JP5855011B2 - 少なくとも1種の金属元素を錯化することができる新規な化合物およびこれらの化合物をベースとする配位錯体 - Google Patents
少なくとも1種の金属元素を錯化することができる新規な化合物およびこれらの化合物をベースとする配位錯体 Download PDFInfo
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- JP5855011B2 JP5855011B2 JP2012542523A JP2012542523A JP5855011B2 JP 5855011 B2 JP5855011 B2 JP 5855011B2 JP 2012542523 A JP2012542523 A JP 2012542523A JP 2012542523 A JP2012542523 A JP 2012542523A JP 5855011 B2 JP5855011 B2 JP 5855011B2
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- group
- formula
- bipyridine
- compound
- triazole
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 69
- 229910052751 metal Inorganic materials 0.000 title claims description 30
- 239000002184 metal Substances 0.000 title claims description 24
- 230000000536 complexating effect Effects 0.000 title claims description 19
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 12
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052699 polonium Inorganic materials 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 150000003852 triazoles Chemical group 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- IKHJQSZZJNHUIF-UHFFFAOYSA-N 4-azido-1-oxido-2-pyridin-2-ylpyridin-1-ium Chemical compound [O-][N+]1=CC=C(N=[N+]=[N-])C=C1C1=CC=CC=N1 IKHJQSZZJNHUIF-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 235000010378 sodium ascorbate Nutrition 0.000 description 5
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 5
- 229960005055 sodium ascorbate Drugs 0.000 description 5
- -1 sodium nitride Chemical class 0.000 description 5
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 4
- TXORGAZSDCKPSN-UHFFFAOYSA-N 4-nitro-1-oxido-2-pyridin-2-ylpyridin-1-ium Chemical compound [O-][N+](=O)C1=CC=[N+]([O-])C(C=2N=CC=CC=2)=C1 TXORGAZSDCKPSN-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000001345 alkine derivatives Chemical group 0.000 description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KIKATWFLYDKKOL-UHFFFAOYSA-N 1-oxido-2-pyridin-2-ylpyridin-1-ium Chemical compound [O-][N+]1=CC=CC=C1C1=CC=CC=N1 KIKATWFLYDKKOL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 0 *c(cc1)ccc1-c1c[n](-c2ccnc(-c3ccccn3)c2)nn1 Chemical compound *c(cc1)ccc1-c1c[n](-c2ccnc(-c3ccccn3)c2)nn1 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical compound FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JWAWEQBUZOGIBZ-UHFFFAOYSA-N C[n]1nncc1 Chemical compound C[n]1nncc1 JWAWEQBUZOGIBZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- JPGRSTBIEYGVNO-UHFFFAOYSA-N methyl 4-ethynylbenzoate Chemical compound COC(=O)C1=CC=C(C#C)C=C1 JPGRSTBIEYGVNO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Description
