JP2008222654A - Vitamin b12-titania hybrid compound and dehalogenation catalyst - Google Patents
Vitamin b12-titania hybrid compound and dehalogenation catalyst Download PDFInfo
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- JP2008222654A JP2008222654A JP2007064940A JP2007064940A JP2008222654A JP 2008222654 A JP2008222654 A JP 2008222654A JP 2007064940 A JP2007064940 A JP 2007064940A JP 2007064940 A JP2007064940 A JP 2007064940A JP 2008222654 A JP2008222654 A JP 2008222654A
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- Prior art keywords
- vitamin
- titania
- hybrid compound
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- titania hybrid
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 9
- 229930003231 vitamin Natural products 0.000 title description 2
- 235000013343 vitamin Nutrition 0.000 title description 2
- 239000011782 vitamin Substances 0.000 title description 2
- 229940088594 vitamin Drugs 0.000 title description 2
- 150000003722 vitamin derivatives Chemical class 0.000 title description 2
- FDJOLVPMNUYSCM-UVKKECPRSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2,7, Chemical class [Co+3].N#[C-].C1([C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)[N-]\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O FDJOLVPMNUYSCM-UVKKECPRSA-L 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000004820 halides Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 10
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 208000017983 photosensitivity disease Diseases 0.000 abstract description 2
- 231100000434 photosensitization Toxicity 0.000 abstract description 2
- 229930003270 Vitamin B Natural products 0.000 abstract 4
- 235000019156 vitamin B Nutrition 0.000 abstract 4
- 239000011720 vitamin B Substances 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- -1 vitamin B 12 compound Chemical class 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001867 cobalamins Chemical class 0.000 description 4
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 4
- RMRCNWBMXRMIRW-BYFNXCQMSA-M cyanocobalamin Chemical compound N#C[Co+]N([C@]1([H])[C@H](CC(N)=O)[C@]\2(CCC(=O)NC[C@H](C)OP(O)(=O)OC3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)C)C/2=C(C)\C([C@H](C/2(C)C)CCC(N)=O)=N\C\2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O RMRCNWBMXRMIRW-BYFNXCQMSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LNKQQZFLNUVWQQ-UHFFFAOYSA-N 1-chloro-2,2-bis(4'-chlorophenyl)ethylene Chemical group C=1C=C(Cl)C=CC=1C(=CCl)C1=CC=C(Cl)C=C1 LNKQQZFLNUVWQQ-UHFFFAOYSA-N 0.000 description 2
- CHBOSHOWERDCMH-UHFFFAOYSA-N 1-chloro-2,2-bis(4-chlorophenyl)ethane Chemical compound C=1C=C(Cl)C=CC=1C(CCl)C1=CC=C(Cl)C=C1 CHBOSHOWERDCMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229960002104 cyanocobalamin Drugs 0.000 description 2
- 235000000639 cyanocobalamin Nutrition 0.000 description 2
- 239000011666 cyanocobalamin Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006049 ring expansion reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KEUPLGRNURQXAR-UHFFFAOYSA-N (4-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=C(Cl)C=C1 KEUPLGRNURQXAR-UHFFFAOYSA-N 0.000 description 1
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 1
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical compound CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 description 1
- GTVUABAMGVJSQR-UHFFFAOYSA-N 1-chloro-4-[2,3-dichloro-1,4,4-tris(4-chlorophenyl)but-2-enyl]benzene Chemical compound C=1C=C(Cl)C=CC=1C(C=1C=CC(Cl)=CC=1)C(Cl)=C(Cl)C(C=1C=CC(Cl)=CC=1)C1=CC=C(Cl)C=C1 GTVUABAMGVJSQR-UHFFFAOYSA-N 0.000 description 1
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UDRDATXHBQGSKG-UHFFFAOYSA-N CCOC(=O)C(CBr)(C(=O)OCC)C1=CC=CC=C1 Chemical compound CCOC(=O)C(CBr)(C(=O)OCC)C1=CC=CC=C1 UDRDATXHBQGSKG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AHJKRLASYNVKDZ-UHFFFAOYSA-N DDD Chemical compound C=1C=C(Cl)C=CC=1C(C(Cl)Cl)C1=CC=C(Cl)C=C1 AHJKRLASYNVKDZ-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- ZWWWLCMDTZFSOO-UHFFFAOYSA-N diethoxyphosphorylformonitrile Chemical compound CCOP(=O)(C#N)OCC ZWWWLCMDTZFSOO-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- YLRVJPQVDQQBOX-UHFFFAOYSA-N ethyl 3-oxocyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCCC(=O)C1 YLRVJPQVDQQBOX-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
本発明は、ビタミンＢ12−チタニアハイブリッド化合物および脱ハロゲン化触媒に関する。 The present invention relates to a vitamin B 12 -titania hybrid compound and a dehalogenation catalyst.
有機ハロゲン化物を還元的に脱ハロゲン化したり化学変換するためには、ビタミンＢ12錯体を還元し触媒として用いる方法が知られている（非特許文献１、非特許文献２、非特許文献３参照）。さらに触媒となるビタミンＢ12錯体を電極や高分子などの基材に担持させ使用する方法が知られている（非特許文献４参照）。これらは、電気化学還元や化学試薬によりビタミンＢ12錯体を還元活性化しており、支持電解質や化学還元剤が必要であったり、非共有結合により基材に担持しているため（特許文献１参照）、環境対策や安全性および安定性に大きな問題があった。
本発明は、光増感作用を示す固体光触媒であるチタニアの表面に触媒部位となるビタミンＢ12化合物を、シロキサン結合を主鎖に有する結合部を介して強固に固定化することによる、様々なｐＨ条件で耐久性の高いビタミンＢ12−チタニアハイブリッド光触媒の提供、およびビタミンＢ12を固体上に固定化することで、触媒を容易に回収・再利用できる方法を提供することを課題とする。 The present invention provides a variety of compounds by firmly fixing a vitamin B 12 compound serving as a catalytic site on the surface of titania, which is a solid photocatalyst exhibiting a photosensitizing action, via a bonding part having a siloxane bond in the main chain. It is an object of the present invention to provide a vitamin B 12 -titania hybrid photocatalyst that is highly durable under pH conditions, and to provide a method for easily recovering and reusing the catalyst by immobilizing vitamin B 12 on a solid.
本発明者らは、上記目的を達成するために鋭意検討した結果、ビタミンＢ12化合物を結合部を介してチタニアに固定化した触媒を合成した。本触媒は、様々なｐＨ条件で高い耐久性を示し、光照射により、脱ハロゲン化反応のみならず、様々な有機合成化学反応へも適用することができる。また、固体上に固定化しているため、触媒を容易に回収・再利用できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have synthesized a catalyst in which a vitamin B 12 compound is immobilized on titania via a binding portion. This catalyst exhibits high durability under various pH conditions, and can be applied not only to a dehalogenation reaction but also to various organic synthetic chemical reactions by light irradiation. Further, the present invention has been completed by finding that the catalyst can be easily recovered and reused because it is immobilized on a solid.
