WO2014050982A1 - 新規なアミン化合物及びその用途 - Google Patents
新規なアミン化合物及びその用途 Download PDFInfo
- Publication number
- WO2014050982A1 WO2014050982A1 PCT/JP2013/076097 JP2013076097W WO2014050982A1 WO 2014050982 A1 WO2014050982 A1 WO 2014050982A1 JP 2013076097 W JP2013076097 W JP 2013076097W WO 2014050982 A1 WO2014050982 A1 WO 2014050982A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mmol
- compound
- amine compound
- dibenzothienyl
- Prior art date
Links
- -1 amine compound Chemical class 0.000 title claims abstract description 202
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 32
- 230000005525 hole transport Effects 0.000 claims abstract description 27
- 125000001424 substituent group Chemical group 0.000 claims abstract description 22
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 4
- 125000004431 deuterium atom Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 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 claims description 8
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 7
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 26
- 150000001875 compounds Chemical class 0.000 description 114
- 239000010410 layer Substances 0.000 description 61
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- 230000015572 biosynthetic process Effects 0.000 description 49
- 238000003786 synthesis reaction Methods 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 238000005160 1H NMR spectroscopy Methods 0.000 description 45
- 239000012044 organic layer Substances 0.000 description 44
- 238000000434 field desorption mass spectrometry Methods 0.000 description 43
- 238000005259 measurement Methods 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 38
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 229940078552 o-xylene Drugs 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 238000001816 cooling Methods 0.000 description 22
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 22
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 18
- SJOPCGRHSQILOP-UHFFFAOYSA-N 2-chloro-9-dibenzothiophen-2-ylcarbazole Chemical compound ClC1=CC=2N(C3=CC=CC=C3C2C=C1)C1=CC2=C(SC3=C2C=CC=C3)C=C1 SJOPCGRHSQILOP-UHFFFAOYSA-N 0.000 description 17
- 239000012046 mixed solvent Substances 0.000 description 17
- 238000010898 silica gel chromatography Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000001914 filtration 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
- 238000001953 recrystallisation Methods 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- IUCHFMLSSJMAMR-UHFFFAOYSA-N 2-chloro-9-dibenzofuran-2-ylcarbazole Chemical compound ClC1=CC=2N(C3=CC=CC=C3C2C=C1)C1=CC2=C(OC3=C2C=CC=C3)C=C1 IUCHFMLSSJMAMR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 3
- WDGWXEMQTQVWAC-UHFFFAOYSA-N 2-chloro-9-dibenzothiophen-2-yl-6-phenylcarbazole Chemical compound ClC1=CC=2N(C3=CC=C(C=C3C2C=C1)C1=CC=CC=C1)C1=CC2=C(SC3=C2C=CC=C3)C=C1 WDGWXEMQTQVWAC-UHFFFAOYSA-N 0.000 description 3
- FJRZSUVSIYAEIA-UHFFFAOYSA-N 3,6-dibromo-2-chloro-9-dibenzothiophen-2-ylcarbazole Chemical compound ClC1=CC=2N(C3=CC=C(C=C3C2C=C1Br)Br)C1=CC2=C(SC3=C2C=CC=C3)C=C1 FJRZSUVSIYAEIA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJICRIUYZZESMW-UHFFFAOYSA-N 2-bromodibenzothiophene Chemical compound C1=CC=C2C3=CC(Br)=CC=C3SC2=C1 IJICRIUYZZESMW-UHFFFAOYSA-N 0.000 description 2
- LOQQFCPPDBFFSO-UHFFFAOYSA-N 2-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Cl)C=C3NC2=C1 LOQQFCPPDBFFSO-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- 229930184652 p-Terphenyl Natural products 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- CRJISNQTZDMKQD-UHFFFAOYSA-N 2-bromodibenzofuran Chemical compound C1=CC=C2C3=CC(Br)=CC=C3OC2=C1 CRJISNQTZDMKQD-UHFFFAOYSA-N 0.000 description 1
- QXTMKTSSQSCSBL-UHFFFAOYSA-N 2-chloro-6-phenyl-9H-carbazole Chemical compound ClC1=CC=2NC3=CC=C(C=C3C2C=C1)C1=CC=CC=C1 QXTMKTSSQSCSBL-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- LTGCSADVYJFGJO-UHFFFAOYSA-N 3-bromo-9-dibenzofuran-2-ylcarbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=C(OC=2C3=CC=CC=2)C3=C1 LTGCSADVYJFGJO-UHFFFAOYSA-N 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- RTVGVLGMPQMGNB-UHFFFAOYSA-N 4-carbazol-9-yl-n-phenylaniline Chemical compound C=1C=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=CC=1NC1=CC=CC=C1 RTVGVLGMPQMGNB-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
- IGLKULAEHPBIJL-UHFFFAOYSA-N 9h-carbazol-2-amine Chemical class C1=CC=C2C3=CC=C(N)C=C3NC2=C1 IGLKULAEHPBIJL-UHFFFAOYSA-N 0.000 description 1
- LRSYZHFYNDZXMU-UHFFFAOYSA-N 9h-carbazol-3-amine Chemical class C1=CC=C2C3=CC(N)=CC=C3NC2=C1 LRSYZHFYNDZXMU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VZSNNUDOANMGNX-UHFFFAOYSA-K aluminum;4-phenylphenolate Chemical compound [Al+3].C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC([O-])=CC=C1C1=CC=CC=C1 VZSNNUDOANMGNX-UHFFFAOYSA-K 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CYDMPPUSIGLPPK-UHFFFAOYSA-N c(cc1)ccc1N(c(cc1)cc(c2ccccc22)c1[n]2-c1ccc2[o]c3ccccc3c2c1)c(cc1c2ccccc22)ccc1[n]2-c(cc1)cc2c1[o]c1ccccc21 Chemical compound c(cc1)ccc1N(c(cc1)cc(c2ccccc22)c1[n]2-c1ccc2[o]c3ccccc3c2c1)c(cc1c2ccccc22)ccc1[n]2-c(cc1)cc2c1[o]c1ccccc21 CYDMPPUSIGLPPK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- IABICDIEOYDAFF-UHFFFAOYSA-N n-phenyldibenzofuran-2-amine Chemical compound C=1C=C2OC3=CC=CC=C3C2=CC=1NC1=CC=CC=C1 IABICDIEOYDAFF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-BJUDXGSMSA-N palladium-105 Chemical compound [105Pd] KDLHZDBZIXYQEI-BJUDXGSMSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Definitions
- the present invention relates to a novel 9-dibenzothienyl- or 9-dibenzofuranyl-2-aminocarbazole compound and an organic EL device using the same.
- An organic EL element is a surface-emitting element in which an organic thin film is held between a pair of electrodes, and has features such as a thin and light weight, a high viewing angle, and a high-speed response, and is expected to be applied to various display elements. . Recently, some practical applications such as mobile phone displays have begun.
