WO2015104961A1 - シクロメタル化イリジウム錯体の原料及び製造方法 - Google Patents
シクロメタル化イリジウム錯体の原料及び製造方法 Download PDFInfo
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- WO2015104961A1 WO2015104961A1 PCT/JP2014/083217 JP2014083217W WO2015104961A1 WO 2015104961 A1 WO2015104961 A1 WO 2015104961A1 JP 2014083217 W JP2014083217 W JP 2014083217W WO 2015104961 A1 WO2015104961 A1 WO 2015104961A1
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- WIPO (PCT)
- Prior art keywords
- compound
- iridium
- raw material
- group
- iridium complex
- Prior art date
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 146
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000002994 raw material Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003446 ligand Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007983 Tris buffer Substances 0.000 claims abstract description 11
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 202
- 125000004432 carbon atom Chemical group C* 0.000 claims description 90
- 230000001815 facial effect Effects 0.000 claims description 38
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 150000002503 iridium Chemical class 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical class [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical group CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 claims 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 64
- AZFHXIBNMPIGOD-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;iridium Chemical compound [Ir].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O AZFHXIBNMPIGOD-LNTINUHCSA-N 0.000 abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 69
- -1 n-octyl group Chemical group 0.000 description 64
- 238000005160 1H NMR spectroscopy Methods 0.000 description 60
- 239000000047 product Substances 0.000 description 56
- 238000003786 synthesis reaction Methods 0.000 description 50
- 230000015572 biosynthetic process Effects 0.000 description 45
- 239000012300 argon atmosphere Substances 0.000 description 33
- 239000000126 substance Substances 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 29
- 239000007787 solid Substances 0.000 description 29
- 238000001816 cooling Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 230000002378 acidificating effect Effects 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 6
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical class C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 description 5
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 5
- 150000005360 2-phenylpyridines Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 5
- 150000004842 1-phenylimidazoles Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical class C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- SHWNDUJCIYUZRF-UHFFFAOYSA-N imidazo[1,2-f]phenanthridine Chemical class C1=CC=C2N3C=CN=C3C3=CC=CC=C3C2=C1 SHWNDUJCIYUZRF-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 150000002397 1-phenylpyrazoles Chemical class 0.000 description 2
- RSNQVABHABAKEZ-UHFFFAOYSA-N 2,3-diphenylquinoxaline Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 RSNQVABHABAKEZ-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- XNCMQRWVMWLODV-UHFFFAOYSA-O 3-phenyl-1h-benzimidazol-3-ium Chemical class C=1NC2=CC=CC=C2[N+]=1C1=CC=CC=C1 XNCMQRWVMWLODV-UHFFFAOYSA-O 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-O 3-phenyl-1h-imidazol-3-ium Chemical class C1=NC=C[NH+]1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-O 0.000 description 2
- RBJOTRVJJWIIER-UHFFFAOYSA-N 3-phenylisoquinoline Chemical class C1=CC=CC=C1C1=CC2=CC=CC=C2C=N1 RBJOTRVJJWIIER-UHFFFAOYSA-N 0.000 description 2
- LUEYUHCBBXWTQT-UHFFFAOYSA-N 4-phenyl-2h-triazole Chemical class C1=NNN=C1C1=CC=CC=C1 LUEYUHCBBXWTQT-UHFFFAOYSA-N 0.000 description 2
- NYMLZIFRPNYAHS-UHFFFAOYSA-N 5-phenyl-1h-1,2,4-triazole Chemical class C1=NNC(C=2C=CC=CC=2)=N1 NYMLZIFRPNYAHS-UHFFFAOYSA-N 0.000 description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical class N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 2
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical class N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical class C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C1C(C(*(C2C(C)C=C)C2P)NC)C1*)C=C Chemical compound CC(C1C(C(*(C2C(C)C=C)C2P)NC)C1*)C=C 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002785 azepinyl group Chemical group 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- FCEUOTOBJMBWHC-UHFFFAOYSA-N benzo[f]cinnoline Chemical class N1=CC=C2C3=CC=CC=C3C=CC2=N1 FCEUOTOBJMBWHC-UHFFFAOYSA-N 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical class C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 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 2
- 238000010657 cyclometalation reaction Methods 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007040 multi-step synthesis reaction Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- KBBSSGXNXGXONI-UHFFFAOYSA-N phenanthro[9,10-b]pyrazine Chemical class C1=CN=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 KBBSSGXNXGXONI-UHFFFAOYSA-N 0.000 description 2
- RIYPENPUNLHEBK-UHFFFAOYSA-N phenanthro[9,10-b]pyridine Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 RIYPENPUNLHEBK-UHFFFAOYSA-N 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- YGRSXJJORLXYPT-UHFFFAOYSA-N 1-naphthalen-1-ylisoquinoline Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=NC=CC2=C1 YGRSXJJORLXYPT-UHFFFAOYSA-N 0.000 description 1
- IIMMYPSINSFUBX-UHFFFAOYSA-N 1-naphthalen-2-ylisoquinoline Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=C3)=NC=CC2=C1 IIMMYPSINSFUBX-UHFFFAOYSA-N 0.000 description 1
- AZQJQRTZFPAGNV-UHFFFAOYSA-N 1-phenylindazole Chemical class C12=CC=CC=C2C=NN1C1=CC=CC=C1 AZQJQRTZFPAGNV-UHFFFAOYSA-N 0.000 description 1
- VSKZGHVPGOMFAV-UHFFFAOYSA-N 1-pyridin-2-ylindole Chemical class C1=CC2=CC=CC=C2N1C1=CC=CC=N1 VSKZGHVPGOMFAV-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- DZYGAGZGZOLVCI-UHFFFAOYSA-N 2-(1-benzofuran-2-yl)pyridine Chemical class O1C2=CC=CC=C2C=C1C1=CC=CC=N1 DZYGAGZGZOLVCI-UHFFFAOYSA-N 0.000 description 1
