JP2013031806A - Immobilized palladium catalyst - Google Patents
Immobilized palladium catalyst Download PDFInfo
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- JP2013031806A JP2013031806A JP2011169030A JP2011169030A JP2013031806A JP 2013031806 A JP2013031806 A JP 2013031806A JP 2011169030 A JP2011169030 A JP 2011169030A JP 2011169030 A JP2011169030 A JP 2011169030A JP 2013031806 A JP2013031806 A JP 2013031806A
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- JP
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- Prior art keywords
- palladium
- catalyst
- polydimethylsilane
- metal oxide
- solvent
- Prior art date
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 76
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002198 insoluble material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 6
- 230000003100 immobilizing effect Effects 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 229920000548 poly(silane) polymer Polymers 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 9
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 9
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 9
- 229940031439 squalene Drugs 0.000 description 9
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 1
- JAGZUIGGHGTFHO-UHFFFAOYSA-N Ethyl 3-phenylpropanoate Chemical compound CCOC(=O)CCC1=CC=CC=C1 JAGZUIGGHGTFHO-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000003820 Medium-pressure liquid chromatography Methods 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- -1 alumina Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003819 low-pressure liquid chromatography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
この発明は、ポリジメチルシランを利用した固定化パラジウム触媒に関する。 The present invention relates to an immobilized palladium catalyst using polydimethylsilane.
パラジウムは種々の化学反応の触媒として古くから使用されており、化学プロセスでは安定性に優れ、生成物との分離や再利用が容易な不均一系パラジウム触媒が多用されている(特許文献1など)。このような不均一系パラジウム触媒の多くは、アルミナなどの金属酸化物、硫酸バリウム、炭酸カルシウム、活性炭などの不溶性担体にパラジウム金属が固定されている。近年、電子顕微鏡など分析技術の進歩に伴いパラジウムが数個から数千個集まった状態(パラジウムクラスター)の観察が可能になり、不均一系パラジウム触媒反応においてはパラジウムクラスターのサイズが小さいほど触媒活性が増大することが明らかになってきている。
白金系触媒の固定化方法として、白金錯体をポリシランのマイクロカプセルに封入した例が知られているが(特許文献2など)、ここで用いられるポリシランは容易に軟化又は溶媒に溶解するものであったため、長期の使用や再利用の必要性が高い産業用の有機合成用触媒として使用することは難しかった。
本発明者らは、微小金属クラスターの製造方法としてマイクロカプセル化(MC)法やポリマーインカルセランド(PI)法を開発し、ポリ(メチルフェニルシラン)を担体とした数ナノメートルのパラジウムクラスターを安定に単離し、これらが合成用触媒として有用であることを報告している(特許文献3,4、非特許文献1)。ここで用いられたポリ(メチルフェニルシラン)は可溶性であるため、産業用の有機合成用触媒として用いるためには、このポリシランを加熱して架橋させることが必要であった。
一方、ポリジメチルシランは、他のポリシランとは異なり、ほとんどの溶媒に対して不溶性であるため(非特許文献2など)、MC法やPI法による金属触媒の担体としては利用されていなかった。
Palladium has long been used as a catalyst for various chemical reactions, and heterogeneous palladium catalysts that are excellent in stability and easy to separate and reuse from products are widely used in chemical processes (Patent Document 1, etc.) ). In many of such heterogeneous palladium catalysts, palladium metal is fixed to an insoluble carrier such as a metal oxide such as alumina, barium sulfate, calcium carbonate, or activated carbon. In recent years, with the advancement of analytical techniques such as electron microscopes, it has become possible to observe several to thousands of palladium (palladium clusters). In heterogeneous palladium catalyzed reactions, the smaller the palladium cluster size, the more catalytic activity It has become clear that increases.
As a method for immobilizing a platinum-based catalyst, an example in which a platinum complex is encapsulated in a microcapsule of polysilane is known (eg, Patent Document 2), but the polysilane used here is easily softened or dissolved in a solvent. Therefore, it has been difficult to use as a catalyst for organic synthesis for industrial use, which has a high necessity for long-term use and reuse.
The present inventors have developed a microencapsulation (MC) method or a polymer incalcelland (PI) method as a method for producing a fine metal cluster, and a palladium cluster of several nanometers using poly (methylphenylsilane) as a carrier. It has been reported that these are isolated stably and are useful as catalysts for synthesis (Patent Documents 3 and 4, Non-Patent Document 1). Since poly (methylphenylsilane) used here is soluble, it has been necessary to heat and crosslink this polysilane in order to use it as an industrial organic synthesis catalyst.
On the other hand, unlike other polysilanes, polydimethylsilane is insoluble in most solvents (such as Non-Patent Document 2), and thus has not been used as a support for metal catalysts by the MC method or PI method.
ポリジメチルシランは安価であるため金属触媒の固定用のポリシランとして使用することができたならば、産業上のメリットは大きい。
しかしながら、ポリジメチルシランは、ポリシランの中では唯一いかなる溶媒にも溶解しないため(非特許文献1など)、いかなる方法によって金属触媒をポリジメチルシランにより固定化するかについては従来知られていなかった。
更に、産業上で使用するポリシラン固定化金属触媒としては、高活性かつ繰り返し使用や長期間使用しても活性低下が起こらないことが求められている。
即ち、本発明は、安価なポリジメチルシランを利用した、高活性かつ繰り返し使用や長期間使用しても活性低下が起こらない固定化パラジウム触媒を提供することを目的とする。
Since polydimethylsilane is inexpensive, if it can be used as a polysilane for fixing a metal catalyst, the industrial merit is great.
However, since polydimethylsilane is the only polysilane that is not soluble in any solvent (Non-patent Document 1, etc.), it has not been known how to fix the metal catalyst with polydimethylsilane by any method.
Furthermore, the polysilane-immobilized metal catalyst used in the industry is required to have high activity and no decrease in activity even after repeated use or long-term use.
That is, an object of the present invention is to provide an immobilized palladium catalyst that uses an inexpensive polydimethylsilane and does not cause a decrease in activity even when used repeatedly or for a long time.
