TW201348234A - 以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物 - Google Patents
以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物 Download PDFInfo
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- TW201348234A TW201348234A TW102109367A TW102109367A TW201348234A TW 201348234 A TW201348234 A TW 201348234A TW 102109367 A TW102109367 A TW 102109367A TW 102109367 A TW102109367 A TW 102109367A TW 201348234 A TW201348234 A TW 201348234A
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- lower alkyl
- complex
- imidazo
- reaction
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- JMANUKZDKDKBJP-UHFFFAOYSA-N imidazo[1,5-a]pyridine Chemical class C1=CC=CC2=CN=CN21 JMANUKZDKDKBJP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003446 ligand Substances 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 125000003367 polycyclic group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 11
- 125000002950 monocyclic group Chemical group 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 39
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 17
- 239000012327 Ruthenium complex Substances 0.000 description 15
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001728 carbonyl compounds Chemical class 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 150000005232 imidazopyridines Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LIZPHSZFCWFEJQ-UHFFFAOYSA-N C(=O)=[Ru+]=C=O.C(C)(=N)N Chemical compound C(=O)=[Ru+]=C=O.C(C)(=N)N LIZPHSZFCWFEJQ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- -1 imidazopyridine compound Chemical class 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 108020004414 DNA Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001638 boron Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000000179 1,2-aminoalcohols Chemical class 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MSPJFCGXTICBEG-UHFFFAOYSA-N CCCCCCCCCC(C)(C)C.Cl Chemical compound CCCCCCCCCC(C)(C)C.Cl MSPJFCGXTICBEG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000053602 DNA Human genes 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- PMCLRBQCDGAJJW-UHFFFAOYSA-N bis(oxomethylidene)ruthenium Chemical compound O=C=[Ru]=C=O PMCLRBQCDGAJJW-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZGZUKKMFYTUYHA-HNNXBMFYSA-N (2s)-2-amino-3-(4-phenylmethoxyphenyl)propane-1-thiol Chemical compound C1=CC(C[C@@H](CS)N)=CC=C1OCC1=CC=CC=C1 ZGZUKKMFYTUYHA-HNNXBMFYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- BMYPMWNIHPGGQM-UHFFFAOYSA-N 1,3-bis(10,10-dimethylundecyl)urea Chemical compound CC(CCCCCCCCCNC(=O)NCCCCCCCCCC(C)(C)C)(C)C BMYPMWNIHPGGQM-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 1