- NRSBAUDUBWMTGL-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine Chemical class S1C2=CC=CC=C2C=C1C1=CC=CC=N1 NRSBAUDUBWMTGL-UHFFFAOYSA-N 0.000 description 1
- RIAJQFIZKHZWMP-UHFFFAOYSA-N 2-(furan-2-yl)pyridine Chemical class C1=COC(C=2N=CC=CC=2)=C1 RIAJQFIZKHZWMP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical class C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- VLRSADZEDXVUPG-UHFFFAOYSA-N 2-naphthalen-1-ylpyridine Chemical class N1=CC=CC=C1C1=CC=CC2=CC=CC=C12 VLRSADZEDXVUPG-UHFFFAOYSA-N 0.000 description 1
- IXVWMXLBXQAMMW-UHFFFAOYSA-N 2-naphthalen-1-ylquinoline Chemical class C1=CC=C2C(C3=NC4=CC=CC=C4C=C3)=CC=CC2=C1 IXVWMXLBXQAMMW-UHFFFAOYSA-N 0.000 description 1
- DBENTMPUKROOOE-UHFFFAOYSA-N 2-naphthalen-2-ylpyridine Chemical class N1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 DBENTMPUKROOOE-UHFFFAOYSA-N 0.000 description 1
- LPNLFJKYHYLXPE-UHFFFAOYSA-N 2-naphthalen-2-ylquinoline Chemical class C1=CC=CC2=NC(C3=CC4=CC=CC=C4C=C3)=CC=C21 LPNLFJKYHYLXPE-UHFFFAOYSA-N 0.000 description 1
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 description 1
- FIISKTXZUZBTRC-UHFFFAOYSA-N 2-phenyl-1,3-benzoxazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2O1 FIISKTXZUZBTRC-UHFFFAOYSA-N 0.000 description 1
- RQCBPOPQTLHDFC-UHFFFAOYSA-N 2-phenyl-1,3-oxazole Chemical class C1=COC(C=2C=CC=CC=2)=N1 RQCBPOPQTLHDFC-UHFFFAOYSA-N 0.000 description 1
- WYKHSBAVLOPISI-UHFFFAOYSA-N 2-phenyl-1,3-thiazole Chemical class C1=CSC(C=2C=CC=CC=2)=N1 WYKHSBAVLOPISI-UHFFFAOYSA-N 0.000 description 1
- QLPKTAFPRRIFQX-UHFFFAOYSA-N 2-thiophen-2-ylpyridine Chemical class C1=CSC(C=2N=CC=CC=2)=C1 QLPKTAFPRRIFQX-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- YTTYNMGFPQYWKE-UHFFFAOYSA-N 3-naphthalen-1-ylisoquinoline Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=N3)=CC=CC2=C1 YTTYNMGFPQYWKE-UHFFFAOYSA-N 0.000 description 1
- CKUOKPSIXGRHSY-UHFFFAOYSA-N 3-naphthalen-2-ylisoquinoline Chemical class C1=CC=C2C=NC(C3=CC4=CC=CC=C4C=C3)=CC2=C1 CKUOKPSIXGRHSY-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ROLKDXFFBNOIDS-UHFFFAOYSA-N 5,6-dihydroquinoline Chemical class C1=CN=C2C=CCCC2=C1 ROLKDXFFBNOIDS-UHFFFAOYSA-N 0.000 description 1
- QCRWZQPISCKABP-UHFFFAOYSA-N 6-naphthalen-1-ylphenanthridine Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=NC3=CC=CC=C3C2=C1 QCRWZQPISCKABP-UHFFFAOYSA-N 0.000 description 1
- RBIMXMFIMHZNFR-UHFFFAOYSA-N 6-naphthalen-2-ylphenanthridine Chemical class C1=CC=C2C(C3=CC4=CC=CC=C4C=C3)=NC3=CC=CC=C3C2=C1 RBIMXMFIMHZNFR-UHFFFAOYSA-N 0.000 description 1
- XXWONCALJGBUFK-UHFFFAOYSA-N 6-phenylphenanthridine Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2C2=CC=CC=C12 XXWONCALJGBUFK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JDINBEDUGBFLEC-UHFFFAOYSA-N 9-pyridin-2-ylcarbazole Chemical class N1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JDINBEDUGBFLEC-UHFFFAOYSA-N 0.000 description 1
- OAPPEBNXKAKQGS-UHFFFAOYSA-N Benz[c]acridine Chemical class C1=CC=C2C3=NC4=CC=CC=C4C=C3C=CC2=C1 OAPPEBNXKAKQGS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MHDLAWFYLQAULB-UHFFFAOYSA-N anilinophosphonic acid Chemical compound OP(O)(=O)NC1=CC=CC=C1 MHDLAWFYLQAULB-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- SEXRCKWGFSXUOO-UHFFFAOYSA-N benzo[a]phenazine Chemical class C1=CC=C2N=C3C4=CC=CC=C4C=CC3=NC2=C1 SEXRCKWGFSXUOO-UHFFFAOYSA-N 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- NBAUUSKPFGFBQZ-UHFFFAOYSA-N diethylaminophosphonic acid Chemical compound CCN(CC)P(O)(O)=O NBAUUSKPFGFBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 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
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- GUZBPGZOTDAWBO-UHFFFAOYSA-N phenanthro[9,10-b]quinoline Chemical class C1=CC=C2C3=CC4=CC=CC=C4N=C3C3=CC=CC=C3C2=C1 GUZBPGZOTDAWBO-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoric acid amide group Chemical group P(N)(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 125000005030 pyridylthio group Chemical group N1=C(C=CC=C1)S* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
-
- 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
- C07F15/004—Iridium compounds without a metal-carbon linkage
Definitions
- the present invention relates to a raw material and a production method of a cyclometalated iridium complex, and is applicable to an organic electroluminescence (EL) element, an organic electrochemiluminescence (ECL) element, a luminescence sensor, a photosensitizing dye, various light sources, and the like.
- EL organic electroluminescence
- ECL organic electrochemiluminescence
- the present invention relates to a technique for providing an iridium iodide complex.
- the cyclometalated iridium complex is a general term for an organic iridium complex in which a polydentate ligand is coordinated cyclically to an iridium atom and has at least one iridium-carbon bond.
- a polydentate ligand is coordinated cyclically to an iridium atom and has at least one iridium-carbon bond.
- tris (2-phenylpyridine) Examples include iridium Ir (ppy) 3 (Chemical Formula 1).
- aromatic heterocyclic bidentate ligands such as 2-phenylpyridine derivatives, 2-phenylquinoline derivatives, and 1-phenylisoquinoline derivatives are coordinated.
- phosphorescent materials such as organic electroluminescence (EL) elements and organic electrochemiluminescence (ECL) elements (Patent Document 1).
- EL organic electroluminescence
- ECL organic electrochemiluminescence
- Cyclometalated iridium complexes include biscyclometalated iridium complexes in which two aromatic heterocyclic bidentate ligands are coordinated to the iridium atom, and three aromatic heterocyclic bidentate ligands to the iridium atom. Triscyclometalated iridium complexes. Among these, the triscyclometalated iridium complex has particularly high thermal stability, and can be expected to have a long life when applied to an organic EL device or the like.
- the above cyclometalated iridium complex can be synthesized in one step by reacting, for example, iridium trichloride with an aromatic heterocyclic bidentate ligand such as 2-phenylpyridine (ppy).
- an aromatic heterocyclic bidentate ligand such as 2-phenylpyridine (ppy).
