WO2020149693A1 - 루테늄 착화합물, 이의 제조를 위한 리간드 및 이의 용도 - Google Patents
루테늄 착화합물, 이의 제조를 위한 리간드 및 이의 용도 Download PDFInfo
- Publication number
- WO2020149693A1 WO2020149693A1 PCT/KR2020/000855 KR2020000855W WO2020149693A1 WO 2020149693 A1 WO2020149693 A1 WO 2020149693A1 KR 2020000855 W KR2020000855 W KR 2020000855W WO 2020149693 A1 WO2020149693 A1 WO 2020149693A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- alkyl
- ruthenium complex
- complex compound
- formula
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 121
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 55
- 239000003446 ligand Substances 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- 239000004711 α-olefin Substances 0.000 claims abstract description 26
- 238000005686 cross metathesis reaction Methods 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229910052736 halogen Inorganic materials 0.000 claims description 33
- 150000002367 halogens Chemical class 0.000 claims description 33
- 125000000623 heterocyclic group Chemical group 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 10
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- -1 cyclic alkene compounds Chemical class 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000005649 metathesis reaction Methods 0.000 claims description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 3
- 238000010535 acyclic diene metathesis reaction Methods 0.000 claims description 2
- 238000012691 depolymerization reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 10
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 11
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 11
- 229940073769 methyl oleate Drugs 0.000 description 11
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 10
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 4
- 229940125961 compound 24 Drugs 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CELKOWQJPVJKIL-UHFFFAOYSA-N 3-fluoropyridine Chemical compound FC1=CC=CN=C1 CELKOWQJPVJKIL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229940125833 compound 23 Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- HASUVWMICRFLAS-UHFFFAOYSA-M fluororuthenium Chemical compound [Ru]F HASUVWMICRFLAS-UHFFFAOYSA-M 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000005872 self-metathesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WRXMUGOMZOGXCX-UHFFFAOYSA-N 2,6-di(pentan-3-yl)aniline Chemical compound CCC(CC)C1=CC=CC(C(CC)CC)=C1N WRXMUGOMZOGXCX-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- MBVFRSJFKMJRHA-UHFFFAOYSA-N 4-fluoro-1-benzofuran-7-carbaldehyde Chemical compound FC1=CC=C(C=O)C2=C1C=CO2 MBVFRSJFKMJRHA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CCC1C(C)=CC=C*1(CC*C)C(C)** Chemical compound CCC1C(C)=CC=C*1(CC*C)C(C)** 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical group [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- KYOIPUDHYRWSFO-UHFFFAOYSA-N [Br].[Li] Chemical group [Br].[Li] KYOIPUDHYRWSFO-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 125000002619 bicyclic group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000005752 bromopyridines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- GGRHYQCXXYLUTL-UHFFFAOYSA-N chloromethyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCCl GGRHYQCXXYLUTL-UHFFFAOYSA-N 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- SFJMFSWCBVEHBA-UHFFFAOYSA-M copper(i)-thiophene-2-carboxylate Chemical compound [Cu+].[O-]C(=O)C1=CC=CS1 SFJMFSWCBVEHBA-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BONJEVTUQJXNGQ-UHFFFAOYSA-L dichlorocopper tricyclohexylphosphane Chemical compound [Cu](Cl)Cl.C1(CCCCC1)P(C1CCCCC1)C1CCCCC1 BONJEVTUQJXNGQ-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
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- B01J2540/20—Non-coordinating groups comprising halogens
- B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
- B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
Definitions
- the present invention relates to ruthenium complex compounds, ligands for their preparation and uses thereof. Specifically, the present invention relates to a novel ruthenium complex compound used as a catalyst having high selectivity and stability, a ligand for its preparation, and a method for producing a linear ⁇ -olefin using the same.
- LAOs Linear ⁇ -olefins with olefins at the ends are used as essential raw materials for various chemicals.
- natural seed oil may be used instead of petroleum raw materials.
- a catalyst of methyl oleate and ethylene obtained from renewable seed oil raw materials the internal carbon-carbon double bond is decomposed through cross metathesis, that is, ethenolysis reaction.
- a linear ⁇ -olefin having an olefin at the terminal such as 1-decene in Scheme 3 below.
