CA2534324C - Ruthenium metathesis catalysts - Google Patents
Ruthenium metathesis catalysts Download PDFInfo
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- CA2534324C CA2534324C CA2534324A CA2534324A CA2534324C CA 2534324 C CA2534324 C CA 2534324C CA 2534324 A CA2534324 A CA 2534324A CA 2534324 A CA2534324 A CA 2534324A CA 2534324 C CA2534324 C CA 2534324C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000005649 metathesis reaction Methods 0.000 title claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title description 2
- 229910052707 ruthenium Inorganic materials 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims description 40
- -1 C7-18-aralkyl Chemical group 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 claims description 14
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 5
- 238000005686 cross metathesis reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003303 ruthenium Chemical class 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005980 hexynyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- HVLDZXPAKHKEPX-UHFFFAOYSA-N methyl 2-(2-phenyl-6-prop-1-enylphenoxy)propanoate Chemical compound COC(=O)C(C)OC1=C(C=CC=C1C1=CC=CC=C1)C=CC HVLDZXPAKHKEPX-UHFFFAOYSA-N 0.000 description 2
- CQHVKIKUMGANHB-UHFFFAOYSA-N methyl 2-(2-prop-1-enylphenoxy)propanoate Chemical compound COC(=O)C(C)OC1=CC=CC=C1C=CC CQHVKIKUMGANHB-UHFFFAOYSA-N 0.000 description 2
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000005981 pentynyl group Chemical group 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- YICXPBLPCKUFMS-UHFFFAOYSA-N 1-phenyl-2-prop-2-enoxybenzene Chemical group C=CCOC1=CC=CC=C1C1=CC=CC=C1 YICXPBLPCKUFMS-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- QEDJRVOBBIJGRL-UHFFFAOYSA-N 2-phenyl-6-prop-1-enylphenol Chemical group CC=CC1=CC=CC(C=2C=CC=CC=2)=C1O QEDJRVOBBIJGRL-UHFFFAOYSA-N 0.000 description 1
- WHGXZPQWZJUGEP-UHFFFAOYSA-N 2-prop-1-enylphenol Chemical compound CC=CC1=CC=CC=C1O WHGXZPQWZJUGEP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- SNOPMSXDMMRDGF-UHFFFAOYSA-N diethyl 3-methylcyclopent-3-ene-1,1-dicarboxylate Chemical compound CCOC(=O)C1(C(=O)OCC)CC=C(C)C1 SNOPMSXDMMRDGF-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-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
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- GRAKJTASWCEOQI-UHFFFAOYSA-N tridodecylphosphane Chemical compound CCCCCCCCCCCCP(CCCCCCCCCCCC)CCCCCCCCCCCC GRAKJTASWCEOQI-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- VFXLYMQGYAHEHB-UHFFFAOYSA-N tris(2-methylcyclohexyl)phosphane Chemical compound CC1CCCCC1P(C1C(CCCC1)C)C1C(C)CCCC1 VFXLYMQGYAHEHB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to new compounds of formula 1, the preparation thereof, intermediate products for preparing them and the use of the compounds of formula 1 as catalysts in various metathesis reactions (see formula 1) The new metathesis catalysts, which are obtained from readily accessible preliminary products, have a high activity and can be used for all kinds of metathesis reactions.
Description
RUTHENIUM METATHESIS CATALYSTS
The present invention relates to new compounds of formula 1, the preparation thereof, intermediate products for preparing them and the use of the compounds of formula 1 as catalysts in various metathesis reactions X'Ru_ a Z
R O / b I-R10d c BACKGROUND TO THE INVENTION
Ruthenium complexes of formula A are known from WO 02/14376 A2 and are described as active, air-stable and recoverable metathesis catalysts. Catalysts of this kind which have an even greater activity than A have also become known (Angew. Chem. 2002, 114, No. 5, 832-834; Angew. Chem. 2002, 114, No. 13, 2509-2511; Angew. Chem. 2002, 114, No.
21, 4210-4212), and are described by the formulae B, C and D.
Mes-N. N-Mes Mes-N~ N-Mes /-\ CI.,,, , Mes-NON-Mes CIO': - CI'''=Ru_ CIS Mes-NvN-Mes CL,,, Ru_ Pro \ / -CI~ Pro _ ~Pr \ / CI.,,.
CI~Ru_ -iPrO ~ / NOZ
A B C D
The improvement in the activity of B, C and D compared with A is due to steric and electronic effects of the substituents at the phenyl nucleus of the isopropoxy-phenylmethylene ligand. It has now been found, surprisingly, that a major increase in the activity of metathesis catalysts of type A can be achieved by making particular changes to the aliphatic moiety of the ether group.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to new ruthenium complexes of formula 1 and their use as metathesis catalysts, R a XI
Rz O u_ b d c wherein X and X denote anionic ligands; preferably halogen, particularly preferably Cl or Br;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C1_12-alkyl, C1-12-alkoxy or phenyl, while phenyl may optionally be substituted by a group selected from among C1_6-alkyl and C1_6-alkoxy;
R' denotes C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R2 denotes H, C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R3 denotes H, C1_12-alkyl, C2_12-alkenyl, C2_12-alkynyl, aryl.
Preferred compounds are the compounds of formula 1, wherein X and X' denote halogen;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C 1.6-alkyl, C 1.6-alkoxy or phenyl, while phenyl may optionally be substituted by a group selected from among C 1-4-alkyl and C 1 4-alkoxy;
R denotes C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
RZ denotes H, C1.6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R3 denotes H, C1_6-alkyl, C2_6-alkenyl, C2_6-alkynyl, aryl;
particularly preferred compounds being the compounds of formula 1 wherein X and X' denotes Cl or Br;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, methyl, ethyl, iso-propyl, methoxy, or phenyl, while phenyl may optionally be substituted by a group selected from among methyl and methoxy;
R' denotes methyl, ethyl , n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-heptyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, o-, m-, p-tolyl and 3,5-dimethylphenyl.