発明者らは上記課題を鋭意検討した結果、ポリジメチルシランを溶媒に溶解させようとせずに、ポリジメチルシランと金属酸化物を溶媒に分散させた状態でこれらにパラジウムを担持させ、不溶物を溶媒から分離することにより、固定化パラジウム触媒が得られることを見出した。溶媒中にポリジメチルシランと金属酸化物が存在することにより、大部分のパラジウムは径が数nmの0価のクラスターとなって固定化される。
この固定化段階は常温で行うことができ、従来のように(特許文献3,4、非特許文献1)、ポリシランを安定化させるために、加熱して架橋させる必要はない。
このようにして得られた固定化パラジウム触媒は、高活性であって、繰り返し使用や長期間使用しても活性低下が起こりにくいという顕著な特性を持つことが確認された(実施例15〜29、実施例30〜34参照)。
As a result of intensive studies on the above problems, the inventors have supported palladium in a state where polydimethylsilane and a metal oxide are dispersed in a solvent without trying to dissolve polydimethylsilane in the solvent, It has been found that an immobilized palladium catalyst can be obtained by separating from the solvent. Due to the presence of polydimethylsilane and metal oxide in the solvent, most palladium is immobilized as a zero-valent cluster having a diameter of several nm.
This immobilization step can be performed at room temperature, and as in the past (Patent Documents 3 and 4, Non-Patent Document 1), it is not necessary to heat and crosslink in order to stabilize polysilane.
It was confirmed that the immobilized palladium catalyst thus obtained has a high activity and has a remarkable characteristic that the activity is hardly lowered even after repeated use or long-term use (Examples 15 to 29). , See Examples 30-34).
即ち、本発明は、ポリジメチルシラン、金属酸化物及びパラジウムクラスターから成る固定化パラジウム触媒であって、該パラジウムクラスターが該ポリジメチルシラン及び該金属酸化物に担持されたことを特徴とする固定化パラジウム触媒である。
また本発明は、以下の工程からなる固定化パラジウム触媒の製法である。
(1)−20〜60℃で、パラジウム塩又はパラジウム錯体が溶解又は分散し、ポリジメチルシラン及び金属酸化物が分散した溶液又は分散液を用意する工程、及び
(2)前記溶液又は分散液から不溶物を分離する工程
更に本発明は、上記触媒又は上記製法により製造された触媒を、水素化反応又は鈴木−宮浦カップリング反応に使用する方法である。
That is, the present invention is an immobilized palladium catalyst comprising polydimethylsilane, a metal oxide and a palladium cluster, wherein the palladium cluster is supported on the polydimethylsilane and the metal oxide. It is a palladium catalyst.
Moreover, this invention is a manufacturing method of the fixed palladium catalyst which consists of the following processes.
(1) a step of preparing a solution or dispersion in which a palladium salt or a palladium complex is dissolved or dispersed at −20 to 60 ° C. and polydimethylsilane and a metal oxide are dispersed; and (2) from the solution or the dispersion. Step of separating insoluble matter Further, the present invention is a method of using the above catalyst or the catalyst produced by the above production method in a hydrogenation reaction or a Suzuki-Miyaura coupling reaction.
従来のポリジメチルシラン以外のポリシラン(即ち、可溶性ポリシラン)を用いる(ポリシラン−金属酸化物)担持パラジウム触媒の製法においては、パラジウムを還元した後ポリシランに対する貧溶媒を加えてポリシランを析出させる工程や、加熱によりポリシランを不溶化する工程が必要であったが(特許文献3,4、非特許文献1)、本発明の不溶性であるポリジメチルシランを利用した製法においては、このような工程が不要であることから、製造コストを大幅に下げることができる。 In the conventional method for producing a (polysilane-metal oxide) -supported palladium catalyst using a polysilane other than polydimethylsilane (ie, soluble polysilane), a step of precipitating polysilane by adding a poor solvent for polysilane after reducing palladium, Although a process for insolubilizing polysilane by heating was necessary (Patent Documents 3 and 4, Non-Patent Document 1), such a process is unnecessary in the production method using insoluble polydimethylsilane of the present invention. As a result, the manufacturing cost can be greatly reduced.
本発明の(ポリジメチルシラン−金属酸化物)担持パラジウム触媒は、ポリジメチルシラン及び金属酸化物にパラジウムクラスターを固定したものである。 The (polydimethylsilane-metal oxide) -supported palladium catalyst of the present invention is obtained by fixing a palladium cluster to polydimethylsilane and a metal oxide.
本発明で用いるポリジメチルシラン(以下「PMPSi」とも表す。)は、ケイ素−ケイ素結合が繋がった主鎖とメチル基のみの置換基からなる高分子で、結晶性が高く、ほとんど全ての溶媒に溶解しない。その分子量は好ましくは約1,000〜約10,000である。このようなポリジメチルシランは、通常、ジクロロジメチルシランと金属ナトリウムからKipping法により製造することができる。 Polydimethylsilane (hereinafter also referred to as “PMPSi”) used in the present invention is a polymer composed of a main chain having a silicon-silicon bond and a substituent of only a methyl group. Does not dissolve. Its molecular weight is preferably from about 1,000 to about 10,000. Such polydimethylsilane can usually be produced from dichlorodimethylsilane and metallic sodium by the Kipping method.
本発明で用いる金属酸化物(以下「MO」とも表す。)は、アルミニウム、ケイ素、ジルコニウム、マグネシウム又はこれらの組み合わせの酸化物である。このような金属酸化物として、γ−アルミナ、α−アルミナ、シリカ−アルミナが好ましい。
α−アルミナは、通常、可溶性アルミニウム塩の水溶液から水酸化アルミニウムを沈澱・ろ過・加熱することにより得られ(バイヤー法)、コランダム型の結晶形態を持ち、化学的に安定であり、融点が高い(1999〜2032℃)。γ−アルミナは、三水化物やα水化アルミナを加熱脱水し、更に900℃に保つことにより得られ、スピネル型の結晶形態を持つ。シリカ−アルミナは、シリカ及びアルミナヒドロゲルを混練して得られた粗シリカアルミナヒドロゲルを焼成して製造され、固体酸性を有し、多くは非晶質である。
触媒をカラムに充填してフロー方式で使用する場合は、この金属酸化物はカラムクロマトグラフィー用などの粒径が揃っているもの(例えば、粒径10〜200μm)が好ましい。金属酸化物の粒径が大きすぎると触媒活性が低下するが、小さ過ぎるとろ過速度の低下や、フロー方式で用いる場合は圧損が大きくなる。
The metal oxide (hereinafter also referred to as “MO”) used in the present invention is an oxide of aluminum, silicon, zirconium, magnesium, or a combination thereof. As such a metal oxide, γ-alumina, α-alumina, and silica-alumina are preferable.