- This ethenolysis reaction can be carried out under mild conditions of a temperature of 25 to 100° C. and a pressure of 1 to 10 bar, and has a narrow carbon number distribution of the synthesized linear ⁇ -olefin.
- ruthenium complex compound containing a symmetrical N-heterocyclic carbene (NHC) ligand and a methylidene species is known (Richard L. Pederson et al., Clean 2008, 36 (8), 669-673).
- ruthenium complexes having asymmetrically substituted N-heterocyclic carbene ligands are promising catalysts of ethenolis which can exhibit high selectivity of cross metathesis products by ethylene compared to by-products by self-metathesis.
- RM Thomas et al J. Am. Chem. Soc. 2011, 133, 7490-7496
- Imidazo[1,5-a]pyridine-3-ylidene (ImPy), first reported in 2005, is a structurally asymmetric NHC ligand and has various electronic properties.
- the ImPy ligand can be synthesized as an abnormal ImPy (aImPy) ligand having improved electron donating properties.
- the present inventors studied the effect of aImPy ligand-based ruthenium catalyst structure and its electronic properties on catalytic activity, selectivity and stability, and were able to synthesize a new ruthenium catalyst having high activity and selectivity and stable at high temperature.
- the present inventors have found that it is possible to further improve the catalytic activity through additives.
- an object of the present invention is to provide a novel ruthenium complex compound that can be usefully used as a catalyst having high activity, selectivity and stability.
- Another object of the present invention is to provide a ligand for the preparation of the ruthenium complex.
- Another object of the present invention is to provide a catalyst having high selectivity and high activity and stability in the formation of ⁇ -olefins including the ruthenium complex compound.
- Another object of the present invention is to provide a method for manufacturing a linear ⁇ -olefin with high efficiency using the catalyst.
- the present invention provides a ruthenium complex compound represented by Formula 1 below:
- R 1 is halogen, amino, C 1-3 alkyl or C 1-3 alkoxy
- R 2 , R 3 and R 4 are each independently hydrogen, halogen, amino, C 1-5 alkyl or C 1-5 alkoxy;
- R 5 and R 6 are each independently C 5-10 carbocycle or 5-10 membered heterocycle
- R 7 and R 8 are each independently halogen
- R 9 is C 1-10 alkyl, C 5-10 carbocycle or 5-10 membered heterocycle
- R 10 and R 11 are each independently C 1-10 alkyl, or fused to each other to form a C 5-10 carbocycle or a 5-10 membered heterocycle;
- R 12 is N or O
- alkyl and alkoxy are each independently substituted or unsubstituted with at least one of halogen, hydroxy and amino;
- the carbocycle and heterocycle are each independently substituted or unsubstituted with at least one selected from the group consisting of halogen, nitro, C 1-5 alkyl, halo C 1-5 alkyl, C 1-5 alkoxy and phenyl, A saturated or unsaturated ring;
- the heterocycle contains at least one heteroatom selected from N, S and O.
- the present invention provides a ligand for the preparation of a ruthenium complex, comprising a compound represented by Formula 2:
- R 1 to R 6 are as defined in Formula 1 above.
- the present invention provides a catalyst comprising the ruthenium complex compound.
- the present invention provides a method for producing a linear ⁇ -olefin comprising adding ethylene to an unsaturated fatty acid in the presence of the catalyst.
- the ruthenium complex compound of the present invention can exhibit high activity, selectivity and stability when used as a catalyst.
- the ruthenium complex compound may provide improved selectivity when acting as a catalyst due to an asymmetric structure having substituents having a relative size difference.
- the activity is improved due to the improved electron donating properties due to the abnormal structure of the ruthenium complex compound, and the activity can be further improved by controlling the additive.
- the ruthenium complex compound is used as a catalyst for a cross metathesis reaction including ethenolysis, and can produce a desired linear ⁇ -olefin compound or the like in high yield even under relatively mild conditions.
- Figure 1 shows the preparation and structure of the compound of formula 1 according to the embodiment.
- halogen may be fluorine, chlorine, bromine or iodine, and may be referred to as fluoro, chloro, bromo or iodo as a substituent.
- alkyl can mean a straight or branched hydrocarbon residue.