R2 denotes H, methyl, ethyl , n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-heptyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, o-, m-, p-tolyl and 3,5-dimethylphenyl.
R3 denotes H, methyl, ethyl, phenyl .
Particularly preferred compounds among the above-mentioned compounds of general formula 1 are those wherein R', R2, R3, X, X' and L may have the meanings specified and a, b, c denote H; and d denotes phenyl which may be substituted by a group selected from among C 1.6-alkyl and C 1.6-alkoxy;
or a, c, d denote H; and b denotes -NO2.
particularly preferred among the above-mentioned compounds of general formula 1 are those wherein R', R2, R3, X, X', a, b, c and d may have the meanings specified and L denotes P(R4)3 or a ligand of formula L1, L2, L3 or L4, wherein R7 R8 . R7 R8 Y Y' R8 RS NN-R8 R5 NON-R8 RS NON-R8 RS N ,N-R8 L' L2 L3 L4 R4 denotes C1-6-alkyl, cycloalkyl or aryl R5 and R6 independently of one another denote H, C1.6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1.6-alkyl, C2_6-alkenyl or aryl;
or R7 and R8 together form a 3- or 4-membered alkylene bridge; and Y and Y' denote halogen; preferably Cl or Br.
Most preferred are compounds of general formula 1, wherein X and X denote Cl;
L denotes L';
a, b, c, d -denote H;
The present invention relates to new compounds of formula 1, the preparation thereof, intermediate products for preparing them and the use of the compounds of formula 1 as catalysts in various metathesis reactions X'Ru_ a Z
R O / b I-R10d c BACKGROUND TO THE INVENTION
Ruthenium complexes of formula A are known from WO 02/14376 A2 and are described as active, air-stable and recoverable metathesis catalysts. Catalysts of this kind which have an even greater activity than A have also become known (Angew. Chem. 2002, 114, No. 5, 832-834; Angew. Chem. 2002, 114, No. 13, 2509-2511; Angew. Chem. 2002, 114, No.
21, 4210-4212), and are described by the formulae B, C and D.
Mes-N. N-Mes Mes-N~ N-Mes /-\ CI.,,, , Mes-NON-Mes CIO': - CI'''=Ru_ CIS Mes-NvN-Mes CL,,, Ru_ Pro \ / -CI~ Pro _ ~Pr \ / CI.,,.
CI~Ru_ -iPrO ~ / NOZ
A B C D
The improvement in the activity of B, C and D compared with A is due to steric and electronic effects of the substituents at the phenyl nucleus of the isopropoxy-phenylmethylene ligand. It has now been found, surprisingly, that a major increase in the activity of metathesis catalysts of type A can be achieved by making particular changes to the aliphatic moiety of the ether group.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to new ruthenium complexes of formula 1 and their use as metathesis catalysts, R a XI
Rz O u_ b d c wherein X and X denote anionic ligands; preferably halogen, particularly preferably Cl or Br;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C1_12-alkyl, C1-12-alkoxy or phenyl, while phenyl may optionally be substituted by a group selected from among C1_6-alkyl and C1_6-alkoxy;
R' denotes C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R2 denotes H, C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R3 denotes H, C1_12-alkyl, C2_12-alkenyl, C2_12-alkynyl, aryl.
Preferred compounds are the compounds of formula 1, wherein X and X' denote halogen;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C 1.6-alkyl, C 1.6-alkoxy or phenyl, while phenyl may optionally be substituted by a group selected from among C 1-4-alkyl and C 1 4-alkoxy;
R denotes C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
RZ denotes H, C1.6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R3 denotes H, C1_6-alkyl, C2_6-alkenyl, C2_6-alkynyl, aryl;
particularly preferred compounds being the compounds of formula 1 wherein X and X' denotes Cl or Br;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, methyl, ethyl, iso-propyl, methoxy, or phenyl, while phenyl may optionally be substituted by a group selected from among methyl and methoxy;
R' denotes methyl, ethyl , n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-heptyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, o-, m-, p-tolyl and 3,5-dimethylphenyl.
R2 denotes H, methyl, ethyl , n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-heptyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl benzyl, 1-phenylethyl, 2-phenylethyl, phenyl, o-, m-, p-tolyl and 3,5-dimethylphenyl.
R3 denotes H, methyl, ethyl, phenyl .
Particularly preferred compounds among the above-mentioned compounds of general formula 1 are those wherein R', R2, R3, X, X' and L may have the meanings specified and a, b, c denote H; and d denotes phenyl which may be substituted by a group selected from among C 1.6-alkyl and C 1.6-alkoxy;
or a, c, d denote H; and b denotes -NO2.
particularly preferred among the above-mentioned compounds of general formula 1 are those wherein R', R2, R3, X, X', a, b, c and d may have the meanings specified and L denotes P(R4)3 or a ligand of formula L1, L2, L3 or L4, wherein R7 R8 . R7 R8 Y Y' R8 RS NN-R8 R5 NON-R8 RS NON-R8 RS N ,N-R8 L' L2 L3 L4 R4 denotes C1-6-alkyl, cycloalkyl or aryl R5 and R6 independently of one another denote H, C1.6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1.6-alkyl, C2_6-alkenyl or aryl;
or R7 and R8 together form a 3- or 4-membered alkylene bridge; and Y and Y' denote halogen; preferably Cl or Br.
Most preferred are compounds of general formula 1, wherein X and X denote Cl;
L denotes L';
a, b, c, d -denote H;
R' denotes methyl;
R2 denotes methyl;
R3 denotes H;
R5 and R6 denote mesityl;
R7 and R8 denote H.