- the organic EL element uses light emitted when holes injected from the anode and electrons injected from the cathode are recombined in the light emitting layer, and the structure thereof is a hole transport layer, a light emitting layer.
- a multi-layer laminate type in which an electron transport layer and the like are laminated is the mainstream.
- the charge transport layer such as the hole transport layer and the electron transport layer does not emit light by itself, but facilitates the injection of charges into the light emitting layer, and the charge injected into the light emitting layer or the light emitting layer. It plays the role of confining the energy of the generated excitons. Therefore, the charge transport layer plays a very important role in lowering the driving voltage and improving the light emission efficiency of the organic EL element.
- an amine compound having an appropriate ionization potential and hole transport ability is used as the material for the hole transport layer.
- an amine compound having an appropriate ionization potential and hole transport ability is used.
- 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl is used.
- NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
- the driving voltage, light emission efficiency, and durability of an element using NPD as a hole transport layer material are not sufficiently good, and development of a new material is required.
- organic EL devices using a phosphorescent material for the light emitting layer have been developed, and a material for a hole transport layer having a high triplet level is required for an element using phosphorescent light emission. .
- NPD is not sufficient from the point of triplet level, and for example, it has been reported that the organic EL element in which a phosphorescent
- the present invention has a novel 2-aminocarbazole compound that significantly improves the lifetime of an organic EL device, and a long lifetime using the novel 2-aminocarbazole compound, as compared with a conventionally known 2-aminocarbazole compound. Another object is to provide an organic EL element.
- the present inventors have found a novel amine compound represented by the following general formula (1) having a 2-dibenzofuranyl group or a 2-dibenzothienyl group at the 9-position of the carbazole ring.
- the present invention has been completed by using an amine compound.
- the gist of the present invention is as follows.
- (X represents a sulfur atom or an oxygen atom.
- R 1 to R 10 each independently represents a hydrogen atom, a deuterium atom, or a phenyl group.
- Ar 1 and Ar 2 each independently represent a carbon number. 6-18 aromatic hydrocarbon groups, dibenzothienyl groups or dibenzofuranyl groups, each independently from a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group or a 9-carbazolyl group May have a substituent.
- Ar 1 and Ar 2 are each independently A phenyl group optionally having a substituent selected from the group consisting of a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group and a 9-carbazolyl group; A biphenylyl group optionally having a substituent consisting of a methyl group or a methoxy group, A terphenyl group optionally having a substituent consisting of a methyl group or a methoxy group, A 9,9-dimethyl-9H-fluorenyl group optionally having a substituent consisting of a methyl group or a methoxy group, A dibenzothienyl group optionally having a substituent consisting of a methyl group or a methoxy group, Or the amine compound of any one of said (1) thru
- Ar 1 and Ar 2 are each independently a phenyl group, p-tolyl group, p-methoxyphenyl group, 4-biphenylyl group, p-terphenyl-4-yl group, m-terphenyl- 4-yl group, 9,9-dimethylfluoren-2-yl group, dibenzothiophen-2-yl group, dibenzofuran-2-yl group, 4- (dibenzothiophen-2-yl) phenyl group, 4- (dibenzothiophene)
- (6) The amine compound according to any one of (1) to (5), wherein X is a sulfur atom.
- a light emitting layer comprising the amine compound according to any one of (1) to (7) above.
- An organic EL device comprising the amine compound according to any one of (1) to (7) above in at least one of a light emitting layer, a hole transport layer, and a hole injection layer.
- the organic EL device using the amine compound of the present invention is remarkably superior in device life as compared with a conventionally known organic EL device using a 2-aminocarbazole compound.
- the organic EL element can have a longer life, a lower driving voltage, and a higher luminous efficiency than NPD which is a conventionally known hole transport material.
- the amine compound of the present invention can be used as an organic EL material having excellent durability. Therefore, according to the present invention, an organic EL element with low power consumption and excellent element lifetime can be provided.
- X represents an oxygen atom or a sulfur atom. Note that X is preferably a sulfur atom in terms of hole transport properties.
- R 1 to R 10 each independently represents a hydrogen atom, a deuterium atom, or a phenyl group.
- R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , and R 10 are hydrogen atoms. More preferably. R 1 to R 10 are particularly preferably hydrogen atoms in terms of triplet levels, hole transport properties, and availability of raw materials.
- Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms, a dibenzothienyl group, or a dibenzofuranyl group, These may each independently have a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group, or a 9-carbazolyl group.
- the aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar 1 and Ar 2 is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a benzofuryl group.
- Olenyl group (these may each independently have a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group, or a 9-carbazolyl group, and the number of substituents is not particularly limited. ) And the like.
- a phenyl group optionally having a substituent selected from the group consisting of a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group and a 9-carbazolyl group, a methyl group, 9,9-dimethyl- which may have a biphenylyl group which may have a group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group, or a methyl group or a methoxy group
- a 9H-fluorenyl group is preferred.
- the bonding position of the dibenzothienyl group or dibenzofuranyl group in Ar 1 and Ar 2 is not particularly limited, but is preferably the 2-position of the dibenzothienyl group or dibenzofuranyl group. Further, the dibenzothienyl group and dibenzofuranyl group may each independently have a methyl group, a methoxy group, a dibenzothienyl group, a dibenzofuranyl group, or a 9-carbazolyl group. The position of the substituent to which the substituent is bonded and the number of substituents are not particularly limited.
- Ar 1 and Ar 2 include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3, 4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl Group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl Group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 2,
- Ar 1 and Ar 2 in the amine compound represented by the general formula (1) of the present invention are each independently a methyl group, a methoxy group, or a dibenzothienyl group. Having a phenyl group, a methyl group or a methoxy group optionally having a substituent selected from the group consisting of a dibenzofuranyl group and a 9-carbazolyl group, having a methyl group or a methoxy group.
- a terphenyl group optionally having a methyl group or a methoxy group, a 9,9-dimethyl-9H-fluorenyl group, a dibenzothienyl group optionally having a methyl group or a methoxy group, or It is preferably a dibenzofuranyl group which may have a methyl group or a methoxy group.
- Ar 1 and Ar 2 in the amine compound represented by the general formula (1) of the present invention each independently have a substituent selected from the group consisting of a methyl group, a methoxy group, and a 9-carbazolyl group.
- the compound (A1), the compound (A2), the compound (A3), the compound (A8), the compound (A12), the compound (A13), and the compound in terms of the triplet level and the hole transport property is more preferable, and compound (A1), compound (A2), compound (A3), compound (A8), compound (A12), compound (A13), compound (A16), compound ( A21), Compound (A22), Compound (A24), Compound (A25), Compound (A36), Compound (A46), Compound (A47), Compound (B4) or compound (B8) is more preferable, and compound (A1), compound (A2), compound (A3), compound (A8), compound (A12), compound (A13), compound (A16), compound ( A21), Compound (A22), Compound (A24), Compound (A25), Compound (A36), Compound (A46), Compound (A47), Compound (B4), or Compound ( 8) it is more preferred.
