JP5532434B2 - 有機無機複合材料およびその利用 - Google Patents
有機無機複合材料およびその利用 Download PDFInfo
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- JP5532434B2 JP5532434B2 JP2010501943A JP2010501943A JP5532434B2 JP 5532434 B2 JP5532434 B2 JP 5532434B2 JP 2010501943 A JP2010501943 A JP 2010501943A JP 2010501943 A JP2010501943 A JP 2010501943A JP 5532434 B2 JP5532434 B2 JP 5532434B2
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- 229910003471 inorganic composite material Inorganic materials 0.000 title claims description 78
- 239000003054 catalyst Substances 0.000 claims description 78
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 49
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 42
- 229910052723 transition metal Inorganic materials 0.000 claims description 41
- 150000003624 transition metals Chemical class 0.000 claims description 41
- -1 phosphino group Chemical group 0.000 claims description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 39
- 239000002131 composite material Substances 0.000 claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 22
- 238000006880 cross-coupling reaction Methods 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 150000003377 silicon compounds Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 125000000962 organic group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000002883 imidazolyl group Chemical group 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical group C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002905 metal composite material Substances 0.000 claims 1
- 238000006263 metalation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000002904 solvent Substances 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006069 Suzuki reaction reaction Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000005859 coupling reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 125000001188 haloalkyl group Chemical group 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 125000000262 haloalkenyl group Chemical group 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 150000001502 aryl halides Chemical group 0.000 description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- CYSFUFRXDOAOMP-UHFFFAOYSA-M magnesium;prop-1-ene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C=C CYSFUFRXDOAOMP-UHFFFAOYSA-M 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 3
