JP6932685B2 - 金属担持高分子 - Google Patents
金属担持高分子 Download PDFInfo
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- JP6932685B2 JP6932685B2 JP2018500197A JP2018500197A JP6932685B2 JP 6932685 B2 JP6932685 B2 JP 6932685B2 JP 2018500197 A JP2018500197 A JP 2018500197A JP 2018500197 A JP2018500197 A JP 2018500197A JP 6932685 B2 JP6932685 B2 JP 6932685B2
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- polymer
- zinc
- reaction
- metal
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- 229920000642 polymer Polymers 0.000 title claims description 177
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 86
- 229910052725 zinc Inorganic materials 0.000 claims description 83
- 239000011701 zinc Substances 0.000 claims description 79
- 239000003054 catalyst Substances 0.000 claims description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- 239000002904 solvent Substances 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 125000005843 halogen group Chemical group 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000005647 linker group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001869 cobalt compounds Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 128
- -1 zinc carboxylate compound Chemical class 0.000 description 128
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 125000003277 amino group Chemical group 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 125000001424 substituent group Chemical group 0.000 description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 20
- 238000005809 transesterification reaction Methods 0.000 description 20
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 16
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 125000002883 imidazolyl group Chemical group 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000001476 alcoholic effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 238000004448 titration Methods 0.000 description 11
- 239000005792 Geraniol Substances 0.000 description 10
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 10
- 229940113087 geraniol Drugs 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003381 deacetylation reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000006239 protecting group Chemical group 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006063 methoxycarbonylation reaction Methods 0.000 description 8