- the amine compound represented by the general formula (1) is, for example, a 9H-carbazole compound halogenated at the 2-position as a raw material, and a known method (Tetrahedron Letters, 1998, Vol. 39, page 2367). Can be synthesized. Specifically, it can be synthesized by the following route.
- a 9H-carbazole compound halogenated at the 2-position represented by the general formula (2) and a compound having a halogen atom represented by the general formula (3) are treated with a copper catalyst or a palladium catalyst in the presence of a base.
- a 2-halogenated-9-substituted carbazole compound represented by the general formula (4) is treated with a copper catalyst or in the presence of a base.
- the obtained 2-halogenated-9-substituted carbazole compound represented by the general formula (4) and the secondary amine compound represented by the general formula (5) are reacted with a copper catalyst or in the presence of a base. The reaction is carried out using a palladium catalyst.
- Ar 1 , Ar 2 , R 1 to R 10 , and X represent the same definitions as in the general formula (1).
- a and B each independently represent a halogen atom (iodine, bromine, chlorine, or fluorine).
- the compound represented by the general formula (2) can be synthesized based on a generally known method (for example, described in JP2011-1349A).
- the compound represented by the general formula (3) can be synthesized based on a generally known method (for example, described in Journal of Heterocyclic Chemistry, 1987, Vol. 24, page 749).
- the compound represented by the general formula (5) can be a commercially available compound or can be synthesized based on a generally known method.
- the amine compound represented by the general formula (1) of the present invention can be used as a material for a light emitting layer, a hole transport layer, or a hole injection layer of an organic EL device.
- the amine compound represented by the general formula (1) has high purity in terms of hole transport characteristics and device lifetime.
- the amine compound represented by the general formula (1) is any one of a hole injection layer, a hole transport layer, and a light emitting layer in an element using not only a fluorescent light emitting material but also a phosphorescent light emitting material as a light emitting layer.
- a hole injection layer a hole transport layer
- a light emitting layer in an element using not only a fluorescent light emitting material but also a phosphorescent light emitting material as a light emitting layer.
- One or more layers can be preferably used.
- the amine compound represented by the general formula (1) when used as a material for the hole injection layer and / or the hole transport layer of the organic EL device, a known fluorescence that has been conventionally used is used. Alternatively, a phosphorescent material can be used.
- the light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.
- two or more kinds of materials may be contained or laminated as necessary.
- oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexa
- a known electron-accepting material such as azatriphenylene may be contained or laminated.
- the amine compound represented by the general formula (1) is used as a material for the light emitting layer of the organic EL device, the amine compound is used alone, used by doping a known light emitting host material, or a known It can be used by doping with a luminescent dopant.
- a method for forming a hole injection layer, a hole transport layer, or a light emitting layer containing the amine compound represented by the general formula (1) for example, a known method such as a vacuum deposition method, a spin coating method, or a casting method is used. The method can be applied.
- the light emission characteristics of the organic EL element were evaluated by applying a direct current to the produced element and using a luminance meter of LUMINANCEMETER (BM-9) manufactured by TOPCON.
- the compound was identified by 1 H-NMR measurement and 13 C-NMR measurement.
- Synthesis Example 2 (Synthesis of 2-chloro-3,6-dibromo-9- (2-dibenzothienyl) carbazole)
- 6.2 g (16.3 mmol) of 2-chloro-9- (2-dibenzothienyl) carbazole obtained in Synthesis Example 1 was dissolved in 60 ml of dichloromethane, and 2.9 g (16.3 mmol) of NBS was dissolved. And stirred at room temperature for 30 minutes. The reaction solution was washed with pure water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
- the compound was identified by 1 H-NMR measurement and 13 C-NMR measurement.
- the compound was identified by 1 H-NMR measurement and 13 C-NMR measurement.
- the compound was identified by FDMS measurement.
- the compound was identified by FDMS and 1 H-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- Example 2 (Synthesis of Compound (A2)) In a 50 mL three-necked flask under a nitrogen stream, 2.7 g (7.0 mmol) of 2-chloro-9- (2-dibenzothienyl) carbazole obtained in Synthesis Example 1 and N- (p-tolyl) -N-biphenylamine were obtained. 2.0 g (7.7 mmol), sodium-tert-butoxide 0.94 g (9.8 mmol), o-xylene 15 mL, palladium acetate 22 mg (0.09 mmol), and tri (tert-butyl) phosphine 69 mg (0.34 mmol) ) Was added and stirred at 140 ° C. for 18 hours.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS and 1 H-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- Example 6 (Synthesis of Compound (A13)) In a 50 mL three-necked flask under a nitrogen stream, 2.9 g (7.5 mmol) of 2-chloro-9- (2-dibenzothienyl) carbazole obtained in Synthesis Example 1 and N, N-bis (p-terphenyl) amine were obtained. 3.5 g (7.5 mmol), sodium-tert-butoxide 1.0 g (10.6 mmol), o-xylene 20 mL, palladium acetate 35 mg (0.15 mmol), and tri (tert-butyl) phosphine 112 mg (0.55 mmol) ) Was added and stirred at 140 ° C. for 6 hours.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- Fluoren-2-yl) amine 4.0 g (11.0 mmol), sodium-tert-butoxide 1.4 g (15.4 mmol), o-xylene 20 mL, palladium acetate 74 mg (0.33 mmol), and tri (tert-butyl) ) 234 mg (1.15 mmol) of phosphine was added and stirred at 140 ° C. for 12 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the organic layer was washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
- the compound was identified by FDMS and 1 H-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- the compound was identified by FDMS and 1 H-NMR measurement.
- the compound was identified by FDMS, 1 H-NMR measurement, and 13 C-NMR measurement.
- Example 17 (Synthesis of Compound (B4)) In a 50 mL three-necked flask under nitrogen flow, 1.9 g (5.2 mmol) of 2-chloro-9- (2-dibenzofuranyl) carbazole obtained in Synthesis Example 5 and N-biphenyl-N- (m-terphenyl) were obtained. ) Amine 2.0 g (5.2 mmol), sodium-tert-butoxide 0.7 g (7.3 mmol), o-xylene 10 mL, palladium acetate 35 mg (0.15 mmol), and tri (tert-butyl) phosphine 110 mg (0 0.5 mmol) was added and stirred at 140 ° C. for 5 hours.
- the compound was identified by FDMS and 1 H-NMR measurement.
- the compound was identified by FDMS and 1 H-NMR measurement.
- Example 19 (Element evaluation of compound (A1))
- BAlq bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum
- Alq 3 Tris (8-quinolinolato) aluminum
- lithium fluoride was deposited as an electron injection layer by 1 nm at a deposition rate of 0.01 nm / second
- aluminum was deposited by 100 nm at a deposition rate of 0.25 nm / second to form a cathode.