α-Alumina is usually obtained by precipitating, filtering and heating aluminum hydroxide from an aqueous solution of a soluble aluminum salt (Bayer method), has a corundum type crystal form, is chemically stable, and has a high melting point. (1999-2032 ° C). γ-alumina is obtained by heating and dehydrating trihydrate or α-hydrated alumina, and keeping it at 900 ° C., and has a spinel crystal form. Silica-alumina is produced by firing a crude silica-alumina hydrogel obtained by kneading silica and alumina hydrogel, has a solid acidity, and is mostly amorphous.
When the catalyst is packed in a column and used in a flow system, the metal oxide is preferably one having a uniform particle size for column chromatography (for example, a particle size of 10 to 200 μm). If the particle size of the metal oxide is too large, the catalytic activity is lowered, but if it is too small, the filtration rate is lowered, and the pressure loss is increased when used in the flow method.
本発明の触媒中のパラジウムは0価のパラジウムクラスターとしてポリジメチルシランと金属酸化物に固定されるが、2価のパラジウムが混在してもよい。このクラスターのサイズは2〜10nm程度であり、電子顕微鏡により観察可能である。
本発明の触媒中のパラジウム/PMPSi/MO比は、0.01〜0.5mmol/0.02〜0.5g/1g、好ましくは0.02〜0.2mmol/0.05〜0.25g/1gである。
Palladium in the catalyst of the present invention is fixed to polydimethylsilane and metal oxide as a zero-valent palladium cluster, but divalent palladium may be mixed. The size of this cluster is about 2 to 10 nm and can be observed with an electron microscope.
The palladium / PMPSi / MO ratio in the catalyst of the present invention is 0.01 to 0.5 mmol / 0.02 to 0.5 g / 1 g, preferably 0.02 to 0.2 mmol / 0.05 to 0.25 g / 1 g.
本発明の(ポリジメチルシラン−金属酸化物)担持パラジウム触媒は、溶媒中でパラジウム源からのPdをポリジメチルシランと金属酸化物に固定することにより得ることができる。
パラジウム源としては、一般に、パラジウム塩又はパラジウム錯体が用いられる。このようなパラジウム源としては、例えば、酢酸パラジウム、塩化パラジウム、臭化パラジウム、ヨウ化パラジウム、酸化パラジウム、硝酸パラジウム、硫酸パラジウム、パラジウム(II)アセチルアセトナート、テトラキス(トリフェニルホスフィン)パラジウム(0)が挙げられ、好ましくは酢酸パラジウム又は塩化パラジウムである。
The (polydimethylsilane-metal oxide) -supported palladium catalyst of the present invention can be obtained by fixing Pd from a palladium source to polydimethylsilane and a metal oxide in a solvent.
In general, a palladium salt or a palladium complex is used as the palladium source. Examples of such a palladium source include palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium oxide, palladium nitrate, palladium sulfate, palladium (II) acetylacetonate, tetrakis (triphenylphosphine) palladium (0 And preferably palladium acetate or palladium chloride.
パラジウム塩をポリジメチルシランと金属酸化物を含む溶媒中で混合することにより、パラジウムは還元される。パラジウム塩によっては、還元反応を促進するために、この溶媒中に還元剤を共存させてもよい。この還元剤としては、水素化ホウ素ナトリウム、ヒドロシラン化合物、水素ガスなどが好適である。金属酸化物を用いずにポリジメチルシランのみにパラジウムを担持させた場合には、重量あたりの担持量を大きくすることができない(例えば、触媒O、表1、2参照)。
この際用いる溶媒は、パラジウム源を溶解させる溶媒が好ましい。しかし、パラジウム源を単に分散させる溶媒を使用してもよい。また、ポリジメチルシランと金属酸化物は、溶媒に溶解しないので、溶媒中に分散させる。さらに、テトラヒドロフランやジオキサンなどの水と混和する有機溶媒を用いた場合は、パラジウム塩を水溶液として添加してもよい。
このような溶媒として、脂肪族炭化水素、芳香族炭化水素、エーテル、アルコールなどが利用でき、中でもトルエン、テトラヒドロフランなどが好適である。また、低分子量のアルコールを溶媒に共存させることでパラジウムの還元反応を促進及び完結させることができる。低分子量のアルコールとしては炭素数3以下のアルコールが好ましく、中でもメタノールが好適であり、アルコールを添加するタイミングとしては溶媒中にあらかじめ加えておいても、又は混合の途中で添加してもよい。添加するアルコールの量は、主溶媒に対して1〜100%(V/V)である。
Palladium is reduced by mixing the palladium salt in a solvent containing polydimethylsilane and a metal oxide. Depending on the palladium salt, a reducing agent may coexist in this solvent in order to promote the reduction reaction. As the reducing agent, sodium borohydride, hydrosilane compound, hydrogen gas and the like are suitable. When palladium is supported only on polydimethylsilane without using a metal oxide, the supported amount per weight cannot be increased (for example, see Catalyst O, Tables 1 and 2).
The solvent used at this time is preferably a solvent that dissolves the palladium source. However, a solvent in which the palladium source is simply dispersed may be used. Moreover, since polydimethylsilane and a metal oxide do not melt | dissolve in a solvent, they are dispersed in a solvent. Furthermore, when an organic solvent miscible with water such as tetrahydrofuran or dioxane is used, a palladium salt may be added as an aqueous solution.
