WO2015190718A1 - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
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- WO2015190718A1 WO2015190718A1 PCT/KR2015/005080 KR2015005080W WO2015190718A1 WO 2015190718 A1 WO2015190718 A1 WO 2015190718A1 KR 2015005080 W KR2015005080 W KR 2015005080W WO 2015190718 A1 WO2015190718 A1 WO 2015190718A1
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- WIPO (PCT)
- Prior art keywords
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- substituted
- unsubstituted
- formula
- aryl
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- 150000001875 compounds Chemical class 0.000 claims description 65
- 125000003118 aryl group Chemical group 0.000 claims description 63
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 125000004429 atom Chemical group 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 125000001072 heteroaryl group Chemical group 0.000 claims description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- 239000002019 doping agent Substances 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 22
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 21
- 125000000304 alkynyl group Chemical group 0.000 claims description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 21
- 125000005104 aryl silyl group Chemical group 0.000 claims description 20
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 19
- -1 alkyl boron Chemical compound 0.000 claims description 19
- 229910052805 deuterium Inorganic materials 0.000 claims description 19
- 239000011368 organic material Substances 0.000 claims description 19
- 125000004104 aryloxy group Chemical group 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 17
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 125000005264 aryl amine group Chemical group 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 description 120
- 238000003786 synthesis reaction Methods 0.000 description 119
- 239000010410 layer Substances 0.000 description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 37
- 238000002360 preparation method Methods 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000004440 column chromatography Methods 0.000 description 27
- 125000001424 substituent group Chemical group 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 12
- OVNPUJOZNPAVJQ-UHFFFAOYSA-N 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound ClC1=CC=CC(C=2N=C(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 OVNPUJOZNPAVJQ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 8
- RHUICOIYTTZMKP-UHFFFAOYSA-N 5-(2-nitrophenyl)-1-phenylindole Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C(N(C=C2)C=3C=CC=CC=3)C2=C1 RHUICOIYTTZMKP-UHFFFAOYSA-N 0.000 description 8
- NRDZHTMNMSJGKG-UHFFFAOYSA-N 5-(2-nitrophenyl)-1h-indole Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C(NC=C2)C2=C1 NRDZHTMNMSJGKG-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 4
- NIXVFOYHOLAUPX-UHFFFAOYSA-N 5-(5-bromo-2-nitrophenyl)-1-phenylindole Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1C1=CC=C(N(C=C2)C=3C=CC=CC=3)C2=C1 NIXVFOYHOLAUPX-UHFFFAOYSA-N 0.000 description 4
- JQBBFPJVYGHUAT-UHFFFAOYSA-N 5-(5-bromo-2-nitrophenyl)-1h-indole Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1C1=CC=C(NC=C2)C2=C1 JQBBFPJVYGHUAT-UHFFFAOYSA-N 0.000 description 4
- CPTLFWJWYCQARE-UHFFFAOYSA-N 6-(2-nitrophenyl)-2-phenyl-1,3-benzothiazole Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C(N=C(S2)C=3C=CC=CC=3)C2=C1 CPTLFWJWYCQARE-UHFFFAOYSA-N 0.000 description 4
- YVZIBDQASKHGFK-UHFFFAOYSA-N 6-bromo-2-phenyl-1,3-benzoxazole Chemical compound O1C2=CC(Br)=CC=C2N=C1C1=CC=CC=C1 YVZIBDQASKHGFK-UHFFFAOYSA-N 0.000 description 4
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 4
- FUBBIMKGJUIOCJ-UHFFFAOYSA-N O1C(C)(C)C(C)(C)OB1C1=CC=C(N=C(O2)C=3C=CC=CC=3)C2=C1 Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N=C(O2)C=3C=CC=CC=3)C2=C1 FUBBIMKGJUIOCJ-UHFFFAOYSA-N 0.000 description 4
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- BFEPIECBWQYKLN-UHFFFAOYSA-N [N+](=O)([O-])C1=C(C=CC=C1)C1=CC2=C(N=C(O2)C2=CC=CC=C2)C=C1 Chemical compound [N+](=O)([O-])C1=C(C=CC=C1)C1=CC2=C(N=C(O2)C2=CC=CC=C2)C=C1 BFEPIECBWQYKLN-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OMQBGCCUCOETRR-UHFFFAOYSA-N 11-phenylbenzo[b][1]benzazepine Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C=CC2=CC=CC=C21 OMQBGCCUCOETRR-UHFFFAOYSA-N 0.000 description 3
- JBEQRROTSDUCGC-UHFFFAOYSA-N 3-bromo-6,9-diphenylcarbazole Chemical compound C12=CC=C(C=3C=CC=CC=3)C=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 JBEQRROTSDUCGC-UHFFFAOYSA-N 0.000 description 3
- BEWZJUHGBZQONA-UHFFFAOYSA-N 3-bromo-6-phenyl-9h-carbazole Chemical compound C1=C2C3=CC(Br)=CC=C3NC2=CC=C1C1=CC=CC=C1 BEWZJUHGBZQONA-UHFFFAOYSA-N 0.000 description 3
- NSRPRPVECXNOLB-UHFFFAOYSA-N 3-bromo-9-(3-phenylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C(C=1)=CC=CC=1C1=CC=CC=C1 NSRPRPVECXNOLB-UHFFFAOYSA-N 0.000 description 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 3
- YJGAKWIWQUQDRT-UHFFFAOYSA-N 5-(2-nitrophenyl)-1-phenylindazole Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C(N(N=C2)C=3C=CC=CC=3)C2=C1 YJGAKWIWQUQDRT-UHFFFAOYSA-N 0.000 description 3
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- FATPQDPUKVVCLT-UHFFFAOYSA-N 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1h-indole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(NC=C2)C2=C1 FATPQDPUKVVCLT-UHFFFAOYSA-N 0.000 description 3