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 3
- PWZDBNXSMRBBLN-UHFFFAOYSA-N 3-bromopropyl-tris(prop-2-enyl)silane Chemical compound BrCCC[Si](CC=C)(CC=C)CC=C PWZDBNXSMRBBLN-UHFFFAOYSA-N 0.000 description 3
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- WNGOWMCOCMPJCD-UHFFFAOYSA-N ethyl 2-(2-phenylphenyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 WNGOWMCOCMPJCD-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- FCLYZQXPJKJTDR-UHFFFAOYSA-N potassium;diphenylphosphanide Chemical compound C=1C=CC=CC=1P([K])C1=CC=CC=C1 FCLYZQXPJKJTDR-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- ZXFDJWMFCAEGED-UHFFFAOYSA-N 1-chlorocycloocta-1,5-diene;iridium Chemical class [Ir].ClC1=CCCC=CCC1 ZXFDJWMFCAEGED-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FIWILGQIZHDAQG-UHFFFAOYSA-N NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F Chemical compound NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F FIWILGQIZHDAQG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PQHKXSOICTYGQD-OUTSHDOLSA-N [(3s,5s)-5-(diphenylphosphanylmethyl)pyrrolidin-3-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P([C@H]1C[C@H](NC1)CP(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 PQHKXSOICTYGQD-OUTSHDOLSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000009815 homocoupling reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000005373 porous glass Substances 0.000 description 2
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- OWSXDWUAPKBLOI-UHFFFAOYSA-N 1-[2,6-di(propan-2-yl)phenyl]imidazole Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1C=NC=C1 OWSXDWUAPKBLOI-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- CJYDQTAWSHWBIT-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2-hydroxy-2-methylpropyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC(C)(C)O)C=CC=1 CJYDQTAWSHWBIT-UHFFFAOYSA-N 0.000 description 1
- UUNGBOQAZQUJMZ-UHFFFAOYSA-N 3-bromopropyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCBr UUNGBOQAZQUJMZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- JTWDWVCNOLORBR-UHFFFAOYSA-N 3-chloropropyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)CCCCl JTWDWVCNOLORBR-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- CBQJSKKFNMDLON-JTQLQIEISA-N N-acetyl-L-phenylalanine Chemical compound CC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 CBQJSKKFNMDLON-JTQLQIEISA-N 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- 125000005025 alkynylaryl group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HFDWSWIVIITCPJ-UHFFFAOYSA-N diphenyl(3-silylpropyl)phosphane Chemical compound [SiH3]CCCP(c1ccccc1)c1ccccc1 HFDWSWIVIITCPJ-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003395 phenylethylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