- 229940095102 methyl benzoate Drugs 0.000 description 8
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 7
- 230000006196 deacetylation Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- VCQWRGCXUWPSGY-UHFFFAOYSA-L zinc;2,2,2-trifluoroacetate Chemical compound [Zn+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VCQWRGCXUWPSGY-UHFFFAOYSA-L 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 238000005917 acylation reaction Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 5
- 229940007550 benzyl acetate Drugs 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000005530 alkylenedioxy group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 4
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 4
- 125000004474 heteroalkylene group Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000005724 cycloalkenylene group Chemical group 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005549 heteroarylene group Chemical group 0.000 description 3
- 125000005553 heteroaryloxy group Chemical group 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 2
- SDOFMBGMRVAJNF-KVTDHHQDSA-N (2r,3r,4r,5r)-6-aminohexane-1,2,3,4,5-pentol Chemical compound NC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO SDOFMBGMRVAJNF-KVTDHHQDSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
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- RQPNARVLCPWDLS-UHFFFAOYSA-K F[Zn](F)F Chemical compound F[Zn](F)F RQPNARVLCPWDLS-UHFFFAOYSA-K 0.000 description 2
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- 239000005639 Lauric acid Substances 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
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- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006633 tert-butoxycarbonylamino group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
上記の触媒は、均一系触媒として高い活性と選択性を示しているが、湿気に敏感であり反応の際に失活しやすい。その為にリサイクル使用上の問題があった。また、反応後の亜鉛金属の除去が問題となることもある。
上記ラダー亜鉛触媒においては、反応後に貧溶媒を加えることで、触媒を沈殿させて分離することが可能である。しかし、溶媒によっては亜鉛触媒を除くことが難しい場合もある。特にフロー反応等に用いる触媒として使用するには、不均一系である固体触媒が望ましい。
一方、固体触媒でも同様な反応に活性を示すものもあるが、化学構造が必ずしも明確でなく、構造の変化によるチューニングが難しい。両者の特徴を取り入れ、高い活性、安定性及びリサイクル性を満足させる方法として均一系触媒を固相に固定化する方法があるが、十分な性能を有するまでに到っていない。
[1]亜鉛化合物又はコバルト化合物と下記一般式(I)で表される高分子
とを溶媒中で反応させて得られる、亜鉛またはコバルトが担持された金属担持高分子。
[2]前記[1]の式(I)におけるPolymerがポリスチレンであり、Lがメチレン基であることを特徴とする前記[1]に記載の金属担持高分子。
[3]前記[1]及び[2]に記載の金属担持高分子から成る触媒。
[4]前記[3]記載の触媒を用いることを特徴とする、カルボン酸またはそのエステルによる水酸基のアシル化方法。