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- SHBUAEKYJGMKPD-UHFFFAOYSA-N 6-(2-nitrophenyl)-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=CC=C1C1=CC=C(N=CN2)C2=C1 SHBUAEKYJGMKPD-UHFFFAOYSA-N 0.000 description 3
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- BQQPUKVKJAMIDQ-UHFFFAOYSA-N 7-bromo-3-phenyl-10h-pyrrolo[3,2-a]carbazole Chemical compound C12=CC=C3C4=CC(Br)=CC=C4NC3=C2C=CN1C1=CC=CC=C1 BQQPUKVKJAMIDQ-UHFFFAOYSA-N 0.000 description 3
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- 125000000623 heterocyclic group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- SFUIGUOONHIVLG-UHFFFAOYSA-N (2-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1[N+]([O-])=O SFUIGUOONHIVLG-UHFFFAOYSA-N 0.000 description 1
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
- NCWDBNBNYVVARF-UHFFFAOYSA-N 1,3,2-dioxaborolane Chemical compound B1OCCO1 NCWDBNBNYVVARF-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- KRVWTVYQGIOXQE-UHFFFAOYSA-N 1-(2,6-diphenoxyphenoxy)naphthalene Chemical group C=1C=CC(OC=2C=CC=CC=2)=C(OC=2C3=CC=CC=C3C=CC=2)C=1OC1=CC=CC=C1 KRVWTVYQGIOXQE-UHFFFAOYSA-N 0.000 description 1
- PTQROAOBTCPDPA-UHFFFAOYSA-N 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indazole Chemical compound O1C(C)(C)C(C)(C)OB1N1C2=CC=CC=C2C=N1 PTQROAOBTCPDPA-UHFFFAOYSA-N 0.000 description 1
- IOPQERQQZZREDR-UHFFFAOYSA-N 1-bromo-3,5-diphenylbenzene Chemical group C=1C(Br)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 IOPQERQQZZREDR-UHFFFAOYSA-N 0.000 description 1
- USYQKCQEVBFJRP-UHFFFAOYSA-N 1-bromo-3-phenylbenzene Chemical group BrC1=CC=CC(C=2C=CC=CC=2)=C1 USYQKCQEVBFJRP-UHFFFAOYSA-N 0.000 description 1
- KAQUBIATNWQNRE-UHFFFAOYSA-N 1-iodo-3-phenylbenzene Chemical group IC1=CC=CC(C=2C=CC=CC=2)=C1 KAQUBIATNWQNRE-UHFFFAOYSA-N 0.000 description 1
- DXRVYZGVVFZCFP-UHFFFAOYSA-N 2,4-dibromo-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1Br DXRVYZGVVFZCFP-UHFFFAOYSA-N 0.000 description 1
- DYSRXWYRUJCNFI-UHFFFAOYSA-N 2,4-dibromoaniline Chemical compound NC1=CC=C(Br)C=C1Br DYSRXWYRUJCNFI-UHFFFAOYSA-N 0.000 description 1
- YFTHTJAPODJVSL-UHFFFAOYSA-N 2-(1-benzothiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(SC=C2)C2=C1 YFTHTJAPODJVSL-UHFFFAOYSA-N 0.000 description 1
- HNZUKQQNZRMNGS-UHFFFAOYSA-N 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound BrC1=CC=CC(C=2N=C(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HNZUKQQNZRMNGS-UHFFFAOYSA-N 0.000 description 1
- YZFYADJGVHTXTD-UHFFFAOYSA-N 2-(3-chloro-5-methylphenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound CC1=CC(Cl)=CC(C=2N=C(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 YZFYADJGVHTXTD-UHFFFAOYSA-N 0.000 description 1
- KMAKKQXXTUMDTG-UHFFFAOYSA-N 2-(3-chlorophenyl)-4,6-diphenylpyridine Chemical compound ClC1=CC=CC(C=2N=C(C=C(C=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 KMAKKQXXTUMDTG-UHFFFAOYSA-N 0.000 description 1
- BHJFLOOHSMTNSJ-UHFFFAOYSA-N 2-(3-chlorophenyl)-4,6-diphenylpyrimidine Chemical compound ClC1=CC=CC(C=2N=C(C=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BHJFLOOHSMTNSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- DDGPPAMADXTGTN-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 DDGPPAMADXTGTN-UHFFFAOYSA-N 0.000 description 1
- JNGKNTZYAKKNLQ-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1h-triazine Chemical compound N=1N(Cl)NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 JNGKNTZYAKKNLQ-UHFFFAOYSA-N 0.000 description 1
- ROTVYQUGLYGYKI-UHFFFAOYSA-N 2-chloro-4,6-diphenylpyridine Chemical compound N=1C(Cl)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 ROTVYQUGLYGYKI-UHFFFAOYSA-N 0.000 description 1
- QNGVEVOZKYHNGL-UHFFFAOYSA-N 2-chloro-4,6-diphenylpyrimidine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 QNGVEVOZKYHNGL-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 1
- STVHMYNPQCLUNJ-UHFFFAOYSA-N 5-bromo-1h-indazole Chemical compound BrC1=CC=C2NN=CC2=C1 STVHMYNPQCLUNJ-UHFFFAOYSA-N 0.000 description 1
- LCGTWRLJTMHIQZ-UHFFFAOYSA-N 5H-dibenzo[b,f]azepine Chemical compound C1=CC2=CC=CC=C2NC2=CC=CC=C21 LCGTWRLJTMHIQZ-UHFFFAOYSA-N 0.000 description 1
- VNDFXJNIKZCQRY-UHFFFAOYSA-N 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1h-indole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=CN2)C2=C1 VNDFXJNIKZCQRY-UHFFFAOYSA-N 0.000 description 1
- GEDVWGDBMPJNEV-UHFFFAOYSA-N 6-bromo-1h-benzimidazole Chemical compound BrC1=CC=C2N=CNC2=C1 GEDVWGDBMPJNEV-UHFFFAOYSA-N 0.000 description 1
- MAWGHOPSCKCTPA-UHFFFAOYSA-N 6-bromo-1h-indole Chemical compound BrC1=CC=C2C=CNC2=C1 MAWGHOPSCKCTPA-UHFFFAOYSA-N 0.000 description 1
- XPPZHNMLPDIYQI-UHFFFAOYSA-N Bc(cccc1)c1[N+]([O-])=O Chemical compound Bc(cccc1)c1[N+]([O-])=O XPPZHNMLPDIYQI-UHFFFAOYSA-N 0.000 description 1
- APMIASYVZNGMEM-UHFFFAOYSA-N Brc(cc1)cc2c1[nH]c1c2ccc2c1cc[n]2C1=CCCC=C1 Chemical compound Brc(cc1)cc2c1[nH]c1c2ccc2c1cc[n]2C1=CCCC=C1 APMIASYVZNGMEM-UHFFFAOYSA-N 0.000 description 1
- FXHGBACNYDFALU-UHFFFAOYSA-N CC1(C)OB(c2cccc(-c3nc(-c4ccccc4)nc(-c4ccccc4)n3)c2)OC1(C)C Chemical compound CC1(C)OB(c2cccc(-c3nc(-c4ccccc4)nc(-c4ccccc4)n3)c2)OC1(C)C FXHGBACNYDFALU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- CYUOOCRXNZWQQG-UHFFFAOYSA-N c(c(cc1)c2c3c1c(cccc1)c1[n]3-c1cc(-c3nc(-c4ccccc4)nc(-c4ccccc4)n3)ccc1)c[n]2-c1ccccc1 Chemical compound c(c(cc1)c2c3c1c(cccc1)c1[n]3-c1cc(-c3nc(-c4ccccc4)nc(-c4ccccc4)n3)ccc1)c[n]2-c1ccccc1 CYUOOCRXNZWQQG-UHFFFAOYSA-N 0.000 description 1
- LVFIPQCKIHUZBJ-UHFFFAOYSA-N c(c1c2ccc(c3cc(-c4cccc(-c5nc(-c6ccccc6)nc(-c6ccccc6)n5)c4)ccc33)c1[n]3-c1ccccc1)c[n]2-c1ccccc1 Chemical compound c(c1c2ccc(c3cc(-c4cccc(-c5nc(-c6ccccc6)nc(-c6ccccc6)n5)c4)ccc33)c1[n]3-c1ccccc1)c[n]2-c1ccccc1 LVFIPQCKIHUZBJ-UHFFFAOYSA-N 0.000 description 1