- Non-Patent Document 1 the three 2,4-pentanedione is coordinated to iridium tris (2,4-pentanedionato) iridium (III) (hereinafter, Ir (acac) 3, also referred to) as a raw material, 2-phenylpyridine (
- a cyclometalated iridium complex can be obtained in one step by reacting an aromatic heterocyclic bidentate ligand such as (ppy) (Chemical Formula 3, Non-Patent Document 2).
- Patent Document 2 discloses a multi-step synthesis method using iridium trichloride as a raw material, reacting an aromatic heterocyclic bidentate ligand such as 2-phenylpyridine (ppy), and the like via a chlorine-bridged dimer. (Chemical formula 4).
- Non-Patent Document 1 the cyclometalated iridium complex obtained by one-step synthesis using iridium trichloride as a raw material has a problem that the chlorine content derived from iridium trichloride remains in the cyclometalated iridium complex. There is. It has been pointed out that these chlorine components adversely affect the light emission characteristics when applied to organic EL elements (Patent Document 3).
- Non-Patent Document 2 since chlorine-free tris (2,4-pentanedionato) iridium (III) is used as a raw material, no chlorine content derived from the iridium raw material remains.
- tris (2,4-pentanedionato) iridium (III) has a problem that it is thermally stable and poor in reactivity, and the synthesis yield of the cyclometalated iridium complex is low.
- Tris (2,4-pentanedionato) iridium (III) has a symmetrical ⁇ -diketone ligand, and therefore has good crystallinity and is in a solid state at room temperature.
- Such solid-state tris (2,4-pentanedionato) iridium (III) has sublimation properties, and according to the knowledge of the present inventors, in the process of producing a cyclometalated iridium complex, In some cases, tris (2,4-pentanedionato) iridium (III) may come out of the reaction system. This is also considered to be a cause of reducing the yield of the cyclometalated iridium complex.
- Patent Document 5 describes that a Lewis acid is added to the reaction system as a reaction accelerator and Patent Document 3 adds a Bronsted acid as a reaction accelerator to obtain a cyclometalated iridium complex.
- Patent Document 3 and Patent Document 5 have an essential problem that they cannot be applied when an aromatic heterocyclic bidentate ligand or a reaction product is unstable to an acid. For this reason, in these manufacturing methods, the yield of a cyclometalated iridium complex cannot necessarily be improved sufficiently, and development of a new manufacturing method is desired. Furthermore, since the production method disclosed in Patent Document 2 is a multi-step synthesis method, it requires labor and time, and it is necessary to isolate and purify the product at each step. Has a disadvantageous problem.
- the present invention relates to a raw material of a non-chlorinated cyclometalated iridium complex (hereinafter sometimes referred to as an organic iridium material or an iridium raw material), and the cyclometalated iridium complex is converted to tris (2,4-pentane).
- the object is to provide a technique that can be obtained in a high yield by a one-step synthesis reaction from an iridium raw material at a lower reaction temperature than when using diato) iridium (III).
- the present inventor has used tris (2,4-pentanedionato) iridium (III), which is a raw material not containing a chlorine atom, as a starting point to form an aromatic heterocyclic bidentate ligand.
- III tris (2,4-pentanedionato) iridium
- the present invention relates to an organic iridium material, which is a raw material for producing a cyclometalated iridium complex, wherein the organic iridium material is tris ( ⁇ --coordinated with an asymmetric ⁇ -diketone on iridium represented by the general formula (1).
- Diketonato) iridium (III) relates to a raw material and a method for producing a cyclometalated iridium complex.
- R a and R b are a hydrocarbon group or a heterocyclic group
- R c is a hydrogen atom, a hydrocarbon group or a heterocyclic group
- O is an oxygen atom
- Ir is an iridium atom.
- the raw material of the present invention is characterized by an organic iridium material in which three ⁇ -diketones having the same structure are coordinated to iridium, and these ⁇ -diketones are asymmetric.
- the substituents R a and R b of the ⁇ -diketone have different types of substituents.
- a cyclometalated iridium complex can be produced in a high yield at a lower reaction temperature than tris (2,4-pentanedionato) iridium (III), which has been conventionally used as a raw material. .
- substituents R a , R b , and R c of the ⁇ -diketone can include the following substituents.
- the substituents R a and R b are hydrocarbon or heterocyclic substituents, and R a and R b are not the same because of asymmetry.
- R c is a hydrogen atom, a hydrocarbon group or a heterocyclic group.
- R a and R c , or R b and R c may be bonded to each other to form a saturated hydrocarbon ring or an unsaturated hydrocarbon ring.
- R a and / or R b is a hydrocarbon group, it is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an aliphatic hydrocarbon group, linear or branched Particularly preferred is a hydrocarbon group.
- the aliphatic hydrocarbon in the present invention means a hydrocarbon other than an aromatic hydrocarbon, and includes a cyclic hydrocarbon other than an aromatic hydrocarbon.
- R a and / or R b is an aliphatic hydrocarbon group
- an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkyl group (preferably having 1 to 10 carbon atoms, more preferably a carbon number). 1 to 5.
- alkenyl group preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms.
- alkenyl group preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms.
- alkynyl group preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms.
- propargyl, 3-pentini And the like. are more preferable, more preferably an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, and particularly preferably a n- butyl group, or t- butyl group. It is particularly preferred that either R a or R b is a methyl group.
- the hydrogen atom in these aliphatic hydrocarbon groups may be substituted with a substituent defined by R and R 1 to R 48 described later, and is preferably substituted with fluorine.
- R a and / or R b is an aromatic hydrocarbon group, it is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
- the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a triphenylenyl group, a terphenyl group, a pyrenyl group, a mesityl group, a tolyl group, a xylyl group, and an azulenyl group.
- the hydrogen atom in these aromatic hydrocarbon groups may be substituted with a substituent defined by R and R 1 to R 48 described later, and is preferably substituted with fluorine.
- R a and / or R b is a heterocyclic group, it is preferably a heterocyclic group having 1 to 20 carbon atoms, more preferably a heterocyclic group having 1 to 10 carbon atoms.
- the heterocyclic group include pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, quinolyl, furyl Group, thienyl group, selenophenyl group, tellurophenyl group, piperidyl group, piperidino group, morpholino group, pyrrolidyl group, pyrrolidino group, benzoxazolyl group, benzoimidazolyl group, benzothiazolyl group, carbazolyl group, azepinyl group, silo
- R a and R b are the same as those in General Formula (1), and the preferred ranges are also the same.
- X represents a 5-membered or 6-membered saturated or unsaturated hydrocarbon ring, preferably having 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms.
- Examples of the asymmetric ⁇ -diketone in the present invention include, for example, JP-A-8-85873, JP-A-2000-212744, JP-A-2003-64019, JP-A-2003-321416, JP-A-2005-2005. Nos. 35902, 2013-136567, and the like.