[5]前記[3]記載の触媒を用いることを特徴とする、カルボン酸エステルの脱アシル化方法。
[6]前記[3]記載の触媒を用いることを特徴とする、炭酸エステルとアルコールとを反応させるカーボネート化方法。
[7]下記一般式(II)
MX2・xH2O (II)
(一般式(II)中、Xは、ハロゲン原子で置換されていてもよい炭素数2〜5のアルカノイルオキシ基、ハロゲン原子、及びトリフルオロメタンスルホニルオキシ基を示す。xは整数を表す。Mは亜鉛又はコバルト原子を表す。)
で表される亜鉛化合物又はコバルト化合物を、下記一般式(I)
で示される高分子と反応させることを特徴とする前記[1]又は[2]に記載の金属担持高分子の製造方法。
[8]下記一般式(III)
Zn4O(OCOR)6(RCOOH)n (III)
(一般式(III)中、Rはハロゲン原子で置換されていてもよい炭素数1〜4のアルキル基を表し、nは0〜1を表す。)
で表される亜鉛四核クラスター化合物を、下記一般式(I)
で示される高分子と反応させることを特徴とする前記[1]又は[2]に記載の金属担持高分子の製造方法。
本発明の金属担持高分子は、リンカーLを介して高分子主鎖と結合したイミダゾリル基を有する、一般式(I)で示される高分子化合物と、亜鉛又はコバルト化合物とを反応させて得られる。
アルキレンジオキシ基としては、例えば炭素数1〜3のアルキレンジオキシ基が挙げられ、具体的にはメチレンジオキシ基、エチレンジオキシ基、プロピレンジオキシ基等が挙げられる。
アルコキシカルボニル基としては、直鎖状でも分岐状でも或いは環状でもよい、例えば炭素数2〜19のアルコキシカルボニル基が挙げられ、具体的にはメトキシカルボニル基、エトキシカルボニル基、n−プロポキシカルボニル基、イソプロポキシカルボニル基、n−ブトキシカルボニル基、tert−ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、2−エチルヘキシルオキシカルボニル基、ラウリルオキシカルボニル基、ステアリルオキシカルボニル基、シクロヘキシルオキシカルボニル基等が挙げられる。
アリール基で置換されたアミノ基の具体例としては、N−フェニルアミノ基、N−(3−トリル)アミノ基、N,N−ジフェニルアミノ基、N,N−ジ(3−トリル)アミノ基、N−ナフチルアミノ基、N−ナフチル−N−フェニルアミノ基等のモノ又はジアリールアミノ基が挙げられる。
アラルキルオキシカルボニル基で置換されたアミノ基の具体例としては、ベンジルオキシカルボニルアミノ基等が挙げられる。
スチレン系モノマーとしては、芳香族ビニルモノマー、例えば、スチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、2,4−ジメチルスチレン、エチルスチレン、p−t−ブチルスチレン、α−メチルスチレン、α−メチル−p−メチルスチレン、1,1−ジフェニルエチレン、p−(N,N−ジエチルアミノエチル)スチレン、p−(N,N−ジエチルアミノメチル)スチレン、ビニルピリジン、ビニルナフタレンなどが挙げられる。
溶媒の使用量は反応が十分に進行できる量であれば特に制限はないが、上述の高分子主鎖及びリンカー部位を有するポリマー(例えばクロロメチル基を有するスチレンとジビニルベンゼンとの共重合体)とイミダゾールに対して通常1〜500倍容量、好ましくは2〜200倍容量、より好ましくは2〜100倍容量の範囲から適宜選択される。
MX2・xH2O (II)
(一般式(II)中、Xは、ハロゲン原子で置換されていてもよい炭素数2〜5のアルカノイルオキシ基、ハロゲン原子、及びトリフルオロメタンスルホニルオキシ基を示す。xは整数を表す。Mは亜鉛又はコバルト原子を表す。)
で表される亜鉛又はコバルト化合物を、一般式(I)
で示される高分子化合物と反応させることで金属担持高分子を合成する方法が挙げられる。
Zn4O(OCOR)6(RCOOH)n (III)
(一般式(III)中、Rはハロゲン原子で置換されていてもよい炭素数1〜4のアルキル基を表し、nは0〜1を表す。)
で表される亜鉛四核クラスターを、一般式(I)で示される高分子と反応させることで亜鉛担持高分子を合成する方法が挙げられる。
通常、アシル化反応は、ピリジンやトリエチルアミンなどの塩基存在下、塩化アシルや酸無水物を作用させることで行われるが、本発明の金属担持高分子を触媒として用いることにより、中性条件下でカルボン酸エステルとアルコール性水酸基を有する化合物とのエステル交換反応によるアシル化反応が可能である。
アルコール性水酸基を有する化合物は、不飽和結合を有してもよく、置換基を有してもよい。置換基を有する場合、この置換基は、反応を阻害しないものであれば特に限定されず、例えば、アルキル基、アルケニル基、アルキニル基、芳香族基、水酸基、メルカプト基、アミノ基、アルコキシ基、アルキルチオ基、ホルミル基、カルボキシル基、シアノ基、ニトロ基、ハロゲン原子、水素原子等を示すことができ、これらの置換基上に別種の置換基を有していてもよい。