The new compounds of formula 1 are obtained by reacting preligands of formula 2 with ruthenium complexes of formula 3 R11R12C- a R2 0 b R9 Ru4 10 R,O O d c X R
where R3, a, b, c and d have the meanings given for formula 1 and R1 denotes Ci_12-alkyl, C5-6-cycloalkyl, C7_18-aralkyl, aryl; preferably C1.6-alkyl, C5-6-cycloalkyl, C7_11-aralkyl, aryl;
R2 denotes H, C1-12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl; preferably C1_6-alkyl, C5_6-cycloalkyl, C7.1t-aralkyl, aryl;
R" and R12 independently of one another denote H, C1_6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C 1.6-alkyl; preferably H, C 1.6-alkyl or aryl; in particular and L denotes a neutral ligand; preferably L', L2, L3 or L4;
R9 and R10 independently of one another denote H, C1-6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C1_6-alkyl; preferably H, C1.6-alkyl or aryl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Therefore in another aspect the invention relates to a compound of formula 2, R11R12C- a R2 O b II dc wherein R3, a, b, c and d have the meanings given in claim 1; and R1 denotes C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R2 denotes H, C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R" and R12 independently of one another denote H, C1.6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C1_6-alkyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Preferred compounds are the compounds of formula 2, wherein R1 denotes C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R2 denotes H, C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R11 and R12 independently of one another denote H, C14-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or methyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Particularly preferred are the compounds of formula 2 wherein R1 denotes methyl, cyclohexyl, benzyl, phenyl;
R2 denotes H, methyl, cyclohexyl, benzyl, phenyl;
R11 denotes H;
R12 denotes H or methyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
The ligands and complexes shown may occur as pure enantiomers or pairs of enantiomers.
Within the scope of the invention therefore the pure enantiomers to certain racemates may also be present, which may transfer the enantiomerism to a substrate through the stereocentre during the catalysis.
In an additional aspect the invention relates to a process for carrying out metathesis reactions, in which two compounds are reacted each of which contains an olefinic double bond or wherein one of the compounds contains at least two olefinic double bonds and wherein one of the above-mentioned compounds of formula 1 is used as catalyst, or a process for carrying out ring-closing metathesis (RCM) or cross metathesis (CM) which involves a compound which contains two olefinic double bonds as substrate and one of the compounds of formula 1 as catalyst.
TERMS AND DEFINITIONS USED
By "anionic ligands" (X or X') are meant, within the scope of the invention, negatively charged molecules or atoms with electron donor properties. Examples which may be mentioned here include halogens, such as fluorine, chlorine, bromine or iodine.
By "neutral ligands" (L) are meant, within the scope of the invention, uncharged or charge-neutral molecules or atoms with electron donor properties. Examples which may be mentioned here include tertiary phosphines which contain aliphatic, cycloaliphatic and aromatic hydrocarbon groups, such as trioctylphosphine, tridodecylphosphine, tricyclohexylphosphine, tris-(2-methylcyclohexyl)phosphine and tris-(o-tolyl) phosphine.
Examples of particularly preferred neutral ligands include NHC ligands such as e.g. the compounds described by formulae L', L2, L3 and L4:
R7 R8 R7 R8 Y Y' R8 H RS NON-RB R5 NON-RB R5 NON-RB RS N jjN-RB
L' L2 L3 L4 wherein R5 and R6 independently of one another denote H, C1.6-alkyl or aryl, R7 and R8 independently of one another denote H, C1_6-alkyl, C1_6-alkenyl or aryl or together form a 3 or 4-membered alkylene bridge and Y and Y' denote halogen.
By the term "C1_12-alkyl" (including those which are part of other groups) are meant branched and unbranched alkyl groups with 1 to 12 carbon atoms, and accordingly by the term "C1_6-alkyl" are meant branched and unbranched alkyl groups with I to 6 carbon atoms and by the term "C 1.4-alkyl" are meant branched and unbranched alkyl groups with I
to 4 carbon atoms. Alkyl groups with 1 to 6 carbon atoms are preferred while those with 1 to 4 carbon atoms are particularly preferred. Examples include: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or hexyl. In some cases the abbreviations Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, etc. may be used for the above-mentioned groups. Unless stated otherwise, the definitions propyl, butyl, pentyl and hexyl include all the possible isomeric forms of the groups in question. Thus, for example, propyl includes n-propyl and iso-propyl, butyl includes iso-butyl, sec-butyl and tert-butyl, etc.
By the term "C2_12-alkenyl" (including those which are part of other groups) are meant branched and unbranched alkenyl groups with 2 to 12 carbon atoms, provided that they have at least one double bond. Accordingly, the term "C2-6-alkenyl" denotes alkenyl groups with 2 to 6 carbon atoms and the term "C24-alkenyl" denotes branched and unbranched alkenyl groups with 2 to 4 carbon atoms. Alkenyl groups with 2 to 6 carbon atoms are preferred, those with 2 to 4 carbon atoms are particularly preferred. Examples include: ethenyl or vinyl, propenyl, butenyl, pentenyl, or hexenyl. Unless otherwise specified, the definitions propenyl, butenyl, pentenyl and hexenyl include all possible isomeric forms of the groups in question.
Thus for example propenyl includes 1-propenyl and 2-propenyl, butenyl includes 1, 2- and 3-butenyl, 1-methyl- l -propenyl, 1-methyl-2-propenyl etc.
By the term "C2_12-alkynyl" (including those which are part of other groups) are meant branched and unbranched alkynyl groups with 2 to 12 carbon atoms, provided that they have at least one triple bond. Accordingly, the term "C2.6-alkynyl" refers to alkynyl groups with 2 to 6 carbon atoms and the term "C2.4-alkynyl" refers to branched and unbranched alkynyl groups with 2 to 4 carbon atoms. Alkynyl groups with 2 to 6 carbon atoms are preferred, those with 2 to 4 carbon atoms are particularly preferred. The following are mentioned by way of example: ethynyl, propynyl, butynyl, pentynyl, or hexynyl. Unless otherwise specified, the definitions propynyl, butynyl, pentynyl and hexynyl include all possible isomeric forms of the groups in question. Thus for example propynyl includes 1-propynyl and 2-propynyl, butynyl includes 1, 2- and 3-butynyl, 1-methyl-l-propynyl, 1-methyl-2-propynyl, etc.