- These asymmetric ⁇ -diketone ligands can be obtained commercially.
- R c in the general formula (1) is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom.
- Preferred hydrocarbon groups or heterocyclic groups for R c are the same as the preferred substituents for R a and R b above.
- the iridium raw material of the present invention represented by the general formula (1) is disclosed in JP-A-7-316176, JP-A-2003-321415, JP-A-2003-321416, JP-A-2003-64019, Organometallics, 1995. It can be produced with reference to the method described in Yon, Vol. 14, No. 3, p.
- Examples of the iridium raw material represented by the general formula (1) are shown in (A-1) to (A-80). Among these, (A-1) to (A-50) are preferable, and more preferable. Are (A-1) to (A-25), and (A-3) and (A-7) are particularly preferred.
- the 5% weight loss temperature measured by the TG-DTA simultaneous measurement apparatus is higher than the measurement temperature of tris (2,4-pentandionato) iridium (III). Is also preferred.
- the 5% weight loss temperature varies depending on the measurement conditions. For example, a raw material having a temperature increase rate of 5 ° C./min, a nitrogen gas stream (200 mL / min), and a 5% weight reduction temperature at normal pressure of less than 222 ° C. is preferable.
- the iridium raw material represented by the general formula (1) has a three-dimensional structure in which three ⁇ -diketone ligands are arranged in an octahedral shape with an iridium metal as a center.
- ⁇ -diketone as a ligand is asymmetric, there are two kinds of geometric isomers (facial and meridional). Facial and meridional isomers are nomenclature of hexacoordinate octahedral complex isomers and are described in Organometallic Chemistry-Fundamentals and Applications-Akio Yamamoto (Touhuabo), p.143.
- the facial isomer is an isomer having a structure in which R b always exists on the extension in which R a and Ir are bonded via O. is there.
- R a may be present in addition to R b on the extension where R a and Ir are bonded via O, and R b and Ir are bonded via O.
- an isomer of structure that is the presence of R b is other than R a above.
- Geometric isomer of iridium raw material represented by general formula (1)
- the iridium raw material of the general formula (1) When the iridium raw material of the general formula (1) is produced, it is often obtained as a mixture of a facial body and a meridional body.
- These geometric isomers can be separated into a facial isomer and a meridional isomer according to the purpose by a method such as column chromatography or distillation.
- a method such as column chromatography or distillation.
- geometric isomers can be separated by silica gel chromatography.
- a mixture of a facial body and a meridional body from the viewpoint of operability in the production process of the cyclometalated iridium complex.
- either one of the geometric isomers is contained in an amount of 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 10 mol% or more. Is particularly preferred.
- Geometric isomers can be identified by various instrumental analyzes such as 1 H-NMR. Each content of the facial body and the meridional body can be quantified using 1 H-NMR, gas chromatography, high performance liquid chromatography or the like.
- the cyclometalated iridium complex comprises an organic iridium material (raw material) coordinated with an asymmetric ⁇ -diketone, and an aromatic heterocyclic bidentate ligand capable of forming an iridium-carbon bond. It can be produced by a reaction method.
- a cyclometalated iridium complex is obtained in one step at a lower reaction temperature and in a higher yield than when tris (2,4-pentanedionato) iridium (III) is used. It becomes possible.
- the aromatic heterocyclic bidentate ligand to be reacted with the organic iridium material (raw material) is an aromatic heterocyclic bidentate ligand capable of forming an iridium-carbon bond, one iridium-nitrogen bond and one iridium.
- An aromatic heterocyclic bidentate ligand that forms a carbon bond, or an aromatic heterocyclic bidentate ligand that forms two iridium-carbon bonds, preferably one iridium-nitrogen bond and one iridium -Aromatic heterocyclic bidentate ligands that form carbon bonds are more preferred.
- aromatic heterocyclic bidentate ligands include 2-phenylpyridine derivatives, 2-phenylquinoline derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives, 2- (2-benzothiophenyl) Pyridine derivatives, 2-thienylpyridine derivatives, 1-phenylpyrazole derivatives, 1-phenyl-1H-indazole derivatives, 2-phenylbenzothiazole derivatives, 2-phenylthiazole derivatives, 2-phenylbenzoxazole derivatives, 2-phenyloxazole derivatives, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine derivative, 7,8-benzoquinoline derivative, 7,8-benzoquinoxaline derivative, dibenzo [f, h] quinoline derivative, dibenzo [f, h] quinoxaline derivative , Benzo [h] 5,6-dihydroquinoline derivatives, 9- (2-pyridyl) carbazole derivatives,
- aromatic heterocyclic bidentate ligand among the above, 2-phenylpyridine derivative, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 1-phenylpyrazole derivative, 7,8- Benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 6-phenylphenanthridine derivatives 2-phenylquinoxaline derivative, 2,3-diphenylquinoxaline derivative, 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltriazole derivative, 5-phenyltetrazole More preferred is a phenyl derivative, 5-phenyl-1,2,4-triazole derivative, imidazo
- a 2-phenylpyridine derivative, a 1-phenylisoquinoline derivative, a 1-phenylimidazole derivative, or an imidazo [1,2-f] phenanthridine derivative is particularly preferable, and a 2-phenylpyridine derivative, 1-phenylisoquinoline is preferable.
- Derivatives, 1-phenylimidazole derivatives are particularly preferred.
- Specific examples of the structure of the aromatic heterocyclic bidentate ligand used in the present invention include those shown in Structural Examples 1 to 3 below. Of these, those having the structures represented by the general formulas (3) to (7) are particularly preferred. * In Structural Examples 1 to 3 and General Formulas (3) to (7) is a binding site with iridium.
- R and R 1 to R 48 are a hydrogen atom or a substituent shown below.
- substituents include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl).
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon 2 to 10, for example, propargyl, 3-pentynyl, etc.
- an aryl group preferably a carbon number
- 6 to 20 carbon atoms particularly preferably having 6 to 12 carbon atoms, such as phenyl, p- methylphenyl, naphthyl, anthranyl.
- An amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino;
- alkoxy groups preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy
- An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms such as phenyloxy, 1-naphthyloxy, 2- Naphthyloxy, etc.), heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably Or 1 to 12 carbon atoms, particularly preferably 1 to 12 carbon
- 1 to 20 particularly preferably 1 to 12 carbon atoms such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably 2 to 30 carbon atoms, more preferably 2 to 2 carbon atoms). 20, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably Has 7 to 12 carbon atoms, such as phenyloxycarbonyl That.),
- An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy, etc.), an acylamino group (preferably having a carbon number) 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), an aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably carbon atoms) 7 to 20, particularly preferably 7 to 12 carbon atoms, for example phenyloxycarbonyla Roh and the like.),
- a sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), a sulfamoyl group ( The number of carbon atoms is preferably 0 to 30, more preferably 0 to 20, and particularly preferably 0 to 12, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl.