具体的には、次のような化合物が例示される。ベンジルアルコール、1−ナフチルメタノール、2−ナフチルメタノール、1−(1−ナフチル)エタン−1−オール、1−(1−ナフチル)プロパン−1−オール、1−(1−ナフチル)ブタン−1−オール、9−フルオレニルメタノール、テトラリン−1−オール、2−ピリジンメタノール、3−ピリジンメタノールなどの水酸基と結合するα 位炭素に芳香族置換基を有するアルコール。プロペン−3−オール、1−ブテン−3−オール、シクロヘキセン−3−オールなどのオレフィン系アルコール。D−グルカール、D−ガラクタール、L−ランナールなどの分子内に不飽和結合を有する糖類。3−ヒドロキ−4−アンドロステン−11,17−ジオン、4−アンドロステン−3,17−ジオール、5−エストレン−3,17−ジオールなどの分子内に不飽和結合と水酸基を有するステロイド。
脂肪族カルボン酸としては、炭素数2〜30のモノ−又はポリカルボン酸が挙げられ、具体的には、酢酸、プロピオン酸、酪酸、吉草酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、シュウ酸、プロパンジカルボン酸、ブタンジカルボン酸、ヘキサンジカルボン酸、セバシン酸、アクリル酸等が挙げられる。
また、これら芳香族カルボン酸は前記したようなアルキル基、アルコキシ基、ハロゲン原子、アミノ基、アリール基、ヘテロアリール基、アラルキル基、水酸基等で置換されていてもよい。本反応は溶媒中で通常行われ、溶媒としてはアルコール、即ちメタノール、エタノール、プロパノール、イソプロパノール、1-ブタノール、2-ブタノール、3-ブタノールが挙げられる。また、驚くことに本発明の触媒を用いた場合、水を用いることでも脱アシル化が可能である。また、上記アルコールも含めた有機溶媒と水の混合溶媒においても反応が行うことが可能である。
本発明の金属担持高分子を触媒として用いた種々の反応は、大気下、空気中又は窒素ガス若しくはアルゴンガス等の不活性ガス雰囲気下で行うことができる。
本発明の金属担持高分子を触媒として用いた種々の反応時間は、特に限定されないが、通常約1〜45時間、好ましくは約6〜18時間程度で行うことができる。反応温度は、特に限定されないが、室温〜約180℃、好ましくは50〜150℃、より好ましくは80〜150℃程度で行われる。これらの条件は使用される原料等の種類及び量により適宜変更される。
・熱分析:EXSTAR 6000 TG/DTA 6200 (SII)、測定範囲:30〜600℃、加熱速度:6℃/min、測定量:約5mg、サンプルパン:アルミニウム、雰囲気:窒素(10mL/min)又は真空中(2Torr)
・金属含量は滴定法によって求めた(「キレート滴定」上野景平著(南江堂出版))。
・クロロメチルポリスチレン樹脂1%DVB(ジビニルベンゼン)架橋樹脂(Merrifield Resin cross-linked with 1% DVB (200-400mesh))(以下、CH2−Polymerと略す)
・トリフルオロ酢酸亜鉛水和物(Alfa Aesar社製、亜鉛含量21.24%(亜鉛滴定測定))(以下、Zn(OAcF)2と略す)
・核磁気共鳴スペクトル(NMR);Bruker Advanced III
・高分解能質量分析装(HRMS);ACQITY UPLC−LCT−Premier/XE, Bruker MicroTOF II
イミダゾリル基を有する高分子の合成に関しては、Journal of Molecular Catalysis A: Chemical, 2012, 353-354, 178-184を参照した。
イミダゾール5.3g(78mmol)とヨウ化カリウム78mg(0.47mmol)を10mLトルエンに溶解して、窒素下40℃で加熱攪拌した。反応溶液にナトリウムメトキシドメタノール溶液(MeONa 4.2g(78mmol,1当量)、メタノール15mL)を滴下した。その後、CH2−Polymerとアセトニトリル30mLを加えた。65℃で12時間加熱攪拌を行った後、冷却濾過した。濾物をメタノールで洗浄後、真空下、60℃で乾燥を行なった。
得られた高分子は、窒素ガス10mL/min中において示差熱重量同時測定(TG/DTA)を行なった。イミダゾリル基を有する高分子im−CH2−Polymerは、約3wt%の溶媒等を含んでいたが、340℃付近まで重量減少が観測されなかった340℃付近でポリマーの分解が起きることが確認できた。
参考例1で合成したim−CH2−Polymer1.00gにZn(OAcF)20.30g(亜鉛原子63.3mg)を加えた。テトラヒドロフラン10mL中で、窒素下、5時間還流した後に室温まで冷却、濾過し、濾物をテトラヒドロフラン10mLで3回、さらにヘプタン30mLで洗浄を行い、得られた固体物をシュレンク管に入れ、65℃、真空中で加熱乾燥を行い、目的の高分子1.16gが得られた。
上記で濾過した反応溶液及び洗浄液を減圧留去した後に溶液中に含まれる亜鉛含量を上記滴定法によって求めたところ、1.4mgの亜鉛原子が含まれることが分かった。上記結果より、ポリマーに吸着された亜鉛原子は61.9mgであり、高分子中に亜鉛原子を53.4mg/g(0.83mmol/g)含有されていた。
この亜鉛担持高分子を窒素ガス10mL/min中において示差熱重量同時測定(TG/DTA)を行ったところ(図1)、340℃付近でポリマー分解が起きる前に210℃付近で重量減少が観測された(Δ7.2%)。
原料であるトリフルオロ酢酸亜鉛水和物のTG/DTA測定を行ったところ、同温度でトリフルオロ酢酸基に相当する重量比が減少した。210℃付近の重量減少はトリフルオロ酢酸基の脱離現象であることが分かった。
実施例1と同様にトリフルオロ酢酸亜鉛担持高分子を種々の条件で合成した。以下の表1に実施例1〜6の結果を示す。