- POHYEIHXPQCOHL-UHFFFAOYSA-N c(c1ccc(c(cccc2)c2[nH]2)c2c11)c[n]1-c1ccccc1 Chemical compound c(c1ccc(c(cccc2)c2[nH]2)c2c11)c[n]1-c1ccccc1 POHYEIHXPQCOHL-UHFFFAOYSA-N 0.000 description 1
- MHTPESFJWCJELK-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(ccc(-c(cc2c3c4cccc3)ccc2[n]4-c2ccccc2)c2)c2c2ccccc12 Chemical compound c(cc1)ccc1-[n]1c(ccc(-c(cc2c3c4cccc3)ccc2[n]4-c2ccccc2)c2)c2c2ccccc12 MHTPESFJWCJELK-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002962 imidazol-1-yl group Chemical group [*]N1C([H])=NC([H])=C1[H] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl 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
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Definitions
- the present invention relates to an organic electroluminescent device comprising at least one organic material layer.
- the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to its function.
- a light emitting material mixed with a host material and a dopant material may be used.
- the dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt.
- metal complex compounds including Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and CBP is known as a phosphorescent host material.
- the conventional materials do not have a satisfactory level in terms of lifespan in the organic electroluminescent device because of the low glass transition temperature and poor thermal stability. Therefore, there is a demand for the development of an organic EL device including a light emitting material having excellent performance.
- an object of the present invention is to provide an organic electroluminescent device having improved characteristics such as driving voltage, luminous efficiency and lifetime.
- the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers includes a first host and a second host, wherein the first host is represented by Formula 1 below. It is a compound, wherein the second host provides an organic electroluminescent device, characterized in that the compound represented by the formula (2).
- R a to R d are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 40 alkyl group, and a substituted or unsubstituted C 6 to C 60 aryl group Selected,
- X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
- Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein when there are a plurality of C (R 1 ), a plurality of R 1 are the same or different, and each of them is adjacent to a group; Can form condensed rings;
- X 2 and X 3 are the same or different from each other, and each independently N or C (R 2 ), wherein when there are a plurality of C (R 2 ), a plurality of R 2 are each the same or different, and they are condensed with adjacent groups May form a ring;
- R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C 1 to C 40
- an alkyl group alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group
- an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group and an arylamine group are substituted, each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 a ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, a nuclear atoms, 3 to 40 hetero cycloalkyl group, C 6 ⁇ C 40 of the An aryl group,
- the organic material layer including the first host and the second host is preferably a phosphorescent layer.
- the light emitting layer preferably includes a metal complex compound dopant.
- the organic electroluminescent device of the present invention comprises an organic material layer comprising a first host and a second host, by mixing the compound represented by the formula (1) and the compound represented by the formula (2) as the first host and the second host, respectively.
- the driving voltage, luminous efficiency, and lifespan of the device can be improved. Therefore, when manufacturing a display panel using the organic electroluminescent device of the present invention, it is possible to provide a display panel with improved performance and lifespan.
- the organic electroluminescent device of the present invention includes an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, and at least one of the at least one organic layer includes a first host and a second host.
- the first host is a compound represented by Chemical Formula 1
- the second host is a compound represented by Chemical Formula 2 below.
- the compound represented by Chemical Formula 1, which is used as the first host in the present invention, substitutes hydrogen, deuterium, an alkyl group of C 1 to C 40 or an aryl group of C 6 to C 60 to a 3,3'-biscarbazole base skeleton. Can be.
- the carbazole skeleton has the characteristics of an electron donating group having high electron donating and hole transporting properties. Therefore, as shown in Formula 1, when two carbazole skeletons are included in the molecule, the carbazole skeleton has a high hole transporting property, and when the carbazole skeleton is one, the molecular weight is significantly increased to have high thermal stability.
- the basic skeleton in the form of 3,3 'bonded biscarbazole is the main binding site of carbazole, and can firmly connect two carbazoles to enhance the thermal and electrical stability of the molecule itself.
- R a to R d are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group of C 1 to C 40 and an aryl group of C 6 to C 60 . Selected from the group. More specifically, R a to R d are the same as or different from each other, and each independently may be selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, t-butyl, phenyl, biphenyl, and the like. .