As such a solvent, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, alcohols and the like can be used, and among these, toluene, tetrahydrofuran and the like are preferable. Moreover, the reduction reaction of palladium can be promoted and completed by allowing a low molecular weight alcohol to coexist in a solvent. As the low molecular weight alcohol, an alcohol having 3 or less carbon atoms is preferable, and methanol is particularly preferable. The timing of adding the alcohol may be previously added to the solvent or may be added during the mixing. The amount of alcohol to be added is 1 to 100% (V / V) with respect to the main solvent.
パラジウム塩は、還元が進行するに従い反応系の色が黒変する。この還元反応は、通常、−20℃〜60℃、好ましくは0〜40℃、より好ましくは0℃〜室温で、反応時間が1分間〜24時間で行われる。温度は高すぎるとクラスターサイズが大きくなるため、低い方が好ましく、還元反応を速くする目的で加熱する場合も60℃以下で実施する。
還元反応終了後、上記溶液又は分散液から不溶物を分離する。この分離方法としては、ろ過や遠心操作が行われる。通常、溶媒から分離した不溶物をその後十分に洗浄後、乾燥する。このろ過や洗浄工程により、固定されなかったパラジウムや還元剤由来の不純物等は除去される。洗浄溶媒としては反応に使用した溶媒、メタノール、水などが好適である。乾燥方法に制約は無いが、減圧下で加熱乾燥するのが簡便である。
As for the palladium salt, the color of the reaction system changes to black as the reduction proceeds. This reduction reaction is usually performed at -20 ° C to 60 ° C, preferably 0 to 40 ° C, more preferably 0 ° C to room temperature, and a reaction time of 1 minute to 24 hours. If the temperature is too high, the cluster size increases, so a lower one is preferable. Even when heating is performed for the purpose of speeding up the reduction reaction, the heating is performed at 60 ° C. or lower.
After completion of the reduction reaction, insoluble matters are separated from the solution or dispersion. As this separation method, filtration or centrifugation is performed. Usually, the insoluble matter separated from the solvent is then thoroughly washed and dried. By this filtration or washing step, the impurities that are not fixed and impurities derived from the reducing agent are removed. The washing solvent is preferably the solvent used in the reaction, methanol, water or the like. Although there is no restriction | limiting in the drying method, it is easy to heat-dry under reduced pressure.
パラジウム源としてパラジウム(0)錯体を用いる場合には、パラジウム錯体をポリジメチルシラン及び金属酸化物と共に溶媒中で混合することにより配位子交換し、パラジウムは、パラジウムクラスターとしてポリメチルフェニルシラン及び金属酸化物に固定される。この配位子交換は、通常0〜40℃で、反応時間が0.5〜24時間で行われる。0価でない錯体を使用する場合は還元操作が必要であり、この還元操作として上述の還元操作を行えばよい。溶媒は上記と同様の溶媒が用いられる。 When a palladium (0) complex is used as a palladium source, ligand exchange is performed by mixing the palladium complex with polydimethylsilane and a metal oxide in a solvent, and palladium is converted into a polymethylphenylsilane and a metal as a palladium cluster. Fixed to oxide. This ligand exchange is usually performed at 0 to 40 ° C. and a reaction time of 0.5 to 24 hours. When a non-valent complex is used, a reduction operation is necessary, and the above-described reduction operation may be performed as this reduction operation. As the solvent, the same solvent as described above is used.
溶媒中のパラジウム源の濃度は、Pdとして0.01〜0.2M、ポリメチルシランの量は20〜200g/リットル、金属酸化物の量は100〜500g/リットルである。
還元剤を用いる場合には、還元剤の使用量はパラジウム源に対して当量から10当量程度である。
このようにして得られた(ポリジメチルシラン−金属酸化物)担持パラジウム触媒は、水添反応や水素化分解反応等の水素化反応や鈴木−宮浦カップリング反応などに利用できる。
The concentration of the palladium source in the solvent is 0.01 to 0.2 M as Pd, the amount of polymethylsilane is 20 to 200 g / liter, and the amount of metal oxide is 100 to 500 g / liter.
When the reducing agent is used, the amount of the reducing agent used is about 10 to 10 equivalents with respect to the palladium source.
The (polydimethylsilane-metal oxide) -supported palladium catalyst thus obtained can be used for hydrogenation reactions such as hydrogenation reactions and hydrocracking reactions, and Suzuki-Miyaura coupling reactions.
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。
パラジウムの担持量はICP発光分析装置((株)島津製作所製ICPS-7510)により測定した。1H-NMRは重クロロホルムを溶媒として核磁気共鳴装置(日本電子株式会社製 JNM−LA500)により測定した。
The following examples illustrate the invention but are not intended to limit the invention.
The amount of palladium supported was measured with an ICP emission spectrometer (ICPS-7510, manufactured by Shimadzu Corporation). 1 H-NMR was measured with a nuclear magnetic resonance apparatus (JNM-LA500, manufactured by JEOL Ltd.) using deuterated chloroform as a solvent.
実施例1
ポリジメチルシラン(日本曹達株式会社製 パーメチルポリシラン、数平均分子量2,500、5.0 g)と活性アルミナ(和光純薬工業株式会社、300 mesh、45.0 g)が入ったセパラブルフラスコ(300 ml)に、アルゴン気流下でトルエン(100 ml)を加えた。氷冷下で攪拌しながら酢酸パラジウム(アルドリッチ社製、5.0 mmol)を加え、5分後に氷浴を水浴(25℃)に代えた。15分後、メタノール(100 ml)を10分間で滴下し、さらに15分間攪拌を続けた。生成物をろ過し、固形物をトルエン(3回)、メタノール(3回)、水(4回)で順次洗浄した。得られた粉末を減圧下、80℃で乾燥して灰茶色粉末((ポリジメチルシラン−γ−アルミナ)担持パラジウム、以下「触媒A」と呼ぶ。)を得た(50.1 g)。
Example 1
In a separable flask (300 ml) containing polydimethylsilane (Nippon Soda Co., Ltd. permethylpolysilane, number average molecular weight 2,500, 5.0 g) and activated alumina (Wako Pure Chemical Industries, Ltd., 300 mesh, 45.0 g) Toluene (100 ml) was added under an argon stream. Palladium acetate (Aldrich, 5.0 mmol) was added while stirring under ice cooling, and the ice bath was replaced with a water bath (25 ° C.) after 5 minutes. After 15 minutes, methanol (100 ml) was added dropwise over 10 minutes and stirring was continued for another 15 minutes. The product was filtered and the solid was washed sequentially with toluene (3 times), methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a grayish brown powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst A”) (50.1 g).