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical compound CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- FNHWSSPBLBPXIQ-UHFFFAOYSA-N 2-diphenoxyboranylethanamine Chemical compound C=1C=CC=CC=1OB(CCN)OC1=CC=CC=C1 FNHWSSPBLBPXIQ-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- FYDYYNBALSEMHM-UHFFFAOYSA-N 5,6,7,8-tetrahydroimidazo[1,5-a]pyridine Chemical class C1CCCN2C=NC=C21 FYDYYNBALSEMHM-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- COQYUAJAXLUAHF-UHFFFAOYSA-N CC(CCCCCCCCCOC)(C)C Chemical compound CC(CCCCCCCCCOC)(C)C COQYUAJAXLUAHF-UHFFFAOYSA-N 0.000 description 1
- ICLWANDVDRTPBG-UHFFFAOYSA-N CC(CCCCCCCCCOCC)(C)C Chemical compound CC(CCCCCCCCCOCC)(C)C ICLWANDVDRTPBG-UHFFFAOYSA-N 0.000 description 1
- MSWHSTCOOXSTSV-UHFFFAOYSA-N CC1=C(C(=C(C=C1)N(C(=O)NC1=CC=CC=C1)CCCCCCCCCC)C)C Chemical compound CC1=C(C(=C(C=C1)N(C(=O)NC1=CC=CC=C1)CCCCCCCCCC)C)C MSWHSTCOOXSTSV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 238000005672 Willgerodt-Kindler rearrangement reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000000879 anti-atherosclerotic effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000020832 chronic kidney disease Diseases 0.000 description 1
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004857 imidazopyridinyl group Chemical group N1C(=NC2=C1C=CC=N2)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DSWNRHCOGVRDOE-UHFFFAOYSA-N n,n-dimethylmethanimidamide Chemical compound CN(C)C=N DSWNRHCOGVRDOE-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 208000037803 restenosis Diseases 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- LENLQGBLVGGAMF-UHFFFAOYSA-N tributyl([1,2,4]triazolo[1,5-a]pyridin-6-yl)stannane Chemical class C1=C([Sn](CCCC)(CCCC)CCCC)C=CC2=NC=NN21 LENLQGBLVGGAMF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
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Abstract
本發明係關於一種以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物、其合成方法及該錯合物之用途,上述錯合物之特徵在於由通式(I)表示。該錯合物可由容易獲取之原料藉由簡略化之製造方法而獲得。□
Description
本發明係關於一種以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物。進而,本發明係關於該錯合物之製造、及錯合物作為觸媒或螢光發光材料之用途。
含有兩個氮原子之咪唑并吡啶衍生物表現出各種藥理活性而用作醫藥品或其中間物。例如提出有:具有血小板凝集抑制作用、抗動脈硬化作用等之新穎之咪唑并[1,5-a]吡啶衍生物(專利文獻1),可用作血栓症治療藥之咪唑并吡啶衍生物(專利文獻2),對慢性腎衰竭、再狹窄、動脈粥狀硬化症等之預防、發展之延遲等有效之咪唑并[1,5-a]吡啶衍生物(專利文獻3),對5HT2A受體相關損傷之預防或治療有效之咪唑并[1,5-a]吡啶或咪唑并[1,5-a]哌啶衍生物(專利文獻4),可用作抗癌劑之可成為DNA(deoxyribonucleic acid,去氧核糖核酸)損傷檢測點活化劑之具有咪唑并[1,5-a]吡啶骨架之化合物(專利文獻5),或作為其他各種醫藥用組合物而提出(專利文獻6、7、8、9、10、11)。
該等文獻中提出有各種衍生物,充分地顯示該衍生物所具有之作為醫藥品之可能性。另一方面,由於咪唑并吡啶衍生物為10π電子系雜環化合物,故而作為其他用途,亦可積極地用於咪唑并吡啶系化合物及具備含有其之有機膜之有機發光元件(專利文獻12)、組合有磷光性與發光材料之有機電致發光元件(專利文獻13)、含有具有咪唑并吡啶骨架之化合物之發光元件(專利文獻14)等其他用途。