すなわち、本発明は、第１観点として、一つ以上のビタミンＢ12化合物が、結合部を介してチタニアに固定化されていることを特徴とするビタミンＢ12−チタニアハイブリッド化合物、
第２観点として、前記結合部が、シロキサン結合を主鎖に有する、第１観点記載のビタミンＢ12−チタニアハイブリッド化合物、
第３観点として、式（１）で表されるトリアルコキシシリル基を有するビタミンＢ12化合物をチタニアと反応させて得られる第２観点記載のビタミンＢ12−チタニアハイブリッド化合物、
原子数１ないし２０のアルコキシ基又は−ＮＲ8−（ＣＨ2）n−Ｓｉ（ＯＲ9）3（式中、
ｎは１から２０までの整数を表し、Ｒ8は水素原子又は炭素原子数１〜１０のアルキル基
を表し、Ｒ9は同一又は異なって、炭素原子数１〜１０のアルキル基を表す。）を表すが
、但し、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7の少なくとも１つ以上は−ＮＲ8−（ＣＨ2）n−Ｓｉ（ＯＲ9）3を表し、Ｘはシアノ基、ヒドロキシ基またはメチル基を表し、ＹはＣｏ原子に配位している水分子を表す。｝、
第４観点として、式（２）で表されるトリアルコキシシリル基を有するビタミンＢ12化合物をチタニアと反応させて得られる第３観点記載のビタミンＢ12−チタニアハイブリッド化合物、
子数１ないし２０のアルコキシ基を表し、ｎは１から２０までの整数を表し、Ｒ8は水素
原子又は炭素原子数１〜１０のアルキル基を表し、Ｒ9は同一又は異なって、炭素原子数
１〜１０のアルキル基を表し、Ｘはシアノ基、ヒドロキシ基またはメチル基を表し、ＹはＣｏ原子に配位している水分子を表す。｝、
第５観点として、有機ハロゲン化物を光脱ハロゲン化するにあたり、第１観点ないし第４観点のいずれかに記載のビタミンＢ12−チタニアハイブリッド化合物をその表面に担持した基材を用いる、光脱ハロゲン化方法、
第６観点として、第１観点ないし第４観点のいずれかに記載のビタミンＢ12−チタニアハイブリッド化合物を含む光有機合成触媒、
第７観点として、第１観点ないし第４観点のいずれかに記載のビタミンＢ12−チタニアハイブリッド化合物を含む光脱ハロゲン化触媒、
である。
That is, the present invention provides, as a first aspect, a vitamin B 12 -titania hybrid compound characterized in that one or more vitamin B 12 compounds are immobilized on titania via a binding portion,
As a second aspect, the binding part has a siloxane bond in the main chain, the vitamin B 12 -titania hybrid compound according to the first aspect,
As a third aspect, the vitamin B 12 -titania hybrid compound according to the second aspect obtained by reacting a vitamin B 12 compound having a trialkoxysilyl group represented by the formula (1) with titania,
n represents an integer of 1 to 20, R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 is the same or different and represents an alkyl group having 1 to 10 carbon atoms. ), Provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 represents —NR 8 — (CH 2 ) n —Si (OR 9 ) 3 . X represents a cyano group, a hydroxy group or a methyl group, and Y represents a water molecule coordinated to a Co atom. },
As a fourth aspect, the vitamin B 12 -titania hybrid compound according to the third aspect obtained by reacting a vitamin B 12 compound having a trialkoxysilyl group represented by the formula (2) with titania,
As a fifth aspect, in the photodehalogenation of an organic halide, photodehalogenation using a substrate carrying the vitamin B 12 -titania hybrid compound according to any one of the first to fourth aspects on its surface. Conversion method,
As a sixth aspect, a photo-organic synthesis catalyst comprising the vitamin B 12 -titania hybrid compound according to any one of the first to fourth aspects,
As a seventh aspect, a photodehalogenation catalyst comprising the vitamin B 12 -titania hybrid compound according to any one of the first to fourth aspects,
It is.
本発明のビタミンＢ12−チタニアハイブリッド化合物を用いれば、様々なｐＨ条件で高い耐久性を示す触媒を開発することができる。さらに本触媒を用いれば、光照射により、脱ハロゲン化反応のみならず、様々な光有機合成反応へも適用することができる。 If the vitamin B 12 -titania hybrid compound of the present invention is used, a catalyst exhibiting high durability under various pH conditions can be developed. Furthermore, if this catalyst is used, it can be applied not only to a dehalogenation reaction but also to various photo-organic synthesis reactions by light irradiation.
以下、本発明について詳細に説明する。
本発明に用いられるビタミンＢ12化合物とは、ビタミンＢ12骨格を有する化合物であり、例えば、アルコキシシリル基を有するビタミンＢ12（シアノコバラミン）が挙げられる。
Hereinafter, the present invention will be described in detail.
The vitamin B 12 compound used in the present invention is a compound having a vitamin B 12 skeleton, and examples thereof include vitamin B 12 (cyanocobalamin) having an alkoxysilyl group.
続いて、式（１）または式（２）の各置換基を具体的に説明する。
Ｒ1ないしＲ7におけるアルコキシ基としては、例えばメトキシ基、エトキシ基、プロポキシ基、ブトキシ基などの炭素原子数１ないし２０のアルコキシ基が挙げられ、好ましくはメトキシ基である。
Ｒ8は、水素原子又は炭素原子数１〜１０のアルキル基を表すが、炭素原子数１〜１０
のアルキル基としては、メチル基、エチル基、プロピル基等が挙げられ、好ましいＲ8は
水素原子である。
Ｒ9の炭素原子数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基等
が挙げられ、好ましくはメチル基である。
Then, each substituent of Formula (1) or Formula (2) is demonstrated concretely.
Examples of the alkoxy group in R 1 to R 7 include alkoxy groups having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.
R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but 1 to 10 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and the like, and preferred R 8 is a hydrogen atom.
Examples of the alkyl group having 1 to 10 carbon atoms of R 9 include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
本発明において、ビタミンＢ12化合物は、結合部を介してチタニア（酸化チタン）に固定化されるが、チタニア（酸化チタン）は、一般に固体光触媒として使用されている。
固体光触媒とは、光を照射されることにより、励起され高い還元力と酸化力を示す固体であり、バンドギャップエネルギーに相当する紫外光を照射されることにより光増感作用を示す紫外光応答型の光触媒が一般に用いられる。紫外光では金属錯体が分解するおそれがある場合は、可視光を照射されることにより光励起されるバンドギャップエネルギーの小さい光触媒も用いられる。固体光触媒の中で、チタニア（酸化チタン）は、光照射されることにより中性条件の水中で、−０．３ＶｖｓＮＨＥ以下の還元電位を示して、ビタミンＢ12型錯体のコバルト原子（Ｃｏ）を１価に還元することができ、また、安定かつ安価で、光を照射することにより−０．５ＶＮＨＥ以下の還元電位を示すことから、本発明に使用される。
In the present invention, the vitamin B 12 compound is immobilized on titania (titanium oxide) via a binding portion, but titania (titanium oxide) is generally used as a solid photocatalyst.