- Examples 20 to 36 (Element evaluation) Instead of the compound (A1), the compounds (A2), (A3), (A8), (A12), (A13), (A16), (A21), (A22), (A24), (A25), ( An organic EL device was produced in the same manner as in Example 19 except that the procedure was changed to A28), (A32), (A36), (A46), (A47), (B4), or (B8).
- Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm 2 was applied, and the luminance half time when a current of 6.25 mA / cm 2 was applied.
- Comparative Example 2 An organic EL device was produced in the same manner as in Example 19 except that the compound (A1) was changed to NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm 2 was applied, and the luminance half time when a current of 6.25 mA / cm 2 was applied. Comparative Example 3 (Device Evaluation of Compound (b)) An organic EL device was produced in the same manner as in Example 19 except that the compound (A1) was changed to the following compound (b). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm 2 was applied, and the luminance half time when a current of 6.25 mA / cm 2 was applied.
- Reference Example 1 (Device evaluation of compound (a)) An organic EL device was produced in the same manner as in Example 19 except that the compound (A1) was changed to the following compound (a). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm 2 was applied, and the luminance half time when a current of 6.25 mA / cm 2 was applied.
- the amine compound of this invention can be utilized for manufacture of an organic EL element.
- the specification, claims, and abstract of Japanese Patent Application No. 2012-214844 filed on September 27, 2012 and Japanese Patent Application No. 2013-119485 filed on June 6, 2013 are as follows. The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.
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Abstract
Description
また、ジベンゾチオフェンやジベンゾフランとカルバゾールを組み合わせた3-アミノカルバゾール化合物も開示されている(例えば、特許文献3参照。)。
(1)一般式(1)で表されることを特徴とするアミン化合物。
(3)R1~R10が水素原子である上記(1)又は(2)に記載のアミン化合物。
(4)Ar1及びAr2が、各々独立して、
メチル基、メトキシ基、ジベンゾチエニル基、ジベンゾフラニル基及び9-カルバゾリル基からなる群から選ばれる置換基を有していてもよいフェニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいビフェニリル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいターフェニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよい9,9-ジメチル-9H-フルオレニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいジベンゾチエニル基、
又は、メチル基若しくはメトキシ基からなる置換基を有していてもよいジベンゾフラニル基、である上記(1)乃至(3)のいずれか1項に記載のアミン化合物。
(6)Xが、硫黄原子である上記(1)乃至(5)のいずれか1項に記載のアミン化合物。
(9)上記(1)乃至(7)のいずれか1項に記載のアミン化合物を含む正孔注入層。
(10)上記(1)乃至(7)のいずれか1項に記載のアミン化合物を含む発光層。
(11)上記(1)乃至(7)のいずれか1項に記載のアミン化合物を、発光層、正孔輸送層又は正孔注入層の少なくともいずれかに含む有機EL素子。
(12)上記(1)乃至(7)のいずれか1項に記載のアミン化合物を正孔輸送層に含む上記(11)に記載の有機EL素子。
従って、本発明によれば、消費電力が低く、素子寿命に優れる有機EL素子を提供することができる。
一般式(2)で表される化合物は、一般公知の方法(例えば、特開2011-1349に記載)に基づいて合成することができる。
窒素気流下、300mLの三口フラスコに、2-クロロカルバゾール 15.0g(74.3mmol)、2-ブロモジベンゾチオフェン 19.5g(74.3mmol)、炭酸カリウム 15.4g(111.5mmol)、o-キシレン 100mL、酢酸パラジウム 250mg(1.1mmol)、及びトリ(tert-ブチル)ホスフィン 780mg(3.9mmol)を添加して140℃で14時間攪拌した。室温まで冷却後、純水 80mLを加え、有機層を分離した。有機層を水、及び飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:3))で精製し、2-クロロ-9-(2-ジベンゾチエニル)カルバゾールの白色粉末を14.8g(43.7mmol)単離した(収率62%)。
13C-NMR(CDCl3)δ(ppm);141.37,141.17,139.78,138.44,136.65,134.39,133.33,131.33,126.98,125.84,125.26,124.25,123.81,122.55,122.29,121.45,120.75,120.00,119.85,109.45,109.38
合成例2 (2-クロロ-3,6-ジブロモ-9-(2-ジベンゾチエニル)カルバゾールの合成)
200mLの三口フラスコに、合成例1で得られた2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 6.2g(16.3mmol)をジクロロメタン 60mlに溶解させ、NBS 2.9g(16.3mmol)を添加し、室温で30分攪拌した。反応液を純水及び飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:5))で精製し、2-クロロ-3,6-ジブロモ-9-(2-ジベンゾチエニル)カルバゾールの白色粉末を5.5g(10.2mmol)単離した(収率62%)。
13C-NMR(CDCl3)δ(ppm);140.50,140.14,139.79,139.00,136.71,134.15,132.45,131.72,129.24,127.14,124.87,124.48,124.32,124.01,122.76,122.56,121.41,119.65,113.06,111.02,110.95
合成例3 (2-クロロ-3,6-d2-9-(2-ジベンゾチエニル)カルバゾールの合成)