雖然如上所述咪唑并吡啶衍生物正受到關注,但利用以該衍生物為配位基之錯合物之提案極少。認為原因在於咪唑并吡啶衍生物本身有望成為醫藥品,故而未必有以其作為配位基之想法,或於將錯合物形成所必需之羥基、胺基、羧基等導入咪唑并吡啶衍生物之簡易合成法中存在問題或困難性。
專利文獻1:日本專利特開平7-112984號公報
專利文獻2:日本專利特開2004-155774號公報
專利文獻3:日本專利特表2006-508970號公報
專利文獻4:日本專利特表2007-504220號公報
專利文獻5:日本專利特開2008-105963號公報
專利文獻6:日本專利特表2008-533111號公報
專利文獻7:日本專利特表2009-521517號公報
專利文獻8:日本專利特表2009-531391號公報
專利文獻9:日本專利特表2010-503627號公報
專利文獻10:日本專利特表2010-520869號公報
專利文獻11:日本專利再表WO2005/016928號公報
專利文獻12:日本專利特開2008-133277號公報
專利文獻13:日本專利再表WO2004/066685號公報
專利文獻14:日本專利特開2001-6877號公報
本發明係關於一種以咪唑并吡啶衍生物為配位基之新穎之錯合物、其合成方法及該錯合物之用途,其目的在於提出使用容易獲取之原材料而簡略化之製造方法,並將所獲得之新穎錯合物於各種用途進
行發展。
為解決上述課題,達成所期望之目的而進行努力研究,結果本發明中,使強鹼作用於硫醯胺,繼而添加羰基化合物而獲得具有羥基之硫醯胺後,將該羥基經保護之化合物於碘、吡啶存在下進行脫硫環化反應,而獲得具有羥基之咪唑并[1,5-a]吡啶衍生物。使該咪唑并[1,5-a]吡啶衍生物與各種金屬鹽等反應,藉此可獲得新穎之錯合物。
即,本發明係關於一種以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物,其特徵在於以通式(I)表示。
式中,M表示選自金屬原子、過渡金屬原子、半金屬原子中之一種。又,L1、L2相同或不同,為選自烷基、芳基(其中,各基可進而經選自鹵素、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代)、或羰基、鹵素中之一種。R1為選自碳數3~12之支鏈狀或環狀之烷基、單環或多環之1價有機分子基中之基(其中,各基可進而經選自鹵素、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代)。R2、R3相同或不同,表示選自氫(其中,至少一者不為氫)、碳數1~12之直鏈狀之烷基、碳數3~12之支鏈狀或環狀之烷基、
單環或多環之1價有機分子基中之基(其中,各基可進而經選自鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代),或與R2及R3所鍵結之碳原子一同形成5員至12員環之單環或多環之有機分子基(其中,各基可進而經選自鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代)。再者,僅將通式(I)中之R2及R3所鍵結之碳原子以「C」表示。進而,對該錯合物之合成方法於下文敍述。
上述單環或多環之1價有機分子基較佳為選自下式所表示之(i)~(iv)中之任一種有機分子基。
又,上述與R2及R3所鍵結之碳原子一同形成5員至12員環之單環或多環之有機分子基較佳為選自下式所表示之(v)~(vii)中之任一種。
[化3]
上述各式中,R4~R9相同或不同,表示選自氫、鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基。
上述原子M較佳為選自B、Al、Fe、Co、Ni、Ru、Rh、Pd、Re、Os、Ir、及Pt中之一種。例如,於將原子M設為B(硼)之錯合物之情形時,有與咪唑并[1,5-a]吡啶衍生物單體相比具有數倍之螢光發光強度者。又,Rh(銠)之錯合物迄今為止完全未為人所知,但確認到其於某種化學反應中觸媒活性非常高。
本發明之以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物可由容易獲取且廉價之原料不經由複雜之合成路徑而簡易地製造。因此,可通過具有各種取代基之衍生物之結構設計而任意地控制錯合物之穩定性或各種物性(觸媒活性、光學特性等)。與先前技術相比採用可選擇各種原料之合成方法對此貢獻較大。
再者,不僅可將製成錯合物前之咪唑并[1,5-a]吡啶衍生物用作醫藥品、農藥等或其中間物,而且由於為10π電子系雜環化合物,故而亦可期待發展新穎之有機發光元件之開發等廣泛之用途。
圖1係表示本發明之硼錯合物(I-B-2)之X射線結構分析之結果的圖。
圖2係表示本發明之銠錯合物(I-Rh-2)之X射線結構分析之結果的圖。
以下,針對本發明之錯合物進而詳細地進行說明。
本發明係使強鹼作用於硫醯胺,繼而添加羰基化合物而合成具有羥基之硫醯胺,作為加成羥基前之硫醯胺(II)之合成方法,可利用以下反應式(a)作為一例。
式中之R1表示選自碳數3~12之支鏈狀或環狀之烷基、單環或多環之1價有機分子基中之基,上述各基可進而經選自鹵素、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代。作為此種支鏈狀烷基,可列舉異丙基、異丁基、第三丁基等,又,作為環狀烷基,可列舉環丙基、環己基等,又,作為單環之有機分子基,可列舉苄基、甲苯甲醯基、二甲苯基等芳基,或吡啶基、呋喃基、噻吩基等雜芳香族基。進而,作為多環之有機分子基,可列舉萘基或蒽基等。該等於藉由與強鹼之反應而形成硫醯胺二價陰離子時為高產率,故而較佳。
上述反應式(a)係作為硫醯胺之合成法而先前公知之方法。該方法之特徵在於:任一原料均可容易且廉價地獲取,反應體系簡單,產率
非常高,並且,藉由對R1選擇各種取代基,可進行作為最終生成物之咪唑并[1,5-a]吡啶衍生物之設計等。
該反應可使用二甲基甲醯胺、二甲基亞碸、N-甲基吡咯啶酮、甲苯等作為有機溶劑。該等之中,於暫時將硫醯胺純化而進行單離、保管等之情形時,就容易於對反應體系進行水洗之過程中分離生成物之觀點而言,較佳為二甲基甲醯胺。
又,上述反應係於60~110℃、較佳為80~90℃下進行。於低於上述溫度之情形時,存在反應速度降低而使產率降低之傾向,又,於更高溫之情形時,有容易產生副反應而使純化費工夫之虞。