A solid photocatalyst is a solid that is excited when irradiated with light and exhibits a high reducing power and oxidizing power, and an ultraviolet light response that exhibits a photosensitizing action when irradiated with ultraviolet light corresponding to the band gap energy. A type of photocatalyst is generally used. In the case where the metal complex may be decomposed by ultraviolet light, a photocatalyst having a small band gap energy that is photoexcited by irradiation with visible light is also used. Among the solid photocatalysts, titania (titanium oxide) shows a reduction potential of −0.3 V vs NHE or less in water under neutral conditions when irradiated with light, and the cobalt atom (Co) of the vitamin B 12 type complex Since it can be reduced to monovalent, is stable and inexpensive, and exhibits a reduction potential of −0.5 VNHE or less when irradiated with light, it is used in the present invention.
チタニア（酸化チタン）としては、結晶系の異なる、アナターゼ型、ルチル型、アナターゼ・ルチル混合型、ブルッカイト型の酸化チタンなどが用いられるが、還元力の強いアナターゼ型を含むものが望ましい。
このようなチタニア（酸化チタン）としては、以下の市販品の粉末状酸化チタンが一般
に用いられる。例えば、「P-25」（日本エアロジル（株）製）、「ST-01」（石原産業（
株）製）、「ST-21」（石原産業（株）製）、「TKP-101」（テイカ（株）製）、「AKT-600」（テイカ（株）製）、「MT-150A」（テイカ（株）製）、「TP-S201」（住友化学（株
）製）などが挙げられるが、これに限らず通常の酸化チタンのほとんどが使用できる。
As titania (titanium oxide), anatase type, rutile type, anatase / rutile mixed type, brookite type titanium oxide and the like having different crystal systems are used, and those containing anatase type having strong reducing power are desirable.
As such titania (titanium oxide), the following commercially available powdered titanium oxide is generally used. For example, “P-25” (manufactured by Nippon Aerosil Co., Ltd.), “ST-01” (Ishihara Sangyo (
Co., Ltd.), "ST-21" (Ishihara Sangyo Co., Ltd.), "TKP-101" (Taika Co., Ltd.), "AKT-600" (Taika Co., Ltd.), "MT-150A" (Manufactured by Teika Co., Ltd.), “TP-S201” (manufactured by Sumitomo Chemical Co., Ltd.), and the like, but not limited to this, most ordinary titanium oxide can be used.
次に本発明のビタミンＢ12−チタニアハイブリッド化合物を用いる光脱ハロゲン化反応について説明する。
本発明のビタミンＢ12−チタニアハイブリッド化合物を用いて光脱ハロゲン化反応を行うには、例えば溶媒となるエタノール中で、基質（有機ハロゲン化物）とビタミンＢ12−チタニアハイブリッド化合物を混合させ、光照射すればよい。
反応温度は、通常２０℃〜４０℃、好ましくは３０℃〜３５℃程度である。反応に要する時間は、通常３時間〜２４時間程度である。
Next, the photodehalogenation reaction using the vitamin B 12 -titania hybrid compound of the present invention will be described.
In order to perform a photodehalogenation reaction using the vitamin B 12 -titania hybrid compound of the present invention, for example, a substrate (organic halide) and a vitamin B 12 -titania hybrid compound are mixed in ethanol as a solvent, and light is removed. Irradiation is sufficient.
The reaction temperature is usually about 20 ° C to 40 ° C, preferably about 30 ° C to 35 ° C. The time required for the reaction is usually about 3 to 24 hours.
ビタミンＢ12−チタニアハイブリッド化合物において、中心金属原子であるコバルト原子の価数は通常、３価または２価であるが、-1〜-2.0V vs. Ag/AgClの電位をかけると１
価に還元される。よってチタニア（酸化チタン）の励起状態における高い還元作用によりコバルト原子が１価に還元されると、ビタミンＢ12−チタニアハイブリッド化合物は高い求核性を示すので、本発明の光脱ハロゲン化反応では、かかるビタミンＢ12−チタニアハイブリッド化合物が、基質となる有機ハロゲン化物に求核攻撃し、反応するものと考えられる。
In the vitamin B 12 -titania hybrid compound, the valence of the cobalt atom that is the central metal atom is usually trivalent or divalent, but it is 1 when a potential of −1 to −2.0 V vs. Ag / AgCl is applied.
Reduced to a valence. Therefore, when the cobalt atom is reduced to monovalent by the high reduction action in the excited state of titania (titanium oxide), the vitamin B 12 -titania hybrid compound exhibits high nucleophilicity. Therefore, in the photodehalogenation reaction of the present invention, Such a vitamin B 12 -titania hybrid compound is considered to react by nucleophilic attack on the organic halide as a substrate.
反応後のビタミンＢ12−チタニアハイブリッド化合物は、溶解せずに懸濁しているため、反応混合物から生成物を回収した後、再利用することができる。生成物を回収せずに、反応混合物として含んだまま連続して再利用することも可能である。 Since the vitamin B 12 -titania hybrid compound after the reaction is suspended without being dissolved, it can be reused after the product is recovered from the reaction mixture. It is also possible to continuously recycle the product as it is contained in the reaction mixture without recovering the product.
次に、本発明のビタミンＢ12−チタニアハイブリッド化合物の製造方法について説明する。
ビタミンＢ12化合物を、結合部を介してチタニア（酸化チタン）に固定化するには、例えばエタノールなどの溶媒中で、結合部としてシロキサン結合を主鎖に有するビタミンＢ12化合物とチタニア（酸化チタン）を混合して撹拌接触したのち、濾過法により溶媒を除去して集めれば良い。前記反応に用い得る溶媒としては、ビタミンＢ12化合物およびチタニア（酸化チタン）に対して不活性なものが用いられ、具体的には、例えばメタノール、エタノール、プロパノールなどのアルコール類、アセトンなどのケトン類、ベンゼン、トルエンなどの芳香族炭化水素類などが用いられる。接触は通常、攪拌下に行われる。
Next, a method for producing the vitamin B 12 -titania hybrid compound of the present invention will be described.
In order to immobilize the vitamin B 12 compound on titania (titanium oxide) via a bonding part, for example, in a solvent such as ethanol, a vitamin B 12 compound and titania (titanium oxide) having a siloxane bond as a bonding part in the main chain. ) Are mixed and brought into contact with stirring, and then the solvent is removed by filtration and collected. As the solvent that can be used in the reaction, those inert to vitamin B 12 compounds and titania (titanium oxide) are used. Specifically, alcohols such as methanol, ethanol, and propanol, and ketones such as acetone are used. , Aromatic hydrocarbons such as benzene and toluene are used. Contact is usually carried out with stirring.