- Alkyl and aryl groups which are the aforementioned substituents, have electron donating and hole transporting properties, thereby enhancing the characteristics of the electron donating group in the molecule.
- R a to R d are each independently preferably a phenyl group, and the bonding position of the phenyl group is not particularly limited and is not limited.
- the compound represented by the formula (1) according to the present invention can be more embodied in a compound group consisting of the following formula. However, this is not particularly limited.
- the compound represented by Formula 2 which is used as the second host in the present invention, is a condensed carbon ring or a condensed heterocyclic moiety, preferably a condensed heterocyclic moiety, connected to an indole-based skeleton, and is energized by various substituents.
- the level is adjusted to have a wide energy band gap (sky blue to red). Accordingly, when the compound represented by Formula 2 is used as the second host of the organic material layer of the organic light emitting device, the light emitting (phosphorescence) characteristics of the organic light emitting device are improved, and the electron and / or hole transporting ability and the light emitting ability are improved. Can be.
- the compound represented by Formula 2 various aromatic rings are bonded to the indole-based backbone as a substituent to significantly increase the molecular weight of the compound. Therefore, the glass transition temperature (Tg) is improved and thereby may have a higher thermal stability than the conventional CBP.
- Tg glass transition temperature
- the whole molecule has a bipolar characteristic and can enhance the binding force between holes and electrons. Can be represented.
- Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ).
- R 1 when there are a plurality of C (R 1 ), a plurality of R 1 may be the same or different, and each of them may form a condensed ring with an adjacent group.
- X 2 and X 3 are the same as or different from each other, and are each independently N or C (R 2 ). In this case, when there are a plurality of C (R 2 ), a plurality of R 2 are the same or different, and they may form a condensed ring with an adjacent group.
- condensed ring with an adjacent group (adjacent)', two or more adjacent plural substituents are bonded to each other condensed aliphatic ring, condensed aromatic ring, condensed heteroaliphatic ring, or condensation known in the art It means forming a heteroaromatic ring.
- the compound represented by Chemical Formula 2 may be more specific as A-1 to A-24, but is not limited thereto.
- R 2 , Y 1 to Y 4 and Ar 1 to Ar 5 are the same as defined in Formula 2 above.
- the case of A-1 to A-6 is preferable.
- Chemical Formula 2 of the present invention may be used alone as the structure of Chemical Formula 2, or Chemical Formula 2 may be combined with the following Chemical Formula 3 or Chemical Formula 4 to form a condensation structure.
- Y 1 to Y 4 in Formula 2 are a plurality of C (R 1 )
- one of Y 1 and Y 2 , Y 2 and Y 3 or Y 3 and Y 4 is a condensed ring with Formula 3 Can be formed.
- a plurality of R 1 may be the same or different, respectively.
- Y 1 to Y 4 of Chemical Formula 2 may be combined with X 9 and X 10 of Chemical Formula 3.
- a plurality of R 2 may be combined with each of the following formula (3) or formula (4) to form a condensed ring.
- it may be combined with Formula 4 to form a condensed ring.
- X 2 and X 3 of Formula 2 may combine with Y 11 to Y 14 of Formula 4 to form a condensed ring.
- Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), and in the case where there are a plurality of C (R 3 ), a plurality of R 3 are the same as or different from each other, and they are represented by Formula 2 above.
- R 3 N or C
- R 3 condensed ring
- X 4 is the same as X 1 described above, wherein a plurality of Ar 1 to Ar 5 are the same or different, respectively.
- R 3 non-forming a condensed ring with Formula 2 is each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C 1 ⁇ C 40 alkyl, substituted or Unsubstituted C 2 -C 40 alkenyl group, substituted or unsubstituted C 2 -C 40 alkynyl group, substituted or unsubstituted C 3 -C 40 cycloalkyl group, substituted or unsubstituted nuclear atom 3 to 40 heterocycloalkyl groups, substituted or unsubstituted C 6 to C 60 aryl groups, substituted or unsubstituted heteroaryl groups having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 alkyloxy groups , Substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 1 -C 40 alkylsilyl group,
- an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, a phosphine oxide group, and aryl amine groups are each independently selected from deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C case be substituted 2 or an alkynyl group of C 40, C 3 ⁇ C 40 cycloalkyl group, a number of the aryl group, the nucleus of atoms of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ⁇ C 40 of from 5 to 40 heteroaryl group, C 1 ⁇ C
- the compound formed by condensation of Chemical Formula 2 and Chemical Formula 3 may be further embodied as a compound represented by Chemical Formulas 2a to 2f.
- X 1 to X 4 and Y 1 to Y 8 are the same as defined in Chemical Formula 2 and Chemical Formula 3, respectively.
- Y 1 to Y 4 to form a condensed ring ratio ( ⁇ ) is N or C (R 1), wherein if the Y 1 to Y 4 are both C (R 1) is preferred.
- the Y 5 to Y 8 is a case of N or C (R 3) a, wherein Y 5 to Y 8 are both C (R 3) are preferred.
- a plurality of R 1 and R 3 are the same or different, respectively.
- Compounds of the present invention in which Formula 2 and Formula 3 are condensed may be more specifically formulated into a compound group consisting of Formulas B-1 to B-30. However, this is not particularly limited.
- Ar 1 is a substituted or unsubstituted C 6 ⁇ C 40 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms,
- R 1 to R 3 are each independently hydrogen, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, or a substituted or unsubstituted nuclear atom 5 to 40 It is preferable when it is a heteroaryl group of.
- Formulas B-1 to B-30 having a structure formed by condensation of Formulas 2 and 3 include one or more condensed indole or condensed carbazole moieties.
- the compound formed by condensation of Chemical Formula 2 and Chemical Formula 4 may be further embodied as a compound represented by Chemical Formula 2g to 2n.
- X 1 , X 4 and Y 1 to Y 14 are the same as defined in Formula 2 and Formula 4, respectively.
- X 1 and X 4 are each independently O, S or N (Ar 1 ), it is more preferable that both X 1 and X 4 is N (Ar 1 ), wherein a plurality of Ar 1 Are the same or different, respectively.