硫醯胺之合成可於含醛基之化合物:硫:2-(胺基甲基)吡啶=1:1:1~1:1.2:1.2之莫耳比之範圍內進行。該比率之中最佳為1:1.1:1.1,其原因在於可使含醛基之化合物完全地反應而效率良好地進行硫醯胺之純化。再者,該反應稱為維爾格羅特-金德勒(Willgerodt-Kindler)反應,於文獻(Brown,E. V. Synthesis 1975,358)中詳細說明。
使強鹼作用於如此獲得之硫醯胺(II),繼而添加羰基化合物而合成N-硫醯基1,2-胺基醇(III)(反應式(b))。
[化5]
上述反應之中,上段之反應生成硫醯胺二價陰離子。具體而言,為文獻(Murai,T.et al.,J.Org.Chem.2005,70,8153)等中所揭示之反應。該反應開始時之留意點在於必需於脫水條件下,在氮氣或氬氣等惰性氣體環境下進行。其原因在於:與強鹼反應而獲得之硫醯胺二價陰離子有因水或氧氣之存在而容易分解之虞,使其穩定地存在而移至下一反應。再者,作為強鹼,此外亦可使用二異丙基醯胺鋰、氫化鈉、氫化鉀、第三丁醇鉀、氫化鈣、氫氧化鈉、胺化鈉等,但就反應性、價格、容易獲取等方面而言,較佳為式(b)所示之丁基鋰(nBuLi)。又,若使用丁基鋰,則亦有於反應後容易作為丁烷氣體分離之優點。
上述反應中使用四氫呋喃作為溶劑。亦可使用甲苯、二乙醚等作為其他溶劑,但前者有稍進行副反應之虞,後者有反應中間物未溶解而沈澱,而降低反應產率之虞,因此較佳為四氫呋喃。此時之反應溫度可於-78℃~室溫之範圍內實施,但考慮到抑制副反應及效率,宜為0℃前後。
反應之各化合物之混合比率視使用之化合物而定,無法一概而論,但通常,相對於硫醯胺(II)添加約2當量之nBuLi,繼而添加約1當
量之羰基化合物。硫醯胺(II)與nBuLi係於莫耳比1:2之反應下生成二價陰離子,以大致100%之產率進行反應。又,生成之二價陰離子之活性亦較高,因此與羰基化合物產生大致100%之反應。因此,各化合物之莫耳比基本為硫醯胺:nBuLi:羰基化合物=1:2:1。
上述羰基化合物之R2、R3為相同或不同,表示選自氫(其中,至少一者不為氫)、碳數1~12之直鏈狀之烷基、碳數3~12之支鏈狀或環狀之烷基、單環或多環之1價有機分子基中之基(其中,上述各基可進而經選自鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代),或與R2及R3所鍵結之碳原子一同形成5員至7員環之單環或多環之有機分子基(其中,各基可進而經選自鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基取代)。藉由此時之羰基化合物之選擇,可與上述R1之選擇同樣地進行作為最終生成物之咪唑并[1,5-a]吡啶衍生物之設計。因此,可控制本發明之錯合物之穩定性或觸媒活性、光特性。
上述單環或多環之1價有機分子基較佳為選自下式所表示之(i)~(iv)中之任一種有機分子基。
[化6]
又,與R2及R3所鍵結之碳原子一同形成5員至7員環之單環或多環之有機分子基較佳為選自下式所表示之(v)~(vii)中之任一種有機分子基。
上述各式中,R4~R9相同或不同,表示選自氫、鹵素、羥基、低級烷基、低級烷氧基、鹵代低級烷基中之一種以上之取代基。
上述反應式(b)之下段中,導入之後使咪唑并[1,5-a]吡啶衍生物與
金屬等配位而形成錯合物時所鍵結之羥基。
該羥基例如係由氯化三甲基矽烷等保護。具體而言,可採用如下述反應式(c)所示之通常之方法。
除氯化三甲基矽烷以外,作為三甲基矽烷化劑,亦可使用三甲基甲氧基矽烷、三甲基乙氧基矽烷、六甲基二矽氮烷、雙(三甲基矽烷基)乙醯胺、三甲基矽烷基二苯基脲、雙(三甲基矽烷基)脲等矽烷基醯胺類等。只要選擇可確實地保護羥基且以高產率獲得者即可。再者,亦可藉由乙醯化以乙醯基進行保護。
可使如此保護羥基之化合物(IV)於碘、吡啶存在下藉由脫硫環化反應而獲得具有羥基之咪唑并[1,5-a]吡啶衍生物(V)。該反應係以下述反應式(d)表示。
[化9]
作為碘、吡啶存在下之脫硫環化反應之條件,於反應溫度0~70℃下、反應時間為1小時以內(數分鐘左右)則足夠。又,使用四氫呋喃作為反應溶劑。亦可使用甲苯、二乙醚等作為其他溶劑。
另一方面,脫硫環化後之脫三甲基矽烷化只要與酸、鹼之水性溶液反應即可。可藉由使如此獲得之具有羥基之咪唑并[1,5-a]吡啶衍生物(V)與各種金屬鹽等反應而獲得通式(I)所表示之新穎之錯合物。
此處,以反應式(e)表示選擇B(硼)作為上述式中之原子M之情形時之合成法之一例。
上述硼錯合物(I-B)之合成可藉由如下方式獲得:使二芳基酸2-胺基乙酯於醚系中與鹽酸反應而產生酸(Ar2BOH),於該溶液中添加咪唑并[1,5-a]吡啶衍生物(V)並於室溫下進行反應。該反應除二芳基
酸2-胺基乙酯以外,亦可使用二(4-氯苯基)酸、二(4-甲氧基苯基)酸、三芳基硼烷、鹵化硼等。
如此獲得之硼錯合物有顯示優異之螢光發光性者。此種錯合物例如作為有機EL(Electroluminescence,電致發光)元件之可利用性較高。利用電場發光之EL元件具有由於自發光故而視認性較高,且由於為完全固體元件故而耐衝擊性優異等特徵,因此作為各種顯示裝置中之發光元件之用途受到關注。尤其是有機EL元件具有可大幅降低施加電壓,此外容易小型化,且消耗電力較小等特徵。上述式(I-B)所表示之硼錯合物有顯示藍色螢光發光者,可創造可用於有機EL元件中之電子傳輸層等之基盤化合物作為新電子材料。
繼而,以反應式(f)表示選擇Rh(銠)作為上述原子M之情形時之合成之一例。
上述銠錯合物(I-Rh)之合成可藉由使甲苯溶液中之咪唑并[1,5-a]吡啶衍生物(V)與乙醯丙酮二羰基銠(I)於室溫下反應而獲得。該反應除乙醯丙酮二羰基銠(I)以外,亦可使用鹵化羰基銠(I)等。
如此獲得之銠錯合物有顯示優異之觸媒活性者。作為關於銠錯合物之例,例如記載於文獻(J. L. McBee,J. Escalada,T. D. Tilley,J.Am.Chem.Soc.2009,131,12703.)中。又,亦可用於醛類之合成觸媒或以
有機EL元件為代表之電子零件等。
又,以反應式(g)表示選擇Ir(銥)作為原子M之情形時之合成之一例。