他の金属無機塩担持高分子合成を行った。参考例1で合成したim−CH2−Polymerにそれぞれの金属無機塩を加え、反応溶媒中で窒素下5時間還流した後に室温まで冷却、濾過し、濾物をテトラヒドロフランで3回、ヘプタンでさらに1回洗浄を行った。得られた固体物をシュレンク管に入れ、65℃、真空中で加熱乾燥を行い、金属無機塩担持高分子が得られた。以下の表2に実施例7〜12の合成結果を示す。
安息香酸メチル1等量とベンジルアルコール1.2等量にトリフルオロ酢酸亜鉛5mol%(亜鉛原子換算)と参考例1で合成したim−CH2−Polymerを亜鉛原子に対して種々の割合で加え、トルエン溶媒中で、6時間還流し、エステル交換反応を行った。その際の安息香酸メチルの転化率はガスクロマトグラフィー(GC)により測定した結果を以下の表3に示す。亜鉛原子に対してイミダゾリル担持樹脂中のイミダゾリル基の割合(im/Zn)が、4以上において転化率が高いことが分かった。
イミダゾール担持量の異なる3種類のim−CH2−Polymerを用いトリフルオロ酢酸亜鉛添加効果を比較した結果を表4に示す。安息香酸メチル1等量とベンジルアルコール1.2等量にトリフルオロ酢酸亜鉛5mol%(亜鉛原子換算)と参考例1で合成したim−CH2−Polymerを亜鉛原子に対して種々の割合で加え、トルエン溶媒中(0.5M)で、2時間還流し、エステル交換反応を行った。その際の安息香酸メチルの収率はガスクロマトグラフィー(GC)により測定した結果を以下の表4に示す。亜鉛原子に対してイミダゾリル担持樹脂中のイミダゾリル基の割合(im/Zn)が、4以上において転化率が高いことが分かった。1.25mmol/gと1.85mmol/gのイミダゾリル基含有量であるim−CH2−Polymerに対して、4.98mmol/gとイミダゾリル基を多く含有しているものでは活性が低くなることが分かった。
ベンジルアルコール0.50mmol及び実施例1で合成した亜鉛担持高分子(亜鉛原子換算5mol%)を酢酸エチル(0.50M)中で1時間還流を行い、反応液を濾過して濾液を分析したところ、99%以上の転化率でベンジルアルコールの酢酸ベンジル化が進行した。触媒の亜鉛担持高分子は濾物として回収した。
ベンジルアルコール0.50mmol及び実施例1で合成した亜鉛担持高分子(亜鉛原子換算5mol%)を炭酸ジメチル(0.50M)中で30分間還流を行ったところ、99%以上の転化率でベンジルアルコールのメトキシカルボニル化が進行した。
1H NMR (500MHz、CDCl3、27℃): δ 7.40-7.33(m、5H、Ph),5.17(s、2H,CH2)、3.80(s、3H,CH3);13C NMR(125MHz、CDCl3、27℃): δ 155.7、135.3、128.6、128.5、128.3、69.7,54.9
酢酸ベンジル0.50mmol及び実施例1で合成した亜鉛担持高分子(亜鉛原子換算5mol%)をメタノール(0.50M)中で2時間還流を行ったところ、78%の転化率で酢酸ベンジルの脱アセチル化が進行した。
ゲラニオール0.99gに対してZn4(OCOCF3)6O88.0mg(亜鉛含量24wt%(亜鉛滴定測定)、亜鉛原子21.1mg相当、5.03mol%)を加え、酢酸ブチルを溶媒として1時間還流を行った。GC測定によるゲラニオールの転化率は90.2%であった。続いて、参考例1で合成したim−CH2−Polymer204.4mgを加えた後に、さらに1時間 同温度で撹拌した。室温まで冷却した後に濾過を行った。反応物ゲラニルアセテートを含む濾液中に3.2mgの亜鉛原子が亜鉛滴定測定法により検出された。上記反応条件において使用した亜鉛原子量は21.0mgであることから、17.9mg亜鉛原子が高分子に吸着したことが確認できた。即ち、1gのim−CH2−Polymerに対して87.6mgの亜鉛が吸着された。
実施例15で濾過して回収した亜鉛担持高分子を用いてエステル交換反応を行った。ゲラニオール1.00g(6.48mmol)、実施例15で濾過して得られた亜鉛担持高分子204.0mgに1−ブタノール5mLを加えて、還流温度で撹拌した。GC分析により、反応時間8時間でゲラニオールの転化率が87.6%であった。冷却後に反応溶液を濾過して、反応物ゲラニルアセテートを得た。この濾液中に含まれる亜鉛含量を滴定法によって求めた。0.196mgの亜鉛が検出された。触媒は濾過により回収した。上記で濾過して得られた亜鉛担持高分子を用いて同様に、ゲラニオール0.99g(6.41mmol)、亜鉛担持高分子196.29mgに1−ブタノール5mLを加えて、還流温度で撹拌した。GC分析により、反応時間8時間でゲラニオールの転化率が79.8%であった。冷却後に反応溶液を濾過して、反応物ゲラニルアセテートを得た。この濾液中に含まれる亜鉛含量を滴定法によって求めた。0.16mgの亜鉛が検出された。このように本発明の亜鉛担持高分子は、エステル交換の触媒能を有しており、さらに2回、3回とリサイクル使用を行っても、反応活性を有しており、かつ亜鉛の流出(リーチング)が少ない事がわかった。
ゲラニオール1.0gに対してZn(OAcF)2108.6mg(0.353mmol)、さらに参考例1で合成したim−CH2−Polymer204mgを添加して、酢酸ブチル5mL中で5時間、還流温度にて反応を行った。GC測定によりゲラニオールの転化率は78.3%であった。室温まで冷却した後に濾過を行った。濾物として触媒を回収した。