- the alkyl may be composed of, for example, 1 to 10 carbons, and in this case, may be represented as “C 1-10 alkyl”.
- haloalkyl may mean alkyl, alkoxy, etc. substituted with one or more halogens.
- carbocycle means a saturated or unsaturated hydrocarbon ring, may have aromatic or non-aromatic properties, and may be monocyclic or dual/polycyclic.
- the carbocycle may be composed of, for example, 5 to 10 carbons, and in this case, may be indicated as “C 5-10 carbocycle”.
- heterocycle refers to a saturated or unsaturated ring having one or more heteroatoms, may have aromatic or non-aromatic properties, and may be monocyclic or bi/polycyclic.
- the heterocycle may be composed of, for example, 5 to 10 heteroatoms and/or carbon atoms, and in this case, may be represented as "5-10 membered heterocycle”.
- heteroatom may be an atom selected from N, O and S.
- the present invention provides a novel ruthenium complex compound.
- the ruthenium complex compound according to an embodiment of the present invention is represented by the following Chemical Formula 1:
- R 1 is halogen, amino, C 1-3 alkyl or C 1-3 alkoxy
- R 2 , R 3 and R 4 are each independently hydrogen, halogen, amino, C 1-5 alkyl or C 1-5 alkoxy;
- R 5 and R 6 are each independently C 5-10 carbocycle or 5-10 membered heterocycle
- R 7 and R 8 are each independently halogen
- R 9 is C 1-10 alkyl, C 5-10 carbocycle or 5-10 membered heterocycle
- R 10 and R 11 are each independently C 1-10 alkyl, or fused to each other to form a C 5-10 carbocycle or a 5-10 membered heterocycle;
- R 12 is N or O
- alkyl and alkoxy are each independently substituted or unsubstituted with at least one of halogen, hydroxy and amino;
- the carbocycle and heterocycle are each independently substituted or unsubstituted with at least one selected from the group consisting of halogen, nitro, C 1-5 alkyl, halo C 1-5 alkyl, C 1-5 alkoxy and phenyl, A saturated or unsaturated ring;
- the heterocycle contains at least one heteroatom selected from N, S and O.
- R 1 is halogen and more specifically fluoro.
- R 2 and R 4 are hydrogen.
- R 3 is hydrogen or C 1-5 alkyl.
- R 5 and R 6 are each independently C 6-10 carbocycle or 5-10 membered heterocycle having aromaticity;
- the carbocycle and heterocycle are each independently substituted or unsubstituted with at least one selected from the group consisting of halogen, nitro, C 1-5 alkyl, halo C 1-5 alkyl and C 1-5 alkoxy.
- R 5 and R 6 are each independently aromatic C 6-10 carbocycle ;
- the carbocycles are each independently substituted or unsubstituted with one or more C 1-5 alkyl.
- R 7 and R 8 are chloro.
- R 9 is C 1-10 alkyl or C 5-10 carbocycle, and more specifically branched C 3-5 alkyl or aromatic C 6-10 carbocycle .
- R 10 and R 11 fuse to each other to form an aromatic C 6-10 carbocycle, and the carbocycle is substituted or unsubstituted with phenyl.
- the ruthenium complex compound of Chemical Formula 1 may include a mesoionic structure.
- the ruthenium complex compound of Formula 1 may include a carbene ligand having an abnormal structure.
- the ruthenium complex compound of Formula 1 includes an abnormal imidazo[1,5-a]pyridine-3-ylidene (aImPy) structure having improved electron donating properties.
- aImPy abnormal imidazo[1,5-a]pyridine-3-ylidene
- aImPy in Formula 1 has excellent electron donating ability to stabilize the methylidene species, it is possible to improve the stability of the compound of Formula 1.
- R 1 , R 5 , R 6 The stereo effect can be controlled by changing the substituent such as.
- the compound of Formula 1 may improve selectivity when acting as a catalyst.