窒素気流下、200mLの三口フラスコに、合成例2で得られた2-クロロ-3,6-ジブロモ-9-(2-ジベンゾチエニル)カルバゾール 5.2g(9.7mmol)をテトラヒドロフラン 100mLに溶解させ、-78℃に冷却した。n-ブチルリチウムのヘキサン溶液(1.6M) 14.2mL(23.4mmol)を滴下し、-78℃で30分攪拌後、さらに重水 3.2g(160mmol)を滴下した。反応液を室温にした後、純水及び飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をトルエンで再結晶し、2-クロロ-3,6-d2-9-(2-ジベンゾチエニル)カルバゾールの淡黄色粉末を2.5g(6.4mmol)単離した(収率66%)。
13C-NMR(CDCl3)δ(ppm);141.37,141.16,139.75,138.44,136.62,134.37,133.31,131.22,126.65,125.69,125.27,124.23,123.79,122.52,122.25,121.42,120.58,119.99,119.85,119.70,109.39,109.32,97.49
合成例4 (2-クロロ-6-フェニル-9-(2-ジベンゾチエニル)カルバゾールの合成)
窒素気流下、50mLの三口フラスコに、2-クロロ-6-フェニルカルバゾール 4.0g(14.4mmol)、2-ブロモジベンゾチオフェン 3.7g(14.4mmol)、炭酸カリウム 3.9g(28.8mmol)、o-キシレン 20mL、酢酸パラジウム 96mg(0.43mmol)、及びトリ(tert-ブチル)ホスフィン 305mg(1.5mmol)を添加して140℃で7時間攪拌した。室温まで冷却後、純水 10mLを加え、有機層を分離した。有機層を水、及び飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、2-クロロ-6-フェニル-9-(2-ジベンゾチエニル)カルバゾールの白色粉末を5.2g(11.3mmol)単離した(収率78%)。
合成例5 (2-クロロ-9-(2-ジベンゾフラニル)カルバゾールの合成)
窒素気流下、50mLの三口フラスコに、2-クロロカルバゾール 2.8g(14.2mmol)、2-ブロモジベンゾフラン 3.5g(14.2mmol)、炭酸カリウム 3.9g(28.4mmol)、o-キシレン 17mL、酢酸パラジウム 63mg(0.28mmol)、及びトリ(tert-ブチル)ホスフィン 200mg(0.99mmol)を添加して140℃で20時間攪拌した。室温まで冷却後、純水 10mLを加え、有機層を分離した。有機層を水、及び飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:3))で精製し、2-クロロ-9-(2-ジベンゾフラニル)カルバゾールの無色粘張固体を3.8g(10.5mmol)単離した(収率74%)。
1H-NMR(CDCl3)δ(ppm);8.05(d,1H),7.92-7.98(m,2H),7.83(t,2H),7.67(d,1H),7.18-7.59(m,8H)
実施例1 (化合物(A1)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 3.4g(8.8mmol)、N-フェニル-N-ビフェニルアミン 2.3g(9.7mmol)、ナトリウム-tert-ブトキシド 1.1g(12.4mmol)、o-キシレン 20mL、酢酸パラジウム 19mg(0.08mmol)、及びトリ(tert-ブチル)ホスフィン 62mg(0.30mmol)を添加して140℃で12時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A1)の無色ガラス状固体を3.3g(5.5mmol)単離した(収率62%)。
1H-NMR(CDCl3)δ(ppm);8.17(d,1H),8.05(t,2H),7.95(dt,1H),7.92(d,1H),7.82(d,1H)7.54(dd,1H),7.51-7.08(m,20H),6.96(tt,1H)
13C-NMR(CDCl3)δ(ppm);147.43,146.95,145.91,141.61,141.10,140.10,139.69,137.73,136.44,134.45,134.30,133.77,128.72,127.16,126.78,126.23,126.10,124.93,124.12,123.61,123.00,122.98,122.44,122.23,121.30,120.59,119.82,119.34,119.03,117.99,109.12,105.79
実施例2 (化合物(A2)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 2.7g(7.0mmol)、N-(p-トリル)-N-ビフェニルアミン 2.0g(7.7mmol)、ナトリウム-tert-ブトキシド 0.94g(9.8mmol)、o-キシレン 15mL、酢酸パラジウム 22mg(0.09mmol)、及びトリ(tert-ブチル)ホスフィン 69mg(0.34mmol)を添加して140℃で18時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A2)の無色ガラス状固体を3.3g(5.5mmol)単離した(収率79%)。
1H-NMR(CDCl3)δ(ppm);8.15(d,1H),8.07-7.97(m,2H),7.93(t,2H),7.81(d,1H),7.54(dd,1H),7.49-6.98(m,20H),2.26(s,3H)
13C-NMR(CDCl3)δ(ppm);147.45,146.40,145.08,141.86,141.31,140.43,139.97,137.94,136.71,134.74,134.13,134.10,132.50,129.70,128.46,127.36,127.05,126.42,126.35,125.21,125.09,124.57,124.41,123.84,123.27,122.72,121.53,120.78,120.07,119.59,118.99,117.91,109.36,105.49,20.78
実施例3 (化合物(A3)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 3.0g(7.9mmol)、N-(p-メトキシフェニル)-N-ビフェニルアミン 2.4g(8.7mmol)、ナトリウム-tert-ブトキシド 1.0g(9.8mmol)、o-キシレン 17mL、酢酸パラジウム 35mg(0.15mmol)、及びトリ(tert-ブチル)ホスフィン 106mg(0.52mmol)を添加して140℃で10時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A3)の白色粉末を4.0g(6.5mmol)単離した(収率82%)。
1H-NMR(CDCl3)δ(ppm);8.19(d,1H),8.08-7.83(m,5H),7.56(dd,1H),7.49-7.10(m,18H),6.81(d,2H),3.74(s,3H)
13C-NMR(CDCl3)δ(ppm);156.11,147.85,146.77,142.10,141.51,140.84,140.67,140.20,138.15,136.94,134.96,134.34,133.90,128.68,127.56,127.27,127.18,126.59,126.52,125.40,125.24,124.67,124.07,123.54,122.97,122.11,121.78,120.97,120,29,119.80,118.94,117.60,114.78,109.58,105.08,55.53
実施例4 (化合物(A8)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.0g(10.4mmol)、N,N-ジビフェニルアミン 3.3g(10.4mmol)、ナトリウム-tert-ブトキシド 1.4g(14.6mmol)、o-キシレン 23mL、酢酸パラジウム 24mg(0.11mmol)、及びトリ(tert-ブチル)ホスフィン 300mg(0.37mmol)を添加して140℃で12時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(A8)の白色粉末を5.3g(7.9mmol)単離した(収率76%)。
1H-NMR(CDCl3)δ(ppm);8.50(d,1H),8.09(t,2H),7.98(d,1H),7.96(d,1H),7.84(d,1H),7.58(dd,1H),7.54-7.13(m,25H)
実施例5 (化合物(A12)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 2.9g(7.5mmol)、N-ビフェニル-N-(p-ターフェニル)アミン 3.0g(7.5mmol)、ナトリウム-tert-ブトキシド 1.0g(10.6mmol)、o-キシレン 20mL、酢酸パラジウム 35mg(0.15mmol)、及びトリ(tert-ブチル)ホスフィン 112mg(0.55mmol)を添加して140℃で4時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(A12)の淡黄色粉末を3.9g(5.2mmol)単離した(収率69%)。