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- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
ル基、イミダゾリル基、Yは、水酸基、アルコキシ基、アリールオキシ基、イソシア
ナト基、メルカプト基、ホスフィノ基、アミノ基、イミノ基、ハロゲン、複素環
の一つ以上を含む一価の有機基、Aは、二価の炭化水素基、Rはメチル基、
エチル基、ブチル基、フェニル基、Qはメチル基、エチル基、ブチル基、
フェニル基を示し、kは1〜3の整数、nは1または2、mは2または3、
lは0または1を示し、l+m+nは4である。)
または下記一般式(2)
ル基、イミダゾリル基、Y'は、ハロゲンを含む一価の有機基、A'は、二価の炭化水
素基、R'はメチル基、エチル基、ブチル基、フェニル基、Q'はメチル基、
エチル基、ブチル基、フェニル基を示し、eは1〜3の整数、fは2または3、
hは1または2、gは0または1を示し、f+h+gは4である。)
で示される有機ケイ素化合物およびその前駆体である。
X"dQ"3-dSi−A"− (3)
この式において、X"は、塩素、臭素、ヨウ素、シロキシ基、ヒドロキシ基、アルコキシ基、アリル基、イミダゾリル基を示し、好ましくは塩素、アルコキシ基、アリル基、イミダゾリル基である。また、X"のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、t−ブトキシ基等の炭素数が1〜10のものが好ましい。Q"はメチル基、エチル基、ブチル基、フェニル基を示し、好ましくは合成の容易さ、原料の入手の容易さからメチル基である。A"は2価の炭化水素基で、好ましくは炭素数2以上の直鎖のアルキレン基、特に好ましくはプロピレン基である。dは1〜3の整数である。
(1)鈴木カップリング反応
パラジウム等の遷移金属を触媒に用いて塩基性条件下、有機ホウ素化合物と有機ハロゲン化物等をクロスカップリングさせる反応
(2)溝呂木−ヘックカップリング反応
パラジウム等の遷移金属を触媒に用いて塩基性条件下、末端アルケンとハロゲン化アリール等をクロスカップリングさせアルケニルアリール化合物を合成する反応
(3)根岸カップリング反応
パラジウム、ニッケル等の遷移金属を触媒に用いて、有機亜鉛化合物と有機ハロゲン化物等をクロスカップリングさせる反応
(4)スティレカップリング反応
パラジウム等の遷移金属を触媒に用いて、有機スズ化合物と有機ハロゲン化物等をクロスカップリングさせる反応
(5)辻−トロストカップリング反応
パラジウム等の遷移金属を触媒に用いて塩基性下、アリルエステル等と有機求核剤をクロスカップリングさせアリル位アルキル化生成物を合成する反応
(6)薗頭カップリング反応
パラジウム等の遷移金属を触媒に用いて塩基性条件下、末端アルキンとハロゲン化アリール等をクロスカップリングさせアルキニルアリール化合物を合成する反応
(7)熊田−玉尾カップリング反応
ニッケル、パラジウム等の遷移金属を触媒に用いて、グリニャール試薬と有機ハロゲン化物等をクロスカップリングさせる反応
(8)ブッフバルト−ハートウィックカップリング反応
パラジウム等の遷移金属を触媒に用いて塩基性条件下、ハロゲン化アリールとアミンまたはアルコールをクロスカップリングさせアリールアミンまたはアリールエーテルを合成する反応
有機ケイ素化合物の合成(1):
3−ブロモプロピルトリクロロシラン(化合物I)の14.0g(54.6mmol)、アリルマグネシウムクロライドTHF溶液の82ml(アリルマグネシウムクロライドを163.8mmol含む)を、280mlのTHF中、室温で5時間反応させた。反応後、水溶性塩類を除去し、更に、乾燥、蒸留し、目的化合物である3−ブロモプロピルトリアリルシラン(化合物II)を11.2g得た。
0.02(s, 18H), 0.61−0.68(m, 12H), 0.78−0.88(m, 2H), 1.40−1.52(m, 12H), 2.05−2.09(m, 4H), 4.92(d, J=15.9Hz, 6H), 5.74−5.83(m, 3H), 7.0−7.14(m,6H), 7.42(t, J=6.1Hz, 4H)
有機ケイ素化合物の合成(2):
上記実施例1で合成した化合物IIIの1.93g(3.36mmol)、カリウムシアナートの0.68g(8.38mmol)、よう化カリウムの0.13g(0.78g)を、5mlのDMF中、100℃に加熱し、2時間反応させた。反応後、室温まで冷却し、反応溶液にヘキサン10mlを加え、不溶物をろ過した後、減圧下で溶媒を留去し、有機ケイ素化合物である化合物Vを1.53g得た。この化合物VについてNMRを測定した。その結果を以下に示した。