- the ruthenium complex compound according to another embodiment of the present invention is represented by the following formula 1a:
- R 1 is halogen, amino, C 1-3 alkyl, haloC 1-3 alkyl or C 1-3 alkoxy;
- R 5 and R 6 are each independently aromatic C 6-10 carbocycle or 5-10 membered heterocycle
- R 9 is C 1-3 alkyl or phenyl
- R d and R e are each independently hydrogen, nitro or phenyl
- the carbocycle and heterocycle are each independently substituted or unsubstituted with at least one selected from the group consisting of halogen, nitro, C 1-5 alkyl, halo C 1-5 alkyl and C 1-5 alkoxy;
- the heterocycle contains at least one heteroatom selected from N, S and O.
- R 1 is halogen, and more specifically fluoro.
- R 5 and R 6 are each independently C 6-10 carbocycle or 5-10 membered heterocycle having aromaticity;
- the carbocycle and heterocycle are each independently substituted or unsubstituted with at least one selected from the group consisting of halogen, nitro, C 1-5 alkyl, halo C 1-5 alkyl and C 1-5 alkoxy.
- R 5 and R 6 are each independently an aromatic C 6-10 carbocycle (eg, a benzene or naphthalene ring);
- the carbocycles are each independently substituted or unsubstituted with one or more C 1-5 alkyl.
- the ruthenium complex compound according to another embodiment of the present invention is represented by the following formula 1b:
- R 1 is halogen
- R a , R b and R c are each independently hydrogen, halogen, C 1-5 alkyl, halo C 1-5 alkyl and C 1-5 alkoxy.
- R a and R b are each independently C 1-5 alkyl.
- R a and R b are each independently branched C 3-5 alkyl.
- R c is hydrogen
- the ruthenium complex compound in the X-ray crystal structure analysis, may represent a distance of 2.85 to 3.15 ⁇ , or 2.7 to 3.0 ⁇ between ruthenium (Ru) and the substituent R 1 .
- the ruthenium complex compound in the X-ray crystal structure analysis, may represent a distance of 2.28 ⁇ 2.32 km between ruthenium (Ru) and oxygen (O).
- the present invention also provides a ligand for the preparation of the ruthenium complex.
- the ligand includes a compound represented by Formula 2:
- R 1 to R 6 are as defined in Formula 1 above.
- R 1 to R 6 are as described in the ruthenium complex.
- the ligand of Chemical Formula 2 may be synthesized as a mesoionic or abnormal carben ligand (aImPy). It has improved electron donating properties. As a result, since the ligand has excellent electron donating ability to stabilize the methylidene species, stability of the ruthenium complex can be improved.
- R 1 , R 5 , R 6 The stereo effect can be controlled by changing the substituent such as.
- the ligand of Chemical Formula 2 may improve selectivity when the ruthenium complex compound acts as a catalyst due to its asymmetric structure.
- the present invention also provides a catalyst comprising the ruthenium complex compound.
- the catalyst can be used in a cross metathesis reaction.
- the catalyst can be used in a cross metathesis reaction using an alkene compound.
- the catalyst may be used in an alkenolysis reaction.
- the catalyst can be used for ethenolysis reaction using ethylene.
- the catalyst can be used for the ethenolysis reaction of unsaturated fatty acids such as methyl oleate.
- the catalyst may be used in a metathesis reaction by ethenolysis of a linear or cyclic alkene compound.
- the catalyst is an intramolecular cross-metathesis reaction, a ring-opening metathesis reaction, a ring-closing metathesis reaction, and a ring-closing metathesis reaction. It can be used for opening metathesis polymerization reaction, or acyclic diene metathesis polymerization reaction.
- the catalyst may be used in a depolymerization reaction or an ethenolysis reaction of an unsaturated linear polymer containing a double bond.
- the catalyst may further include at least one additional compound for improving catalyst activity in addition to the ruthenium complex compound. That is, the ruthenium complex compound may be used in combination with one or more additional compounds for improving activity when used as a catalyst.
- the additional compound is not particularly limited as long as it helps to improve the catalytic activity, and may be, for example, a metal-based compound such as a metal halide.
- the catalyst may further include a copper compound.
- the copper compound may be a compound in which an anionic chemical species including halogen is bound to a copper cation.
- the copper compound is tricyclohexylphosphine-copper chloride (PCy 3 CuCl), copper chloride (CuCl), copper iodide (CuI) and copper(I)-thiophene-2-carboxylate (CuTc). It may be one or more selected from the group consisting of.