上述銥錯合物(I-Ir)之合成可藉由使二氯甲烷溶液中之咪唑并[1,5-a]吡啶衍生物(V)與乙醯丙酮二羰基銥(I)於室溫下反應而獲得。該反應除乙醯丙酮二羰基銥(I)以外,亦可使用鹵化羰基銥(I)等。
以下,為更具體明確本發明之錯合物,示出若干實施例。再者,用於各實施例中之咪唑并[1,5-a]吡啶衍生物之結構式如下。
[化13]
於2-胺基乙基二苯基酸(0.05g,0.22mmol)之醚溶液(1mL)中添加鹽酸水溶液(10%,0.5mL),進行15分鐘攪拌。分離有機層並進行水
洗。對該有機層於室溫下添加咪唑并[1,5-a]吡啶衍生物Ia(0.078g,0.2mmol)之二氯甲烷溶液(4mL)。攪拌黃色溶液兩小時,濃縮反應混合液。使殘渣自二氯甲烷及醚中再結晶,以淡黃色固體獲得對應之硼錯合物(I-B-1)(0.062g,0.11mmol,55%)。
硼錯合物(I-B-1)之1H-核磁共振譜及13C-核磁共振譜係使用日本電子製造之JNMα-400型號,於氘氯仿中,在25℃下,1H-核磁共振譜以累計次數8次進行測定,13C-核磁共振譜以累計次數100-200次進行測定。其結果如下所示。再者,IR(Infrared Spectroscopy,紅外光譜)或MS(Mass Spectroscopy,質譜)之資料亦一併示於以下。
IR(KBr)3065,3040,2921,1430,1184,1148,105,741,702cm-1;1H NMR(CDCl3)δ 2.40(s,3H,CH3),6.49(d,J=9.3Hz,1H,Ar),6.54(dd,J=7.3Hz,6.3Hz,1H,Ar),6.59(dd,J=7.3Hz,6.3Hz,1H,Ar),7.04(d,J=8.3Hz,2H,Ar),7.08-7.12(m,4H,Ar),7.16-7.20(m,8H,Ar),7.31(dd,J=7.3Hz,6.3Hz,2H,Ar),7.38(d,J=6.8Hz,2H,Ar),7.39(d,J=6.3Hz,2H,Ar),7.68(d,J=7.3Hz,2H,Ar),7.85(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.5(CH3),85.7(COB),115.7,117.8,119.5,120.8,121.5,124.3,125.9,126.0,126.8,128.0,128.8,129.9,130.4,130.9,132.1,133.4,134.7,135.8,139.5,141.2,149.1(Ar);MS(EI)m/z 552(M+);C39H29BN2O之HRMS計算值:552.2373,實測值:552.2374;m.p.147-154℃(分離).
於2-胺基乙基二苯基酸(0.05g,0.22mmol)之醚溶液(1mL)中添加鹽酸水溶液(10%,0.5mL),進行15分鐘攪拌。分離有機層並進行水洗。對該有機層於室溫下添加咪唑并[1,5-a]吡啶衍生物Ib(0.078g,0.2mmol)之二氯甲烷溶液(4mL)。攪拌黃色溶液兩小時,濃縮反應混合液。使殘渣自二氯甲烷及醚中再結晶,以淡黃色固體獲得對應之硼錯
合物(I-B-2)(0.072g,0.13mmol,65%)。
將對硼錯合物(I-B-2)之核磁共振譜等之測量結果示於以下。又,將X射線結構分析之結果之ORTEP圖示於圖1。各橢圓球表示以50%之概率發現碳、氮、氧、或硼原子之座標,較小之球表示氫原子。
IR(KBr)3064,1476,1446,1430,1186,1143,1053,853,738,699cm-1;1H NMR(CDCl3)δ 2.35(s,3H,CH3),6.69(dd,J=7.3Hz,6.3Hz,1H,Ar),6.86(dd,J=9.3Hz,6.3Hz,1H,Ar),6.94(d,J=7.8Hz,2H,Ar),6.97-7.10(m,12H,Ar),7.19-7.24(m,6H,Ar),7.44(d,J=7.3Hz,2H,Ar),7.44(d,J=9.3Hz,1H,Ar),7.44(d,J=7.8Hz,2H,Ar),7.85(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.5(CH3),85.0(COB),115.4,118.8,121.2,121.5,121.9,122.4,125.4,126.4,126.9,127.7,127.7,128.2,129.7,130.0,130.2,133.7,136.3,141.1,146.2(Ar);MS(EI)m/z 554(M+);m.p.166-176℃(分離).
於2-胺基乙基二苯基硼酸(0.05g,0.22mmol)之醚溶液(1mL)中添加鹽酸水溶液(10%,0.5mL),進行15分鐘攪拌。分離有機層並進行水洗。對該有機層於室溫下添加咪唑并[1,5-a]吡啶衍生物If(0.082g,0.2mmol)之二氯甲烷溶液(4mL)。攪拌黃色溶液兩小時,濃縮反應混合液。使殘渣自二氯甲烷及醚中再結晶,以橙色固體獲得對應之硼錯合物(I-B-3)(0.084g,0.15mmol,73%)。
將對硼錯合物(I-B-3)之核磁共振譜等之測量結果示於以下。
IR(KBr)2957,2359,1951,1884,1810,1647,1599,1563,1518,1489,1466,1446,1429,1371,1340,1327,1263,1190,1143,1093,1038,958,904,877,840,753,693,561,532cm-1;1H NMR(CDCl3)δ 6.75(t,J=6.8Hz,1H,Ar),6.91(m,1H,Ar),7.03(m,12H,Ar),7.21(m,7H,Ar),7.42(m,6H,Ar),7.82(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 85.1
(CO),115.9,119.0,121.6,121.9,122.6,122.9,125.6,126.5,127.0,127.7,128.1,129.4,129.5,131.7,133.6,136.9,137.1,146.0(Ar);MS(EI)m/z 574(M+);C38H28BClN2O之HRMS計算值:574.1983,實測值:574.1995;m.p.230-233℃(分離).