濾液中には4.53mgの亜鉛原子が亜鉛滴定測定法により検出された。上記反応において使用した触媒の亜鉛原子量は23.1mgであることから、18.5mg亜鉛原子が高分子に吸着したことが確認できた。即ち、1gのim−CH2−Polymerに対して87.6mgの亜鉛が吸着された。吸着後の高分子を減圧乾燥後にTGA熱分析測定を行ったところ、実施例1のポリマー担持亜鉛錯体合成時の触媒と同様な分析結果を得た。
ゲラニオール1.0gに対して参考例1で合成したim−Ch2−Polymer214.8mgを添加して、酢酸ブチル5mL中で8時間、還流温度にて反応を行った。しかし、エステル交換反応はほとんど生じなかった。これより参考例2で合成したim−CH2−Polymerには、エステル交換活性が無いことを確認した。
安息香酸メチル0.2gとシクロヘキシルメタノール0.202g(1.2当量)及びクロロベンゼン4mLに、触媒として実施例1で合成した亜鉛担持高分子(4mol%)を添加した。空気中、5時間還流後、GCで転化率(Conv.)を測定したところ、安息香酸メチルの転化率が99.8%以上であった。反応後、冷却した反応溶液を濾過、濾物である触媒をヘプタン洗浄し、室温、真空中で乾燥した。回収した亜鉛触媒を用いてリサイクル実験を上記反応条件と同様に行い、GCで反応の転化率を測定した(図3)。図3のように9回リサイクル反応を行っても80%以上の転化率を示した。このことより坦持した亜鉛は反応によってほとんど流出することなく、反応活性を保持することが確認できた。本触媒はフロー反応などにも有用と考える。
安息香酸メチル0.2g、シクロヘキシルメタノール0.202g(1.2当量)及びクロロベンゼン4mLに、触媒として種々の亜鉛担持高分子を添加して比較を行った。空気中、5時間還流後、GCで転化率変化を求めた結果、トリフルオロ酢酸基を有する触媒が最も高い活性を示した。ハロゲン原子又はトリフラート基を有する触媒は、トリフルオロ酢酸を有する触媒よりも活性が低かった。
また、一番触媒活性の高かったトリフルオロ酢酸コバルト担持高分子を用いて、上記エステル交換反応のリサイクル実験を行った。3回反応に使用しても転化率が90%以上を示した。金属滴定測定により反応液中のコバルト流出(リーチング)は少ないことも確認した。
参考例2で合成したim−CH2−Polymer410mg、Zn4(OCOCF3)6O19.4mg(1.0mol%)、N−メチルイミダゾール20.1mg(3.4mmol)及びL−メントール0.2gを酢酸ブチル中で、窒素下、23時間還流しエステル交換反応を行った。GCでL−メントールの転化率を測定したところ98.4%であった。反応後、ヘプタン投入、濾過、溶媒留去のみで得られたエステル化合物が回収できた(GC純度 96.0%、4%は原料のl−メントールであった)。N−メチルイミダゾールを添加することで触媒活性が高まることを確認できた。
反応中に亜鉛担持高分子触媒から反応液中に流出した亜鉛含量を、濾液の滴定測定によって分析したところ、亜鉛含量が分析限界以下(1ppm以下)であった。亜鉛担持高分子は、反応中に亜鉛原子が留出することがほとんどないことが確かめられた。
参考例2で合成したim−CH2−Polymer210mgとZn4(OCOCF3)6O6.7mg(0.34mol%)及びN−メチルイミダゾール3.1mg(0.52mmol)及びL−メントール0.2gを酢酸ブチル中で窒素下、34時間還流を行った。GCでL−メントールの転化率を測定したところ93.8%であった。
反応後にヘプタンを加えずに反応液を濾過して、亜鉛担持高分子触媒を除去した。貧溶媒であるヘプタンを加えずに濾過した場合における反応物中の亜鉛含量を亜鉛滴定測定で分析した。亜鉛含量は30ppmであり、この結果からも亜鉛金属の反応による留出が少ない事が明らかとなった。
上記実施例24で反応を行った後に濾過することで回収した亜鉛担持高分子触媒を用いて、実施例24と同じ基質を用い、再度アセチル化反応を行った(反応時間19時間)。GCでL−メントールの転化率を測定したところ75.7%であった。
参考例2で合成したim−CH2−Polymer77.1mgとZn4(OCOCF3)6O49.0mg及びN−メチルイミダゾール24.7mgを加えてエステル交換反応を行った。反応時間9時間で転化率99.8%を示した。
参考例2で合成したim−CH2−Polymer210mgとZn4(OCOCF3)6O19.4mg(1mol%)、N−メチルイミダゾール20.1mg(3.4mmol%)及びL−メントール0.2gを酢酸ブチル中で窒素下、23時間還流を行った。GCでL−メントールの転化率を測定したところ98.4%であった。反応後、ヘプタン5mL添加後、濾過、溶媒留去を行い、生成物を得た。1H−NMR測定結果から純度96.0%であった。濾液である反応液には亜鉛は含まれていなかった。このことから高い転化率ながら亜鉛原子は流出していないことを確認した。
上記の結果より、im−CH2−Polymerを用いて系中で錯体合成を行う(in situ法)場合、亜鉛原子を完全に担持させるには、im−CH2−Polymerを多めに添加することが必要であることが分かった。適切な比率で反応を行うことで、高い転化率で、かつ、亜鉛流出が無く反応を完結することが確認できた。
酢酸シンナミル及び酢酸ゲラニル各0.2gを用い、メタノール溶媒中(0.50M)に実施例1で合成したトリフルオロ酢酸亜鉛担持高分子(触媒比5mol%亜鉛換算)を加え、還流温度、反応時間6時間で脱アセチル化反応を行った。両化合物とも濾過と溶媒留去のみで目的物を得た(両化合物とも収率99%以上)。