接触させることにより、チタニア（酸化チタン）表面でトリアルコキシシリル基部位のゾル-ゲル反応が進行し、ビタミンＢ12化合物がチタニア（酸化チタン）上に担持されて
、目的のビタミンＢ12−チタニアハイブリッド化合物を得ることができる。接触後、通常は濾過操作により、結合部を介してビタミンＢ12化合物がチタニアに固定化されたビタミンＢ12−チタニアハイブリッド化合物を得ることができる。
By contacting, the sol-gel reaction of the trialkoxysilyl group site proceeds on the titania (titanium oxide) surface, and the vitamin B 12 compound is supported on titania (titanium oxide), and the target vitamin B 12 -titania hybrid is obtained. A compound can be obtained. After the contact, a vitamin B 12 -titania hybrid compound in which the vitamin B 12 compound is immobilized on titania through a binding portion is usually obtained by filtration.
本発明のビタミンＢ12−チタニアハイブリッド化合物は、光有機合成触媒として使用することができる。
ここで、光有機合成触媒は、脱ハロゲン化反応に加えて、例えば、官能基転移反応、環拡大反応、二量化反応、還元反応、ラジカル付加反応等の有機合成反応を触媒する。
また、光脱ハロゲン化触媒とは、紫外線などの光照射により、例えば、１，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン［ＤＤＴ］、クロロホルム、塩化メチレン、ブロモホルム、臭化メチレン等の有機ハロゲン化合物からハロゲン原子を脱離させることができる触媒である。
Vitamin B 12 of the present invention - titania hybrid compounds can be used as an optical organic synthesis catalyst.
Here, in addition to the dehalogenation reaction, the photo-organic synthesis catalyst catalyzes an organic synthesis reaction such as a functional group transfer reaction, a ring expansion reaction, a dimerization reaction, a reduction reaction, or a radical addition reaction.
The photodehalogenation catalyst is, for example, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane [DDT], chloroform, methylene chloride, bromoform, bromide by irradiation with light such as ultraviolet rays. It is a catalyst capable of removing a halogen atom from an organic halogen compound such as methylene.
前記光有機合成触媒が触媒する光有機合成は、例えば溶媒中で基質をビタミンＢ12−チタニアハイブリッド化合物と混合し、光照射を行うことにより達成される。
前記反応に用いうる溶媒としては、基質（有機ハロゲン化物等）およびビタミンＢ12−チタニアハイブリッド化合物に対して反応しないもの、例えばメタノール、エタノール、プロパノールなどのアルコール類、アセトンなどのケトン類、ベンゼン、トルエンなどの芳香族炭化水素類、アセトニトリル、ベンゾニトリルなどが挙げられる。チタニア（酸化チタン）が光増感作用を効率良く起こすためには、価電子帯のホールと高い反応性を示す、アルコール類を含む溶媒系が望ましい。
The photo-organic synthesis catalyzed by the photo-organic synthesis catalyst can be achieved, for example, by mixing a substrate with a vitamin B 12 -titania hybrid compound in a solvent and performing light irradiation.
Solvents that can be used for the reaction include those that do not react with substrates (organic halides, etc.) and vitamin B 12 -titania hybrid compounds, such as alcohols such as methanol, ethanol, and propanol, ketones such as acetone, benzene, Aromatic hydrocarbons such as toluene, acetonitrile, benzonitrile and the like can be mentioned. In order for titania (titanium oxide) to efficiently cause photosensitization, a solvent system containing alcohols that exhibits high reactivity with holes in the valence band is desirable.
照射使用する光は、バンドギャップエネルギーに相当する波長の光が用いられ、紫外光、可視光等が用いられる。
反応温度は、通常２０℃〜４０℃の範囲で３０℃〜３５℃程度が最も適切である。反応に要する時間は、通常３時間〜２４時間程度である。
The light used for irradiation is light having a wavelength corresponding to the band gap energy, and ultraviolet light, visible light, or the like is used.
The reaction temperature is usually 20 ° C to 40 ° C, and most preferably about 30 ° C to 35 ° C. The time required for the reaction is usually about 3 to 24 hours.
ビタミンＢ12−チタニアハイブリッド化合物において、中心金属原子であるコバルト原子は通常、３価であるが、チタニア（酸化チタン）の存在下に光を照射すると、チタニア（酸化チタン）の還元作用によって１価に還元される。コバルト原子が１価に還元されたビタミンＢ12−チタニアハイブリッド化合物は、高い求核性を示すので、本発明のビタミンＢ12−チタニアハイブリッド化合物を用いる光有機合成反応では、かかるビタミンＢ12−チタニアハイブリッド化合物が、基質（有機ハロゲン化物等）に作用して反応し、様々な反応活性種を与え、多くはラジカル中間体を経て光有機合成反応が進行するものと考えられる。 Vitamin B 12 - in titania hybrid compound, a cobalt atom is usually a central metal atom, but is a trivalent, titania is irradiated with light in the presence of (titanium oxide), a monovalent by the reducing action of titania (titanium oxide) Reduced to Since the vitamin B 12 -titania hybrid compound in which the cobalt atom has been reduced to monovalent value exhibits high nucleophilicity, in the photo-organic synthesis reaction using the vitamin B 12 -titania hybrid compound of the present invention, such vitamin B 12 -titania It is considered that the hybrid compound acts on the substrate (organic halide or the like) and reacts to give various reactive species, and in many cases, the photo-organic synthesis reaction proceeds via a radical intermediate.
反応後のビタミンＢ12−チタニアハイブリッド化合物は、反応混合物から回収して、再利用することができる。具体的には、セライトを敷いた濾紙による濾過操作や遠心分離操作が、容易にビタミンＢ12−チタニアハイブリッド化合物を反応混合物から回収することができるため、好ましい。また、ビタミンＢ12−チタニアハイブリッド化合物を基材に担持させて用いた場合には、反応器から引き上げるだけで容易に反応後の反応混合物から回収することができるので、簡便である。 The vitamin B 12 -titania hybrid compound after the reaction can be recovered from the reaction mixture and reused. Specifically, a filtration operation or a centrifugal separation operation using a filter paper with celite is preferable because the vitamin B 12 -titania hybrid compound can be easily recovered from the reaction mixture. In addition, when the vitamin B 12 -titania hybrid compound is supported on a substrate and used, it can be easily recovered from the reaction mixture after the reaction simply by pulling it up from the reactor.
ビタミンＢ12−チタニアハイブリッド化合物は、粉末状で用いられてもよいが、触媒反応後の反応混合物から容易に取り出すことができる形状に加工されていることが好ましく、基材や反応容器の内壁に固定化して使用するのが望ましい。
また、ビタミンＢ12−チタニアハイブリッド化合物は、反応混合物から容易に取り出すことのできる形状の基材に担持されていると反応操作が簡便となり望ましい。基材としては、光照射により分解しないものや有機溶媒に対して安定で不活性なものであればよく、例えば無機ガラス、アルミナなどのセラミックス、白金、金などの金属などが挙げられる。基材の形状は、触媒反応後の混合物から取り出し易く加工されたものが好ましく、例えば板状、球状、リング状、網状の基材が用いられ、具体的には、例えば、ガラスビーズ等も含まれる。反応を効率良く進ませるためには、多孔質性で基質との接触面積が大きいものが望ましい。またガラス反応器の内壁に直接固定化されるのが最も好ましい。
The vitamin B 12 -titania hybrid compound may be used in a powder form, but is preferably processed into a shape that can be easily taken out from the reaction mixture after the catalytic reaction, and is formed on the inner wall of the substrate or reaction vessel. It is desirable to fix and use.