於2-胺基乙基二苯基酸(0.05g,0.22mmol)之醚溶液(1mL)中添加鹽酸水溶液(10%,0.5mL),進行15分鐘攪拌。分離有機層並進行水洗。對該有機層於室溫下添加咪唑并[1,5-a]吡啶衍生物Ig(0.10g,0.2mmol)之二氯甲烷溶液(4mL)。攪拌黃色溶液兩小時,濃縮反應混合液。使殘渣自二氯甲烷及醚中再結晶,以白色固體獲得對應之硼錯合物(I-B-4)(0.12g,0.18mmol,88%)。
將對硼錯合物(I-B-4)之核磁共振譜等之測量結果示於以下。
IR(KBr)3435,3065,2955,2359,1748,1649,1590,1431,1396,1187,1092,1952,948,754,704cm-1;1H NMR(CDCl3)δ 6.77(t,J=6.8Hz,1H,Ar),6.96(m,5H,Ar),7.07(m,6H,Ar),7.20(m,4H,Ar),7.29(s,1H,Ar),7.32(dd,J=6.3Hz,J=2.0Hz,1H,Ar),7.40(m,6H,Ar),7.48(t,J=7.3Hz,1H,Ar),7.56(t,J=6.8Hz,1H,Ar),7.83(m,2H,Ar),7.97(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 115.8,118.5,120.8,122.1,122.3,122.6,125.3,125.8,126.7,126.9,127.6,127.9,128.0,128.9,129.0,129.1,132.2,132.6,133.0,133.6,133.8,144.4(Ar);MS(EI)m/z 658;m.p.241-244℃(分離).
此處,將上述實施例1至4之硼錯合物之結構式示於以下供參考。
[化14]
上述實施例1至4中任一硼錯合物均於溶液中、或固體狀態下顯示藍色螢光發光。將螢光波長及相對螢光量子產率示於下表1。
於室溫下在二(4-氯苯基)酸(0.055g,0.22mmol)之醚溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ig(0.10g,0.2mmol)之二氯甲烷溶液(3mL),攪拌2小時。過濾反應液並加以乾燥,以白色固體獲得硼錯合物(I-B-5)(0.11g,0.15mmol,76%)。將對該硼錯合物之核磁共振譜等之測量結果示於以下。
IR(KBr)1577,1523,1486,1383,1329,1182,1148,1087,1047,1012,962,932,916,878,862,809,784,749,525,477cm-1;1H NMR(CDCl3)δ 6.80(t,J=7.3Hz,1H,Ar),6.94(dd,J=8.8Hz,2.0Hz,8H,Ar),7.00(m,1H,Ar),7.23(d,J=8.8,4H,Ar),7.29(sex,J=1.5Hz,2.9Hz,1.5Hz,2H,Ar),7.34(d,J=8.8Hz,4H,Ar),7.44(dd,J=9.8Hz,9.3Hz,8.3Hz,2H,Ar),7.55(dt,J=6.3Hz,1.0Hz,1H,Ar),7.60(dt,J=6.8Hz,1.2Hz,1H,Ar),7.87(dd,J=4.2Hz,2H,Ar),7.95(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 84.3(COB),116.1,118.4,120.5,122.1,122.7,125.1,126.8,127.3,127.8,128.1,128.4,128.7,129.0,129.2,131.2,131.9,132.0,132.6,133.3,133.9,134.9,135.4,144.0(Ar);m.p.246-254℃(分離).
於室溫下在二(4-甲氧基苯基)酸(0.053g,0.22mmol)之醚溶液(3mL)中添加咪唑并[1,5-a]吡啶衍生物Ig(0.10g,0.2mmol)之二氯甲烷溶液(1.5mL),攪拌2小時。過濾反應液並加以乾燥,以白色固體獲得硼錯合物(I-B-6)(0.025g,0.034mmol,17%)。進而,藉由管柱層析進行純化,將對該硼錯合物之核磁共振譜等之測量結果示於以下。
IR(KBr)3052,2957,2835,2361,1719,1645,1596,1503,1486,1278,1242,1171,1142,1091,1056,1032,1011,956,930,825,798,752,734cm-1;1H NMR(CDCl3)δ 3.73(s,6H,OMe),6.56(d,J=8.8,4H,Ar),6.76(t,J=6.6,1H,Ar),6.96(d,J=8.8,5H,Ar),7.21(d,J=8.3,
4H,Ar),7.30-7.42(m,7H,Ar),7.47-7.51(m,2H,Ar),7.56(dt,J=1.5Hz,4.9Hz,1H,Ar),7.84(d,J=8.3Hz,2H,Ar)7.95(d,J=7.3,1H,Ar);13C NMR(CDCl3)δ 55.0(OMe),112.2,115.8,118.5,120.9,122.1,122.2,122.5,125.4,126.9,127.7,128.0,128.9,129.1,132.1,132.7,133.0,133.8,134.7,144.5,158.0(Ar);MS(EI)m/z 702(M+-CH3);m.p.224-228℃
上述實施例6及7中任一硼錯合物均於溶液中、或於固體狀態下顯示藍色螢光發光。將各硼錯合物之結構式示於以下。又,將螢光波長及相對螢光量子產率示於下表2。
於室溫下在乙醯丙酮二羰基銠(I)(0.052g,0.2mmol)之甲苯溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ia(0.082g,0.21mmol)之甲苯溶液(4mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銠錯合物(I-Rh-1)(0.083g,0.15mmol,76%)。
將對銠錯合物(I-Rh-1)之核磁共振譜等之測量結果示於以下。
IR(KBr)νco 2065,1989cm-1;1H NMR(CDCl3)δ 2.49(s,3H,CH3),6.07(d,J=9.3Hz,1H,Ar),6.35(dd,J=9.3Hz,6.3Hz,1H,Ar),6.44(dd,J=7.1Hz,6.3Hz,1H,Ar),7.23(t,J=7.3Hz,2H,Ar),7.32(t,J=7.3Hz,2H,Ar),7.44(d,J=7.9Hz,2H,Ar),7.58(d,J=7.9Hz,2H,Ar),7.61(d,J=7.3Hz,2H,Ar),7.67(d,J=7.3Hz,2H,Ar),7.68(d,J=7.1Hz,1H,Ar);13C NMR(CDCl3)δ 21.6(CH3),89.1(RhOC),114.9,117.8,119.4,119.8,120.8,122.5,124.3,124.6,128.4,130.0,130.4(Ar),136.6(d,JRh-C=4.1Hz,Ar),139.3,141.4,142.1,151.2(Ar),184.6(d,JRh-C=62.7Hz,CO),185.2(d,JRh-C=74.4Hz,CO);MS(EI)m/z 546(M+),490(M+-(CO)2);C29H19N2O3Rh之HRMS計算值:546.0451,實測值:546.0457;m.p.122-128℃(分離).