実施例2
ポリジメチルシラン(5.0 g)と活性アルミナ(300 mesh、45.0 g)と水素化ホウ素ナトリウム(和光純薬工業株式会社、25 mmol)が入ったセパラブルフラスコ(300 ml)に、アルゴン気流下でトルエン(100 ml)を加えた。氷冷下で攪拌しながら塩化パラジウム(アルドリッチ社製、5.0 mmol)のメタノール(25 ml)懸濁液を加えた後、氷浴を水浴(25℃)に代えた。5分後、メタノール(75 ml)を5分間で滴下し、さらに30分間攪拌を続けた。生成物をろ過し、固形物をメタノール(3回)、水(4回)で順次洗浄した。得られた粉末を減圧下、80℃で乾燥して白灰色粉末((ポリジメチルシラン−γ−アルミナ)担持パラジウム、以下「触媒B」と呼ぶ。)を得た(51.4 g)。
Example 2
In a separable flask (300 ml) containing polydimethylsilane (5.0 g), activated alumina (300 mesh, 45.0 g) and sodium borohydride (Wako Pure Chemical Industries, Ltd., 25 mmol), toluene was added under an argon stream. (100 ml) was added. A methanol (25 ml) suspension of palladium chloride (Aldrich, 5.0 mmol) was added with stirring under ice cooling, and then the ice bath was replaced with a water bath (25 ° C.). After 5 minutes, methanol (75 ml) was added dropwise over 5 minutes and stirring was continued for another 30 minutes. The product was filtered and the solid was washed sequentially with methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain white gray powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst B”) (51.4 g).
実施例3
ポリジメチルシラン(5.0 g)と活性アルミナ(300 mesh、45.0 g)が入ったセパラブルフラスコ(300 ml)に、アルゴン気流下でトルエン/メタノールの混合溶媒(100 ml/1 ml)を加えた。氷冷下で攪拌しながら酢酸パラジウム(アルドリッチ社製、5.0 mmol)を加え、5分後に氷浴を水浴(25℃)に代えた。5分後、メタノール(4 ml)を30分間で滴下し、さらに20分間攪拌を続けた。生成物をろ過し、固形物をトルエン(3回)、メタノール(3回)、水(4回)で順次洗浄した。得られた粉末を減圧下、80℃で乾燥して灰茶色粉末((ポリジメチルシラン−γ−アルミナ)担持パラジウム、以下「触媒C」と呼ぶ。)を得た(52.0 g)。
Example 3
A toluene / methanol mixed solvent (100 ml / 1 ml) was added to a separable flask (300 ml) containing polydimethylsilane (5.0 g) and activated alumina (300 mesh, 45.0 g) under an argon stream. Palladium acetate (Aldrich, 5.0 mmol) was added while stirring under ice cooling, and the ice bath was replaced with a water bath (25 ° C.) after 5 minutes. After 5 minutes, methanol (4 ml) was added dropwise over 30 minutes and stirring was continued for another 20 minutes. The product was filtered and the solid was washed sequentially with toluene (3 times), methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a grayish brown powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst C”) (52.0 g).
実施例4〜8
表1に示すように、酢酸パラジウム、ポリジメチルシラン、アルミナの比率を変えて、実施例1と同様にして、(ポリジメチルシラン−γ−アルミナ)担持パラジウムを合成した。得られた触媒をそれぞれ「触媒D〜H」と呼ぶ。
実施例9〜14
表1に示すように金属酸化物の種類を変えて、実施例1と同様にして、(ポリジメチルシラン−金属酸化物)担持パラジウムを合成した。γ−アルミナ、シリカ−アルミナ及びマグネシアはアルドリッチ社、ジルコニアは関東化学株式会社、ゼオライトは東ソー株式会社のものを用いた。得られた(ポリジメチルシラン−金属酸化物)担持パラジウムをそれぞれ「触媒I〜N」と呼ぶ。
Examples 4-8
As shown in Table 1, (polydimethylsilane-γ-alumina) -supported palladium was synthesized in the same manner as in Example 1 except that the ratios of palladium acetate, polydimethylsilane, and alumina were changed. The obtained catalysts are called “catalysts D to H”, respectively.
Examples 9-14
As shown in Table 1, (polydimethylsilane-metal oxide) -supported palladium was synthesized in the same manner as in Example 1 except that the type of metal oxide was changed. For γ-alumina, silica-alumina and magnesia, Aldrich was used, for zirconia, Kanto Chemical Co., and for zeolite, Tosoh Corp. The obtained (polydimethylsilane-metal oxide) -supported palladium is referred to as “catalysts I to N”, respectively.
比較例1
ポリジメチルシラン(5.0 g)をフラスコ(100 ml)に秤量し、アルゴン気流下でトルエン(20 ml)を加えた。氷冷下で攪拌しながら酢酸パラジウム(アルドリッチ社製、0.2 mmol)を加え、90分後にメタノール(50 ml)を滴下し、さらに15分間攪拌を続けた。生成物をろ過し、固形物をメタノール(3回)洗浄した。得られた粉末を減圧下、80℃で乾燥して灰色粉末(ポリジメチルシラン担持パラジウム、以下「触媒O」と呼ぶ。)を得た(5.0 g)。
Comparative Example 1
Polydimethylsilane (5.0 g) was weighed into a flask (100 ml), and toluene (20 ml) was added under an argon stream. Palladium acetate (manufactured by Aldrich, 0.2 mmol) was added with stirring under ice-cooling, and methanol (50 ml) was added dropwise after 90 minutes, and stirring was further continued for 15 minutes. The product was filtered and the solid was washed with methanol (3 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a gray powder (polydimethylsilane-supported palladium, hereinafter referred to as “catalyst O”) (5.0 g).