The vitamin B 12 -titania hybrid compound is preferably carried on a substrate having a shape that can be easily taken out from the reaction mixture, because the reaction operation is simple. The substrate may be any substrate that does not decompose by light irradiation or that is stable and inert to organic solvents. Examples thereof include inorganic glass, ceramics such as alumina, and metals such as platinum and gold. The shape of the substrate is preferably processed so that it can be easily taken out from the mixture after the catalytic reaction. For example, a plate-like, spherical, ring-like, or net-like substrate is used, and specifically includes, for example, glass beads. It is. In order to advance the reaction efficiently, a porous material having a large contact area with the substrate is desirable. Most preferably, it is directly fixed to the inner wall of the glass reactor.
ビタミンＢ12−チタニアハイブリッド化合物を基材上に担持するには、例えばバインダーを含む市販のコーティング液に粉末状のビタミンＢ12−チタニアハイブリッド化合物を分散させ、基材上にキャスティング法やデイップコーティング法、スピンコーティング法により塗布した後、乾燥させ溶媒を揮発させればよい。コーティング液に用いうる溶媒としては、例えばエタノールなどのアルコール類、水などが挙げられる。このようなコーティング液として一般に入手可能なものを用いることもでき、例えば「ＴＫＣ−３０３」（テイカ(株)製）、「ＴＫＣ−３０４」（テイカ(株)製）、「ＴＳ−Ｓ４１１０」（住友化学(株)製）などが挙げられる。溶媒を揮発させることにより、バインダーにより粉末状の
ビタミンＢ12−チタニアハイブリッド化合物が基材上に担持することができる。
In order to carry the vitamin B 12 -titania hybrid compound on the substrate, for example, a powdered vitamin B 12 -titania hybrid compound is dispersed in a commercially available coating solution containing a binder, and the casting method or the dip coating method is performed on the substrate. After applying by spin coating, the solvent may be evaporated by drying. Examples of the solvent that can be used for the coating liquid include alcohols such as ethanol, water, and the like. As such a coating liquid, a generally available one can be used. For example, “TKC-303” (manufactured by Teika), “TKC-304” (manufactured by Teica), “TS-S4110” ( Sumitomo Chemical Co., Ltd.). By volatilizing the solvent, the powdered vitamin B 12 -titania hybrid compound can be supported on the substrate by the binder.
以下、本発明について実施例を挙げて詳述するが、本発明はこれらの実施例に何ら限定されるものではない。なお、下記において、電子スペクトル（ＵＶ−Ｖｉｓ）、赤外吸収スペクトル（ＩＲ）、核磁気共鳴スペクトル（ＮＭＲ）、質量スペクトル（ＧＣ−ＭＳ、ＭＡＬＤＩ−ＴＯＦ−ＭＳ）は下記の装置によりそれぞれ測定した。
［１］電子スペクトル（ＵＶ−Ｖｉｓ）
Ｕ−３０００型紫外可視分光光度計（（株）日立製作所製）
［２］赤外吸収スペクトル（ＩＲ）
ＦＴ−ＩＲ ４６０ｐｌｕｓ分光光度計（（株）日本分光社製）
［３］核磁気共鳴スペクトル（ＮＭＲ）
ＮＭＲ：ＡＶＡＮＣＥ ５００ 核磁気共鳴装置（（株）ブルカー製）
［４］ＧＣ−ＭＳ
ＧＣＭＳ−ＱＰ５０５０ＡＨガスクロマトグラフ質量分析計（（株）島津製作所製）
「５」ＭＡＬＤＩ−ＴＯＦ−ＭＳ
Ｂｒｕｋｅｒ Ａｕｔｏｆｌｅｘ質量分析装置（（株）ブルカーダルトニクス社製）
Hereinafter, although an example is given and the present invention is explained in full detail, the present invention is not limited to these examples at all. In the following, an electron spectrum (UV-Vis), an infrared absorption spectrum (IR), a nuclear magnetic resonance spectrum (NMR), and a mass spectrum (GC-MS, MALDI-TOF-MS) were measured by the following apparatuses. .
[1] Electronic spectrum (UV-Vis)
U-3000 type UV-visible spectrophotometer (manufactured by Hitachi, Ltd.)
[2] Infrared absorption spectrum (IR)
FT-IR 460plus spectrophotometer (manufactured by JASCO Corporation)
[3] Nuclear magnetic resonance spectrum (NMR)
NMR: AVANCE 500 nuclear magnetic resonance apparatus (manufactured by Bruker)
[4] GC-MS
GCMS-QP5050AH gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation)
"5" MALDI-TOF-MS
Bruker Autoflex mass spectrometer (manufactured by Bruker Daltonics)
参考例１（ビタミンＢ12誘導体（カルボキシル基）の合成）
シアノコバラミン2.0 g（1.5×10-3 mol）を0.1 mol/L酢酸水溶液300 mLに溶解し、N-
ブロモスクシンイミド0.35 g（2.0×10-3 mol）を加え、室温で20時間撹拌した。反応溶
液からフェノールで抽出し（200 mL×3）、フェノール層を水で洗浄した（100 mL×2）。得られたフェノール溶液にジエチルエーテル300mLと水100mLを加え、水層に目的物を逆抽出した。水を減圧留去した後、残査をアセトン/水で再沈殿を行い、赤色粉末(c-lac)cobalamin (2.0 g 収率91%)を得た。
(c-lac)cobalaminは、UV-visスペクトル（図１）、IRスペクトル（図２）で同定を行った。
上記操作で得られた赤色粉末2.0 g（1.5×10-3 mol）のメタノール溶液300 mLに、98%
冷濃硫酸 30 mLを滴下した。遮光条件下、窒素雰囲気下で120 時間加熱還流した。反応混合物を減圧濃縮し、冷水100 mLを加えた後、固体炭酸ナトリウムで中和し、シアン化カリウム2.0 g（3.1×10-2 mol）を加えた。四塩化炭素(100 mL×2)で抽出を行い、抽出液を
水(100 mL×2)で洗浄し、硫酸ナトリウムで乾燥後、減圧乾固した。ベンゼン/n-へキサンで再沈殿を行い、紫色粉末の(c-lac)6C1ester(0.75 g 収率47%)を得た。
(c-lac)6C1esterは、UV-visスペクトル（図３）、IRスペクトル（図４）で同定を行っ
た。
上記操作で得られた紫色粉末0.6 g（0.6×10-3 mol）の酢酸 溶液100 mLに窒素ガスを
バブリングして脱気した後、亜鉛粉末2.4gを加え窒素雰囲気下で2時間撹拌した。亜鉛を
濾別後、水100 mLを加えた後、塩化メチレン(100 mL×2)で抽出を行い、抽出液を水(100 mL×2)で洗浄し、シアン化カリウム水溶液と振とうし、硫酸ナトリウムで乾燥後、減圧乾固した。得られた紫色粉末を薄層クロマトグラフ法（Klesegel 60H、塩化メチレン：メタノール=14：1）により精製した。得られた化合物をベンゼン/n-へキサンで再沈殿を行い
、赤紫色粉末(CN)2Cob(III)6C1ester(0.37 g 収率67%)を得た。
(CN)2Cob(III)6C1esterは、UV-visスペクトル（図５）、IRスペクトル（図６）、MALDI-TOF-MSで同定を行った。
MALDI-TOF-MS：(M-2CN)=1021.7
Reference Example 1 (Synthesis of vitamin B 12 derivative (carboxyl group))
Dissolve 2.0 g (1.5 × 10 -3 mol) of cyanocobalamin in 300 mL of 0.1 mol / L acetic acid aqueous solution, and add N-
Bromosuccinimide 0.35 g (2.0 × 10 −3 mol) was added, and the mixture was stirred at room temperature for 20 hours. The reaction solution was extracted with phenol (200 mL × 3), and the phenol layer was washed with water (100 mL × 2). To the obtained phenol solution, 300 mL of diethyl ether and 100 mL of water were added, and the target product was back-extracted into the aqueous layer. After distilling off water under reduced pressure, the residue was reprecipitated with acetone / water to obtain a red powder (c-lac) cobalamin (2.0 g yield 91%).
