·004 mmol,1 mol·。/。)之CH2C12 (1 ml)溶液。所得溶液於該相同溫 度下額外攪拌18小時。自GC進行換算。(藉由添加經計算所 得之數量的乙基乙稀基醚之1 Μ溶液,立即使反應混合物之 等分試樣(Aliquot)淬火’並藉由GC技術進行分析。)所得之 結果如圖1中之曲線1〇(命)所示。 利用觸媒A,重複檢測受質S3(丙二酸2_烯丙基_2_(2_甲基 烯丙基)二乙酯)之環化速度。在除了將觸媒A的量提高至2.5 mo 1 ·/〇之外,其餘與上述條件相同之條件下進行實驗。所得 之結果如圖1中之曲線2(·)所示。 實例9 比較1 .II觸媒與C觸媒在交又複分解反應中之效率…广a_ TBSO·^ + 2 /^-COOMe 54 S2b TBSO^t^W^COOMe P4 (E): (2) = 95 : 5 條件· a)l .II觸媒(i m〇I°/〇)、室溫、3〇分鐘、産率95〇/〇。 b)C觸媒(2.5 Mol%)、室溫、2〇分鐘、産率91〇/〇。 於烯烴S4 (107 mg,0.5 ramol)與丙烯酸曱酯S2b (86 mg, i mmol)之CH2C12 (10 ml)攪拌溶液中,添加ln觸媒(3·4 mg,丄 mol%)之CH'hC2 ml)溶液。接著在室溫下將所得之混合物 攪拌30分鐘。壓移除溶冑,並藉切膠管柱層析法(環己 WEKMc 8: 2)對殘留物進行純化。生成無色油狀産物p4 ’其爲⑻與⑻異構體以95 : 5之比率混合之混合物⑽ mg,產率 95%)。 88125 -28 - !310768 根據 Angew. Chemie 2002, 1 14, 2509-25 U 中之資料’式C 觸媒於類似反應中以9 1 %的産率産生P4。 實例10 比較1 .II觸媒與A觸媒在交叉複分解反應中之功效。 COOEt + 一 COOEt 2 i^CN a)或 b> EtOOC. , /\ CN EtOOC S5 S5a P5 (iE): {2) = 1 ; 2 條件:a)l .II觸媒(5 Mol%)、室溫、30分鐘、産率87%。 b)A觸媒(8 Mol%)、室溫、6小時、産率79°/〇。 於烯丙基丙二酸二乙酯S5 (1〇〇 mg,〇.5 mmol)與S5a(53 mg,1 mmol)之CH2C12 (5 ml)攪拌溶液中,添加ι·π觸媒(16.8 mg,5 mol%)之CHf〗2 (5 m丨)溶液。在室溫下將所得之溶液 攪拌30分鐘。減壓移除溶劑,並藉由藉由矽膠管柱層析法( 環己烧/Et〇Ac 8: 2)對殘留物進行純化。生成無色油狀産物 p5’其爲(E)與(Z)異構體以1:2之比率混合之混合物(98呵, 産率87%)。 ’ 根據咖扣2〇01,430·431,A觸媒於類似反應中以79% 的產率産生P5。 【圖式簡單說明】 習知之釕觸媒 之環化速度對 圖1係§使用根據本發明之釕觸媒與使用 時’丙二酸2-稀丙基_2_(2_甲基烯丙基)二乙雖 比圖。 88125 -29·
Claims (1)
- 28427號專利申請案 專利範圍替換本(97年12月) y,V 申請專利範圍 1 一種式1之化合物其中, L1爲中性配位體; X/V爲陰離子配位體; Rl係-Cw-烷基; %係Η、-CW烷基、-CW稀基、〇2 2。_快基或芳基; r係m、-Cl_6_院氧基或芳基,其中芳基視情況 可經-Cn烧基或_c,·6-烧氧基取代; η 爲 〇、1、2 或 3。 2. 如申請專利範圍第!項之化合物,係式1&之化合物: L1 〇2其中,L1、 X、 X1、 R1、R2、R3 尺及11如申請專利範圍 第1項之定義。 3.