於室溫下在乙醯丙酮二羰基銠(I)(0.052g,0.2mmol)之甲苯溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ib(0.082g,0.21mmol)之甲苯溶液(5mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銠錯合物(I-Rh-2)(0.082g,0.15mmol,74%)。
將對銠錯合物(I-Rh-2)之核磁共振譜等之測量結果表示如下。又,將X射線結構分析之結果之ORTEP圖示於圖2。各橢圓球表示以50%之
概率發現碳、氮、氧、或銠原子之座標,較小之球表示氫原子。
IR(KBr)νco 2063,1991cm-1;1H NMR(CDCl3)δ 2.39(s,3H,CH3),6.48(dd,J=7.3Hz,6.3Hz,1H,Ar),6.54(dd,J=9.3Hz,6.3Hz,1H,Ar),6.69(d,J=9.3Hz,1H,Ar),7.12(t,J=7.3Hz,2H,Ar),7.21(t,J=7.3Hz,4H,Ar),7.32(d,J=8.1Hz,2H,Ar),7.36(d,J=7.1Hz,4H,Ar),7.45(d,J=8.1Hz,2H,Ar),7.66(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.6(CH3),86.9(RhOC),114.8,118.9,120.0,121.3,124.3,124.5,126.8,127.7,127.7,129.9,130.6,136.9,141.4,145.8(Ar),184.5(d,JRh-C=62.9Hz,CO),185.7(d,JRh-C=75.3Hz,CO);MS(EI)m/z 520(M+-CO),492(M+-(CO)2);m.p.132-134℃(分離).
於室溫下在乙醯丙酮二羰基銠(I)(0.052g,0.2mmol)之甲苯溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ic(0.097g,0.21mmol)之甲苯溶液(5mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銠錯合物(I-Rh-3)(0.085g,0.14mmol,69%)。
將對銠錯合物(I-Rh-3)之核磁共振譜等之測量結果表示如下。
IR(KBr)νco 2065,1989cm-1;1H NMR(CDCl3)δ 2.46(s,3H,CH3),6.60(dd,J=7.3Hz,6.3Hz,1H,Ar),6.68(dd,J=9.3Hz,6.3Hz,1H,Ar),6.75(d,J=9.3Hz,1H,Ar),7.25(d,J=8.8Hz,4H,Ar),7.35(d,J=8.8Hz,4H,Ar),7.40(d,J=7.8Hz,2H,Ar),7.51(d,J=7.8Hz,2H,Ar),7.75(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.6(CH3),86.0(RhOC),114.9,118.3,120.7,121.5,124.0,124.5,128.0,129.1,130.0,130.5,132.8(Ar),137.3(d,JRh-C=4.1Hz,Ar),141.6,144.6,147.3(Ar),184.2(d,JRh-C=62.9Hz,CO),185.3(d,JRh-C=74.4Hz,CO);MS(EI)m/z 588(M+-CO),560(M+-(CO)2);C29H19Cl2N2O3Rh-CO之HRMS計
算值:587.9879,實測值:587.9822,C29H19Cl2N2O3Rh-(CO)2之計算值:559.9929,實測值:559.9918;m.p.138-140℃(分離).
於室溫下在乙醯丙酮二羰基銠(I)(0.052g,0.2mmol)之甲苯溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Id(0.097g,0.21mmol)之甲苯溶液(5mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銠錯合物(I-Rh-4)(0.086g,0.14mmol,71%)。
將對銠錯合物(I-Rh-4)之核磁共振譜等之測量結果示於以下。
IR(KBr)νco 2062,1993cm-1;1H NMR(CDCl3)δ 2.44(s,3H,CH3),3.77(s,6H,OCH3),6.53(dd,J=7.3Hz,6.3Hz,1H,Ar),6.59(dd,J=9.3Hz,6.3Hz,1H,Ar),6.75(d,J=9.3Hz,1H,Ar),6.79(d,J=8.8Hz,4H,Ar),7.32(d,J=8.8Hz,4H,Ar),7.36(d,J=8.1Hz,2H,Ar),7.49(d,J=8.1Hz,2H,Ar),7.70(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.5(CH3),55.2(OCH3),86.0(RhOC),113.0,114.7,118.9,119.9,121.2,124.3,124.4,128.8,129.9,130.6(Ar),136.8(d,JRh-C=5.0Hz,Ar),141.3,141.7,146.1,158.4(Ar),184.6(d,JRh-C=62.9Hz,CO),185.7(d,JRh-C=75.3Hz,CO);MS(EI)m/z 580(M+-CO);C31H25N2O5Rh-CO之HRMS計算值:580.0869,實測值:580.0891;m.p.105-108℃(分離).