(c-lac) cobalamin was identified by UV-vis spectrum (FIG. 1) and IR spectrum (FIG. 2).
To 300 mL of methanol solution of 2.0 g (1.5 × 10 -3 mol) of red powder obtained by the above operation, 98%
30 mL of cold concentrated sulfuric acid was added dropwise. The mixture was heated to reflux for 120 hours under a nitrogen atmosphere under light-shielding conditions. The reaction mixture was concentrated under reduced pressure, 100 mL of cold water was added, neutralized with solid sodium carbonate, and 2.0 g (3.1 × 10 −2 mol) of potassium cyanide was added. Extraction was performed with carbon tetrachloride (100 mL × 2), and the extract was washed with water (100 mL × 2), dried over sodium sulfate, and then dried under reduced pressure. Reprecipitation was performed with benzene / n-hexane to obtain a purple powder of (c-lac) 6C 1 ester (0.75 g, yield 47%).
(c-lac) 6C 1 ester was identified by UV-vis spectrum (FIG. 3) and IR spectrum (FIG. 4).
Nitrogen gas was bubbled into 100 mL of an acetic acid solution of 0.6 g (0.6 × 10 −3 mol) of the purple powder obtained by the above operation, 2.4 g of zinc powder was added, and the mixture was stirred under a nitrogen atmosphere for 2 hours. After removing the zinc by filtration, add 100 mL of water, extract with methylene chloride (100 mL × 2), wash the extract with water (100 mL × 2), shake with aqueous potassium cyanide solution, and add sodium sulfate. And dried under reduced pressure. The resulting purple powder was purified by thin layer chromatography (Klesegel 60H, methylene chloride: methanol = 14: 1). The obtained compound was reprecipitated with benzene / n-hexane to obtain a reddish purple powder (CN) 2 Cob (III) 6C 1 ester (0.37 g yield 67%).
(CN) 2 Cob (III) 6C 1 ester was identified by UV-vis spectrum (FIG. 5), IR spectrum (FIG. 6), and MALDI-TOF-MS.
MALDI-TOF-MS: (M-2CN) = 1021.7
参考例２（トリメトキシシリルビタミンＢ12錯体の合成）
素酸水溶液 80 mLを加え振とうした。分液ロートで水層を除き、塩化メチレン溶液を水(50 mL×2)で洗浄し、硫酸ナトリウムで乾燥後、減圧乾固した。得られた化合物をベンゼン/n-へキサンで再沈殿を行い、赤紫色粉末(H2O) (CN)Cob(III)6C1ester(69 mg 収率70%)を得た。この赤紫色粉末(H2O) (CN)Cob(III)6C1ester0.05 g（4.7×10-5 mol）を無水N,N-
ジメチルホルムアミド10 mLに溶解し、窒素雰囲気下でシアノリン酸ジエチル15 mg（9.2
×10-5 mol）を加え0℃で30分間撹拌した。そこへ3-アミノプロピルトリメトキシシラン1
8 mg（8.0×10-5 mol）およびトリエチルアミン0.016mL（9.6×10-5 mol）を加え0℃で6
時間、室温で15時間撹拌した。反応溶液に水100mLを加え、塩化メチレン(50 mL×3)で抽
出した後、さらに水(100 mL×3)で洗浄した。硫酸ナトリウムで乾燥後、減圧乾固した。
得られた化合物をベンゼン/n-へキサンで再沈殿を行い、赤紫色粉末トリメトキシシリル
ビタミンＢ12錯体(52 mg 収率88%)を得た。
トリメトキシシリルビタミンＢ12錯体は、UV-visスペクトル（図７）、NMRスペクトル
（図８）、元素分析、MALDI-TOF-MSで同定を行った。
元素分析：理論値 H, 7.01; C, 57.32; N, 7.93、分析値 H, 6.99; C, 56.91; N, 7.52MALDI-TOF-MS：(M-CN)=1209.5
Reference Example 2 (Synthesis of trimethoxysilyl vitamin B 12 complex)
Dissolve in 10 mL of dimethylformamide and add 15 mg of diethyl cyanophosphate (9.2 mg under a nitrogen atmosphere).
× 10 -5 mol) was added and the mixture was stirred at 0 ° C for 30 minutes. 3-aminopropyltrimethoxysilane 1 there
Add 8 mg (8.0 × 10 -5 mol) and triethylamine 0.016 mL (9.6 × 10 -5 mol) and add 6 at 0 ° C.
Stir for 15 hours at room temperature. To the reaction solution was added 100 mL of water, and the mixture was extracted with methylene chloride (50 mL × 3), and further washed with water (100 mL × 3). After drying with sodium sulfate, it was dried under reduced pressure.
The obtained compound was reprecipitated with benzene / n-hexane to obtain a reddish purple powder trimethoxysilylvitamin B 12 complex (52 mg, yield 88%).
The trimethoxysilyl vitamin B 12 complex was identified by UV-vis spectrum (FIG. 7), NMR spectrum (FIG. 8), elemental analysis, and MALDI-TOF-MS.