- the catalyst may further include a sodium compound.
- the sodium compound may be a compound in which an anionic species including halogen is bonded to a sodium cation.
- the sodium compound may be at least one selected from the group consisting of sodium bromide (NaBr), sodium iodide (NaI), sodium acetate (NaOAc) and sodium benzoate (PhCOONa).
- the amount of the catalyst used may range from 1 ppm to 100 ppm, from 1 ppm to 50 ppm, or from 5 ppm to 20 ppm.
- the catalyst is very good in terms of selectivity and turnover number (TON).
- the catalyst may have a selectivity of 80% or more, 85% or more, 90% or more, or 95% or more.
- the catalyst may have a TON of 10000 or more, 15000 or more, 20000 or more, or 25000 or more.
- the catalyst may have a conversion of 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more.
- the present invention also provides a method for producing a linear ⁇ -olefin comprising adding ethylene to an unsaturated fatty acid in the presence of the catalyst.
- the unsaturated fatty acid includes a compound represented by Formula 3 below;
- the linear ⁇ -olefin may have 2 to 10 carbon atoms.
- R is C 1-6 alkyl; p and q are each independently an integer of 1 to 10.
- the unsaturated fatty acid may be methyl oleate
- the linear ⁇ -olefin may be 1-decene
- the catalyst may be used at a concentration of 1 ppm to 100 ppm.
- the catalyst may be used in a concentration of 1 ppm to 50 ppm.
- the catalyst may be used in a molar concentration of 1 ppm to 50 ppm, 1 ppm to 40 ppm, 10 ppm to 40 ppm, or 5 ppm to 20 ppm based on the number of moles of the unsaturated fatty acid.
- the manufacturing method can be performed at relatively low pressure and temperature conditions.
- the pressure conditions of the manufacturing method may range from 50 psi to 300 psi, or from 100 psi to 200 psi.
- the temperature conditions of the manufacturing method may be in the range of 20 °C to 100 °C, or 30 °C to 60 °C.
- the reaction may be performed for 30 minutes to 20 hours, 30 minutes to 10 hours, 30 minutes to 5 hours, or 1 hour to 3 hours.
- selectivity may be 80% or more, 85% or more, 90% or more, or 95% or more.
- TON may be 10000 or more, 15000 or more, 20000 or more, or 25000 or more.
- the conversion rate may be 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more.
- the yield may be 20% or more, 30% or more, 40% or more, 50% or more, or 60% or more.
- the amine (compounds c6 to c8 ) is reacted with an aromatic acyl chloride to form an amide (compounds c9 to c16 ), and cyclized in the presence of an amine base with trifluorosulfonyl anhydride (Tf 2 O) to form a carbene ligand (compound) c17 to c24 ).
- the ruthenium catalysts (compounds c25 to c32 ) were synthesized by exchanging the carbene ligands (compounds c17 to c24 ) with the phosphine ligand of the first-generation Grubbs-Hoveyda catalyst (GH1).
- n-Butyllithium (1.1 eq) was added to a diethyl ether solution (1.1 M) of 1,4-diazabicyclo[2.2.2]octane (DABCO) (1 eq) and stirred for 1 hour.
- DABCO 1,4-diazabicyclo[2.2.2]octane
- the mixture was cooled at -60°C, and a solution of 3-fluoropyridine (Compound c1 ) (2 M, 1 eq) was added dropwise.
- the mixture was stirred at -60°C for 2 hours, and dimethylformamide (DMF, 2 M, 2 eq) was added.
- DMF dimethylformamide
- Test Example 1 X-ray crystal analysis
- X-ray crystal analysis was performed on the compounds prepared in the above Example.
- the single crystal used for X-ray crystal analysis was grown by slow diffusion of hexane through a catalyst solution in dichloromethane at 25°C.
- Test Example 3 Evaluation of catalyst performance in the ethenolysis reaction of methyl oleate
- Each of the above example compounds was used as a catalyst to perform an ethenolysis reaction of methyl oleate.
- methyl oleate (Compound 11, 1 mmol) was reacted with 150 psi of C 2 H 4 (purity 99.95%) in the presence of a catalyst (0.005 mol%, 50 ppm) at 40° C. for 1 hour.