得られた触媒のパラジウムの担持量とパラジウムの回収率を表1に示す。
実施例15〜28
この実施例では、フロー方式で、下式のスクアレンの水素化反応を行った。
In this example, the squalene hydrogenation reaction of the following formula was performed by a flow method.
この実施例で用いたフロー方式の水素化反応装置を図1に示す。この装置は、送液ポンプ((株)島津製作所製LC-6AD)、マスフローコントローラー(リンテック株式会社製MC-3000E及びRP-300)、及び反応容器として中・低圧液クロ用ガラスカラム(東京理化器械株式会社製、10φ×100 mm又は5φ×50 mm、ガラスフィルターポアサイズ:10μm)を使用し、これらを1/16インチ(1.6mm)SUSチューブ又はPEEKチューブで接続した。送液ポンプによりサーバーから送られた原料と、マスフローコントローラーを通して送られた水素ガスは触媒を充填したカラムの上端で混合され、恒温槽内の触媒が充填されたカラムに送り込まれる。生成物はカラムの下端から余剰水素ガスとともに流出する。
表2に示す量の触媒A〜Nを、上記水素化反応装置のガラスカラム(内径10φ×100 mm)に充填し、スクワレン(和光純薬工業株式会社)の水添反応を下記条件で行った。スクワレン:200μl/min、水素ガス:120 ml/min、カラム温度:40℃又は60℃。
A flow-type hydrogenation reactor used in this example is shown in FIG. This equipment consists of a liquid feed pump (LC-6AD manufactured by Shimadzu Corporation), a mass flow controller (MC-3000E and RP-300 manufactured by Lintec Corporation), and a glass column for medium / low pressure liquid chromatography (Tokyo Rika as a reaction vessel). Instrument Co., Ltd., 10φ × 100 mm or 5φ × 50 mm, glass filter pore size: 10 μm) was used, and these were connected by 1/16 inch (1.6 mm) SUS tube or PEEK tube. The raw material sent from the server by the liquid feed pump and the hydrogen gas sent through the mass flow controller are mixed at the upper end of the column filled with the catalyst, and sent to the column filled with the catalyst in the thermostatic bath. The product flows out from the lower end of the column together with excess hydrogen gas.
The amount of catalyst A to N shown in Table 2 was packed in the glass column (inner diameter 10φ × 100 mm) of the hydrogenation reactor, and the hydrogenation reaction of squalene (Wako Pure Chemical Industries, Ltd.) was performed under the following conditions. . Squalene: 200 μl / min, hydrogen gas: 120 ml / min, column temperature: 40 ° C. or 60 ° C.
比較例2
触媒Oをガラスカラム(内径5φ×50 mm)に充填し、実施例15と同様に、スクワレンの水添反応を以下の条件で行った。スクワレン(neat):50μl/min、水素ガス:30 ml/min、カラム温度:80℃。
アルミナを含まない触媒は嵩比重が低いため同容量のカラムに充填できるパラジウム量は少ない(表2)。
実施例29
触媒Oの代わりに触媒Gを用いて、比較例2と同様にして、スクワレンの水添反応を行った。
比較例3
触媒Aの代わりに市販の1%パラジウム/アルミナ(アルドリッチ社製、以下「触媒P」と呼ぶ。)を用いて、実施例15と同様の方法でスクワレンの水添反応を行った。
Comparative Example 2
The catalyst O was packed in a glass column (inner diameter 5φ × 50 mm), and the squalene hydrogenation reaction was carried out under the following conditions in the same manner as in Example 15. Squalene (neat): 50 μl / min, hydrogen gas: 30 ml / min, column temperature: 80 ° C.
Since the catalyst not containing alumina has a low bulk specific gravity, the amount of palladium that can be packed in the same volume column is small (Table 2).
Example 29
Using catalyst G instead of catalyst O, a hydrogenation reaction of squalene was carried out in the same manner as in Comparative Example 2.
Comparative Example 3
Instead of the catalyst A, a commercially available 1% palladium / alumina (manufactured by Aldrich, hereinafter referred to as “catalyst P”) was used to carry out a hydrogenation reaction of squalene in the same manner as in Example 15.
結果を表2に示す。生成物の還元率は、1H-NMRで測定したビニルプロトンとメチル及びメチレンプロトンとの積分比から算出した。
金属酸化物がγ−アルミナ、α−アルミナ、シリカ−アルミナの場合(実施例15〜25、触媒A〜K)、温和な条件下でもスクワレンの水添反応が効率的に進行した。時間の経過とともに還元率が低下するのは原料スクワレン中の不純物によるものと考えられ、反応終了後、触媒を洗浄することにより初期活性は回復する(実施例30〜34参照)。
一方、パラジウムをポリジメチルシランのみに担持した触媒(触媒O)を用いて同様の反応を行った場合(比較例2)、高い還元率(quant)が3時間以上維持された本願発明の触媒(実施例29)に比べて、還元率は低く、かつ早期に失活した。
また、パラジウムを金属酸化物のみに担持した触媒(触媒P)を用いて同様の反応を行った場合(比較例3)、本願発明の触媒(実施例15等)に比べて還元率は低かった(比較例3、40℃で56〜58%)。
When the metal oxide was γ-alumina, α-alumina, or silica-alumina (Examples 15 to 25, catalysts A to K), the squalene hydrogenation reaction proceeded efficiently even under mild conditions. It is considered that the reduction rate decreases with the passage of time due to impurities in the raw material squalene, and the initial activity is recovered by washing the catalyst after completion of the reaction (see Examples 30 to 34).
On the other hand, when the same reaction was carried out using a catalyst (catalyst O) in which palladium was supported only on polydimethylsilane (Comparative Example 2), the catalyst of the present invention in which a high reduction rate (quant) was maintained for 3 hours or more ( Compared with Example 29), the reduction rate was low, and it was deactivated early.
Moreover, when the same reaction was performed using the catalyst (catalyst P) which supported palladium only on the metal oxide (comparative example 3), the reduction rate was low compared with the catalyst (Example 15 etc.) of this invention. (Comparative Example 3, 56-58% at 40 ° C).