By the term "C1_12-alkoxy" (including those which are part of other groups) are meant branched and unbranched alkoxy groups with 1 to 12 carbon atoms, and similarly the term "C1_6-alkoxy" denotes branched and unbranched alkoxy groups with 1 to 6 carbon atoms and the term "C1_4-alkoxy" denotes branched and unbranched alkoxy groups with 1 to 4 carbon atoms. Alkoxy groups with I to 6 carbon atoms are preferred, those with I to 4 carbon atoms are particularly preferred. The following are mentioned by way of example:
methoxy, ethoxy, propoxy, butoxy or pentoxy. The abbreviations MeO, EtO, PrO, etc. may also be used in some cases for the above-mentioned groups. Unless otherwise specified, the definitions propoxy, butoxy and pentoxy include all possible isomeric forms of the groups in question.
Thus for example propoxy includes n-propoxy and iso-propoxy, butoxy includes iso-butoxy, sec-butoxy and tert-butoxy etc.
By the term "CS_6-cycloalkyl" (including those which are part of other groups) are meant cyclic alkyl groups with 5 or 6 carbon atoms. The following are mentioned by way of example: cyclopentyl or cyclohexyl. Unless otherwise specified, the cyclic alkyl groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
By the term "aryl" (including those which are part of other groups) are meant aromatic ring systems with 6 or 10 carbon atoms. The following are mentioned by way of example: phenyl or naphthyl, the preferred aryl group being phenyl. Unless otherwise specified, the aromatic groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
By the term " C7_lg-aralkyl" (including those which are part of other groups) are meant branched and unbranched alkyl groups with 1 to 8 carbon atoms which are substituted by an aromatic ring system with 6 or 10 carbon atoms, and similarly the term "C7_1 I-aralkyl" denotes branched and unbranched alkyl groups with 1 to 4 carbon atoms which are substituted by an aromatic ring system with 6 carbon atoms. The following are mentioned by way of example:
benzyl, 1- or 2-phenylethyl. Unless otherwise specified, the aromatic groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
PREPARATION OF THE COMPOUNDS
The reaction of the ruthenium complexes of formula 3 with the preligands of formula 2 is carried out in inert solvents, e.g. CH2C12 at approx. 0 to 80 C. It is advantageous to add CuCI to the reaction mixture. The reactants are generally used in equivalent amounts, but in order to increase the yield the more valuable component in each case may be used in a smaller amount. It may also be useful to produce the complex of formula 3 in situ from other ruthenium compounds and ligand pre-products, e.g. dihydroimidazolinium salts, in order to arrive at the new metathesis catalysts of formula 1 with the desired ligand combination in each case, via the resulting complexes of formula 3.
The metathesis catalysts of formula 1 prepared by ligand exchange reaction may be separated off from other reaction products which are insoluble in the reaction mixture, by filtration of the solution thereof and, after concentration of the solution, are obtained in pure form by chromatography or crystallisation. However, it is also possible to use the crude products or the catalysts produced in situ directly to carry out metathesis reactions.
The preligands of formula 2 may be prepared in a manner known per se from aromatic aldehydes which contain corresponding substituents, by reactions of olefination, e.g. by reaction with phosphorylidene according to Wittig.
Particularly preferred is a new combined process which starts from optionally correspondingly substituted phenylallylethers, and leads by Claisen rearrangement and catalytic double bond isomerisation to optionally correspondingly substituted 2-alkenyl-phenols which are subsequently reacted by alkylation with a-halocarboxylic acid esters to obtain compounds of formula 2.
The alkylation of phenols to form alkyl-phenylethers is well known in the art and is usually carried out in a solvent in the presence of basic substances by reaction with nucleophilic reagents. The reaction with a-halocarboxylic acid esters proceeds particularly smoothly and with good yields. Suitable solvents include, for example, alcohols such as ethanol or aprotic polar solvents such as dimethylformamide. The alkylation may also be carried out under phase transfer conditions. Examples of basic substances include alkali metal carbonates, and similarly the alkali metal salts of the intermediate products which contain a free aromatically bound OH group may be used for this reaction.
In order to illustrate the sequence of synthesis which is preferably used to prepare compounds of formula 2, the preparation of (3-propenyl-biphen-2-yl) (1-methoxycarbonyl-ethyl)ether will now be described as a specific example:
Starting from 2-hydroxybiphenyl, 2-allyloxy-biphenyl is obtained by alkylation with allyl chloride in DMF as solvent in the presence of potassium carbonate. By thermal rearrangement at 190 C in trichlorobenzene, 3-allyl-2-hydroxy-biphenyl is then obtained, which is catalytically rearranged (RhCl3 H2O) in ethanolic solution in the presence of p-toluenesulphonic acid to form an E/Z mixture of 3-propenyl-2-hydroxybiphenyl.
Alkylation of this intermediate product with methyl 2-bromopropionate yields the preligand (3-propenyl-biphen-2-yl)(I-methoxycarbonyl-ethyl)ether.
The compounds of formula 1 are highly active metathesis catalysts which may also be successfully used for carrying out difficult metathesis reactions, including all types of reactions of this kind (RCM, CM, ROMP etc.).
EXAMPLE I
Preparation of a metathesis catalyst of formula la.
1.1) Preparation of the new preligand of formula 2a:
A mixture of 500 mg (3.72 mmol) of 2-propenylphenol (E/Z mixture), prepared by Claisen rearrangement of phenylallylether followed by double bond isomerisation, 1.02 g of potassium carbonate (0.74 mmol) and 745 mg of rac. methyl 2-bromopropionate (4.46 mmol) and 10 ml of dimethylformamide was stirred overnight at RT and then for 4 hours at 80 C.