−0.03(s, 18H), 0.48−0.59(m, 14H), 1.26−1.34(m, 8H), 1.48(d, J=8.1Hz, 6H), 3.23(t, J=6.7Hz, 1H), 4.80(d, J=7.9Hz, 3H), 4.81(d, J=17.8Hz, 3H), 5.76(ddt, J=17.8, 7.9, 6.7Hz, 3H)
−0.05(s, 18H), 0.48−0.59(m, 14H), 1.23−1.31(m, 8H), 1.48(d, J=8.1Hz, 6H), 1.60(br, 1H), 2.12(dd, J=11.9, 10.7Hz, 1H), 2.27−2.29(m, 1H), 2.79−2.82(m, 1H), 3.01−3.06(m, 3H), 3.18(q, J=9.8Hz, 1H), 3.53(br, 1H), 3.85−3.94(m, 2H), 4.79(d, J=9.2Hz, 3H), 4.80(d, J=17.3Hz, 3H), 5.73(ddt, J=17.3, 9.2, 8.1Hz, 3H), 7.24−7.39(m, 16H), 7.41−7.45(m, 2H), 7.52−7.56(m, 2H)
有機無機複合材料の調製:
化合物IIIの0.45g(0.78mmol)を、シリカ粉末(BET比表面積:1039m2/g、平均細孔径:4nm)の2.1gとともにアルゴン雰囲気下、ヘプタン中で48時間還流を行った後、ろ過、洗浄、80℃での減圧乾燥を行い、表2中のNo.2−19に該当する有機無機複合材料(以下、「有機無機複合材料2−19」という)を得た。元素分析より求めた有機無機複合材料2−19における固定化された配位子の固定化量は0.33mmol/gであった。得られた有機無機複合材料2−19について29Si CP−MAS NMRスペクトル解析を行った。その結果を図1に示す。有機無機複合材料2−19は3点でケイ素化合物とシリカゲルとが強固に結合ししている事がわかった。
有機無機複合材料の調製:
化合物IVのトリス[(ジメチルアリルシリル)プロピル]ジフェニルホスフィノプロピルシラン(表1中のNo.1−1に該当)の0.23gを、シリカ粉末(BET比表面積:1039m2/g、平均細孔径:4nm)の3.5gとともにアルゴン雰囲気下、トルエン中で88時間還流を行った後、ろ過、洗浄、80℃での減圧乾燥を行い、表2中のNo.2−25に該当する有機無機複合材料(以下、「有機無機複合材料2−25」という)を得た。元素分析より求めた有機無機複合材料2−25における固定化された配位子の固定化量は0.07mmol/gであった。得られた有機無機複合材料2−25について29Si CP−MAS NMRスペクトル解析を行った。その結果を図2に示す。有機無機複合材料2−25は2点でケイ素化合物とシリカゲルとが強固に結合ししている事がわかった。
鈴木カップリング反応用触媒の調製:
上記実施例4で調製した配位子を固定化した有機無機複合材料2−25の1gと酢酸パラジウム2.6mgをTHF中で24時間、室温にて撹拌した。その後、ろ過、洗浄を行い80℃で減圧乾燥を行い、有機無機複合触媒1を得た。有機無機複合触媒1の調製で生じたろ液中のPdを定量したところ分析下限値以下であった。
鈴木カップリング反応:
上記実施例5で得られた有機無機複合触媒1を用いて鈴木カップリング反応を行った。すなわち、p−ブロモ安息香酸の1ml、フェニルボロン酸の846mg(p−ブロモ安息香酸に対して1.1倍モル)、炭酸カリウムの1692mg(p−ブロモ安息香酸に対して2倍モル)、内標準物質であるp−tert−ブチルトルエンを1ml、上記実施例5で得られた有機無機複合触媒1の250mg(p−ブロモ安息香酸に対してPd換算で0.05mol%)を、6mlのトルエン中、100℃で5時間撹拌した。ガスクロマトグラフィーでビフェニル安息香酸エチルの収率を求めたところ84%であった。このときのPdの生成物中への溶出量は検出下限値以下であった。
有機ケイ素化合物の合成(3):
3−ブロモプロピルトリアリルシラン(化合物II)6.0g(21.8mmol)、ジメチルクロロシラン0.34g(3.6mmol)、クロロ−1,5−シクロオクタジエン イリジウムダイマー16.2mg(0.024mmol)、1,5−シクロオクタジエン11.9mg(0.11mmol)を、1.2mlのトルエン中、60℃で1時間反応させた。反応後、室温まで冷却し、減圧下で溶媒を留去した。この反応混合物をジエチルエーテル80mlに溶解した後、イソプロピルアルコール10mlを加えた。次いで、トリエチルアミン18mlを滴下し、室温で18時間撹拌した。析出した塩をろ別し、減圧下で溶媒を留去した。シリカゲルカラムクロマトグラフィー(ヘキサン/酢酸エチル=100/1)で精製を行い、化合物VIIを12.0g得た。
0.05(s, 18H), 0.49−0.64(m, 14H), 1.11(d, J=6.2Hz, 18H), 1.26−1.40(m, 6H), 1.75−1.83(m, 2H), 3.34(t, J=7.0Hz, 2H), 3.94(sept,J=6.2Hz, 3H)
有機ケイ素化合物の合成(4):
化合物VIIの1.20g(3.36mmol)、カリウムシアナートの0.68g(8.38mmol)、よう化カリウムの0.13g(0.78g)を、5mlのDMF中、100℃に加熱し、2時間反応させた。反応後、室温まで冷却し、反応溶液にヘキサン10mlを加え、不溶物をろ過した後、減圧下で溶媒を留去し、有機ケイ素化合物である化合物VIIIを1.53g得た。この化合物VIIIについてNMRを測定した。その結果を以下に示した。