酢酸シンナミル0.50mmolに対して、参考例2で合成したim−CH2−Polymer1mol%を加えて、メタノール溶媒中(0.50M)で還流温度、反応時間6時間で反応を行ったが、反応は進行しなかった。このことから、参考例2で合成したim−CH2−Polymerには、エステル交換活性が無いことを確認した。
4−アセトキシスチレンに対して、実施例1で合成したトリフルオロ酢酸担持高分子1.0mol%を用いて反応を行ったところ、反応時間6時間で4−ビニルフェノールが得られた(転化率95.3%)。また、上記反応条件にN−メチルイミダゾール(NMI)4.0mol%を添加することで反応が加速した(転化率97.8%、反応時間5時間)。
4−アセトキシスチレン0.20g(1.04mmol)と実施例1で合成したトリフルオロ酢酸亜鉛担持高分子52.7mgに溶媒として水4mLを用いて加水分解を行なった(反応時間9時間、転化率43.7%)。反応時間に対して転化率は、比例関係を示すことからも亜鉛触媒は活性が消失することなく、反応が進行することが分かった。従来の亜鉛触媒は、水中で分解することで活性を失うが、本発明の触媒は活性が消失することなく反応が進行することが確認できた。
酢酸ラウリル0.2g(0.88mmol)に参考例2で合成したim−CH2−Polymerにトリフルオロ酢酸亜鉛を担持した触媒(実施例1で合成した亜鉛担持高分子)1mol%及びメタノール4mL及びメタノール4mLを用いてメタノリシス反応の検討を行った(反応時間15時間、68.7%転化率)。同様にNMI添加(4mol%)効果により転化率向上が見られた(反応時間7時間、転化率91.4%)。
シンナミルアルコール及びゲラニオール各0.2gを基質として、実施例1で合成した亜鉛担持高分子にトリフルオロ酢酸亜鉛を担持した触媒5mol%を用いて、炭酸ジメチル(0.50M)中でメトキシカルボニル化反応の検討を行った。反応時間3時間で、シンナミルメチルカーボネートが収率99%以上、ゲラニルメチルカーボネートが収率97%でそれぞれ得られた。濾過と溶媒留去のみで目的物が得られた。
シンナミルメチルカーボネート;1H NMR (500MHz、CDCl3、27℃): δ 7.40-7.39(m, 2H,Ph)、7.28-7.25(m, 1H,Ph)、6.68(d, 1H,J = 16.0、PhCH)、6.30(dt, 1H,J = 16.0、6.5、PhCHCH)、4.79(m、2H、CH2),3.81(s、3H、CH3);13C NMR(125MHz、CDCl3、27℃): δ 155.7、135.3,128.6、128.5、128.3、69.7、54.9
ゲラニルメチルカーボネート;;1H NMR (500MHz、CDCl3、27℃): δ 5.37(m, 1H,OCH2CH)、5.07(m, 1H,CH3CH)、4.66(d、2H,J = 7.0、OCH2)、3.78(s, 3H,OCH)、;13C NMR(125MHz、CDCl3、27℃): δ 155.9、143.2、131.9、123.7.117.7、64.7、54.6、39.5、26.2、25.7、17.7,16.5
1−フェノキシエタンー1,2−ジオール0.2g及び実施例1で合成したトリフルオロ酢酸担持高分子5mol%を、炭酸ジメチル中(0.5M)、で3時間還流したところ、単離収率95%で4−フェノキシ−1,3−ジオキソラン−2−オンを得た。
1H NMR (500MHz、CDCl3、27℃): δ 7.31 (t, 2H,J = 7.5、Ph)、7.02(t, 1H,J = 7.5、Ph)、6.91(d, 2H,J =8.0、Ph)、5.03(m, 1H,OCH)、4.62((t, 1H,J =8.5、OCH)、4.55(t, 1H,J = 8.5、OCH)、4.24(m, 1H,OCH)、4.17(m, 1H,OCH);13C NMR(125MHz、CDCl3、27℃): δ 157.8、154.7、129.7、122.0、114.6、74.1
また、メタノール溶媒中(0.5M)、4−フェノキシ−1,3−ジオキソラン−2−オン0.2g及び実施例1で合成したトリフルオロ酢酸担持高分子5mol%を加え、6時間還流を行い、単離収率97%で1−フェノキシエタンー1,2−ジオールを得た。両反応において濾過と溶媒留去のみで目的物を得た。
プロパルギルアルコール(0.1g、1.78mmol)を炭酸ジメチル溶媒(4mL)中、種々の亜鉛担持高分子5mol%を触媒として加え、空気中、還流を行いメトキシカルボニル化を行った。結果を表5に示す。
実施例1で合成したトリフルオロ酢酸亜鉛担持高分子5mol%を、6−アミノ−1−ヘキサノール0.6mmol及び安息香酸メチル0.7mmolのトルエン溶液0.8mL中に加えて、5時間還流を行なった。反応後、触媒を濾過した後に溶媒を留去し、塩化メチレンを加え、二炭酸ジ−tert−ブチル(0.30mL、1.3mmol)とトリエチルアミン(0.18ml、1.3mmol)を加えた後、中室温で1時間反応させた。反応後、有機層を蒸留水10mlで2回洗浄後、分液し、得られた有機層を濃縮した後にフラッシュカラムクロマトグラフィーを行ったところ、安息香酸6−((tert−ブトキシカルボニル)アミノ)ヘキシル0.46mmolを得た。収率91%。水酸基/アミノ基 選択率=>20/1