- a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl).
- An alkylthio group (preferably having 1 to 30 carbon atoms, More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms).
- it has 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to carbon atoms). 12 and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio), and the like.
- a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a sulfinyl group (preferably having 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide groups (preferably 1 to 30 carbon atoms, more preferably carbon atoms) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide I
- hydroxy group mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, trifluoromethyl group, hydroxamic acid group, sulfino group, hydrazino group,
- An imino group or a heterocyclic group preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically imidazolyl, pyridyl, quinolyl) , Furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atom
- it has 3 to 24 carbon atoms, for example trimethylsilyl Triphenylsilyl, etc.), silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc. And the like.
- Particularly preferred substituents are a cyano group, a trifluoromethyl group, a halogen atom, an alkyl group, an aryl group, an amino group, and a heterocyclic group.
- the reaction for synthesizing the cyclometalated iridium complex is performed by reacting the iridium raw material represented by the general formula (1) of the present invention with the above-described aromatic heterocyclic bidentate ligand.
- the above reaction can be performed in an atmosphere of air or an inert gas (such as nitrogen or argon), and is preferably performed in an inert gas atmosphere.
- an inert gas such as nitrogen or argon
- a solvent may be added to the reaction system of the synthesis reaction in order to make the above reaction proceed more smoothly.
- the reaction temperature of the synthesis reaction is preferably 200 ° C. to 300 ° C.
- the reaction time is preferably 10 hours to 20 hours.
- Solvents added to the reaction system include saturated aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ketones, amides, esters, aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing aromatic compounds, ethers And various organic solvents such as nitriles, alcohols and ionic liquids. Specifically, tridecane, ethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol, N, N-dimethylformamide, N-methylpyrrolidone, imidazolium salt, dimethyl sulfoxide, 1,2-propanediol, 1, Examples include 3-propanediol and 1,3-butanediol. It is also preferable to use a mixed solvent containing two or more of the above solvents.
- the solvent preferably has a boiling point at normal pressure of 160 ° C. to 300 ° C., more preferably 170 ° C. to 300 ° C., and particularly preferably 180 ° C. to 300 ° C.
- the concentration of the iridium raw material of the general formula (1) in the reaction system is not limited, but is 0.001 mol / L to 10.0 mol / L is preferable, 0.001 mol / L to 1.0 mol / L is more preferable, 0.01 mol / L to 1.0 mol / L is particularly preferable, 0.05 mol / L to 0.5 mol / L L is most preferred.
- the organic iridium raw material of the general formula (1) Since the organic iridium raw material of the general formula (1) has an asymmetric structure having an asymmetric ⁇ -diketone, it has a low melting point and is liable to be in a liquid state at room temperature or by heating. For this reason, this raw material is particularly suitable for synthesis in the absence of a solvent.
- the above-described synthesis reaction of the cyclometalated iridium complex may be carried out by appropriately adding an acidic substance or a basic substance in order to accelerate the reaction.
- the acidic substance promotes the elimination of the ⁇ -diketone ligand, while the basic substance promotes the cyclometalation reaction of the aromatic heterocyclic bidentate ligand.
- the iridium raw material, aromatic heterocyclic bidentate ligand, or cyclometalated iridium complex may be decomposed, and the yield and purity of the cyclometalated iridium complex may be reduced. Since it tends to decrease, it is desirable not to add an acidic substance or a basic substance.
- the above acidic substance one that acts as a proton source in the reaction system or one that can accept an electron pair such as a Lewis acid or a solid acid can be applied.
- organic acids such as acetic acid, oxalic acid, valeric acid, butyric acid and tartaric acid, and Bronsted acids such as inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid are preferred.
- These acidic substances preferably have a boiling point of 150 ° C. or higher. This is because if the boiling point of the acidic substance is lower than the reaction temperature, the acidic substance is refluxed, and the temperature in the reaction system does not easily rise to a temperature sufficient to cause the reaction to proceed.
- the molar ratio of the acidic substance to the iridium raw material is 0.5 mol or more with respect to 1 mol of the iridium raw material, and preferably 0.5: 1 to (acidic substance: iridium raw material) 20: 1, more preferably 3: 1 to 20: 1. If the amount of the acidic substance is less than 0.5 mol relative to 1 mol of the iridium raw material, a sufficient reaction promoting effect cannot be obtained and the reaction cannot be completed in a short time, which is not preferable. If the acidic substance is 0.5 mol or more with respect to 1 mol of the iridium raw material, there is no particular upper limit. However, if the addition amount of the acidic substance is larger than necessary, it is economically inefficient.
- examples include inorganic bases containing alkali metals, organic amines such as aliphatic amines and aromatic amines, alkali metal alkoxides, etc., and these can be used alone or as a mixture of two or more. .
- the molar ratio of the basic substance and the iridium raw material is preferably such that the molar ratio of the basic substance and the iridium raw material is 0.001 mol or more of the basic substance with respect to 1 mol of the iridium raw material.
- (basic substance: iridium raw material) is 0.01: 1 to 5: 1, particularly preferably 0.01: 1 to 3: 1.
- the reaction temperature is preferably 100 ° C to 300 ° C, more preferably 150 ° C to 300 ° C, and particularly preferably 180 ° C to 300 ° C.
- the reaction time is preferably 1 to 100 hours, more preferably 3 to 80 hours, and particularly preferably 5 to 50 hours.
- the heating means is not particularly limited. Specifically, an oil bath, a sand bath, a mantle heater, a block heater, external heating by a heat circulation jacket, heating by microwave irradiation, or the like can be used.
- the synthesis of the cyclometalated iridium complex is usually carried out at normal pressure, but may be carried out under pressure or under reduced pressure as necessary.
- the amount of the aromatic heterocyclic bidentate ligand used is not particularly limited, but is preferably 3 to 100 times mol, more preferably 3 to 50 times mol, relative to the iridium raw material, 3 to 30 times mole is particularly preferred, and 3 to 10 times mole is most preferred.
- the production method of the present invention it is also preferable to synthesize the asymmetric ⁇ -diketone by-produced in the synthesis of the cyclometalated iridium complex while distilling it out of the reaction system.
- the method for distilling off the ⁇ -diketone is not particularly limited, but for example, the methods described in JP-A No. 2004-337802, WO 2006/014599, etc. can be used.
- the cyclometalated iridium complex obtained by the synthesis method described above can be used as a high-purity product without any purification after purification by a general post-treatment method, if necessary.