- a catalyst 0.005 mol%, 50 ppm
- Test Example 4 Evaluation of catalyst performance according to reaction conditions
- Example 1 Using the compound c25 prepared in Example 1 as a catalyst, an ethenolysis reaction of methyl oleate was performed in the same manner as in Test Example 3, but the amount of catalyst added, the temperature and time during the reaction were controlled as shown in the table below. Did. The catalyst performance at the time of reaction was evaluated in the same manner and criteria as in Test Example 3 above, and the results are summarized in the following table.
- Test Example 5 Evaluation of catalyst performance according to additives
- Example 1 Using the compound c25 prepared in Example 1 as a catalyst, an ethenolysis reaction of methyl oleate was performed in the same manner as in Test Example 3, but various additives were used in combination, and the amount of catalyst added, the temperature and time during the reaction, It was adjusted as shown in the table below. The catalyst performance at the time of reaction was evaluated in the same manner and criteria as in Test Example 3 above, and the results are summarized in the following table.
- Test Example 6 Evaluation of catalyst performance according to ligand change
- Test Example 7 Catalyst performance evaluation according to catalyst changes and additives
- the following compounds 21 to 23 can be synthesized according to the method of Richard L. Pederson et al. [Clean 2008, 36 (8), 669-673], and the following compound 24 is Robert H. Grubbs et al. [J. Am. Chem. Soc. 2011, 133, 7490-7496.
- the compounds 21 to 23 having symmetric NHC ligands were lower in selectivity and yield than the ruthenium complex compounds of Formula 1 of the present invention, and in the case of Compound 24, they were very low in terms of reaction yield and TON. .
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Abstract
Description
번호 | 촉매 | 전환율(%) | 선택도(%) | 수율(%) | TON |
1 | 화합물 c25 | 72 | 94 | 67 | 13400 |
2 | 화합물 c26 | 64 | 95 | 61 | 12200 |
3 | 화합물 c27 | 73 | 94 | 68 | 13600 |
4 | 화합물 c28 | 71 | 95 | 68 | 13600 |
5 | 화합물 c29 | 72 | 94 | 68 | 13600 |
6 | 화합물 c30 | 71 | 95 | 67 | 13500 |
7 | 화합물 c31 | 23 | 86 | 20 | 4000 |
번호 | 촉매량(ppm) | 압력(psi) | 온도(℃) | 시간(hr) | 전환율(%) | 선택도(%) | 수율(%) | TON |
1 | 50 | 150 | 40 | 1 | 71 | 94 | 67 | 13400 |
2 | 30 | 150 | 40 | 3 | 63 | 95 | 60 | 20000 |
3 | 20 | 150 | 40 | 12 | 34 | 97 | 33 | 16500 |
4 | 10 | 150 | 40 | 20 | 4 | 98 | 4 | 4000 |
5 | 50 | 150 | 60 | 1 | 69 | 94 | 65 | 13000 |
6 | 50 | 150 | 80 | 1 | 60 | 93 | 56 | 11200 |