1H-NMR(CDCl3)δ(ppm);8.20(d,1H),8.09(t,2H),7.99(d,1H),7.97(d,1H),7.84(d,1H),7.14-7.65(m,30H)
13C-NMR(CDCl3)δ(ppm);146.79,146.66,145.63,141.60,141.11,140.19,140.03,139.64,139.00,137.74,136.44,134.65,134.39,133.73,128.27,128.18,127.21,127.06,126.88,126.73,126.42,126.26,126.09,124.94,124.90,124.13,123.58,123.37,123.26,122.87,122.41,121.17,120.60,119.79,119.37,119.33,119.18,118.04,115.97,109.12,105.93
実施例6 (化合物(A13)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 2.9g(7.5mmol)、N,N-ビス(p-ターフェニル)アミン 3.5g(7.5mmol)、ナトリウム-tert-ブトキシド 1.0g(10.6mmol)、o-キシレン 20mL、酢酸パラジウム 35mg(0.15mmol)、及びトリ(tert-ブチル)ホスフィン 112mg(0.55mmol)を添加して140℃で6時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(A13)の淡黄色粉末を4.7g(5.7mmol)単離した(収率76%)。
1H-NMR(CDCl3)δ(ppm); 8.20(d,1H),8.09(t,2H),7.98(d,1H),7.96(d,1H),7.83(d,1H),7.19-7.65(m,34H)
13C-NMR(CDCl3)δ(ppm);146.75,145.61,141.60,141.11,140.18,139.64,139.00,138.93,137.74,136.44,134.39,134.02,133.73,128.27,127.08,126.90,126.73,126.45,126.40,124.96,124.89,124.13,123.58,123.35,122.87,122.41,121.17,120.64,119.81,119.40,119.30,119.19,118.05,109.14,105.93
実施例7 (化合物(A16)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.0g(10.4mmol)、N-ビフェニル-N-(m-ターフェニル)アミン 4.1g(10.4mmol)、ナトリウム-tert-ブトキシド 1.4g(14.6mmol)、o-キシレン 20mL、酢酸パラジウム 70mg(0.31mmol)、及びトリ(tert-ブチル)ホスフィン 221mg(1.0mmol)を添加して140℃で14時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A16)の無色ガラス状固体を5.3g(7.1mmol)単離した(収率68%)。
1H-NMR(CDCl3)δ(ppm);8.20(d,1H),8.09(t,2H),7.96(d,2H),7.82(d,1H),7.74(s,1H),7.13-7.64(m,29H)
13C-NMR(CDCl3)δ(ppm);146.86,146.69,145.65,141.60,141.20,141.09,140.72,140.61,140.05,139.63,137.72,136.44,134.61,134.50,134.37,133.73,128.62,128.24,128.18,127.32,127.21,126.83,126.73,126.26,126.11,125.16,125.10,124.95,124.89,124.13,123.58,123.29,122.87,122.39,121.15,120.62,119.79,119.30,119.19,118.09,109.12,105.97
実施例8 (化合物(A21)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 1.9g(4.9mmol)、N-フェニル-N-(9,9-ジメチルフルオレン-2-イル)アミン 1.5g(5.4mmol)、ナトリウム-tert-ブトキシド 0.66g(6.9mmol)、o-キシレン 10mL、酢酸パラジウム 11mg(0.05mmol)、及びトリ(tert-ブチル)ホスフィン 34mg(0.17mmol)を添加して140℃で18時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A21)の白色粉末を2.4g(3.7mmol)単離した(収率76%)。
1H-NMR(CDCl3)δ(ppm);8.17(d,1H),8.05(t,2H),7.90(t,1H),7.80(d,1H),7.58(dt,1H),7.52(d,1H),7.51(d,1H),7.44-6.91(m,18H),1.34(s,6H)
13C-NMR(CDCl3)δ(ppm);154.66,153.21,148.03,147.43,146.57,141.97,141.42,139.92,138.82,138.05,136.73,134.66,134.04,133.56,128.95,127.06,126.75,126.15,125.21,125.12,124.34,123.84,123.66,123.24,122.25,121.57,120.80,120.07,119.70,119.59,119.15,119.01,118.02,117.87,109.41,105.66
実施例9 (化合物(A22)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 5.0g(13.0mmol)、N-(p-トリル)-N-(9,9-ジメチルフルオレン-2-イル)アミン 4.2g(14.3mmol)、ナトリウム-tert-ブトキシド 1.7g(18.2mmol)、o-キシレン 25mL、酢酸パラジウム 58mg(0.26mmol)、及びトリ(tert-ブチル)ホスフィン 184mg(0.91mmol)を添加して140℃で16時間攪拌した。室温まで冷却後、純水を15mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A22)の淡黄色粉末を6.4g(9.9mmol)単離した(収率75%)。
1H-NMR(CDCl3)δ(ppm);8.19(d,1H),8.07(d,1H),8.02(d,1H),7.99-7.94(m,1H),7.90(d,1H),7.61-7.21(m,14H),7.06(t,6H),2.28(s,3H),1.34(s,6H)
13C-NMR(CDCl3)δ(ppm);154.26,152.87,147.34,146.50,145.12,141.68,141.10,139.65,138.59,137.71,136.43,134.41,133.81,132.84,131.89,129.34,126.74,126.41,125.71,124.98,124.69,124.05,123.99,123.53,122.99,122.42,121.91,121,81,121.25,120.39,119.93,119.71,119.43,119,21,118.76,118.37,117.38,117.00,109.07,104,80,46.33,26.67,20,48
実施例10 (化合物(A24)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.5g(11.7mmol)、N-(p-メトキシフェニル)-N-(9,9-ジメチルフルオレン-2-イル)アミン 4.0g(12.9mmol)、ナトリウム-tert-ブトキシド 1.5g(16.4mmol)、o-キシレン 25mL、酢酸パラジウム 52mg(0.23mmol)、及びトリ(tert-ブチル)ホスフィン 165mg(0.81mmol)を添加して140℃で10時間攪拌した。室温まで冷却後、純水を15mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A24)の白色粉末を6.3g(9.5mmol)単離した(収率81%)。
1H-NMR(CDCl3)δ(ppm);8.18(d,1H),8.05(dd,1H),8.09(d,1H),7.95(dd,1H),7.88(d,1H),7.82(d,1H),7.58-7.03(m,16H),6.94(dd,1H),6.80(dt,2H),3.74(s,3H),1.33(s,6H)