- a post-treatment method for example, extraction, cooling, crystallization by adding water or an organic solvent, an operation of distilling off the solvent from the reaction mixture, and the like can be performed alone or in combination.
- a purification method recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.
- the cyclometalated iridium complex produced by the production method of the present invention is preferably a biscyclometalated iridium complex or a triscyclometalated iridium complex, and more preferably a triscyclometalated iridium complex.
- Specific examples of such a cyclometalated iridium complex include JP 2007-224025 A, JP 2006-290891 A, JP 2006-213723 A, JP 2006-111623 A, and JP 2006-2006 A. No.
- JP-A-2006-063080 JP-T 2009-541431, JP-T 2009-526071, JP-T 2008-505076, JP-T 2007-513159, JP-T 2007-513158 Gazette, special table 2002-540572, special table 2009-544167, special table 2009-522228, special table 2008-51405, special table 2008-504342, special table 2007-504272, Special Table 2006-523231 Kohyo 2005-516040 JP, it is described in WO 2010/086089 pamphlet or the like.
- the boiling point of the ⁇ -diketone ligand constituting the raw material of the present invention is higher than that of 2,4-pentanedione, which is a ligand of tris (2,4-pentanedionato) iridium (III), and It can be mentioned that the ⁇ -diketone generated with the progress is difficult to lower the temperature of the reaction solution.
- the raw material of the present invention has a ⁇ -diketone ligand having an asymmetric structure, the crystallinity of the raw material is deteriorated, the melting point is lowered, and it is liable to be in a liquid state at room temperature or by heating. Such a tendency is remarkable especially when two kinds of geometric isomers are included. It is considered that the affinity for the aromatic heterocyclic bidentate ligand was improved and the reactivity was improved by the raw material being in a liquid state.
- the raw material of the present invention becomes a liquid state by heating during the synthesis reaction of the cyclometalated iridium complex and sublimation is suppressed, the problem of tris (2,4-pentanedionato) iridium (III) It is considered that the point (removal of the raw material to the outside of the reaction system by sublimation) has been solved.
- the ⁇ -diketone ligand is easily released from the raw material of the present invention at a temperature lower than that of tris (2,4-pentanedionato) iridium (III). This was clarified as a result of evaluating the thermal stability of the iridium raw material using a TG-DTA simultaneous measurement apparatus (see Examples below).
- the cyclometalated iridium complex obtained using the raw material of the present invention does not contain chlorine derived from the iridium raw material and adversely affects the characteristics of the light emitting device, and this complex is composed of a light emitting layer of the light emitting device or a plurality of organic compounds containing the light emitting layer. By making it contain in a layer, it can be set as the light emitting element excellent in luminous efficiency and durability rather than before.
- the cyclometalated iridium complex can be obtained in a higher yield at a lower reaction temperature than when tris (2,4-pentanedionato) iridium (III) is used. Is possible.
- the iridium raw material (A-3) of the present invention was synthesized with reference to JP-A No. 2003-321416.
- the molar ratio of facial to meridional was 1: 3.
- synthesis examples of cyclometalated iridium complexes they were used as they were.
- the iridium raw material (A-7) of the present invention was synthesized with reference to JP-A No. 2003-64019.
- the molar ratio of facial to meridional was 1: 3.
- synthesis examples of cyclometalated iridium complexes they were used as they were.
- Tris (2,4-pentanedionato) iridium (III) and tris (dipivaloylmethanato) iridium (III) Ir (DPM) 3 which are known iridium raw materials are disclosed in JP-A-7-316176 and JP-A-7-316176.
- the compound was synthesized with reference to JP-A-8-85873. It used for the synthesis example (comparative example) of the cyclometalation iridium complex shown below.
- Example 1 Synthesis of Compound (1)
- Compound (A-7) (344 mg), Compound (A) (558 mg), and ethylene glycol (30 ml) were added at 180 ° C. (oil bath temperature) in an argon atmosphere for 15 hours. The reaction was heated. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 22%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 2 Synthesis of Compound (1)
- Compound (A-7) (95 mg), Compound (A) (158 mg), and ethylene glycol (8.5 ml) were added at 140 ° C. (oil bath temperature) under an argon atmosphere. The reaction was heated for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 9%. The obtained compound (1) was a facial product, and no meridional product was detected in 1 H-NMR.
- Example 3 Synthesis of Compound (1)
- Compound (A-7) (344 mg), Compound (A) (558 mg), and 1,3-propanediol (5 ml) were added at 190 ° C. (oil bath temperature) under an argon atmosphere. ) For 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 35%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 4 Synthesis of Compound (1) Compound (A-3) (369 mg), Compound (A) (558 mg), and ethylene glycol (5 ml) were added at 180 ° C. (oil bath temperature) for 15 hours in an argon atmosphere. The reaction was heated. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 7%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 5 Synthesis of Compound (1) Compound (A-7) (344 mg), Compound (A) (558 mg), 85% phosphoric acid aqueous solution (69 mg), and ethylene glycol (5 ml) were added in an argon atmosphere at 180 ° C. The reaction was carried out at 15 ° C (oil bath temperature) for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 36%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 6 Synthesis of Compound (1)
- Compound (A-7) (344 mg), Compound (A) (558 mg), 85% phosphoric acid aqueous solution (69 mg), and ethylene glycol (5 ml) were placed in an eggplant flask. It set to the microwave irradiation apparatus which attached the reflux condenser, and was irradiated with the microwave for 30 minutes in argon atmosphere. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 31%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 7 Synthesis of Compound (1) Compound (A-3) (369 mg), Compound (A) (558 mg), 85% phosphoric acid aqueous solution (69 mg), and ethylene glycol (5 ml) were placed in an eggplant flask. It set to the microwave irradiation apparatus which attached the reflux condenser, and was irradiated with the microwave for 30 minutes in argon atmosphere. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 17%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 8 Synthesis of Compound (1)
- Compound (A-7) (344 mg) and compound (A) (558 mg) were added to the reaction system at 250 ° C. (sand bath temperature) in an argon atmosphere without adding a solvent. For 17 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 80%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 9 Synthesis of Compound (1)
- Compound (A-7) (344 mg) and Compound (A) (558 mg) were added at 250 ° C. (sand bath temperature) under an argon atmosphere without adding a solvent to the reaction system. For 7 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (1). The isolated yield of compound (1) was 55%. The obtained compound (1) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 10 Synthesis of Compound (2) Compound (A-7) (344 mg), Compound (B) (738 mg), and ethylene glycol (5 ml) were added at 180 ° C. (oil bath temperature) for 15 hours in an argon atmosphere. The reaction was heated. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (2). The isolated yield of compound (2) was 25%. The obtained compound (2) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 11 Synthesis of Compound (3)
- Compound (A-7) (172 mg), Compound (C) (396 mg), and ethylene glycol (2.5 ml) were added at 180 ° C. (oil bath temperature) under an argon atmosphere. The reaction was heated for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (3). The isolated yield of compound (3) was 18%. The obtained compound (3) was a facial product, and no meridional product was detected in 1 H-NMR.