如申請專利範圍第1或2項之化合物,其中 L1 係 P(R")3 ; R"爲-cN6-烷基、_c3-8-環烷基或芳基; 或L1係式6a、6b、6c或6d之配位體: 88125-971205.doc 1310768 R9 R10 7 w 8 B—N…N—R6b 6a Y ν' W R~NVN-Re 6c6d R7與R8各獨立爲H、-Cw烧基、_C22〇_烯基或苯基, 其中苯基視情況可經獨立選自-C^6-烷基、_Ci 6_院氧基或 鹵素的多至三個基團所取代; R9與各獨立爲H、-C卜20-烷基、_C22〇_烯基或苯基, 其中苯基視情況可經獨立選自-c^烷基、_Ci 6_烷氧基或 鹵素的多至三個基團所取代;或 員 R9與Ri«與彼等所附著之碳原子—起組合以形成一 3至8 碳環;Y及Y'爲鹵素。 如申請專利範圍第3項之化合物,其十 R7與R8各獨立爲Η、-Cw烷基、 中苯基視情況可經獨立選自-CK6-院基 素之多至三個基團所取代; _C2_6·烯基或苯基 其 -Cl·6·燒氧基或鹵 中 素 R9與f各獨立爲h、_Ci.6{基、〜.烯基或苯基,A 苯基視情況可經獨立選自Awn道氧基或_ 之多至三個基團所取代;或 員 R9與R〗G與彼等所附著之碳原子_ 碳環。 起組合以形成一5至7 5.如申請專利範圍第〗或2項之化合物,其中 R2係Η、-Cw-烷基或芳基; X及X各爲齒素。 88125-971205.doc -2 - 1310768 如申請專利範圍第1或2項之化合物,其中 L1係PCy3或式6a、6b、6c或6d之配位體; Cy係環己基; X及X’各爲氯。 如申請專利範圍第3項之化合物,其中 L1係式6a、6b、6c或6d之配位體;且 R7與R8係2-甲基苯基、2,6-二曱基苯基或2,4,6-三甲基 笨基。 如申請專利範圍第1或2項之化合物,其中 η爲〇。 如申請專利範圍第1或2項之化合物,其中 …爲卞1·; R2爲 Η。 使式2或2a之化合物 種製備如申請專利範圍第1或2項之化合物之方法,其中烷基或-C]-6_烷氧基取代; R4係-Cuo-烧基; m係0 ' 1或2 ;及 其中, 係-Cm-烷基; R2係Η、-C丨·2〇-烷基 R3係-Cw烷基、 -C2-2〇-炔基或芳基; 基,其中芳基可經 88125-971205.doc 1310768 η係 〇、1、2或 3, 與通式5之釕複合物反應, χ, Τ Rs X a R6 5 其中, L1及L2爲中性配位體; -C2.2〇-炔基或芳基· R 爲 Η、-Cwo-烷基、-C2_2()_烯基 R爲芳基、乙稀基或丙二烯基; x/x'爲陰離子配位體。 11. 12. 如申請專利範圍第1G項之方法,係在銅鹽存在下進行 一種製備式2或2a之化合物的方法,其中, Rl係-Cy烷基; ^係H、_Cl-2〇-烷基、42.20_烯基、_c2_2Q_炔基或芳基; R係-C^-烷基、_Cl,6_烷氧基或芳基,其中芳基可經 Cl-6_院基或-Ci_6_烷氧基取代; R係-C 1 .2Q-烧基; m係〇、1或2 ;及 n係〇、1、2或 3, 其包含以下步驟: a)藉由式Riz(9)之試劑來烷化通式3化合物, 88125-971205.doc 1310768 R2以生成式4中間體: R2;及 b)使式4之該中間體與式10之烯烴化試劑進行反應10 以生成通式2化合物,W爲適合於烯烴化反應之離去基團; Z爲鹵素、-Cw-烷基-s(0)2-、-Cj.6-氟烷基-s(0)2-、芳 基-S(0)2-或芳基-s(0)3-。 13. 14. 一種複分解反應之方法,包含使具有一 C = c雙鍵之兩種化 合物或具有至少兩個c=c雙鍵的一種化合物與一觸媒接 觸,其中該觸媒包括如申請專利範圍第1或2項之化合物。 一種執行閉環複分解或交叉複分解反應之方法,該方法包 括使二烯基化合物與如申請專利範圍第1或2項之化合物 接觸。 88125-971205.doc -5-
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