0.06(s, 18H), 0.49−0.64(m, 14H), 1.11(d, J=6.2Hz, 18H), 1.26−1.40(m, 6H), 1.75−1.83(m, 2H), 3.21(t, J=6.6Hz, 2H), 3.96(sept,J=6.2Hz,3H)
有機ケイ素化合物の合成(5):
化合物VIIIの0.71g(1.49mmol)、(2S,4S)−4−(ジフェニルホスフィノ)−2−[(ジフェニルホスフィノ)メチル]ピロリジン0.50g(1.10mmol)を、10mlの塩化メチレン中、室温で15時間反応させた。反応後、減圧下で溶媒を留去し、更にシリカゲルカラムクロマトグラフィー(ヘキサン/酢酸エチル=4/1)にて精製し、有機ケイ素化合物である化合物1−32を0.36g得た。この化合物IXについてNMRを測定した。その結果を以下に示した。
0.11(s, 18H), 0.48−0.59(m, 14H), 1.06(d,J=6.2Hz)1.23−1.31(m, 8H), 1.60(br, 1H),2.27−2.29 (m, 1H), 2.79−2.82(m, 1H), 3.01−3.06(m, 3H), 3.18(q, J=9.8Hz, 1H), 3.53(br, 1H), 3.71−3.83(m, 2H), 3.91(sept,J=6.2Hz,6H, )7.24−7.39(m, 16H),7.41−7.45(m, 2H), 7.52−7.56(m, 2H)
水素化反応用触媒の調製:
80℃で真空乾燥したシリカ粉末(BET比表面積:1039m2/g、平均細孔径:4nm)の0.7gに、化合物VIの0.13g(0.13mmol)のトルエン溶液10mlを室温で加えた後、72時間加熱還流した。得られた固体を溶媒で洗浄し、80℃で減圧乾燥して表2中のNo.2−13に該当する有機無機複合材料(以下、「有機無機複合材料2−13」)を得た。元素分析より求めた有機無機複合材料2−13における化合物VIの担持量は、0.33mmol/gであった。
不斉水素化反応:
有機無機複合材料2−13(50mg)とビス(シクロオクタジエン)ロジウム(I)テトラフルオロボレート2mg(4.9mmol)を3mlのメタノール中、1気圧の水素雰囲気下、室温で30分撹拌した。α−(アセトアミド)けい皮酸の105mg(0.51mmol)を加え、室温で30分間反応させ、N−アセチル−フェニルアラニンを得た。HPLC分析(ダイセル製:Chirace AD−H)にて決定したD体の鏡像異性体過剰率は、97%e.e.であった。
有機無機複合材料の調製:
実施例3で調製した有機無機複合材料2−19(1.0g)にメチルアミンのメタノール溶液(40%)を10ml加えた。80℃で20時間反応させた後、得られた固体を溶媒で洗浄し、80℃で減圧乾燥して表2中のNo.2-22に該当する有機無機複合材料(以下、「有機無機複合材料2−22」)を得た。
鈴木カップリング反応用触媒の調製:
上記実施例12で調製した配位子を固定化した有機無機複合材料2−22の0.3gと酢酸パラジウム4.0mgをTHF中で24時間、室温にて撹拌した。その後、ろ過、洗浄を行い80℃で減圧乾燥を行い、有機無機複合触媒2を得た。有機無機複合触媒2の調製で生じたろ液中のPdを定量したところ分析下限値以下であった。
鈴木カップリング反応:
上記実施例13で得られた有機無機複合触媒2を用いて鈴木カップリング反応を行った。すなわち、p−ブロモ安息香酸の1ml、フェニルボロン酸の846mg(p−ブロモ安息香酸に対して1.1倍モル)、炭酸カリウムの1692mg(p−ブロモ安息香酸に対して2倍モル)、内標準物質であるp−tert−ブチルトルエンを1ml、上記実施例14で得られた有機無機複合触媒2の60mg(p−ブロモ安息香酸に対してPd換算で0.05mol%)を、6mlのトルエン中、100℃で1時間撹拌した。ガスクロマトグラフィーでビフェニル安息香酸エチルの収率を求めたところ100%であった。このときのPdの生成物中への溶出量は検出下限値以下であった。
有機無機複合材料の調製:
実施例3で調製した有機無機複合材料2−19(0.5g)とジフェニルリン化カリウムのTHF溶液(0.5mol/L)を30mlのTHF中で17時間加熱還流させた。得られた固体を溶媒で洗浄し、80℃で減圧乾燥して表2中のNo.2-1に該当する有機無機複合材料(以下、「有機無機複合材料2−1」)を得た。
鈴木カップリング反応用触媒の調製:
上記実施例15で調製した配位子を固定化した有機無機複合材料2−1の0.37gと酢酸パラジウム3.3mgをTHF中で24時間、室温にて撹拌した。その後、ろ過、洗浄を行い80℃で減圧乾燥を行い、有機無機複合触媒3を得た。有機無機複合触媒3の調製で生じたろ液中のPdを定量したところ分析下限値以下であった。
鈴木カップリング反応:
上記実施例16で得られた有機無機複合触媒3を用いて鈴木カップリング反応を行った。すなわち、p−ブロモ安息香酸の1ml、フェニルボロン酸の846mg(p−ブロモ安息香酸に対して1.1倍モル)、炭酸カリウムの1692mg(p−ブロモ安息香酸に対して2倍モル)、内標準物質であるp−tert−ブチルトルエンを1ml、上記実施例14で得られた有機無機複合触媒3の77mg(p−ブロモ安息香酸に対してPd換算で0.05mol%)を、6mlのトルエン中、100℃で5時間撹拌した。ガスクロマトグラフィーでビフェニル安息香酸エチルの収率を求めたところ81%であった。このときのPdの生成物中への溶出量は検出下限値以下であった。