Elemental analysis: Theoretical value H, 7.01; C, 57.32; N, 7.93; Analytical value H, 6.99; C, 56.91; N, 7.52 MALDI-TOF-MS: (M-CN) = 1209.5
実施例１（ビタミンＢ12−チタニアハイブリッド化合物の合成）
トリアルコキシシリルビタミンＢ12型錯体17.3mg(1.4×10-5 mol)をエタノール（和光
純薬工業（株）製、試薬特級）1mLに溶解し、アナターゼ/ルチル混合型酸化チタン粉末（日本エアロゾル（株）製、「P-25」）150mgを加える。本懸濁液を室温（約25℃）で24時
間撹拌した後、固形分を濾取し乾燥させて、ビタミンＢ12−チタニアハイブリッド化合物を得た。化合物は、MALDI-TOF-MS（図９）で同定を行った。ビタミンＢ12錯体に由来する分子イオンピークが強く観測された。電子スペクトル法から求めたビタミンＢ12−チタニアハイブリッド化合物の複合化率（表面修飾率）は、酸化チタン粉末の単位表面積あたりで5.0×10-11mol/cm2であった。
Example 1 (vitamin B 12 - synthesis of titania hybrid compound)
Trialkoxysilyl vitamin B 12 complex 17.3mg (1.4 × 10 -5 mol) is dissolved in 1mL of ethanol (made by Wako Pure Chemical Industries, Ltd., special grade reagent), and anatase / rutile mixed titanium oxide powder (Japan Aerosol ( 150 mg of “P-25” manufactured by Co., Ltd. is added. The suspension was stirred at room temperature (about 25 ° C.) for 24 hours, and then the solid content was collected by filtration and dried to obtain a vitamin B 12 -titania hybrid compound. The compound was identified by MALDI-TOF-MS (FIG. 9). A strong molecular ion peak derived from the vitamin B 12 complex was observed. The complexing rate (surface modification rate) of the vitamin B 12 -titania hybrid compound determined from the electron spectrum method was 5.0 × 10 −11 mol / cm 2 per unit surface area of the titanium oxide powder.
実施例２（ビタミンＢ12−チタニアハイブリッド薄膜の合成）
ビタミンＢ12−チタニアハイブリッド化合物10mgをコーティング剤（ＴＳ−Ｓ４１１０、住友化学(株)製）3mLに加え、撹拌する。本懸濁液をガラス基板（MATSUNAMIスライドガラス）上に10〜300μLキャスティングし室温で24時間乾燥させることで、基板上に固定化したビタミンＢ12−チタニアハイブリッド化合物を得た。ガラス基板上に固定化したビタミンＢ12−チタニアハイブリッド化合物は、エタノール（和光純薬工業（株）製、試薬特級）中で超音波照射装置（（株）アズワン社製US-4）にかけても安定であり、強固に基板に固定化されていた。ガラス基板上に固定化されたビタミンＢ12−チタニアハイブリッド化合物の写真を図１０として示した。
Example 2 (Synthesis of vitamin B 12 -titania hybrid thin film)
Vitamin B 12 -titania hybrid compound (10 mg) is added to 3 mL of a coating agent (TS-S4110, manufactured by Sumitomo Chemical Co., Ltd.) and stirred. This suspension was cast on a glass substrate (MATSUNAMI slide glass) at 10 to 300 μL and dried at room temperature for 24 hours to obtain a vitamin B 12 -titania hybrid compound immobilized on the substrate. Vitamin immobilized on a glass substrate B 12 - titania hybrid compound, ethanol (manufactured by Wako Pure Chemical Industries, Ltd., guaranteed reagent) be subjected to ultrasonic irradiation device in (Co. AS ONE Corporation US-4) stable It was firmly fixed to the substrate. A photograph of the vitamin B 12 -titania hybrid compound immobilized on the glass substrate is shown in FIG.
実施例３（ビタミンＢ12−チタニアハイブリッド化合物の耐久性）
ビタミンＢ12−チタニアハイブリッド化合物（粉末）10mgを各種溶媒に懸濁させ、3時
間撹拌した後濾過し、濾液に溶出したビタミンＢ12の吸光度から、耐久性を評価した。
安定度（％）=（溶液浸せき後のビタミンＢ12固定化量 / 溶液浸せき前のビタミンＢ12固定化量）×100
メタノール：99％以上、メタノール（加熱還流）：99％以上、メタノール（超音波処理）：99％以上、メタノール-酢酸(1:1)：99％以上、水（中性）：99％以上、水（pH3）：99％以上、水（pH10）：99％以上
Example 3 (vitamin B 12 - durable titania hybrid compound)
Vitamin B 12 -titania hybrid compound (powder) 10 mg was suspended in various solvents, stirred for 3 hours, filtered, and durability was evaluated from the absorbance of vitamin B 12 eluted in the filtrate.
Stability (%) = (Amount of vitamin B 12 immobilized after immersion in solution / Amount of vitamin B 12 immobilized before immersion in solution) x 100
Methanol: 99% or more, methanol (heating reflux): 99% or more, methanol (sonication): 99% or more, methanol-acetic acid (1: 1): 99% or more, water (neutral): 99% or more, Water (pH 3): 99% or more, Water (pH 10): 99% or more
実施例４（ビタミンＢ12−チタニアハイブリッド化合物を触媒として用いる有機ハロゲン化物の光脱ハロゲン化反応）
第1表に示す１，１−ビス（４−クロロフェニル）−２，２，２−トリクロロエタン〔
ＤＤＴ〕を3ミリモル/L(3mmol/L)の濃度でエタノール（和光純薬工業（株）製、試薬特級）に溶解させ、30mLを秤取り、パイレックス（登録商標）ガラス製セルに入れた。次いで、実施例１で得たビタミンＢ12−チタニアハイブリッド化合物20mgを触媒として加え、撹拌して懸濁させながら窒素ガスをバブリングさせて溶存酸素を除去し、次いで撹拌下にブラックライト[フナコシ（株）製、15W]により、反応セル外表面における紫外光強度1.76mW/cm2で紫外光を3時間照射した。紫外光照射後の反応混合物における有機ハロゲン化物の含有量をガスクロマトグラフィー質量分析装置により求めて、用いた有機ハロゲン化物のうち脱ハロゲン化されたものの割合（転化率、％）を求めた。脱塩素化反応物として、１
，１−ビス（４−クロロフェニル）−２−クロロエチレン〔ＤＤＭＵ〕、１，１−ビス（４−クロロフェニル）−２-クロロエタン〔ＤＤＭＳ〕、１，１−ビス（４−クロロフェ
ニル）−２，２−ジクロロエタン〔ＤＤＤ〕、１，１，４，４−テトラキス（４−クロロフェニル）−２，３−ジクロロ−２−ブテン〔ＴＴＤＢ〕、エチル-１，１−ビス（４−
クロロフェニル）−アセテート〔ＤＤＡ ethyl ester〕が得られた。結果を第１表に示す。
1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane shown in Table 1 [
DDT] was dissolved in ethanol (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) at a concentration of 3 mmol / L (3 mmol / L), 30 mL was weighed and placed in a Pyrex (registered trademark) glass cell. Next, 20 mg of the vitamin B 12 -titania hybrid compound obtained in Example 1 was added as a catalyst, and nitrogen gas was bubbled while suspended by stirring to remove dissolved oxygen, and then blacklight [Funakoshi Co., Ltd. 15 W], UV light was irradiated for 3 hours at an ultraviolet light intensity of 1.76 mW / cm 2 on the outer surface of the reaction cell. The content of the organic halide in the reaction mixture after irradiation with ultraviolet light was determined by a gas chromatography mass spectrometer, and the ratio of the halogenated organic halide used (conversion rate,%) was determined. As dechlorination reactant, 1
1,1-bis (4-chlorophenyl) -2-chloroethylene [DDMU], 1,1-bis (4-chlorophenyl) -2-chloroethane [DDMS], 1,1-bis (4-chlorophenyl) -2,2 -Dichloroethane [DDD], 1,1,4,4-tetrakis (4-chlorophenyl) -2,3-dichloro-2-butene [TTDB], ethyl-1,1-bis (4-
Chlorophenyl) -acetate [DDA ethyl ester] was obtained. The results are shown in Table 1.