13C-NMR(CDCl3)δ(ppm);155.42,154.24,152.80,147.54,146.68,141.74,141.11,140.71,139.65,138.64,137.74,136.43,134.41,133.83,132.42,126.76,126.43,125.64,125.00,124.62,124.08,123.53,123.04,122,44,121.91,121.28,121.01,120.39,119.93,119.73,119.47,119.16,118.70,118.08,116.83,116.16,114.20,109.07,104.07,55.01,46.31,26.70
実施例11 (化合物(A25)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.2g(11.0mmol)、N-ビフェニル-N-(9,9-ジメチルフルオレン-2-イル)アミン 4.0g(11.0mmol)、ナトリウム-tert-ブトキシド 1.4g(15.4mmol)、o-キシレン 20mL、酢酸パラジウム 74mg(0.33mmol)、及びトリ(tert-ブチル)ホスフィン 234mg(1.15mmol)を添加して140℃で12時間攪拌した。室温まで冷却後、純水を10mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A25)の淡黄色粉末を5.2g(7.3mmol)単離した(収率66%)。
1H-NMR(CDCl3)δ(ppm);8.19(d,1H),8.04(t,2H),7.75-7.91(m,3H),6.95-7.59(m,24H),1.34(s,6H)
実施例12 (化合物(A28)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.0g(10.4mmol)、N-(2-ジベンゾチエニル)-N-フェニルアミン 3.1g(11.4mmol)、ナトリウム-tert-ブトキシド 1.4g(14.6mmol)、o-キシレン 20mL、酢酸パラジウム 46mg(0.20mmol)、及びトリ(tert-ブチル)ホスフィン 105mg(0.52mmol)を添加して140℃で15時間攪拌した。室温まで冷却後、純水を15mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A28)の無色ガラス状固体を5.9g(9.4mmol)単離した(収率90%)。
1H-NMR(CDCl3)δ(ppm);8.16(d,1H),8.01-8.10(m,2H),7.77-7.93(m,6H),7.65(d,1H),7.55(d,1H),7.09-7.46(m,14H),6.95(t,1H)
13C-NMR(CDCl3)δ(ppm);147.85,146.31,144.99,141.60,141.07,139.70,139.61,137.67,136.40,136.17,134.76,134.37,133.71,133.05,128.68,126.72,126.20,124.83,124.04,123.97,123.71,123.55,122.91,122.85,122.36,121.81,121.20,120.58,119.78,119.29,119.25,118.82,117.63,116.64,109.10,105.31
実施例13 (化合物(A32)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.0g(10.4mmol)、N-(2-ジベンゾフラニル)-N-フェニルアミン 2.9g(11.4mmol)、ナトリウム-tert-ブトキシド 1.4g(14.6mmol)、o-キシレン 20mL、酢酸パラジウム 46mg(0.20mmol)、及びトリ(tert-ブチル)ホスフィン 105mg(0.52mmol)を添加して140℃で10時間攪拌した。室温まで冷却後、純水を15mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A32)の無色ガラス状固体を5.8g(9.5mmol)単離した(収率91%)。
1H-NMR(CDCl3)δ(ppm);8.14(d,1H),7.99-8.08(m,2H),7.72-7.90(m,5H),7.48-7.55(m,2H),7.08-7.42(m,15H),6.90(t,1H)
13C-NMR(CDCl3)δ(ppm);156.27,152.19,148.23,146.71,143.09,141.64,141.05,139.61,137.65,136.42,134.39,133.77,128.64,126.73,125.05,124.85,124.78,124.68,124.02,123.66,123.55,123.00,122.39,122.21,122.12,121.35,121.20,120.53,120.29,119.79,119.26,118.53,117.27,117.01,111.83,111.22,109.10,104.85
実施例14 (化合物(A36)の合成)
窒素気流下、50mLの三口フラスコに、合成例1で得た2-クロロ-9-(2-ジベンゾチエニル)カルバゾール 4.0g(10.4mmol)、N-(4-(9-カルバゾリル)フェニル)-N-フェニルアミン 3.8g(11.4mmol)、ナトリウム-tert-ブトキシド 1.4g(14.6mmol)、o-キシレン 20mL、酢酸パラジウム 46mg(0.20mmol)、及びトリ(tert-ブチル)ホスフィン 105mg(0.52mmol)を添加して140℃で12時間攪拌した。室温まで冷却後、純水を15mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(A36)の無色ガラス状固体を5.2g(7.6mmol)単離した(収率73%)。
1H-NMR(CDCl3)δ(ppm);8.53(d,1H),8.39-8.44(m,4H),8.28(d,2H),8.15(d,1H),7.88(d,1H),7.47-7.75(m,21H),7.33(t,1H)
13C-NMR(CDCl3)δ(ppm);147.24,146.90,145.67,141.68,141.16,140.52,139.64,137.83,136.49,134.35,133.73,130.65,128.86,127.28,126.83,125.31,125.03,124.94,124.12,123.86,123.57,123.18,122.83,122.65,122.43,121.22,120.73,119.83,119.70,119.41,119.34,119.17,118.11,109.30,109.14,106.12
実施例15 (化合物(A46)の合成)
窒素気流下、50mLの三口フラスコに、合成例3で得た2-クロロ-3,6-d2-9-(2-ジベンゾチエニル)カルバゾール 3.2g(8.4mmol)、N,N-ビスビフェニルアミン 2.7g(8.4mmol)、ナトリウム-tert-ブトキシド 1.1g(11.7mmol)、o-キシレン 20mL、酢酸パラジウム 18mg(0.08mmol)、及びトリ(tert-ブチル)ホスフィン 59mg(0.29mmol)を添加して140℃で14時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(A46)の白色粉末を4.4g(6.6mmol)単離した(収率79%)。
1H-NMR(CDCl3)δ(ppm);8.26(d,1H),8.03-8.13(m,4H),7.91(d,1H),7.16-7.64(m,24H)
実施例16 (化合物(A47)の合成)
窒素気流下、50mLの三口フラスコに、合成例4で得た2-クロロ-6-フェニル-9-(2-ジベンゾチエニル)カルバゾール 5.0g(10.8mmol)、N,N-ビスビフェニルアミン 3.6g(11.4mmol)、ナトリウム-tert-ブトキシド 1.4g(15.2mmol)、o-キシレン 25mL、酢酸パラジウム 73mg(0.32mmol)、及びトリ(tert-ブチル)ホスフィン 230mg(1.14mmol)を添加して140℃で10時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(A47)の白色粉末を4.9g(6.5mmol)単離した(収率60%)。
1H-NMR(CDCl3)δ(ppm);8.29(d,1H),8.17(d,1H),8.08(d,1H),7.94(d,1H),7.91(d,1H),7.81(d,1H),7.70(d,2H),7.12-7.60(m,28H)