- Y 1 to Y 4 are each independently N or C (R 1 ), and preferably Y 1 to Y 4 are all C (R 1 ), wherein a plurality of R 1 are the same or different.
- Y 5 to Y 14 are each independently N or C (R 3 ), and preferably Y 5 to Y 14 are all C (R 3 ), wherein a plurality of R 3 are the same or different.
- Ar 1 and R 1 to R 3 are the same as defined in the above formula (2) and (4).
- the compound represented by any one of Formulas 2a to 2n used as the second host, X 1 and X 4 are each independently It is preferred that it is N (Ar 1 ) or S. That is, it is preferable that X 1 is N (Ar 1 ) and X 4 is S, X 1 is S and X 4 is N (Ar 1 ), or both X 1 and X 4 are N (Ar 1 ).
- Ar 1 is preferably a substituted or unsubstituted C 6 ⁇ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms
- Ar 2 to Ar 5 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group (specifically, a methyl group) or a substituted or unsubstituted C 6 to C 60 aryl group (specifically Phenyl group) is preferable.
- Ar 1 is preferably a substituent represented by the following formula (5) or a phenyl group.
- L is selected from the group consisting of a single bond, a substituted or unsubstituted C 6 ⁇ C 18 arylene group and a substituted or unsubstituted heteroarylene group having 5 to 18 nuclear atoms,
- Z 1 to Z 5 are the same as or different from each other, and each independently N or C (R 11 ), wherein at least one of Z 1 to Z 5 is N,
- R 11 s When there are a plurality of R 11 s , they are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted substituted or unsubstituted C 1 to C 40 alkyl group, substituted or Unsubstituted C 2 -C 40 alkenyl group, substituted or unsubstituted C 2 -C 40 alkynyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl groups, substituted or unsubstituted C 6 -C 60 aryloxy groups, substituted or unsubstituted C 1 -C 40 alkyloxy groups, substituted or unsubstituted C 3 -C 40 cycloalkyl groups, Substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms
- arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl Group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 Alkenyl group, C 2 ⁇ C 40 Alkynyl group, C 6 ⁇ C 60 Aryl group, Nuclear 5 to 60 heteroaryl group, C 6 ⁇ C 40 60 Aryloxy group, C 1 ⁇ C 40 Alkyl Oxy group, C 6 to C 60 arylamine group, C 3 to C 40 cycloalkyl
- L is preferably a single bond, a phenylene group or a biphenylene group.
- * means a part bonded to the formula (2), when two or more of Z 1 to Z 5 is C (R 11 ), a plurality of R 11 may be the same or different from each other.
- the substituent represented by the formula (5) is preferably selected from a substituent group consisting of a structure represented by the following C-1 to C-15.
- R 12 is hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C 1 ⁇ C 40 alkyl group, substituted or unsubstituted C 2 ⁇ C 40 alkenyl group, substituted or unsubstituted C 2 ⁇ C 40 alkynyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryl group, Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 ⁇ C 60 arylamine group, substituted or unsubstituted C 1 ⁇ C 40 Alky
- n is an integer of 1-4.
- Ar 1 to Ar 5 and R 1 to R 3 may be each independently selected from a substituent group (S1-S206) consisting of hydrogen or the following substituents (functional groups). However, this is not particularly limited.
- alkyl in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl. Etc. can be mentioned.
- Alkenyl in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl and allyl. ), Isopropenyl, 2-butenyl, and the like.
- Alkynyl in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having at least one carbon-carbon triple bond, examples of which are ethynyl, 2- Propanyl (2-propynyl) etc. are mentioned.
- Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings.
- a form in which two or more rings are pendant or condensed with each other may also be included.
- aryls include phenyl, naphthyl, phenanthryl, anthryl and the like.
- Heteroaryl in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se.
- a form in which two or more rings are pendant or condensed with each other may also be included, and may also include a form condensed with an aryl group.
- heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like.
- 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furany
- Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
- Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means 1 to 40 alkyl, and includes a linear, branched or cyclic structure
- alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
- Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
- Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
- Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
- Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Substituted with a hetero atom such as Se.
- heterocycloalkyl include morpholine, piperazine and the like.
- Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms
- arylsilyl means silyl substituted with aryl having 5 to 40 carbon atoms.
- Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
- the organic electroluminescent device of the present invention configured as described above may have a long life because at least one of the plurality of organic material layers may balance holes and electrons injected into the device including the first host and the second host. have.
- the mixing ratio of the first host and the second host is not particularly limited when the organic layer is manufactured.
- the first host and the second host may be mixed in a weight ratio of 1:99 to 99: 1. At this time, it is preferable that the use ratio of the first host is higher.
- the light emitting layer may be a single light emitting layer, or may have a plurality of light emitting layers to implement a mixed color thereof. More specifically, in the present invention, a plurality of light emitting layers may be sequentially stacked between the hole transport layer and the electron transport layer to implement a mixed color thereof when voltage and current are applied.
- the stacked organic electroluminescent device of the present invention having a plurality of light emitting layers including a plurality of light emitting layers or heterogeneous materials in series between the hole transport layer and the electron transport layer as described above may realize a mixed color when voltage and current are applied or a plurality of light emitting layers.
- the light emission efficiency can be increased by the number of light emitting layers.
- the organic material layer of the present invention including the first host and the second host is preferably a light emitting layer, wherein the light emitting layer of the present invention may include a dopant together with the first host and the second host.
- the material that can be used as the dopant included in the light emitting layer can be used without limitation conventional dopant components known in the art, it is preferable to use a metal complex compound containing iridium (Ir) as an example.
- the method of manufacturing the light emitting layer including the first host, the second host, and the dopant described above may be manufactured without particular limitation in accordance with methods known in the art.
- two preferable embodiment which manufactures the said light emitting layer is illustrated below, it is not specifically limited to this.
- a first method of the above two embodiments is a co-deposition method of placing a first host and a second host in a first heat source and a second heat source, respectively, and placing a dopant in a third heat source to simultaneously apply heat to form a light emitting layer. .
- a second host having high hole mobility and good hole injection efficiency is placed in the first heat source, and electron mobility is located in the second heat source.