The reaction mixture was then added to 40 ml of water and extracted three times with 30 ml diethyl ether. The organic phase was washed with 5% sodium hydroxide solution, separated off, dried with Na2SO4 and concentrated by evaporation. 685 mg (83.6% of theory) of virtually pure methyl 2-(2-propenyl-phenyloxy)propionate were obtained.
a b -1O d c MeO 0 2a 1.2) Preparation of the metathesis catalyst of formula la.
424 mg (0.5 mmol) of Grubb's catalyst, 2nd generation, n Mes-N,N-Mes Cl 1,,. Ru_ CI.,, PCy3 and 59 mg CuCI (0.6 mmol) were placed in a Schlenk tube, and under argon a solution of 134 mg (0.6 mmol) of methyl 2-(2-propenyl-phenyloxy)propionate, dissolved in 10 ml CH2C12, was added. The mixture was stirred for 1 hour at 40 C, then evaporated down i.v, the residue was taken up in 20 ml of ethyl acetate and the cloudy solution obtained was filtered. The crude product obtained after evaporation of the solvent was purified by chromatography carried out twice (Merck silica gel type 9385, 1st eluent AcOEt / cyclohexane 3:7, 2nd eluent AcOEt / cyclohexane 1:1). 193 mg (58 % of theory) of pure product were obtained.
HRMS(El): C32H38N2O3C12Ru Calculated: [M+]670.13030, found: 670.13467 Mes-NvN-Mes CI,,,. Ru_ CIS ' O
MeO la Use of the catalyst of formula la prepared according to the invention and comparison of its activity with the known catalyst of formula A (see above).
2.1) Ring-closing metathesis (RCM) using 1a:
A solution of 2.7 mg (0.004 mmol) of the catalyst la obtained according to Example I
in 1 ml dichloromethane at 25 C was added to a solution of 100 mg (0.4 mmol) diethyl allyl-methallyl-malonate (substrate) in 20 ml of dichloromethane. The reaction mixture was kept at this temperature for 2 hours. After this time a sample was taken, the catalyst was destroyed by the addition of ethylvinylether and the sample was analysed by gas chromatography (comparison with substrate and ring-closing product prepared in known manner). The level of conversion of the substrate into the metathesis product (1,1-bis-ethoxycarbonyl-3-methyl-cyclopent-3-ene) was 89%.
2.2) RCM using the known catalyst of formula A:
The same substrate was reacted as described in Example 2.1, but using 2.5 mol%
of the known catalyst A. Investigation by gas chromatography showed that the level of conversion into the ring-closing product was 18%.
Use of the catalyst of formula la prepared according to the invention and comparison of its activity with the known catalyst of formula D (see above).
COzMe C%Me O O,NH
O O,NH
No la or D No OYNH OYNH O&
11 O b-S-&Br O O-S Br O O
4 is dissolved in 10 ml of degassed toluene and heated to 80 C, freshly prepared catalyst is added under nitrogen (1st) and the resulting mixture is stirred for 60 min at 80 C. The reaction is tested by HPLC and a further amount of the catalyst is added (2"d). After another 60 min the reaction is tested once more by HPLC.
Figure 1 shows the cyclisation rate of 4 (T = 0 min:0.4 mol%; T = 60 min:0.2 mol%). Table 1 shows the results of an HPLC analysis in which the results are compared with the known catalyst of formula D (Angew. Chem. Int. Ed. 2002, 41, 4038).
Table I
reaction [%peak at 200 nm]
Catalyst 1 t [mol%] 4 [mol] toluene [ml] 5 [60 min] 4 [60 min]
2d [mol%] 5 [120 min] 4 [120 min]
la 0.4 0.0075 554 82.8 0.2 94.6 D 0.4 0.015 1008 77.4 22.6 0.2 92.8 7.2
R2 denotes methyl;
R3 denotes H;
R5 and R6 denote mesityl;
R7 and R8 denote H.
The new compounds of formula 1 are obtained by reacting preligands of formula 2 with ruthenium complexes of formula 3 R11R12C- a R2 0 b R9 Ru4 10 R,O O d c X R
where R3, a, b, c and d have the meanings given for formula 1 and R1 denotes Ci_12-alkyl, C5-6-cycloalkyl, C7_18-aralkyl, aryl; preferably C1.6-alkyl, C5-6-cycloalkyl, C7_11-aralkyl, aryl;
R2 denotes H, C1-12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl; preferably C1_6-alkyl, C5_6-cycloalkyl, C7.1t-aralkyl, aryl;
R" and R12 independently of one another denote H, C1_6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C 1.6-alkyl; preferably H, C 1.6-alkyl or aryl; in particular and L denotes a neutral ligand; preferably L', L2, L3 or L4;
R9 and R10 independently of one another denote H, C1-6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C1_6-alkyl; preferably H, C1.6-alkyl or aryl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Therefore in another aspect the invention relates to a compound of formula 2, R11R12C- a R2 O b II dc wherein R3, a, b, c and d have the meanings given in claim 1; and R1 denotes C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R2 denotes H, C1_12-alkyl, C5_6-cycloalkyl, C7_18-aralkyl, aryl;
R" and R12 independently of one another denote H, C1.6-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or C1_6-alkyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Preferred compounds are the compounds of formula 2, wherein R1 denotes C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R2 denotes H, C1_6-alkyl, C5_6-cycloalkyl, C7_11-aralkyl, aryl;
R11 and R12 independently of one another denote H, C14-alkyl, optionally substituted by one or more halogens, or aryl, optionally substituted by one or more halogens or methyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
Particularly preferred are the compounds of formula 2 wherein R1 denotes methyl, cyclohexyl, benzyl, phenyl;
R2 denotes H, methyl, cyclohexyl, benzyl, phenyl;
R11 denotes H;
R12 denotes H or methyl;
with the proviso that R1 and R2 cannot simultaneously represent methyl.
The ligands and complexes shown may occur as pure enantiomers or pairs of enantiomers.
Within the scope of the invention therefore the pure enantiomers to certain racemates may also be present, which may transfer the enantiomerism to a substrate through the stereocentre during the catalysis.