1H NMR (500MHz、CDCl3、27℃): δ 8.04(m、2H, Ph),7.55(m、1H、Ph)、7.43(m、2H,Ph),4.50(br、1H,CONH),4.32(t、2H,J=6.5、OCH2),3.12(br、2H,NCH2)、1.78(m、2H,CH2)、1.53−1.37(m、15H,CH2、Boc);13C NMR(125MHz、CDCl3、27℃): δ 166.7、156.0、132.8、130.5、129.5、128.3、79.1、64.9、 40.5、30.0、28.7、28.4、26.5、25.8
シクロヘキシルアルコールとシクロヘキシルアミン等量を炭酸ジメチル溶媒4mL中、亜鉛触媒5.5mol%を加え、空気中、5時間還流を行いメトキシカルボニル化反応を行った。ほぼアルコール体のみ反応が起きた(転化率99.9%以上、選択率96%)。
実施例1で合成したトリフルオロ酢酸担持高分子5mol%を、酢酸エチル(AcOEt)溶媒中(0.5M)、還流温度にて反応を行った。各アルコールから以下のアセチル体が高収率で得られた。
酢酸4−ブロモベンジル;1H NMR (500MHz、CDCl3、27℃): δ 7.48(d、2H,J=8.5、Ar),7.23(d、2H、J= 8.5、Ar),5.05(s、2H,ArCH2),2.10(s、3H,CH3);13C NMR(125MHz、CDCl3、27℃): δ 170.7,135.0,131.7、129.9、122.3、65.5、20.9
酢酸4−((メトキシメトキシ)メチル)ベンジル;1H NMR (500MHz、CDCl3、27℃): δ 7.35(m、4H,Ar),5.10(s、2H,OCH2),4.70(s、2H,OCH2)、4.59(s、2H,OCH2),3.41(s、3H,CH3)、2.09(s、3H,CH3);13C NMR(125MHz、CDCl3、27℃): δ 170.8,138.0,135.4,128.4、128.0、95.7、68.8、66.0、55.4、21.0;HRMS(EI) m/z cald. for C12H15O4 223.0976 found 223.0985
酢酸4−(((トリエチルシリル)オキシ)メチル)ベンジル;1H NMR (500MHz、CDCl3、27℃): δ 7.32(m、4H,Ar)、5.09(s、2H,OCH2)、4.73(s、2H,OCH2)、2.09(s、3H,CH3)、0.98(t、9H,J=8.0、SiCH2CH3)、0.65(q、6H、J=8.0、SiCH2);13C NMR(125MHz、CDCl3、27℃): δ 170.9、141.6、128.9.126.3、66.2、64.4、21.0、6.8、4.5
ピバル酸4−(アセトキシメチル)ベンジル;1H NMR (500MHz、CDCl3、27℃): δ 7.36−7.26(m、4H、Ar),5.10(s、4H,OCH2)、2.10(s、3H、CH3)、1.23(s、9H、Piv);13C NMR(125MHz、CDCl3、27℃): δ 178.3、170.8、136.6、135.7、128.4、127.9、66.0、65.7.38.8、27.2、21.0
酢酸コレステリル;1H NMR (500MHz、CDCl3、27℃): δ 5.38(d、1H,J=5.0、CCH)、4.61(m、1H、OCH)、2.32(m、2H),2.03−1.95(m、5H)、1.87−1.84(m、3H)、1.60−0.92(m、27H),0.87(m、6H、CH3);13C NMR(125MHz、CDCl3、27℃): δ 170.5、139.7、122.7、74.0、56.7、56.1、50.0、42.3、39.7、39.5、38.1、37.0、36.6、36.2、35.8、31.9、28.2、27.8、24.3、23.8、22.8、22.6、21.4、21.0、19.3、18.7、11.9
酢酸((1S,4R)−4−(2−アミノ−6−(シクロプロピルアミノ)−9H−プリン−9−イル)シクロペンタ−2−エン−1−イル)メチル;1H NMR (500MHz、CDCl3、27℃): δ 7.51(s、1H、CCH)、5.90(m、1H,CCH),5.66(br、1H、ArNH),5.55(m、1H,NCH)、4.79(br、2H,ArNH2)、4.19−4.10(m、2H、cyclopropyl)、0.61(m、2H、cyclopropyl);13C NMR(125MHz、CDCl3、27℃): δ 171.0、160.0、156.3、151.0、136.9、135.3、130.8、115.0、66.5、58.7、44.4、35.2、23.7、20.9,7.4
実施例1で合成したトリフルオロ酢酸担持高分子5mol%を用い、ベンジルアルコールを酢酸エチル溶媒中(0.5M)で反応させた。反応時間1時間での収率を下表に示す。触媒を濾過して繰返し反応を行っても、触媒活性の低下は見られなかった。
Claims (8)
- 請求項1又は請求項2に記載の金属担持高分子から成る触媒。
- 請求項3に記載の触媒を用いることを特徴とする、カルボン酸またはそのエステルによる水酸基のアシル化方法。
- 請求項3に記載の触媒を用いることを特徴とする、カルボン酸エステルの脱アシル化方法。
- 請求項3に記載の触媒を用いることを特徴とする、炭酸エステルとアルコールとを反応させるカーボネート化方法。
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