- a method of co-depositing at a proper ratio by placing a second host having a high c) and having a good electron injection efficiency and controlling a dopant of a third heat source and an evaporation rate per second.
- the number of co-deposited hosts may be two or more according to the characteristics of the light emitting layer.
- the amount of the first host, the second host, and the dopant is not particularly limited.
- the first host, the second host, and the first host and the second host may be 70 to 99% by weight and the dopant to 1 to 30% by weight.
- the first host and the second host used for forming the light emitting layer are mixed at an appropriate ratio, placed in one heat source, and heat is removed. It is a co-deposition method which adds and forms a light emitting layer.
- This second method has the advantage of reducing the mixing ratio error that occurs when using more than one host, and can form a light emitting layer with a small number of heat sources.
- the amount of the first host, the second host, and the dopant is not particularly limited.
- the first host, the second host, and the dopant may be used in a range of 70 to 99% by weight, and the dopant to 1 to 30% by weight. Specifically, it is preferable to use 80 to 95 wt% of the first host and the second host, and 5 to 20 wt% of the dopant.
- the material usable as the anode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And carbon black.
- metals such as vanadium, chromium, copper, zinc, gold or alloys thereof
- Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb
- the material which can be used as the cathode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead Metals such as these, alloys thereof, and multilayered structure materials such as LiF / Al and LiO 2 / Al.
- the structure of the organic EL device of the present invention is not particularly limited, but a non-limiting example is a structure in which a substrate, an anode, an organic material layer (hole injection layer-> hole transport layer-> light emitting layer-> electron transport layer) and a cathode are sequentially stacked.
- a substrate, an anode, an organic material layer (hole injection layer-> hole transport layer-> light emitting layer-> electron transport layer) and a cathode are sequentially stacked.
- at least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1 as a first host.
- the electron injection layer may be further stacked on the electron transport layer.
- the structure of the organic EL device according to the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the anode and cathode and the organic material layer.
- the organic electroluminescent device of the present invention uses conventional materials and methods known in the art, except that at least one layer (eg, the light emitting layer) of the organic material layer is formed to include the first host and the second host. Another organic material layer can be formed.
- at least one layer eg, the light emitting layer
- Another organic material layer can be formed.
- the substrate used in the manufacture of the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
- 2,4-dibromoaniline 25.09 g, 0.1 mol
- methylene chloride 100 ml
- Benzoyl chloride 11.6 mL, 0.1mol
- pyridine 1.62 mL, 0.02 mol
- N- (2,4-dibromophenyl) benzamide (25.1 g, 71.0 mmol), K 2 CO 3 (19.6 g, 142 mmol) and DMSO (710 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 h.
- 6-bromo-2-phenylbenzo [d] oxazole (14.8 g, 54.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (15.1 g, 59.4 mmol), Pd (dppf) Cl 2 (6.24 g, 5.40 mmol), KOAc (15.25 g, 0.162 mol) and 1,4-Dioxane (280 ml) Mix and stir at 130 ° C. for 12 h.
- N- (2,4-dibromophenyl) benzamide (26.62 g, 0.075 mol) obtained in ⁇ Step 1> of Preparation Example 3 was added to the reactor, toluene (300 ml) was added thereto, followed by stirring. Lawesson's reagent (22.92 g, 0.053 mol) was added dropwise to the reactor, followed by mixing and stirring at 110 ° C. for 4 hours.
- N- (2,4-dibromophenyl) benzothioamide (26.35 g, 71.0 mmol), K 2 CO 3 (19.63 g, 142 mmol) and DMSO (710 ml) obtained in ⁇ Step 1> of Preparation Example 8 under nitrogen stream were prepared. Mix and stir at 140 ° C. for 1.5 h.
- 6-bromo-2-phenylbenzo [d] thiazole (15.66 g, 54.0 mmol) was used instead of 6-bromo-2-phenylbenzo [d] oxazole, and was synthesized in the same manner as in Step 3 of Preparation Example 3 above. , 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (14.02 g, yield 77%) was obtained.
- step 3 of Preparation Example 1 Same as step 3 of Preparation Example 1, except that 5- (2-nitrophenyl) -1H-benzo [d] imidazole (5.2 g, 21.75 mmol) was used instead of 5- (2-nitrophenyl) -1H-indole.
- the synthesis was carried out to obtain 5- (2-nitrophenyl) -1-phenyl-1H-benzo [d] imidazole (6.84 g, 71% yield).
- 6-bromo-1H-indole instead of 5-bromo-1H-indole, 6- (4,4,5,5-tetramethyl was carried out in the same manner as in ⁇ Step 1> of Preparation Example 1 -1,3,2-dioxaborolan-2-yl) -1H-indole was obtained.
- 6- (2-nitrophenyl) -1H-indole instead of 5- (2-nitrophenyl) -1H-indole, 6- (2 -nitrophenyl) -1-phenyl-1H-indole was obtained.
- IC-6 (3.20 g, 7.31 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-), which are the compounds prepared in Preparation Example 6 under nitrogen stream dioxaborolan-2-yl) phenyl) -1,3,5-triazine (3.81 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3 ) 4 (0.25 g, 0.21 mmol) and 1,4 -dioxane, H 2 O (30 ml, 8 ml) was mixed and stirred at 100 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate and filtered with MgSO 4 . After removing the solvent of the organic layer filtered to obtain the target compound Com-14 (2.67 g, 55% yield) using column chromatography.
- the glass substrate coated with ITO Indium tin oxide
- ITO Indium tin oxide
- a solvent such as isopropyl alcohol, acetone, methanol
- UV OZONE cleaner Power sonic 405, Hwashin Tech
- M-MTDATA 60 nm using the C-1 to C-7 as the first host and the compounds represented by the Com-1 to Com-16 as the second host, respectively, on the prepared ITO transparent substrate.
- / TCTA 80 nm) / 90% of the first and second host + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al ( 200 nm) was laminated in order to fabricate an organic EL device.
- the structures of m-MTDATA, TCTA, Ir (ppy) 3 and BCP used are as follows, and the mixing ratio of the first host and the second host is 7: 3.