In an additional aspect the invention relates to a process for carrying out metathesis reactions, in which two compounds are reacted each of which contains an olefinic double bond or wherein one of the compounds contains at least two olefinic double bonds and wherein one of the above-mentioned compounds of formula 1 is used as catalyst, or a process for carrying out ring-closing metathesis (RCM) or cross metathesis (CM) which involves a compound which contains two olefinic double bonds as substrate and one of the compounds of formula 1 as catalyst.
TERMS AND DEFINITIONS USED
By "anionic ligands" (X or X') are meant, within the scope of the invention, negatively charged molecules or atoms with electron donor properties. Examples which may be mentioned here include halogens, such as fluorine, chlorine, bromine or iodine.
By "neutral ligands" (L) are meant, within the scope of the invention, uncharged or charge-neutral molecules or atoms with electron donor properties. Examples which may be mentioned here include tertiary phosphines which contain aliphatic, cycloaliphatic and aromatic hydrocarbon groups, such as trioctylphosphine, tridodecylphosphine, tricyclohexylphosphine, tris-(2-methylcyclohexyl)phosphine and tris-(o-tolyl) phosphine.
Examples of particularly preferred neutral ligands include NHC ligands such as e.g. the compounds described by formulae L', L2, L3 and L4:
R7 R8 R7 R8 Y Y' R8 H RS NON-RB R5 NON-RB R5 NON-RB RS N jjN-RB
L' L2 L3 L4 wherein R5 and R6 independently of one another denote H, C1.6-alkyl or aryl, R7 and R8 independently of one another denote H, C1_6-alkyl, C1_6-alkenyl or aryl or together form a 3 or 4-membered alkylene bridge and Y and Y' denote halogen.
By the term "C1_12-alkyl" (including those which are part of other groups) are meant branched and unbranched alkyl groups with 1 to 12 carbon atoms, and accordingly by the term "C1_6-alkyl" are meant branched and unbranched alkyl groups with I to 6 carbon atoms and by the term "C 1.4-alkyl" are meant branched and unbranched alkyl groups with I
to 4 carbon atoms. Alkyl groups with 1 to 6 carbon atoms are preferred while those with 1 to 4 carbon atoms are particularly preferred. Examples include: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or hexyl. In some cases the abbreviations Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, etc. may be used for the above-mentioned groups. Unless stated otherwise, the definitions propyl, butyl, pentyl and hexyl include all the possible isomeric forms of the groups in question. Thus, for example, propyl includes n-propyl and iso-propyl, butyl includes iso-butyl, sec-butyl and tert-butyl, etc.
By the term "C2_12-alkenyl" (including those which are part of other groups) are meant branched and unbranched alkenyl groups with 2 to 12 carbon atoms, provided that they have at least one double bond. Accordingly, the term "C2-6-alkenyl" denotes alkenyl groups with 2 to 6 carbon atoms and the term "C24-alkenyl" denotes branched and unbranched alkenyl groups with 2 to 4 carbon atoms. Alkenyl groups with 2 to 6 carbon atoms are preferred, those with 2 to 4 carbon atoms are particularly preferred. Examples include: ethenyl or vinyl, propenyl, butenyl, pentenyl, or hexenyl. Unless otherwise specified, the definitions propenyl, butenyl, pentenyl and hexenyl include all possible isomeric forms of the groups in question.
Thus for example propenyl includes 1-propenyl and 2-propenyl, butenyl includes 1, 2- and 3-butenyl, 1-methyl- l -propenyl, 1-methyl-2-propenyl etc.
By the term "C2_12-alkynyl" (including those which are part of other groups) are meant branched and unbranched alkynyl groups with 2 to 12 carbon atoms, provided that they have at least one triple bond. Accordingly, the term "C2.6-alkynyl" refers to alkynyl groups with 2 to 6 carbon atoms and the term "C2.4-alkynyl" refers to branched and unbranched alkynyl groups with 2 to 4 carbon atoms. Alkynyl groups with 2 to 6 carbon atoms are preferred, those with 2 to 4 carbon atoms are particularly preferred. The following are mentioned by way of example: ethynyl, propynyl, butynyl, pentynyl, or hexynyl. Unless otherwise specified, the definitions propynyl, butynyl, pentynyl and hexynyl include all possible isomeric forms of the groups in question. Thus for example propynyl includes 1-propynyl and 2-propynyl, butynyl includes 1, 2- and 3-butynyl, 1-methyl-l-propynyl, 1-methyl-2-propynyl, etc.
By the term "C1_12-alkoxy" (including those which are part of other groups) are meant branched and unbranched alkoxy groups with 1 to 12 carbon atoms, and similarly the term "C1_6-alkoxy" denotes branched and unbranched alkoxy groups with 1 to 6 carbon atoms and the term "C1_4-alkoxy" denotes branched and unbranched alkoxy groups with 1 to 4 carbon atoms. Alkoxy groups with I to 6 carbon atoms are preferred, those with I to 4 carbon atoms are particularly preferred. The following are mentioned by way of example:
methoxy, ethoxy, propoxy, butoxy or pentoxy. The abbreviations MeO, EtO, PrO, etc. may also be used in some cases for the above-mentioned groups. Unless otherwise specified, the definitions propoxy, butoxy and pentoxy include all possible isomeric forms of the groups in question.
Thus for example propoxy includes n-propoxy and iso-propoxy, butoxy includes iso-butoxy, sec-butoxy and tert-butoxy etc.