13C-NMR(CDCl3)δ(ppm);146.69,145.93,142.06,141.42,140.58,140.05,139.68,137.78,136.48,134.70,134.39,133.71,133.35,128.29,128.22,127.25,126.79,126.31,126.13,124.79,124.46,124.19,123.64,123.46,122.43,121.22,120.69,119.21,118.05,117.85,109.39,105.84
実施例17 (化合物(B4)の合成)
窒素気流下、50mLの三口フラスコに、合成例5で得た2-クロロ-9-(2-ジベンゾフラニル)カルバゾール 1.9g(5.2mmol)、N-ビフェニル-N-(m-ターフェニル)アミン 2.0g(5.2mmol)、ナトリウム-tert-ブトキシド 0.7g(7.3mmol)、o-キシレン 10mL、酢酸パラジウム 35mg(0.15mmol)、及びトリ(tert-ブチル)ホスフィン 110mg(0.5mmol)を添加して140℃で5時間攪拌した。室温まで冷却後、純水を5mL添加し攪拌した。水層と有機層を分液し、さらに有機層を純水と飽和塩化ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:2))で精製し、化合物(B4)の無色ガラス状固体を3.0g(4.2mmol)単離した(収率81%)。
1H-NMR(CDCl3)δ(ppm);8.04-8.12(m,3H),7.84(d,1H),7.69(d,1H),7.13-7.60(m,31H)
実施例18 (化合物(B8)の合成)
窒素気流下、50mLの三口フラスコに、合成例5で得た2-クロロ-9-(2-ジベンゾフラニル)カルバゾール 3.6g(9.7mmol)、N,N-ジビフェニルアミン 2.8g(9.7mmol)、ナトリウム-tert-ブトキシド 1.3g(13.7mmol)、o-キシレン 20mL、酢酸パラジウム 66mg(0.29mmol)、及びトリ(tert-ブチル)ホスフィン 207mg(1.0mmol)を添加して140℃で6時間攪拌した。室温まで冷却後、析出した生成物をろ取し、純水及びエタノールで洗浄した。o-キシレンで再結晶し、化合物(B8)の白色粉末を3.6g(7.0mmol)単離した(収率72%)。
1H-NMR(CDCl3);8.10(dt,1H),8.07(d,1H),8.02(d,1H),7.84(dt,1H),7.70(dd,1H),7.61-7.12(m,27H)
窒素気流下、50mLの三口フラスコに、公知文献(WO2011/122132)を参考にして合成した3-ブロモ-9-(2-ジベンゾフラニル)カルバゾール 0.50g(1.2mmol)、アニリン 0.05g(0.60mmol)、ナトリウム-tert-ブトキシド 0.16g(1.6mmol)、o-キシレン 10mL、酢酸パラジウム 5mg(0.02mmol)、及びトリ(tert-ブチル)ホスフィン 14mg(0.07mmol)を添加して140℃で3時間攪拌した。室温まで冷却後、純水 5mLを加え、有機層を分離した。有機層を水、飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー(トルエンとヘキサンの混合溶媒(体積比=1:1))で精製し、化合物(b)の無色ガラス状固体を0.35g(0.47mmol)単離した(収率79%)。
化合物の同定は、FDMS測定により行った。
FDMS(m/z); 755(M+)
厚さ200nmのITO透明電極(陽極)を積層したガラス基板を、アセトン及び純水による超音波洗浄、イソプロピルアルコールによる沸騰洗浄を行なった。さらに、紫外線/オゾン洗浄を行ない、真空蒸着装置へ設置後、1×10-4Paになるまで真空ポンプにて排気した。まず、ITO透明電極上に銅フタロシアニンを蒸着速度0.1nm/秒で蒸着し、10nmの正孔注入層とし、引続き、化合物(A1)を蒸着速度0.3nm/秒で30nm蒸着して正孔輸送層とした。続いて、燐光ドーパント材料であるトリス(2-フェニルピリジン)イリジウム(Ir(ppy)3)とホスト材料である4,4’-ビス(N-カルバゾリル)ビフェニル(CBP)を重量比が1:11.5になるように蒸着速度0.25nm/秒で共蒸着し、30nmの発光層とした。次に、BAlq(ビス(2-メチル-8-キノリノラト)(p-フェニルフェノラート)アルミニウム)を蒸着速度0.3nm/秒で蒸着し、5nmのエキシトンブロック層とした後、さらにAlq3(トリス(8-キノリノラト)アルミニウム)を0.3nm/秒で蒸着し、45nmの電子輸送層とした。引続き、電子注入層として沸化リチウムを蒸着速度0.01nm/秒で1nm蒸着し、さらにアルミニウムを蒸着速度0.25nm/秒で100nm蒸着して陰極を形成した。窒素雰囲気下、封止用のガラス板をUV硬化樹脂で接着し、評価用の有機EL素子とした。このように作製した素子に20mA/cm2の電流を印加し、駆動電圧及び電流効率を測定した。また、素子の輝度半減時間は、6.25mA/cm2の電流を印加して評価した。結果を表1に示した。
化合物(A1)の代わりに、化合物(A2)、(A3)、(A8)、(A12)、(A13)、(A16)、(A21)、(A22)、(A24)、(A25)、(A28)、(A32)、(A36)、(A46)、(A47)、(B4)、又は(B8)に変更した以外は実施例19と同じ方法で有機EL素子を作製した。20mA/cm2の電流を印加した際の駆動電圧及び電流効率、また、6.25mA/cm2の電流を印加した際の輝度半減時間を表1に示した。
化合物(A1)をNPD(4,4’-ビス[N-(1-ナフチル)-N-フェニルアミノ]ビフェニル)に変更した以外は実施例19と同じ方法で有機EL素子を作製した。20mA/cm2の電流を印加した際の駆動電圧及び電流効率、また、6.25mA/cm2の電流を印加した際の輝度半減時間を表1に示した。
比較例3 (化合物(b)の素子評価)
化合物(A1)を下記の化合物(b)に変更した以外は実施例19と同じ方法で有機EL素子を作製した。20mA/cm2の電流を印加した際の駆動電圧及び電流効率、また、6.25mA/cm2の電流を印加した際の輝度半減時間を表1に示した。
化合物(A1)を下記の化合物(a)に変更した以外は実施例19と同じ方法で有機EL素子を作製した。20mA/cm2の電流を印加した際の駆動電圧及び電流効率、また、6.25mA/cm2の電流を印加した際の輝度半減時間を表1に示した。
なお、2012年9月27日に出願された日本特許出願2012-214844号及び2013年6月6日に出願された日本特許出願2013-119485号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (12)
- R1、R2、R4、R5、R7、R8、R9、及びR10が水素原子である請求項1に記載のアミン化合物。
- R1~R10が水素原子である請求項1又は請求項2に記載のアミン化合物。
- Ar1及びAr2が、各々独立して、
メチル基、メトキシ基、ジベンゾチエニル基、ジベンゾフラニル基及び9-カルバゾリル基からなる群から選ばれる置換基を有していてもよいフェニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいビフェニリル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいターフェニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよい9,9-ジメチル-9H-フルオレニル基、
メチル基若しくはメトキシ基からなる置換基を有していてもよいジベンゾチエニル基、
又は、メチル基若しくはメトキシ基からなる置換基を有していてもよいジベンゾフラニル基、である請求項1乃至請求項3のいずれか1項に記載のアミン化合物。 - Ar1及びAr2が、各々独立して、フェニル基、p-トリル基、p-メトキシフェニル基、4-ビフェニリル基、p-ターフェニル-4-イル基、m-ターフェニル-4-イル基、9,9-ジメチルフルオレン-2-イル基、ジベンゾチオフェン-2-イル基、ジベンゾフラン-2-イル基、4-(ジベンゾチオフェン-2-イル)フェニル基、4-(ジベンゾチオフェン-4-イル)フェニル基、4-(ジベンゾフラン-2-イル)フェニル基、又は4-(9-カルバゾリル)フェニル基である請求項1乃至請求項4のいずれか1項に記載のアミン化合物。
- Xが、硫黄原子である請求項1乃至請求項5のいずれか1項に記載のアミン化合物。
- 請求項1~7のいずれか1項に記載のアミン化合物を含む正孔輸送層。
- 請求項1~7のいずれか1項に記載のアミン化合物を含む正孔注入層。
- 請求項1~7のいずれか1項に記載のアミン化合物を含む発光層。
- 請求項1~7のいずれか1項に記載のアミン化合物を、発光層、正孔輸送層又は正孔注入層の少なくともいずれかに含む有機EL素子。
- 請求項1~7のいずれか1項に記載のアミン化合物を正孔輸送層に含む請求項11に記載の有機EL素子。
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