- Example 12 Synthesis of Compound (3) Compound (A-7) (172 mg), Compound (C) (396 mg), and ethylene glycol (2.5 ml) were added at 210 ° C. (oil bath temperature) under an argon atmosphere. The reaction was heated for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (3). The isolated yield of compound (3) was 22%. The obtained compound (3) was a facial product, and no meridional product was detected in 1 H-NMR.
- Example 13 Synthesis of Compound (3)
- Compound (A-7) (172 mg) and compound (C) (396 mg) were added to the reaction system at 250 ° C. (sand bath temperature) in an argon atmosphere without adding a solvent. The reaction was conducted for 17 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (3). The isolated yield of compound (3) was 63%. The obtained compound (3) was a facial product, and no meridional product was detected in 1 H-NMR.
- Example 14 Synthesis of Compound (3)
- Compound (A-7) (172 mg), Compound (C) (396 mg), and tridecane (2.5 ml) were added in an argon atmosphere at 250 ° C. (sand bath temperature). The reaction was heated for an hour. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (3). The isolated yield of compound (3) was 27%. The obtained compound (3) was a facial product, and no meridional product was detected in 1 H-NMR.
- Example 15 Synthesis of Compound (4)
- Compound (A-7) (115 mg), Compound (D) (298 mg), and ethylene glycol (2.5 ml) were added at 180 ° C. (oil bath temperature) under an argon atmosphere. The reaction was heated for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (4). The isolated yield of compound (4) was 15%. The obtained compound (4) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 16 Synthesis of Compound (4)
- Compound (A-7) (115 mg), Compound (D) (298 mg), and ethylene glycol (2.5 ml) were added at 210 ° C. (oil bath temperature) under an argon atmosphere. The reaction was heated for 15 hours. After cooling the reaction mixture to room temperature, the precipitated solid was washed with methanol. The compound was identified using 1 H-NMR and confirmed to be compound (4). The isolated yield of compound (4) was 30%. The obtained compound (4) was a facial product, and no meridional product was detected by 1 H-NMR.
- Example 17 Synthesis of Compound (5) and Compound (6)
- Compound (A-7) (344 mg) and compound (E) (659 mg) were added in a reaction system under an argon atmosphere without adding a solvent.
- the reaction was conducted at 15 ° C. (sand bath temperature) for 15 hours.
- the reaction mixture was cooled to room temperature, dichloromethane (5 ml) was added, and the mixture was filtered through a celite layer to remove the precipitate.
- the obtained orange filtrate was concentrated and the precipitated solid was purified by silica gel chromatography (eluent: mixed solvent of dichloromethane-hexane).
- the compound was identified using 1 H-NMR and confirmed to be compound (5) and compound (6).
- the isolated yield of compound (5) was 27%.
- the isolated yield of compound (6) was 60%.
- the obtained compound (5) was a facial product, and no meridional product was detected by 1 H-NMR.
- the compound was identified using 1 H-NMR and confirmed to be compound (5) and compound (6).
- the isolated yield of compound (5) was 15%.
- the isolated yield of compound (6) was 50%.
- the obtained compound (5) was a facial product, and no meridional product was detected by 1 H-NMR.
- thermal stability of each organic iridium raw material was evaluated using a TG-DTA simultaneous measurement apparatus.
- the rate of temperature increase was set to 5 ° C./min, the temperature was raised at normal pressure under a nitrogen gas stream (200 ml / min), and the 5% weight loss temperature was measured.
- the measurement results are shown in Table 1.
- the 5% weight loss temperatures of the examples (A-3) and (A-7) are 9 ° C. and 41 ° C. lower than the Ir (acac) 3 of the comparative example, respectively. It was revealed. This result suggests that the ⁇ -diketone ligands of (A-3) and (A-7) are eliminated at a temperature lower than that of Ir (acac) 3 .
- the iridium raw material represented by the general formula (1) of the present invention is easily released from the ⁇ -diketone ligand at a temperature lower than that of Ir (acac) 3, and the iridium raw material represented by the general formula (1) of the present invention is used.
- the cyclometalated iridium complex can be synthesized with a good yield under mild conditions.
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Abstract
Description
化合物(A-7)(344mg)、化合物(A)(558mg)、及びエチレングリコール(30ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は22%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(95mg)、化合物(A)(158mg)、及びエチレングリコール(8.5ml)をアルゴン雰囲気下、140℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は9%であった。尚、得られた化合物(1)はフェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)、化合物(A)(558mg)、及び1,3-プロパンジオール(5ml)をアルゴン雰囲気下、190℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は35%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-3)(369mg)、化合物(A)(558mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は7%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(98mg)、化合物(A)(186mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。化合物(1)は全く得られなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(98mg)、化合物(A)(186mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、140℃(オイルバス温度)で15時間加熱反応した。化合物(1)は全く得られなかった。
Ir(DPM)3(71mg)、化合物(A)(93mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。化合物(1)は全く得られなかった。