実施例30
本実施例では、触媒Aをガラスカラム(内径5φ×50 mm)に充填し、実施例15と同様の装置を用い、次の条件でα−メチルスチレン(東京化成工業株式会社)の水添反応を行った。α−メチルスチレン(neat):132μl(1.0 mmol)/min、水素ガス:44.8 ml(2.0 mmol)/min、カラム温度:25℃。1時間ごとに生成物の1H-NMRを測定したところ、3時間まで原料が完全に消失し、2−フェニルプロパンが定量的に得られた。生成物の分析データを下記に示す:
1H-NMR(CDCl3)δ 1.27(d, 6H), 2.88-2.93(m, 1H), 7.16-7.19(m, 1H), 7.22-7.24(m, 2H), 7.26-7.31(m, 2H).
実施例31
本実施例では、実施例30で使用した触媒Aの入ったカラムをイソプロピルアルコール(50ml)で洗浄することにより再利用して、同じ装置を用い、次の条件で2−シクロヘキセン−1−オン(東京化成工業株式会社)の水添反応を行った。2−シクロヘキセン−1−オン(neat):97μl(1.0 mmol)/min、水素ガス:31.4 ml(1.4 mmol)/min、カラム温度:25℃。1時間ごとに生成物の1H-NMRを測定したところ、3時間まで原料が完全に消失し、シクロヘキサノンが定量的に得られた。生成物の分析データを下記に示す:
1H-NMR(CDCl3)δ 1.67-1.72(m, 2H), 1.82-1.87(m, 4H), 2.30-2.33(m, 4H).
Example 30
In this example, the catalyst A was packed in a glass column (inner diameter 5φ × 50 mm), and using the same apparatus as in Example 15, α-methylstyrene (Tokyo Chemical Industry Co., Ltd.) was hydrogenated under the following conditions. Went. α-methylstyrene (neat): 132 μl (1.0 mmol) / min, hydrogen gas: 44.8 ml (2.0 mmol) / min, column temperature: 25 ° C. When 1 H-NMR of the product was measured every 1 hour, starting material completely disappeared until 3 hours, 2-phenylpropane was obtained quantitatively. The analytical data of the product is shown below:
1 H-NMR (CDCl 3 ) δ 1.27 (d, 6H), 2.88-2.93 (m, 1H), 7.16-7.19 (m, 1H), 7.22-7.24 (m, 2H), 7.26-7.31 (m, 2H ).
Example 31
In this example, the column containing catalyst A used in Example 30 was reused by washing with isopropyl alcohol (50 ml), and the same apparatus was used and 2-cyclohexen-1-one ( The hydrogenation reaction of Tokyo Chemical Industry Co., Ltd. was conducted. 2-cyclohexen-1-one (neat): 97 μl (1.0 mmol) / min, hydrogen gas: 31.4 ml (1.4 mmol) / min, column temperature: 25 ° C. When 1 H-NMR of the product was measured every 1 hour, starting material completely disappeared until 3 hours, cyclohexanone was obtained quantitatively. The analytical data of the product is shown below:
1 H-NMR (CDCl 3 ) δ 1.67-1.72 (m, 2H), 1.82-1.87 (m, 4H), 2.30-2.33 (m, 4H).
実施例32
本実施例では、実施例31で使用した触媒Aの入ったカラムをヘキサン(50ml)で洗浄することにより再利用して、同じ装置を用い、次の条件でフェニルアセチレン(東京化成工業株式会社)の水添反応を行った。フェニルアセチレン(neat):110μl(1.0 mmol)/min、水素ガス:62.7 ml(2.8 mmol)/min、カラム温度:25℃。1時間ごとに生成物の1H-NMRを測定したところ、3時間まで原料が完全に消失し、エチルベンゼンが定量的に得られた。生成物の分析データを下記に示す:
1H-NMR(CDCl3)δ 1.28(t, 3H), 2.67(q, 2H), 7.18-7.33(m, 5H).
実施例33
本実施例では、実施例32で使用した触媒Aの入ったカラムをイソプロピルアルコール(50ml)で洗浄することにより再利用して、同じ装置を用い、次の条件でマレイン酸(和光純薬工業株式会社)の水添反応を行った。マレイン酸水溶液(1 M):200μl/min、水素ガス:9.0 ml/min、カラム温度:80℃。1時間ごとに生成物を濃縮し1H-NMRを測定したところ、3時間まで原料が完全に消失し、コハク酸が定量的に得られた。生成物の分析データを下記に示す:
1H-NMR(CD3OD)δ 2.56(s, 4H).
Example 32
In this example, the column containing catalyst A used in Example 31 was reused by washing with hexane (50 ml), and the same apparatus was used and phenylacetylene (Tokyo Chemical Industry Co., Ltd.) was used under the following conditions. The hydrogenation reaction was performed. Phenylacetylene (neat): 110 μl (1.0 mmol) / min, hydrogen gas: 62.7 ml (2.8 mmol) / min, column temperature: 25 ° C. When 1 H-NMR of the product was measured every 1 hour, starting material completely disappeared until 3 hours, ethylbenzene was obtained quantitatively. The analytical data of the product is shown below:
1 H-NMR (CDCl 3 ) δ 1.28 (t, 3H), 2.67 (q, 2H), 7.18-7.33 (m, 5H).
Example 33
In this example, the column containing catalyst A used in Example 32 was reused by washing with isopropyl alcohol (50 ml), and using the same apparatus, maleic acid (Wako Pure Chemical Industries, Ltd.) was used under the following conditions. Company) hydrogenation reaction. Maleic acid aqueous solution (1 M): 200 μl / min, hydrogen gas: 9.0 ml / min, column temperature: 80 ° C. When the product was concentrated every 1 hour and 1 H-NMR was measured, the raw material completely disappeared until 3 hours, and succinic acid was quantitatively obtained. The analytical data of the product is shown below:
1 H-NMR (CD 3 OD) δ 2.56 (s, 4H).
実施例34
本実施例では、実施例33で使用した触媒Aの入ったカラムを水(50ml)で洗浄し続いてメタノール(50ml)で洗浄することにより再利用して、同じ装置を用い、次の条件で4−ニトロトルエン(東京化成工業株式会社)のニトロ基の還元反応を行った。4−ニトロトルエン(0.5 M、メタノール溶液):500μl/min、水素ガス:22.4 ml/min、カラム温度:50℃。1時間ごとに生成物を濃縮し1H-NMRを測定したところ3時間まで原料が完全に消失し、p−トルイジンが定量的に得られた。生成物の分析データを下記に示す:
1H-NMR(CDCl3)δ 2.25(s, 3H), 6.61(d, 2H), 6.97(d, 2H).