- 光化学特性を有し;
- トリアゾールスペーサー基を介する錯化基と他の基の間の良好な電子伝導性を有する化合物を得るための実質的な先験的技術として存在する。
A-T-Z
(I)
(式中:
Aは、ピリジン、ビピリジン、フェナントロリンまたはフタロシアニン基から選択される、少なくとも1個の金属元素を錯化することができる基であり;
Tは、該基Aに直接結合しているトリアゾール基であり;
Zは、ハロゲン原子、ニトロ基、シアノ基、アルキル基、アリール基、複素環式基、式-NR1R2の基、式-SR1の基、式-S(=O)2(OR1)の基、式-O-S(=O)2(OR1)の基、式-O-S(=O)2(R1)の基、式-S(=O)(OR1)の基、式-S(=O)(R1)の基、式-S(=O)2R1の基,式-PR1R2の基、式-P(=O)(OR1)(OR2)の基、式-O-P(=O)(OR1)(OR2)の基、式-O-P(=O)(OR1)(R2)の基、式-OR1の基または式-CO-R1の基であり、R1およびR2は、独立に、水素原子、アルキル基またはアリール基を表し、前記アルキル基またはアリール基は、任意選択で置換されている)
に相当する化合物に関する。
− Zは、担体上への本発明の化合物のグラフト化を可能とするよう意図された基であってよく、このグラフト化は、基Zが有する官能基と担体の官能基との間の化学反応によって起こり、担体は、例えば、シリカ担体、二酸化チタン担体、ケイ素担体、金属担体(例えば、金担体など)、炭素担体、スズおよびインジウム酸化物担体[ITO(インジウムスズ酸化物)担体とも称される]であることができ、この担体は、光起電装置の電極であることができ;
− Zは、触媒機能を果たすよう意図された基であってよく、すなわち、基Zは、金属元素への錯化した後の基Aから、光励起後に、電子を他の化合物に向けて運び、これらの化合物の酸-還元反応を確実にすることができ;
− Zは、別の基のそれが結合している基への特性、例えば、基Aの特性を制御する機能を果たすよう意図された基であってよく;
− Zは、アドレス機能を果たすよう意図された基であってよく、すなわち、所与の目的物、例えば、所与のセル、所与のセルコンパートメント、所与の分子(例えば、核酸分子など)への化学的親和性を有していてよい。
の化合物であり、これらの化合物は、ビピリジンなどの他の化合物と共に組み合わせて同じ錯体において使用することができる。
− 酸化還元反応が関与する燃料の製造分野、例えば、水の光誘起分解または二酸化炭素の光誘起還元による水素および酸素の製造分野。これらの反応は、再生可能なエネルギー源、光エネルギーから燃料を製造する、生態学的に適合する手段であり、この場合、本発明の錯体は、光触媒反応セル、より詳細には光アノードに、例えば、二酸化チタンに含めることができ、ここで、反応剤の酸化(例えば、水が酸素に酸化される)が起こり、次いで、この反応により生じた電子は、別の反応剤の還元(例えば、プロトンの還元)が起こる光カソードに向け導かれ、この酸化還元反応から生じる生成物は、燃料として使用できる;
− 前駆体の酸化または還元によって製造される合成生成物の製造分野;
− 生体分子を酸化または還元することが必要と考えられる治療または診断の分野;
− 発電の分野、本発明の錯体は、光起電装置の構造に組み込むことができる。
実施例1により調製した4'-アジド-2,2'-ビピリジン-N'-オキシド(42.6mg、200μmol、1当量)を、アルゴン雰囲気下で塩化メチレン(1.67mL)中に懸濁させる。フェニルアセチレン(22.0μL、20.4mg、200μmol、1当量)を前の混合物に添加し、次いで、水(1.51mL)、アスコルビン酸ナトリウム(80μL、水1mL当たり49.5mg、20μmol、0.1当量)および硫酸銅5水和物(80μL、水1mL当たり31.2mg、10μmol、0.05当量)を順次添加する。この反応混合物を室温で20時間撹拌する。この時間後、CH2Cl2/メタノール(9/1)中薄層クロマトグラフィーによって、カップリング反応が定量的であることが示される。次いで、反応混合物をCH2Cl2/H2O(1/1)混合物6mLで希釈し、塩化メチレン(3×6mL)で抽出する。有機相を合わせ、水で洗浄し、硫酸ナトリウムで脱水し、ろ過し、濃縮して、以下の式:
塩化メチレン(3.8mL)中の、あらかじめ調製した4'-(4''-フェニル-1H-1'',2'',3''-トリアゾール-1''-イル)-2,2'-ビピリジンN'-オキシド(59.8mg、190μmol、1当量)の溶液に、アルゴン雰囲気下で三塩化リン(49.7μL、78.3mg、570μmol、3.0当量)を0℃で添加する。この反応混合物を3時間還流させ、次いで、氷4mL中に注ぎ入れ、38.5%水酸化ナトリウム水溶液で中和する。水相を、塩化メチレン(3×5mL)で数回抽出する。次いで、有機相を合わせて、水で洗浄し、次いで、硫酸ナトリウムで脱水し、ろ過し、濃縮する。残渣をシリカゲル上のフラッシュクロマトグラフィー(CH2Cl2/メタノール、95/5)で精製して、以下の式:
実施例1により調製した一部の4'-アジド-2,2'-ビピリジンN'-オキシド(32.0mg、150μmol、1当量)を、アルゴン雰囲気下で塩化メチレン(1.20mL)中に懸濁させる。この懸濁液に、一部の1-エチニル-4-フルオロベンゼン(17.5μL、18.4mg、98%、150μmol、1当量)を添加し、続いて、水(1.08mL)、アスコルビン酸ナトリウム(60μL、水1mL当たり49.5mg、15μmol、0.1当量)および硫酸銅5水和物(60μL、水1mL当たり31.2mg、7.5μmol、0.05当量)を順次添加する。この反応混合物を室温で20時間撹拌する。この時間後、CH2Cl2/メタノール(9/1)を用いる薄層クロマトグラフィーによって、カップリング反応が定量的であることが示される。次いで、反応混合物をCH2Cl2/H2O(1/1)混合物5mLで希釈し、塩化メチレン(3×5mL)で抽出する。有機相を合わせ、水で洗浄し、硫酸ナトリウムで脱水し、ろ過し、濃縮して、以下の式:
塩化メチレン(2.9mL)中の、あらかじめ調製した4'-(4''-(4'''-フルオロフェニル-1H-1'',2'',3''-トリアゾール-1''-イル)-2,2'-ビピリジンN'-オキシド(47.5mg、143μmol、1当量)の溶液に、アルゴン雰囲気下、三塩化リン(37.4μL、58.9mg、429μmol、3.0当量)を0℃で添加する。この反応混合物を3時間還流させ、次いで、氷3mL中に注ぎ入れ、38.5%水酸化ナトリウム水溶液で中和する。水相を塩化メチレン(3×5mL)で数回抽出する。次いで、有機相を合わせて、水で洗浄し、次いで、硫酸ナトリウムで脱水し、ろ過し、濃縮する。残渣を、シリカゲル上のフラッシュクロマトグラフィー(CH2Cl2/メタノール、95/5)により精製して、以下の式:
実施例1によって調製した一部の4'-アジド-2,2'-ビピリジンN'-オキシド(32.0mg、150μmol、1当量)を、アルゴン雰囲気下、塩化メチレン(2.50mL)中に懸濁させる。この懸濁液に、メチル-4-エチニルベンゾエート(24.0mg、150μmol、1当量)を添加し、続いて、水(2.38mL)、アスコルビン酸ナトリウム(60μL、水1mL当たり49.5mg、15μmol、0.1当量)、および硫酸銅5水和物(60μL、水1mL当たり31.2mg、7.5μmol、0.05当量)を順次添加する。この反応混合物を室温で40時間撹拌する。この時間後、CH2Cl2/メタノール(9/1)を用いる薄層クロマトグラフィーによって、カップリング反応が定量的であることが示される。次いで、反応混合物を、CH2Cl2/H2O(1/1)混合物10mLで希釈し、塩化メチレン(3×10mL)で抽出する。有機相を合わせ、水で洗浄し、硫酸ナトリウムで脱水し、ろ過し、濃縮して、以下の式:
塩化メチレン(6.0mL)中の、あらかじめ調製した4'-(4''-(4'''-(メトキシカルボニル)フェニル)-1H-1'',2'',3''-トリアゾール-1''-イル)-2,2'-ビピリジンN'-オキシドの溶液に、アルゴン雰囲気下で三塩化リン(80.0μL、126.0mg、916μmol、6.2当量)を0℃で添加する。この反応混合物を3時間還流させ、次いで、氷5mL中に注ぎ入れ、38.5%水酸化ナトリウム水溶液で中和する。水相を塩化メチレン(3×5mL)で数回抽出する。次いで、有機相を合わせて、水で洗浄し、次いで、硫酸ナトリウムで脱水し、ろ過し、濃縮する。残渣を、シリカゲル上のフラッシュクロマトグラフィー(CH2Cl2/メタノール、97/3)により精製して、以下の式:
Claims (14)
- 以下の式(I):
A-T-Z
(I)
(式中:
Aは、以下の式:
Tは、以下の式:
Zは、ハロゲン原子、ニトロ基、シアノ基、アルキル基、アリール基、複素環式基、式-NR1R2の基、式-SR1の基、式-S(=O)2(OR1)の基、式-O-S(=O)2(OR1)の基、式-O-S(=O)2(R1)の基、式-S(=O)(OR1)の基、式-S(=O)(R1)の基、式-S(=O)2R1の基、式-PR1R2の基、式-P(=O)(OR1)(OR2)の基、式-O-P(=O)(OR1)(OR2)の基、式-O-P(=O)(OR1)(R2)の基、式-OR1の基または式-CO-R1の基であり、R1およびR2は、独立に、水素原子、アルキル基またはアリール基を表し、前記アルキル基またはアリール基は、任意選択で置換されていてもよい)
に相当する化合物。 - 基Zが、任意選択で置換されていてもよいアリール基である、請求項1に記載の化合物。
- アリール基が、少なくとも1個の基-NR1R2、少なくとも1個の基-CO2R1(R1およびR2は、請求項1で定義したとおりである)、および/または少なくとも1個のハロゲン原子で置換されている、請求項2に記載の化合物。
- Xが水素原子である、請求項4に記載の化合物。
- Xが基-N(CH3)2である、請求項4に記載の化合物。
- Xが基-CO2CH3である、請求項4に記載の化合物。
- Xがフッ素原子である、請求項4に記載の化合物。
- 少なくとも1種の金属元素と、請求項1から8のいずれか一項に記載の少なくとも1種の化合物との配位錯体。
- 金属元素が、遷移金属、ランタニド元素、アクチニド元素、元素Al、Ga、Ge、In、Sn、Sb、Tl、Pb、Bi、およびPoから選択される、請求項9に記載の配位錯体。
- 金属元素が遷移金属である、請求項9または10に記載の配位錯体。
- 金属元素がルテニウムである、請求項9から11のいずれか一項に記載の配位錯体。
- ビピリジン、ピリジンから選択されるリガンド化合物をさらに含む、請求項9から12のいずれか一項に記載の配位錯体。
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