化合物(A-7)(344mg)、化合物(A)(558mg)、リン酸85%水溶液(69mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は36%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(98mg)、化合物(A)(186mg)、リン酸85%水溶液(69mg)、及びエチレングリコール(10ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は12%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)、化合物(A)(558mg)、リン酸85%水溶液(69mg)、及びエチレングリコール(5ml)をナスフラスコに入れ、還流冷却管を取り付けたマイクロ波照射装置にセッティングし、アルゴン雰囲気下、マイクロ波を30分間照射した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は31%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-3)(369mg)、化合物(A)(558mg)、リン酸85%水溶液(69mg)、及びエチレングリコール(5ml)をナスフラスコに入れ、還流冷却管を取り付けたマイクロ波照射装置にセッティングし、アルゴン雰囲気下、マイクロ波を30分間照射した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は17%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(294mg)、化合物(A)(558mg)、リン酸85%水溶液(69mg)、及びエチレングリコール(5ml)をナスフラスコに入れ、還流冷却管を取り付けたマイクロ波照射装置にセッティングし、アルゴン雰囲気下、マイクロ波を30分間照射した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は8%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)と化合物(A)(558mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は80%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)と化合物(A)(558mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で7時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は55%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(294mg)と化合物(A)(558mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は57%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(294mg)と化合物(A)(558mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で7時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(1)であることを確認した。化合物(1)の単離収率は30%であった。尚、得られた化合物(1)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)、化合物(B)(738mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(2)であることを確認した。化合物(2)の単離収率は25%であった。尚、得られた化合物(2)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(294mg)、化合物(B)(738mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(2)であることを確認した。化合物(2)の単離収率は8%であった。尚、得られた化合物(2)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(172mg)、化合物(C)(396mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は18%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(147mg)、化合物(C)(396mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。化合物(3)は全く得られなかった。
Ir(DPM)3(71mg)、化合物(C)(132mg)、及びエチレングリコール(5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。化合物(3)は全く得られなかった。
化合物(A-7)(172mg)、化合物(C)(396mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、210℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は22%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(147mg)、化合物(C)(396mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、210℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は2%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(172mg)と化合物(C)(396mg)を反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は63%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(147mg)と化合物(C)(396mg)を反応系に溶媒を添加せず、アルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は16%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(172mg)、化合物(C)(396mg)、及びトリデカン(2.5ml)をアルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は27%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(147mg)、化合物(C)(396mg)、及びトリデカン(2.5ml)をアルゴン雰囲気下、250℃(サンドバス温度)で17時間加熱反応させた。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(3)であることを確認した。化合物(3)の単離収率は3%であった。尚、得られた化合物(3)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(115mg)、化合物(D)(298mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(4)であることを確認した。化合物(4)の単離収率は15%であった。尚、得られた化合物(4)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(98mg)、化合物(D)(298mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、180℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(4)であることを確認した。化合物(4)の単離収率は0.5%であった。尚、得られた化合物(4)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(115mg)、化合物(D)(298mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、210℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(4)であることを確認した。化合物(4)の単離収率は30%であった。尚、得られた化合物(4)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(98mg)、化合物(D)(298mg)、及びエチレングリコール(2.5ml)をアルゴン雰囲気下、210℃(オイルバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、析出した固体をメタノールで洗浄した。化合物の同定は1H-NMRを用いて行い、化合物(4)であることを確認した。化合物(4)の単離収率は10%であった。尚、得られた化合物(4)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
化合物(A-7)(344mg)と、化合物(E)(659mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、270℃(サンドバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、ジクロロメタン(5ml)を加え、セライト層を通してろ過を行い、沈殿物を取り除いた。得られたオレンジ色のろ液を濃縮し析出した固体をシリカゲルクロマトグラフィー(溶離液:ジクロロメタン-ヘキサンの混合溶媒)で精製した。化合物の同定は1H-NMRを用いて行い、化合物(5)と化合物(6)であることを確認した。化合物(5)の単離収率は27%であった。化合物(6)の単離収率は60%であった。尚、得られた化合物(5)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
トリス(2,4-ペンタンジオナト)イリジウム(III)(294mg)と、化合物(E)(659mg)を、反応系に溶媒を添加せず、アルゴン雰囲気下、270℃(サンドバス温度)で15時間加熱反応した。反応混合物を室温まで冷却後、ジクロロメタン(5ml)を加え、セライト層を通してろ過を行い、沈殿物を取り除いた。得られたオレンジ色のろ液を濃縮し析出した固体をシリカゲルクロマトグラフィー(溶離液:ジクロロメタン-ヘキサンの混合溶媒)で精製した。化合物の同定は1H-NMRを用いて行い、化合物(5)と化合物(6)であることを確認した。化合物(5)の単離収率は15%であった。化合物(6)の単離収率は50%であった。尚、得られた化合物(5)は、フェイシャル体であり、1H-NMRにおいてメリジオナル体は検出されなかった。
Claims (11)
- Ra及びRbは、いずれも脂肪族炭化水素基である請求項1に記載のシクロメタル化イリジウム錯体の原料。
- Ra及びRbは、いずれも直鎖状又は分岐鎖状炭化水素基である請求項1又は請求項2に記載のシクロメタル化イリジウム錯体の原料。
- Ra及びRbは、いずれも炭素数1~20である請求項1~3のいずれかに記載のシクロメタル化イリジウム錯体の原料。
- Rcが水素原子である請求項1~4のいずれかに記載のシクロメタル化イリジウム錯体の原料。
- β-ジケトンは、5-メチル-2,4-ヘキサンジオン、又は、2,4-オクタンジオンである請求項1~請求項5のいずれかに記載のシクロメタル化イリジウム錯体の原料。
- 有機イリジウム材料が、幾何異性体であるフェイシャル体とメリジオナル体との混合物からなり、いずれか一方の幾何異性体が0.01モル%以上含まれる請求項1~6のいずれかに記載のシクロメタル化イリジウム錯体の原料。
- 有機イリジウム材料からなるシクロメタル化イリジウム錯体の原料と、イリジウム‐炭素結合を形成しうる芳香族複素環2座配位子と、を反応させてシクロメタル化イリジウム錯体を製造する方法において、
前記原料として請求項1~7のいずれかに記載された有機イリジウム材料を用いるシクロメタル化イリジウム錯体の製造方法。 - 原料と芳香族複素環2座配位子とを無溶媒下で反応させる請求項8又は請求項9に記載のシクロメタル化イリジウム錯体の製造方法。
- 原料と芳香族複素環2座配位子とをルイス酸の非存在下で反応させる請求項8~請求項10のいずれかに記載のシクロメタル化イリジウム錯体の製造方法。
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WO2017221847A1 (ja) * | 2016-06-24 | 2017-12-28 | 国立研究開発法人産業技術総合研究所 | イリジウム化合物及び該イリジウム化合物を用いたイリジウム錯体の製造方法 |
WO2017221848A1 (ja) * | 2016-06-24 | 2017-12-28 | 国立研究開発法人産業技術総合研究所 | ハロゲン架橋イリジウムダイマーの製造方法 |
WO2017221849A1 (ja) * | 2016-06-24 | 2017-12-28 | 国立研究開発法人産業技術総合研究所 | シクロメタル化イリジウム錯体の製造方法、及び、当該方法に好適に用いられる新規なイリジウム化合物 |
WO2018079275A1 (ja) * | 2016-10-24 | 2018-05-03 | 国立研究開発法人産業技術総合研究所 | シクロメタル化イリジウム錯体の製造方法、及び、有機イリジウム材料からなるシクロメタル化イリジウム錯体の前駆体 |
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US10053479B2 (en) | 2018-08-21 |
CN106164033B (zh) | 2019-04-19 |
CN106164033A (zh) | 2016-11-23 |
DE112014006141T5 (de) | 2016-10-06 |
JPWO2015104961A1 (ja) | 2017-03-23 |
TW201529591A (zh) | 2015-08-01 |
KR101833656B1 (ko) | 2018-02-28 |
US20160326198A1 (en) | 2016-11-10 |
TWI614258B (zh) | 2018-02-11 |
JP6206887B2 (ja) | 2017-10-04 |
KR20160098398A (ko) | 2016-08-18 |
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