実施例30〜34において、触媒Aを再利用して異なる数種の水素化反応を行ったが、触媒Aは上記のように高い触媒活性を維持した。即ち、本発明の触媒は、繰り返し使用や長期間使用しても活性低下が起こらないという顕著な特性を持つことがわかる。
Example 34
In this example, the column containing catalyst A used in Example 33 was reused by washing with water (50 ml) followed by washing with methanol (50 ml), using the same apparatus and under the following conditions: The reduction reaction of the nitro group of 4-nitrotoluene (Tokyo Chemical Industry Co., Ltd.) was performed. 4-nitrotoluene (0.5 M, methanol solution): 500 μl / min, hydrogen gas: 22.4 ml / min, column temperature: 50 ° C. When the product was concentrated every 1 hour and 1 H-NMR was measured, the raw material completely disappeared until 3 hours, and p-toluidine was quantitatively obtained. The analytical data of the product is shown below:
1 H-NMR (CDCl 3 ) δ 2.25 (s, 3H), 6.61 (d, 2H), 6.97 (d, 2H).
In Examples 30 to 34, the catalyst A was reused to carry out several different hydrogenation reactions, but the catalyst A maintained high catalytic activity as described above. That is, it can be seen that the catalyst of the present invention has a remarkable characteristic that the activity does not decrease even after repeated use or long-term use.
実施例35
この実施例では、バッチ方式でケイ皮酸エチルの水素化反応を行った。
ナス型フラスコ(10 ml)中のケイ皮酸エチル(東京化成工業株式会社、20 mmol)と触媒A(1.09 g、Pd=100μmol)に水素ガス(10 ml/min)を吹き込んだ。1H-NMRで反応の進行を追跡したところ7時間後にケイ皮酸エチルのシグナルは完全に消失し、3−フェニルプロピオン酸エチルのシグナルのみとなった。生成物の分析データを下記に示す:
1H-NMR(CDCl3)δ 1.23(t, 3H), 2.62(t, 2H), 2.95(t, 2H), 4.13(q, 2H), 7.19-7.21(m, 3H), 7.26-7.30(m, 2H).
Example 35
In this example, the hydrogenation reaction of ethyl cinnamate was performed in a batch mode.
Hydrogen gas (10 ml / min) was blown into ethyl cinnamate (Tokyo Chemical Industry Co., Ltd., 20 mmol) and catalyst A (1.09 g, Pd = 100 μmol) in an eggplant-shaped flask (10 ml). When the progress of the reaction was followed by 1 H-NMR, the signal of ethyl cinnamate completely disappeared after 7 hours, and only the signal of ethyl 3-phenylpropionate was obtained. The analytical data of the product is shown below:
1 H-NMR (CDCl 3 ) δ 1.23 (t, 3H), 2.62 (t, 2H), 2.95 (t, 2H), 4.13 (q, 2H), 7.19-7.21 (m, 3H), 7.26-7.30 ( m, 2H).
実施例36
実施例1と同様の方法で(ポリジメチルシラン−γ−アルミナ)担持パラジウムを調製した(Pd:59μmol/g、回収率77%)。得られた触媒の電子顕微鏡写真(STEM)を図2に示す。
この触媒を用いて、下記の鈴木−宮浦カップリング反応を行った。
1H NMR (CDC13) δ 3.59 (s, 3H), 6.79 (d 1H, J= 5.3 Hz), 6.87 (t, 1H, J= 6.2 Hz), 7.15-7.18(m, 3H), 7.25(t, 2H, J= 7.6 Hz), 7.39(d, 2H, J= 7.6 Hz). 13C NMR (CDC13) δ 55.3, 111.1, 120.7, 126.8, 127.0, 128.6, 129.4, 130.6, 130.8, 138.4, 156.3.
Example 36
(Polydimethylsilane-γ-alumina) -supported palladium was prepared in the same manner as in Example 1 (Pd: 59 μmol / g, recovery rate 77%). An electron micrograph (STEM) of the obtained catalyst is shown in FIG.
The following Suzuki-Miyaura coupling reaction was performed using this catalyst.
1 H NMR (CDC1 3 ) δ 3.59 (s, 3H), 6.79 (d 1H, J = 5.3 Hz), 6.87 (t, 1H, J = 6.2 Hz), 7.15-7.18 (m, 3H), 7.25 (t , 2H, J = 7.6 Hz) , 7.39 (d, 2H, J = 7.6 Hz). 13 C NMR (CDC1 3) δ 55.3, 111.1, 120.7, 126.8, 127.0, 128.6, 129.4, 130.6, 130.8, 138.4, 156.3 .
Claims (8)
(1)−20〜60℃で、パラジウム塩又はパラジウム錯体が溶解又は分散し、ポリジメチルシラン及び金属酸化物が分散した溶液又は分散液を用意する工程、及び
(2)前記溶液又は分散液から不溶物を分離する工程 A process for producing an immobilized palladium catalyst comprising the following steps.
(1) a step of preparing a solution or dispersion in which a palladium salt or a palladium complex is dissolved or dispersed at −20 to 60 ° C. and polydimethylsilane and a metal oxide are dispersed; and (2) from the solution or the dispersion. Process for separating insoluble materials
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WO2014065204A1 (en) * | 2012-10-24 | 2014-05-01 | 日本曹達株式会社 | Production method for particles of element having standard electrode potential greater than 0v |
JP2014213225A (en) * | 2013-04-23 | 2014-11-17 | 花王株式会社 | CATALYST CARRYING Pd COMPOUND |
WO2016039479A1 (en) * | 2014-09-12 | 2016-03-17 | 東洋合成工業株式会社 | Polymer-supported transition catalyst |
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