有機無機複合材料の調製:
実施例3で調製した有機無機複合材料2−19(1.0g)に1−(2,6−ジイソプロピルフェニル)−1H−イミダゾールを1.34gとトルエン10mlを加えた。加熱還流下で4日間反応させた後、得られた固体を溶媒で洗浄し、80℃で減圧乾燥して表2中のNo.2−34に該当する有機無機複合材料を得た。
比較有機無機複合材料Aの調製:
3−クロロプロピルトリメトキシシラン0.16g(0.81mmol)を、シリカ粉末(BET比表面積:1039m2/g、平均細孔径:4nm)の2.1gとともにアルゴン雰囲気下、ヘプタン中で48時間還流を行った後、ろ過、洗浄、80℃での減圧乾燥を行い、比較有機無機複合材料Aを得た。元素分析より求めた比較有機無機複合材料Aにおける固定化された配位子の固定化量は1.23mmol/gであった。
比較有機無機複合材料Bの調製:
3−クロロプロピルジメチルメトキシシシラン0.16g(0.91mmol)を、シリカ粉末(BET比表面積:1039m2/g、平均細孔径:4nm)の2.1gとともにアルゴン雰囲気下、ヘプタン中で48時間還流を行った後、ろ過、洗浄、80℃での減圧乾燥を行い、有機無機複合材料Bを得た。元素分析より求めた有機無機複合材料Bにおける固定化された配位子の固定化量は1.19mmol/gであった。
有機無機複合材料の耐リーチング性能評価:
実施例3で調製した有機無機複合材料2−19(0.1g)を水中、80℃で48時間撹拌して耐久試験をおこなった。耐久試験後の有機無機複合材料の元素分析により残存した有機物量を定量し、耐久試験前後の有機物量の差から有機成分のリーチング率を決定した。その結果を表3に示す。また、比較例1で調製した比較有機無機複合材料Aおよび比較例2で調製した比較有機無機複合材料Aについても上記と同様の方法により耐久試験を行い、リーチング率を決定した。それらの結果も表3に示す。
Claims (11)
- 次の一般式(1)又は(2)で示される有機ケイ素化合物を構成する1つのケイ素原子に、分子末端に反応性ケイ素を含有する基を有する置換基を3つおよび分子末端に遷移金属またはその化合物を担持する能力を有する置換基を1つ結合したものである有機ケイ素化合物と、無機酸化物材料とを、前記有機ケイ素化合物の複数の反応性ケイ素を含有する基を介して結合せしめてなる有機無機複合材料。
リル基、イミダゾリル基、Yは、水酸基、アルコキシ基、アリールオキシ基、イソシ
アナト基、メルカプト基、ホスフィノ基、アミノ基、イミノ基、複素環の一つ以上を
含む一価の有機基、Aは、二価の炭化水素基、Rはメチル基、エチル基、ブチル基、
フェニル基、Qはメチル基、エチル基、ブチル基、フェニル基を示し、kは1〜3の
整数、nは1、mは3、lは0を示し、l+m+nは4である。)
アリル基、イミダゾリル基、Y'は、ハロゲンを含む一価の有機基、A'は、二価の炭
化水素基、R'はメチル基、エチル基、ブチル基、フェニル基、Q'はメチル基、エチ
ル基、ブチル基、フェニル基を示し、eは1〜3の整数、fは3、hは1、gは0を
示し、f+h+gは4である。) - 無機酸化物材料の表面の酸素原子と、反応性ケイ素を含有する基のケイ素原子が共有結合しているものである請求項1記載の有機無機複合材料。
- 分子末端に反応性ケイ素を含有する基が、炭素数2以上の直鎖のアルキレン基と反応性ケイ素が結合したものである請求項1または2記載の有機無機複合材料。
- 無機酸化物材料が、チタン、ケイ素、アルミニウム、ジルコニウム、マグネシウムの単独酸化物またはそれらを含む複合酸化物である請求項1ないし3の何れかに記載の有機無機複合材料。
- 請求項1〜4のいずれかに記載の有機無機複合材料に遷移金属またはその化合物を担持させてなる有機無機複合触媒。
- 請求項1〜4のいずれかに記載の有機無機複合材料と遷移金属またはその化合物を含むクロスカップリング反応用触媒。
- 遷移金属またはその化合物が、白金、パラジウム、ニッケルまたはそれらを含む化合物である請求項6記載のクロスカップリング反応用触媒。
- 請求項6または7記載のクロスカップリング反応用触媒を用いるクロスカップリング反応方法。
- 請求項1〜4のいずれかに記載の有機無機複合材料と遷移金属またはその化合物を含む水素化反応用触媒。
- 遷移金属またはその化合物が、ルテニウム、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、白金、金またはそれらを含む化合物である請求項9記載の水素化反応用触媒。
- 請求項9または10記載の水素化反応用触媒を用いる水素化反応方法。
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US20140100401A1 (en) * | 2011-05-09 | 2014-04-10 | Saudi Basic Industries Corporation | Catalyst for the alkylation of aromatic hydrocarbons |
CN102302953B (zh) * | 2011-06-28 | 2013-05-22 | 太原理工大学 | 一种金属配合物官能化类水滑石复合材料的制备方法 |
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