於室溫下在乙醯丙酮二羰基銠(I)(0.052g,0.2mmol)之甲苯溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ie(0.085g,0.21mmol)之甲苯溶液(5mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銠錯合物(I-Rh-5)(0.077g,0.14mmol,68%)。
將銠錯合物(I-Rh-5)之核磁共振譜等之測量結果表示如下。
IR(KBr)νco 2063,1986cm-1;1H NMR(CDCl3)δ 3.87(s,3H,OCH3),6.54(dd,J=7.3Hz,6.3Hz,1H,Ar),6.60(dd,J=9.3Hz,6.3Hz,1H,Ar),6.75(d,J=9.3Hz,1H,Ar),7.07(d,J=8.8Hz,2H,Ar),7.21(t,J=6.8Hz,2H,Ar),7.26(t,J=7.3Hz,4H,Ar),7.42(d,J=7.3Hz,4H,Ar),7.53(d,J=8.8Hz,2H,Ar),7.69(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 55.5(OCH3),86.9(RhOC),114.7,118.9,119.3,120.0,121.3,124.5,126.8,127.7,127.7,132.2(Ar),136.7(d,JRh-C=4.1Hz,Ar),145.6,149.1,161.6(Ar),184.5(d,JRh-C=62.9Hz,CO),185.7(d,JRh-C=75.3Hz,CO);MS(EI)m/z 564(M+);C29H21N2O4Rh之HRMS計算值:564.0556,實測值:564.0590;m.p.111-119℃(分離).
此處,將上述實施例6至10之銠錯合物之結構式示於以下供參考。
[化16]
使用銠錯合物(I-Rh-3),檢查對二苯乙炔之矽氫化反應之觸媒活性。以二苯乙炔之1000分之一當量(0.1mmol%)之銠錯合物(I-Rh-3)為觸媒,以單離產率98%、E體:Z體=98:2獲得作為矽氫化生成物之乙烯基矽烷。反應式係以下式表示。
[化17]
作為關於銠錯合物之例,例如記載於文獻(J. L. McBee,J. Escalada,T. D. Tilley,J.Am.Chem.Soc.2009,131,12703.)中。最近之例中使用5mol%之觸媒,但顯示與其相比,以1/50之觸媒量完成反應。
於溫室下在乙醯丙酮二羰基銥(I)(0.070g,0.2mmol)之二氯甲烷溶液(2mL)中添加咪唑并[1,5-a]吡啶衍生物Ib(0.082g,0.21mmol)之二氯甲烷溶液(5mL)。於室溫下攪拌黃色溶液兩小時,濃縮反應混合液。利用矽膠管柱層析法純化殘渣,藉此以黃色固體獲得銥錯合物(I-Ir-1)(0.095g,0.15mmol,74%)。銥錯合物(I-Ir-1)之結構式係以下式表示。
將銥錯合物(I-Ir-1)之核磁共振譜等之測量結果表示如下。
IR(KBr)νco 2044,1968cm-1;1H NMR(CDCl3)δ 2.47(s,3H,CH3),6.62(dd,J=7.3Hz,6.3Hz,1H,Ar),6.70(dd,J=9.3Hz,6.3Hz,1H,
Ar),6.91(d,J=9.3Hz,1H,Ar),7.24(t,J=7.3Hz,2H,Ar),7.29(t,J=7.3Hz,4H,Ar),7.41(d,J=7.8Hz,2H,Ar),7.43(d,J=6.8Hz,4H,Ar),7.53(d,J=7.8Hz,2H,Ar),7.72(d,J=7.3Hz,1H,Ar);13C NMR(CDCl3)δ 21.6(CH3),87.9(IrOC),115.4,118.3,120.7,121.4,123.5,124.4,127.1,127.6,127.8,130.1,130.7,137.5,141.8,145.5,148.3(Ar),171.3,174.5(CO);MS(EI)m/z 638(M+),610(M+-CO),582(M+-(CO)2),561(M+-Ph);m.p.186-190℃(分離).
本發明之作為配位基之咪唑并[1,5-a]吡啶衍生物可由容易獲取且廉價之原料不經由複雜之合成路徑而簡易地製造。又,可對原料之取代基進行各種設定。因此,可用作可任意控制本發明之錯合物之穩定性、觸媒活性、光特性等之有用之新穎之化合物。
Claims (3)
- 一種以咪唑并[1,5-a]吡啶衍生物為配位基之錯合物,其特徵在於以通式(I)表示,
- 如請求項1之錯合物,其中上述單環或多環之1價有機分子基為選自下式所表示之(i)~(iv)中之任一種有機分子基,
- 如請求項1或2之錯合物,其中上述原子M為選自B、Al、Fe、Co、Ni、Ru、Rh、Pd、Re、Os、Ir、及Pt中之一種。
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