By the term "CS_6-cycloalkyl" (including those which are part of other groups) are meant cyclic alkyl groups with 5 or 6 carbon atoms. The following are mentioned by way of example: cyclopentyl or cyclohexyl. Unless otherwise specified, the cyclic alkyl groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
By the term "aryl" (including those which are part of other groups) are meant aromatic ring systems with 6 or 10 carbon atoms. The following are mentioned by way of example: phenyl or naphthyl, the preferred aryl group being phenyl. Unless otherwise specified, the aromatic groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
By the term " C7_lg-aralkyl" (including those which are part of other groups) are meant branched and unbranched alkyl groups with 1 to 8 carbon atoms which are substituted by an aromatic ring system with 6 or 10 carbon atoms, and similarly the term "C7_1 I-aralkyl" denotes branched and unbranched alkyl groups with 1 to 4 carbon atoms which are substituted by an aromatic ring system with 6 carbon atoms. The following are mentioned by way of example:
benzyl, 1- or 2-phenylethyl. Unless otherwise specified, the aromatic groups may be substituted by one or more groups selected from among methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
PREPARATION OF THE COMPOUNDS
The reaction of the ruthenium complexes of formula 3 with the preligands of formula 2 is carried out in inert solvents, e.g. CH2C12 at approx. 0 to 80 C. It is advantageous to add CuCI to the reaction mixture. The reactants are generally used in equivalent amounts, but in order to increase the yield the more valuable component in each case may be used in a smaller amount. It may also be useful to produce the complex of formula 3 in situ from other ruthenium compounds and ligand pre-products, e.g. dihydroimidazolinium salts, in order to arrive at the new metathesis catalysts of formula 1 with the desired ligand combination in each case, via the resulting complexes of formula 3.
The metathesis catalysts of formula 1 prepared by ligand exchange reaction may be separated off from other reaction products which are insoluble in the reaction mixture, by filtration of the solution thereof and, after concentration of the solution, are obtained in pure form by chromatography or crystallisation. However, it is also possible to use the crude products or the catalysts produced in situ directly to carry out metathesis reactions.
The preligands of formula 2 may be prepared in a manner known per se from aromatic aldehydes which contain corresponding substituents, by reactions of olefination, e.g. by reaction with phosphorylidene according to Wittig.
Particularly preferred is a new combined process which starts from optionally correspondingly substituted phenylallylethers, and leads by Claisen rearrangement and catalytic double bond isomerisation to optionally correspondingly substituted 2-alkenyl-phenols which are subsequently reacted by alkylation with a-halocarboxylic acid esters to obtain compounds of formula 2.
The alkylation of phenols to form alkyl-phenylethers is well known in the art and is usually carried out in a solvent in the presence of basic substances by reaction with nucleophilic reagents. The reaction with a-halocarboxylic acid esters proceeds particularly smoothly and with good yields. Suitable solvents include, for example, alcohols such as ethanol or aprotic polar solvents such as dimethylformamide. The alkylation may also be carried out under phase transfer conditions. Examples of basic substances include alkali metal carbonates, and similarly the alkali metal salts of the intermediate products which contain a free aromatically bound OH group may be used for this reaction.
In order to illustrate the sequence of synthesis which is preferably used to prepare compounds of formula 2, the preparation of (3-propenyl-biphen-2-yl) (1-methoxycarbonyl-ethyl)ether will now be described as a specific example:
Starting from 2-hydroxybiphenyl, 2-allyloxy-biphenyl is obtained by alkylation with allyl chloride in DMF as solvent in the presence of potassium carbonate. By thermal rearrangement at 190 C in trichlorobenzene, 3-allyl-2-hydroxy-biphenyl is then obtained, which is catalytically rearranged (RhCl3 H2O) in ethanolic solution in the presence of p-toluenesulphonic acid to form an E/Z mixture of 3-propenyl-2-hydroxybiphenyl.
Alkylation of this intermediate product with methyl 2-bromopropionate yields the preligand (3-propenyl-biphen-2-yl)(I-methoxycarbonyl-ethyl)ether.
The compounds of formula 1 are highly active metathesis catalysts which may also be successfully used for carrying out difficult metathesis reactions, including all types of reactions of this kind (RCM, CM, ROMP etc.).
EXAMPLE I
Preparation of a metathesis catalyst of formula la.
1.1) Preparation of the new preligand of formula 2a:
A mixture of 500 mg (3.72 mmol) of 2-propenylphenol (E/Z mixture), prepared by Claisen rearrangement of phenylallylether followed by double bond isomerisation, 1.02 g of potassium carbonate (0.74 mmol) and 745 mg of rac. methyl 2-bromopropionate (4.46 mmol) and 10 ml of dimethylformamide was stirred overnight at RT and then for 4 hours at 80 C.
The reaction mixture was then added to 40 ml of water and extracted three times with 30 ml diethyl ether. The organic phase was washed with 5% sodium hydroxide solution, separated off, dried with Na2SO4 and concentrated by evaporation. 685 mg (83.6% of theory) of virtually pure methyl 2-(2-propenyl-phenyloxy)propionate were obtained.
a b -1O d c MeO 0 2a 1.2) Preparation of the metathesis catalyst of formula la.
424 mg (0.5 mmol) of Grubb's catalyst, 2nd generation, n Mes-N,N-Mes Cl 1,,. Ru_ CI.,, PCy3 and 59 mg CuCI (0.6 mmol) were placed in a Schlenk tube, and under argon a solution of 134 mg (0.6 mmol) of methyl 2-(2-propenyl-phenyloxy)propionate, dissolved in 10 ml CH2C12, was added. The mixture was stirred for 1 hour at 40 C, then evaporated down i.v, the residue was taken up in 20 ml of ethyl acetate and the cloudy solution obtained was filtered. The crude product obtained after evaporation of the solvent was purified by chromatography carried out twice (Merck silica gel type 9385, 1st eluent AcOEt / cyclohexane 3:7, 2nd eluent AcOEt / cyclohexane 1:1). 193 mg (58 % of theory) of pure product were obtained.
HRMS(El): C32H38N2O3C12Ru Calculated: [M+]670.13030, found: 670.13467 Mes-NvN-Mes CI,,,. Ru_ CIS ' O
MeO la Use of the catalyst of formula la prepared according to the invention and comparison of its activity with the known catalyst of formula A (see above).