번호 | 촉매량(ppm) | 첨가제 | 온도(℃) | 시간(hr) | 전환율(%) | 선택도(%) | 수율(%) | TON |
1 | 10 | 미첨가 | 40 | 20 | 4 | 98 | 4 | 4000 |
2 | 10 | PCy3CuCl 10 ppm | 40 | 3 | 46 | 96 | 44 | 44000 |
3 | 5 | PCy3CuCl 5 ppm | 40 | 3 | 30 | 97 | 29 | 58000 |
4 | 3 | PCy3CuCl 6 ppm | 40 | 9 | 19 | 97 | 19 | 63000 |
5 | 2 | PCy3CuCl 4 ppm | 40 | 18 | 12 | 98 | 11 | 57000 |
6 | 1 | PCy3CuCl 2 ppm | 40 | 24 | 5 | 97 | 5 | 51000 |
7 | 5 | CuCl 5 ppm | 40 | 3 | 13 | 97 | 12 | 24000 |
8 | 5 | CuI 5 ppm | 40 | 3 | 16 | 96 | 15 | 30000 |
9 | 10 | CuI 10 ppm | 40 | 3 | 28 | 97 | 27 | 27000 |
10 | 5 | CuTc 5 ppm | 40 | 3 | 17 | 93 | 16 | 32500 |
번호 | 촉매화합물 | 촉매량(ppm) | 압력(psi) | 온도(℃) | 시간(hr) | 전환율(%) | 선택도(%) | 수율(%) | TON |
1 | c36 | 50 | 150 | 40 | 1 | 60 | 96 | 57 | 11400 |
2 | c36 | 30 | 150 | 40 | 1 | 50 | 95 | 48 | 16000 |
3 | c36 | 20 | 150 | 40 | 1 | 40 | 95 | 38 | 19000 |
4 | c36 | 20 | 80 | 25 | 3 | 50 | 90 | 45 | 22500 |
5 | c36 | 15 | 150 | 40 | 1 | 31 | 97 | 30 | 20000 |
6 | c36 | 15 | 150 | 40 | 3 | 41 | 95 | 42 | 28000 |
7 | c36 | 10 | 150 | 40 | 3 | 14 | 98 | 14 | 14000 |
8 | c36 | 10 | 150 | 40 | 8 | 29 | 96 | 28 | 28000 |
9 | c37 | 10 | 150 | 40 | 6 | 15 | 97 | 15 | 15000 |
번호 | 촉매 | 첨가제 | 전환율(%) | 선택도(%) | 수율(%) | TON |
1 | c25 5 ppm | PCy3CuCl 5 ppm | 30 | 97 | 29 | 58000 |
2 | c26 5 ppm | PCy3CuCl 5 ppm | 14 | 98 | 14 | 28000 |
3 | c27 5 ppm | PCy3CuCl 5 ppm | 14 | 98 | 14 | 28000 |
4 | c28 5 ppm | PCy3CuCl 5 ppm | 27 | 97 | 26 | 52000 |
5 | c29 5 ppm | PCy3CuCl 5 ppm | 25 | 97 | 24 | 48000 |
6 | c30 5 ppm | PCy3CuCl 5 ppm | 19 | 98 | 19 | 37000 |
7 | c32 5 ppm | PCy3CuCl 5 ppm | 20 | 99 | 20 | 40000 |
8 | c36 5 ppm | PCy3CuCl 5 ppm | 19 | 97 | 19 | 37000 |
9 | c38 5 ppm | PCy3CuCl 5 ppm | 26 | 99 | 26 | 51000 |
촉매 | 촉매량(ppm) | 전환율(%) | 선택도(%) | 수율(%) | TON |
화합물 21 | 10 | 61 | 36 | 22 | 22000 |
화합물 22 | 100 | 60 | 33 | 20 | 2000 |
화합물 23 | 100 | 70 | 56 | 39 | 3900 |
화합물 23 | 35 | 69 | 57 | 39 | 11000 |
화합물 24 | 100 | 15 | 95 | 15 | 1460 |
화합물 24 | 500 | 48 | 95 | 15 | 913 |
Claims (18)
- 하기 화학식 1로 표시되는 루테늄 착화합물:[화학식 1]상기 식에서,R1은 할로겐, 아미노, C1-3알킬 또는 C1-3알콕시이고;R2, R3 및 R4는 각각 독립적으로 수소, 할로겐, 아미노, C1-5알킬 또는 C1-5알콕시이고;R5 및 R6는 각각 독립적으로 C5-10카르보사이클 또는 5-10원 헤테로사이클이고;R7 및 R8은 각각 독립적으로 할로겐이고;R9은 C1-10알킬, C5-10카르보사이클 또는 5-10원 헤테로사이클이고;R10 및 R11은 각각 독립적으로 C1-10알킬이거나, 서로 융합하여 C5-10카르보사이클 또는 5-10원 헤테로사이클을 형성하고;R12은 N 또는 O이고;상기 알킬 및 알콕시는 각각 독립적으로 할로겐, 하이드록시 및 아미노 중 적어도 하나로 치환되거나 비치환되고;상기 카르보사이클 및 헤테로사이클은 각각 독립적으로, 할로겐, 니트로, C1-5알킬, 할로C1-5알킬, C1-5알콕시 및 페닐로 이루어진 군에서 선택되는 적어도 하나로 치환되거나 비치환된, 포화 또는 불포화된 고리이고;상기 헤테로사이클은 N, S 및 O 중에서 선택되는 적어도 하나의 헤테로원자를 함유한다.