実施例５（ビタミンＢ12−チタニアハイブリッド化合物を触媒として用いる光有機合成反応）
実施例４で用いた有機ハロゲン化物に代えて第２表に示す有機ハロゲン化物（ブロモメチルフェニルマロン酸ジエチル）を用いた以外は実施例４と同様に操作し光化学反応を行った。反応物として、単純還元体（メチルフェニルマロン酸ジエチル）に加え、フェニル基が隣接炭素に転位したフェニル基転位体（ベンジルマロン酸ジエチル）が得られた。結果を第2表に示す。
The photochemical reaction was carried out in the same manner as in Example 4 except that the organic halide shown in Table 2 (diethyl bromomethylphenylmalonate) was used instead of the organic halide used in Example 4. As a reaction product, in addition to a simple reduced form (diethyl methylphenylmalonate), a phenyl group rearrangement (diethylbenzylmalonate) in which a phenyl group was rearranged to an adjacent carbon was obtained. The results are shown in Table 2.
実施例６（ビタミンＢ12−チタニアハイブリッド化合物を触媒として用いる光有機合成反応）
実施例４で用いた有機ハロゲン化物に代えて第3表に示す有機ハロゲン化物（フェネチ
ルブロマイド）を用いた以外は実施例４と同様に操作し光化学反応を行った。反応物として、単純還元体（エチルベンゼン）に加え、炭素-炭素結合が生成した二量化体（２，３
−ジフェニルブタン）が得られた。結果を第３表に示す。
The photochemical reaction was carried out in the same manner as in Example 4 except that the organic halide (phenethyl bromide) shown in Table 3 was used instead of the organic halide used in Example 4. As a reactant, in addition to a simple reductant (ethylbenzene), a dimer (2,3 with a carbon-carbon bond formed)
-Diphenylbutane) was obtained. The results are shown in Table 3.
実施例7（ビタミンＢ12−チタニアハイブリッド化合物を触媒として用いる光有機合成反
応）
実施例４で用いた有機ハロゲン化物に代えて第4表に示す有機ハロゲン化物（2-ブロモ
メチル-1-オキソシクロペンタンカルボン酸エチル）を用いた以外は実施例４と同様に操
作し光化学反応を行った。反応物として、環拡大物（3-オキソ-1-シクロヘキサンカルボ
ン酸エチル）が得られた。結果を第4表に示す。
The photochemical reaction was carried out in the same manner as in Example 4 except that the organic halide shown in Table 4 (ethyl 2-bromomethyl-1-oxocyclopentanecarboxylate) was used instead of the organic halide used in Example 4. went. As a reactant, a ring expansion product (ethyl 3-oxo-1-cyclohexanecarboxylate) was obtained. The results are shown in Table 4.
Claims (7)
原子数１ないし２０のアルコキシ基又は−ＮＲ8−（ＣＨ2）n−Ｓｉ（ＯＲ9）3（式中、
ｎは１から２０までの整数を表し、Ｒ8は水素原子又は炭素原子数１〜１０のアルキル基
を表し、Ｒ9は同一又は異なって、炭素原子数１〜１０のアルキル基を表す。）を表すが
、但し、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7の少なくとも１つ以上は−ＮＲ8−（ＣＨ2）n−Ｓｉ（ＯＲ9）3を表し、Ｘはシアノ基、ヒドロキシ基またはメチル基を表し、ＹはＣｏ原子に配位している水分子を表す。｝ Titania hybrid compound - vitamin B 12 vitamin B 12 compound according to claim 2 obtained by reacting titania with a trialkoxysilyl group represented by formula (1).
n represents an integer of 1 to 20, R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 9 is the same or different and represents an alkyl group having 1 to 10 carbon atoms. ), Provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 represents —NR 8 — (CH 2 ) n —Si (OR 9 ) 3 . X represents a cyano group, a hydroxy group or a methyl group, and Y represents a water molecule coordinated to a Co atom. }
原子又は炭素原子数１〜１０のアルキル基を表し、Ｒ9は同一又は異なって、炭素原子数
１〜１０のアルキル基を表し、Ｘはシアノ基、ヒドロキシ基またはメチル基を表し、ＹはＣｏ原子に配位している水分子を表す。｝ Titania hybrid compound - vitamin B 12 vitamin B 12 compound according to claim 3, wherein obtained by reacting titania with a trialkoxysilyl group represented by formula (2).
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| JP2010209044A (en) * | 2009-03-12 | 2010-09-24 | Toyota Motor Corp | Dinuclear metal complex and photocatalyst containing the same |
| JP2012024757A (en) * | 2010-06-24 | 2012-02-09 | Kyushu Univ | Light hydrogen generation catalyst consisting of base metal complex and titanium dioxide |
| JP2012106236A (en) * | 2010-10-22 | 2012-06-07 | Kyushu Univ | Photo-reduction catalyst including base-metal complex and titanium dioxide |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN110981720A (en) * | 2019-12-24 | 2020-04-10 | 河南大学 | Diaryl acetate compound and preparation method thereof |
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| JP2001096154A (en) * | 1999-09-29 | 2001-04-10 | Yamada Sangyo Kk | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method |
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Cited By (6)
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| JP2010209044A (en) * | 2009-03-12 | 2010-09-24 | Toyota Motor Corp | Dinuclear metal complex and photocatalyst containing the same |
| JP2012024757A (en) * | 2010-06-24 | 2012-02-09 | Kyushu Univ | Light hydrogen generation catalyst consisting of base metal complex and titanium dioxide |
| JP2012106236A (en) * | 2010-10-22 | 2012-06-07 | Kyushu Univ | Photo-reduction catalyst including base-metal complex and titanium dioxide |
| CN107744838A (en) * | 2017-10-16 | 2018-03-02 | 辽宁大学 | A kind of photochemical catalyst that catalytic activity is respectively provided with visible region and ultraviolet region and its preparation method and application |
| CN110981720A (en) * | 2019-12-24 | 2020-04-10 | 河南大学 | Diaryl acetate compound and preparation method thereof |
| CN110981720B (en) * | 2019-12-24 | 2020-11-03 | 河南大学 | Diaryl acetate compound and preparation method thereof |
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