2.1) Ring-closing metathesis (RCM) using 1a:
A solution of 2.7 mg (0.004 mmol) of the catalyst la obtained according to Example I
in 1 ml dichloromethane at 25 C was added to a solution of 100 mg (0.4 mmol) diethyl allyl-methallyl-malonate (substrate) in 20 ml of dichloromethane. The reaction mixture was kept at this temperature for 2 hours. After this time a sample was taken, the catalyst was destroyed by the addition of ethylvinylether and the sample was analysed by gas chromatography (comparison with substrate and ring-closing product prepared in known manner). The level of conversion of the substrate into the metathesis product (1,1-bis-ethoxycarbonyl-3-methyl-cyclopent-3-ene) was 89%.
2.2) RCM using the known catalyst of formula A:
The same substrate was reacted as described in Example 2.1, but using 2.5 mol%
of the known catalyst A. Investigation by gas chromatography showed that the level of conversion into the ring-closing product was 18%.
Use of the catalyst of formula la prepared according to the invention and comparison of its activity with the known catalyst of formula D (see above).
COzMe C%Me O O,NH
O O,NH
No la or D No OYNH OYNH O&
11 O b-S-&Br O O-S Br O O
4 is dissolved in 10 ml of degassed toluene and heated to 80 C, freshly prepared catalyst is added under nitrogen (1st) and the resulting mixture is stirred for 60 min at 80 C. The reaction is tested by HPLC and a further amount of the catalyst is added (2"d). After another 60 min the reaction is tested once more by HPLC.
Figure 1 shows the cyclisation rate of 4 (T = 0 min:0.4 mol%; T = 60 min:0.2 mol%). Table 1 shows the results of an HPLC analysis in which the results are compared with the known catalyst of formula D (Angew. Chem. Int. Ed. 2002, 41, 4038).
Table I
reaction [%peak at 200 nm]
Catalyst 1 t [mol%] 4 [mol] toluene [ml] 5 [60 min] 4 [60 min]
2d [mol%] 5 [120 min] 4 [120 min]
la 0.4 0.0075 554 82.8 0.2 94.6 D 0.4 0.015 1008 77.4 22.6 0.2 92.8 7.2
Claims (9)
1. Compounds of general formula 1, wherein X and X' denote anionic ligands;
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C1-12-alkyl, C1-12-alkoxy or phenyl, while phenyl may optionally be substituted by at least one of C1-6-alkyl and C1-6-alkoxy;
R1 denotes C1-12-alkyl, C5-6-cycloalkyl, C7-18-aralkyl, or aryl;
R2 denotes H, C1-12-alkyl, C5-6-cycloalkyl, C7-18-aralkyl, or aryl;
R3 denotes H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, or aryl.
L denotes a neutral ligand;
a, b, c, d independently of one another denote H, -NO2, C1-12-alkyl, C1-12-alkoxy or phenyl, while phenyl may optionally be substituted by at least one of C1-6-alkyl and C1-6-alkoxy;
R1 denotes C1-12-alkyl, C5-6-cycloalkyl, C7-18-aralkyl, or aryl;
R2 denotes H, C1-12-alkyl, C5-6-cycloalkyl, C7-18-aralkyl, or aryl;
R3 denotes H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, or aryl.
2. Compounds of general formula I according to claim 1, wherein a, b, c denote H; and d denotes phenyl substituted by at least one of C1-6-alkyl and C1-6-alkoxy.
3. Compounds of general formula I according to claim 1, wherein a, c, d denote H; and b denotes -NO2.
4. Compounds of general formula I according to any one of claims 1 to 3, wherein L denotes a ligand of formula P(R4)3 wherein R4 denotes C1-6-alkyl, cycloalkyl or aryl.
5. Compounds of general formula 1 according to claim 1, wherein L
denotes a ligand of formula L1, L2, L3 or L4, wherein R5 and R6 independently of one another denote H, C1-6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1-6-alkyl, C2-6-alkenyl or aryl; or R7 and R8 together form a 3 or 4-membered alkylene bridge; and Y and Y' denote halogen.
denotes a ligand of formula L1, L2, L3 or L4, wherein R5 and R6 independently of one another denote H, C1-6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1-6-alkyl, C2-6-alkenyl or aryl; or R7 and R8 together form a 3 or 4-membered alkylene bridge; and Y and Y' denote halogen.
6. Compounds of general formula 1 according to claim 2 or 3, wherein L
denotes a ligand of formula L1, L2, L3 or L4, wherein R5 and R6 independently of one another denote H, C1-6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1-6-alkyl, C2-6-alkenyl or aryl; or R7 and R8 together form a 3 or 4-membered alkylene bridge; and Y and Y' denote halogen.
denotes a ligand of formula L1, L2, L3 or L4, wherein R5 and R6 independently of one another denote H, C1-6-alkyl or aryl;
R7 and R8 independently of one another denote H, C1-6-alkyl, C2-6-alkenyl or aryl; or R7 and R8 together form a 3 or 4-membered alkylene bridge; and Y and Y' denote halogen.
7 Compounds of general formula I according to claim 5, wherein X and X' denote Cl;
L denotes L1;
a, b, c, d denote H;
R1 denotes methyl;
R2 denotes methyl;
R3 denotes H;
R5 and R6 denote mesityl R7 and R8 denote H.
L denotes L1;
a, b, c, d denote H;
R1 denotes methyl;
R2 denotes methyl;
R3 denotes H;
R5 and R6 denote mesityl R7 and R8 denote H.
8. Process for carrying out metathesis reactions, in which two compounds are reacted, each of which contains an olefinic double bond or wherein one of the compounds contains at least two olefinic double bonds and wherein one of the compounds according to claims 1 to 6 is used as a catalyst.
9. Process for carrying out a ring-closing metathesis (RCM) or a cross metathesis (CM) in which a compound containing two olefinic double bonds participates as the substrate and one of the compounds according to claims 1 to 6 participates as a catalyst.
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