- 제 1 항에 있어서,R1이 할로겐인, 루테늄 착화합물.
- 제 1 항에 있어서,R2 및 R4가 수소인, 루테늄 착화합물.
- 제 1 항에 있어서,R5 및 R6는 각각 독립적으로 방향성을 갖는 C6-10카르보사이클 또는 5-10원 헤테로사이클이고;상기 카르보사이클 및 헤테로사이클은 각각 독립적으로 할로겐, 니트로, C1-5알킬, 할로C1-5알킬 및 C1-5알콕시로 이루어진 군에서 선택되는 적어도 하나로 치환되거나 비치환된, 루테늄 착화합물.
- 제 1 항에 있어서,상기 루테늄 착화합물이 메조이온성(mesoionic) 구조를 포함하는, 루테늄 착화합물.
- 하기 화학식 1a로 표시되는 루테늄 착화합물:[화학식 1a]상기 식에서,R1은 할로겐, 아미노, C1-3알킬, 할로C1-3알킬 또는 C1-3알콕시이고;R5 및 R6는 각각 독립적으로 방향성을 갖는 C6-10카르보사이클 또는 5-10원 헤테로사이클이고;R9은 C1-3알킬 또는 페닐이고;Rd 및 Re는 각각 독립적으로 수소, 니트로 또는 페닐이고;상기 카르보사이클 및 헤테로사이클은 각각 독립적으로 할로겐, 니트로, C1-5알킬, 할로C1-5알킬 및 C1-5알콕시로 이루어진 군에서 선택되는 적어도 하나로 치환되거나 비치환되고;상기 헤테로사이클은 N, S 및 O 중에서 선택되는 적어도 하나의 헤테로원자를 함유한다.
- 제 7 항에 있어서,상기 루테늄 착화합물이, X-선 결정 구조 분석에서,루테늄(Ru)과 치환기 R1 간에 2.85~3.15 Å의 거리를 나타내는 루테늄 착화합물.
- 제 1 항의 루테늄 착화합물을 포함하는 촉매.
- 제 10 항에 있어서,상기 촉매가 알켄올리시스(alkenolysis) 반응에 사용되는 촉매.
- 제 10 항에 있어서,상기 촉매가 선형 또는 고리형 알켄 화합물의 에텐올리시스(ethenolysis)에 의한 복분해 반응에 사용되는 촉매.
- 제 10 항에 있어서,상기 촉매가 분자 내 교차-복분해(cross-metathesis) 반응, 개환-복분해(ring-opening metathesis) 반응, 폐환-복분해(ring-closing metathesis) 반응, 개환-복분해 중합(ring-opening metathesis polymerization) 반응, 또는 아크릴 디엔-복분해 중합(acyclic diene metathesis polymerization) 반응에 사용되는 촉매.
- 제 10 항에 있어서,상기 촉매가 이중 결합을 포함하는 불포화 선형 고분자의 해중합(depolymerization) 반응 또는 에텐올리시스(ethenolysis) 반응에 사용되는 촉매.
- 제 10 항에 있어서,상기 촉매가 구리 화합물을 추가로 포함하는 촉매.
- 제 10 항의 촉매 존재 하에서 불포화 지방산에 에틸렌을 가하는 것을 포함하는, 선형 α-올레핀의 제조방법.
- 제 16 항에 있어서,상기 촉매가 상기 불포화 지방산의 몰 수를 기준으로 1 ppm 내지 50 ppm의 몰 농도로 사용되는, 선형 α-올레핀의 제조방법.
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KR20150023672A (ko) * | 2012-07-27 | 2015-03-05 | 아페이론 신세시스 에스.아. | 신규 루테늄 착물, 복분해 반응에서 이의 용도, 및 복분해 반응의 수행 방법 |
CN107987107A (zh) * | 2017-12-15 | 2018-05-04 | 上海克琴科技有限公司 | 钌卡宾催化剂及其催化的降冰片烯开环易位聚合反应 |
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