- Example 1 On the prepared ITO transparent substrate, m-MTDATA (60 nm) / TCTA (80 nm) / 90% of C-3 as the first host and the compound represented by the Com-1 as the second host Organic electroluminescence by stacking the first host and the second host + 10% Ir (ppy) 3 (300nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) The device was produced.
- An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% CBP + 10% Ir (ppy) 3 was used to form the emission layer. At this time, the structure of the CBP used is as follows.
- An organic EL device was manufactured in the same manner as in Example 1, except that 90% of the second host (Com-1) + 10% Ir (ppy) 3 was used to form the emission layer.
- An organic EL device was manufactured in the same manner as in Example 1, except that 90% of the first host (C-3) + 10% Ir (ppy) 3 was used to form the emission layer.
- Example 1 Sample Host Usage Rate Driving voltage (V) Current efficiency (cd / A) Example 1 70% C-1 + 30% Com-1 6.10 42.9 Example 2 70% C-1 + 30% Com-2 6.15 42.8 Example 3 70% C-1 + 30% Com-3 6.15 42.8 Example 4 70% C-1 + 30% Com-4 6.10 42.9 Example 5 70% C-1 + 30% Com-5 6.10 42.5 Example 6 70% C-1 + 30% Com-6 6.25 42.6 Example 7 70% C-1 + 30% Com-7 6.15 42.5 Example 8 70% C-1 + 30% Com-8 6.20 42.9 Example 9 70% C-1 + 30% Com-9 6.25 43.0 Example 10 70% C-1 + 30% Com-10 6.20 42.7 Example 11 70% C-1 + 30% Com-11 6.25 42.9 Example 12 70% C-1 + 30% Com-12 6.35 42.5 Example 13 70% C-1 + 30% Com-13 6.30 43.2 Example 14 70% C-1 + 30% Com-14 6.10 43.0 Example 15 70% C-1 + 30% Com-15 6.25 42.9 Example 16 70% C-2 + 30% Com-1 6.25 43.1 Example 17 70% C-2 + 30% Com-2 6.20 42.9 Example 18 70% C-2 + 30% Com
- the organic electroluminescent device of Examples 1 to 81 using the light emitting layer including the first host and the second host is Comparative Example 1 using a conventional CBP; Or compared with the organic electroluminescent device of Comparative Example 2 and Comparative Example 3 using the light emitting layer containing Com-1 and C-3 as a single host material, it was confirmed that the excellent performance in terms of current efficiency and driving voltage. .
Abstract
The present invention provides an organic electroluminescent device comprising: an anode; a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers includes a first host and a second host.
Description
본 발명은 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to an organic electroluminescent device comprising at least one organic material layer.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때, 유기물층으로 사용되는 물질은 그 기능에 따라, 발광 물질, 정공주입 물질, 정공수송 물질, 전자수송 물질, 전자주입 물질 등으로 분류될 수 있다.In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to its function.
유기 전계 발광 소자의 발광 효율을 높이기 위해서는 색순도 증가와 에너지 전이가 필요한데, 이를 위해 호스트 물질과 도펀트 물질이 혼합된 발광 물질을 사용할 수 있다. 상기 도펀트 물질은 유기 물질을 사용하는 형광 도펀트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도펀트로 나눌 수 있다. 이때, 인광 물질은 이론적으로 형광 물질에 비해 4배까지 발광 효율을 향상시킬 수 있기 때문에, 인광 도펀트 뿐만 아니라 인광 호스트에 대한 연구가 많이 진행되고 있다. 현재 발광층의 인광 도펀트 물질로는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 알려져 있으며, 인광 호스트 물질로는 CBP가 알려져 있다.In order to increase the luminous efficiency of the organic electroluminescent device, it is necessary to increase the color purity and to transfer energy. For this, a light emitting material mixed with a host material and a dopant material may be used. The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphor can theoretically improve the luminous efficiency up to four times as compared to the fluorescent material, studies on phosphorescent hosts as well as phosphorescent dopants have been conducted. Currently, as a phosphorescent dopant material of the light emitting layer, metal complex compounds including Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and CBP is known as a phosphorescent host material.
그러나, 종래의 물질들은 유리전이온도가 낮아 열적 안정성이 좋지 않기 때문에, 유기 전계 발광 소자에서의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다. 따라서, 우수한 성능을 가지는 발광 물질을 포함하는 유기 전계 발광 소자의 개발이 요구되고 있다.However, the conventional materials do not have a satisfactory level in terms of lifespan in the organic electroluminescent device because of the low glass transition temperature and poor thermal stability. Therefore, there is a demand for the development of an organic EL device including a light emitting material having excellent performance.
본 발명은 상기한 문제점을 해결하기 위해, 구동전압, 발광효율 및 수명 등의 특성이 향상된 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide an organic electroluminescent device having improved characteristics such as driving voltage, luminous efficiency and lifetime.
상기한 목적을 달성하기 위해, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 제1 호스트와 제2 호스트를 포함하되, 상기 제1 호스트는 하기 화학식 1로 표시되는 화합물이며, 상기 제2 호스트는 하기 화학식 2로 표시되는 화합물인 것을 특징으로 하는 유기 전계 발광 소자를 제공한다.In order to achieve the above object, the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers includes a first host and a second host, wherein the first host is represented by Formula 1 below. It is a compound, wherein the second host provides an organic electroluminescent device, characterized in that the compound represented by the formula (2).
화학식 1 
Formula 1
상기 화학식 1에서,In Chemical Formula 1,
Ra 내지 Rd는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1~C40의 알킬기, 및 치환 또는 비치환된 C6~C60의 아릴기로 이루어진 군에서 선택되고,R a to R d are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 40 alkyl group, and a substituted or unsubstituted C 6 to C 60 aryl group Selected,
화학식 2 
Formula 2
상기 화학식 2에서,In Chemical Formula 2,
X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고,X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
Y1 내지 Y4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 이때 C(R1)이 복수 개인 경우 복수의 R1은 각각 동일하거나 상이하고, 이들은 각각 인접한 기와 축합 고리를 형성할 수 있고;Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein when there are a plurality of C (R 1 ), a plurality of R 1 are the same or different, and each of them is adjacent to a group; Can form condensed rings;
X2 및 X3는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R2)이고, 이때 C(R2)가 복수 개인 경우 복수의 R2는 각각 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있고;X 2 and X 3 are the same or different from each other, and each independently N or C (R 2 ), wherein when there are a plurality of C (R 2 ), a plurality of R 2 are each the same or different, and they are condensed with adjacent groups May form a ring;
상기 R1 내지 R2 및 Ar1 내지 Ar5는 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C1~C40의 포스핀기, 치환 또는 비치환된 C1~C40의 포스핀옥사이드기 및 치환 또는 비치환된 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C 1 to C 40 An alkyl group, a substituted or unsubstituted C 2 -C 40 alkenyl group, a substituted or unsubstituted C 2 -C 40 alkynyl group, a substituted or unsubstituted C 3 -C 40 cycloalkyl group, a substituted or unsubstituted nucleus Heterocycloalkyl group having 3 to 40 atoms, substituted or unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 An alkyloxy group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 1 -C 40 alkylsilyl group, a substituted or unsubstituted C 6 -C 60 arylsilyl group, Substituted or unsubstituted C 1 to C 40 alkylboron group, substituted or unsubstituted C 6 to C 60 arylboron group, substituted or unsubstituted C Is selected from 1 ~ C 40 of the phosphine group, a substituted or unsubstituted C 1 ~ C 40 phosphine oxide group, and the group consisting of a substituted or unsubstituted C 6 ~ C 60 aryl amine,
상기 Ra 내지 Rd, R1 내지 R2 및 Ar1 내지 Ar5에서, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기가 치환될 경우는, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다.In the R a to R d , R 1 to R 2 and Ar 1 to Ar 5 , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, When an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group and an arylamine group are substituted, each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 a ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, a nuclear atoms, 3 to 40 hetero cycloalkyl group, C 6 ~ C 40 of the An aryl group, a heteroaryl group having 5 to 40 nuclear atoms, an alkyloxy group of C 1 to C 40 , an aryloxy group of C 6 to C 60 , an alkylsilyl group of C 1 to C 40 , and a C 6 to C 60 group aryl silyl group, a C 1 ~ C 40 group of an alkyl boron, C 6 ~ C 60 aryl boron group, a C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ C 60 of the With arylamine groups It may be substituted with one or more selected from the group consisting of.
여기서, 상기 제1호스트와 제2호스트를 포함하는 유기물층은 인광 발광층인 것이 바람직하다. Here, the organic material layer including the first host and the second host is preferably a phosphorescent layer.
또한 상기 발광층은 금속 착체 화합물계 도펀트를 포함하는 것이 바람직하다. In addition, the light emitting layer preferably includes a metal complex compound dopant.
본 발명의 유기 전계 발광 소자는 제1 호스트와 제2 호스트를 포함하는 유기물층을 포함하되, 제1 호스트와 제2호스트로서 각각 상기 화학식 1로 표시되는 화합물과 상기 화학식 2로 표시되는 화합물을 혼용함으로써, 소자의 구동전압, 발광효율 및 수명 등이 향상될 수 있다. 따라서, 본 발명의 유기 전계 발광 소자를 사용하여 디스플레이 패널을 제조할 경우, 성능 및 수명이 향상된 디스플레이 패널을 제공할 수 있다.The organic electroluminescent device of the present invention comprises an organic material layer comprising a first host and a second host, by mixing the compound represented by the formula (1) and the compound represented by the formula (2) as the first host and the second host, respectively The driving voltage, luminous efficiency, and lifespan of the device can be improved. Therefore, when manufacturing a display panel using the organic electroluminescent device of the present invention, it is possible to provide a display panel with improved performance and lifespan.
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명의 유기 전계 발광 소자는 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 제1 호스트와 제2 호스트를 포함하고, 상기 제1 호스트는 상기 화학식 1로 표시되는 화합물이며, 상기 제2 호스트는 하기 화학식 2로 표시되는 화합물인 것을 특징으로 한다.The organic electroluminescent device of the present invention includes an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, and at least one of the at least one organic layer includes a first host and a second host. The first host is a compound represented by Chemical Formula 1, and the second host is a compound represented by Chemical Formula 2 below.
본 발명에서 제 1 호스트로 사용되는, 상기 화학식 1로 표시되는 화합물은 3,3'-비스카바졸 기본 골격에 수소, 중수소, C1~C40의 알킬기 또는 C6~C60의 아릴기가 치환될 수 있다. The compound represented by Chemical Formula 1, which is used as the first host in the present invention, substitutes hydrogen, deuterium, an alkyl group of C 1 to C 40 or an aryl group of C 6 to C 60 to a 3,3'-biscarbazole base skeleton. Can be.
일반적으로 카바졸(carbazole) 골격은 전자 공여성 및 정공 수송성이 큰 전자주게기(Electron Donating Group) 특성을 가진다. 따라서 상기 화학식 1과 같이 카바졸 골격이 분자 내에 2개 포함될 경우 높은 정공 수송성을 가지게 되며, 또한 카바졸 골격이 1개일 때 보다 분자량이 유의적으로 증가하여 높은 열안정성을 가지게 된다. 특히 3,3'결합된 비스카바졸(biscarbazole) 형태의 기본 골격은 카바졸의 주요 결합 부위로, 2개의 카바졸을 견고하게 연결하여 분자 자체의 열적, 전기적 안정성을 강화시킬 수 있다. In general, the carbazole skeleton has the characteristics of an electron donating group having high electron donating and hole transporting properties. Therefore, as shown in Formula 1, when two carbazole skeletons are included in the molecule, the carbazole skeleton has a high hole transporting property, and when the carbazole skeleton is one, the molecular weight is significantly increased to have high thermal stability. In particular, the basic skeleton in the form of 3,3 'bonded biscarbazole is the main binding site of carbazole, and can firmly connect two carbazoles to enhance the thermal and electrical stability of the molecule itself.
본 발명에 따라 상기 화학식 1로 표시되는 화합물에서, Ra 내지 Rd는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, C1~C40의 알킬기 및 C6~C60의 아릴기로 구성된 군에서 선택된다. 보다 구체적으로, 상기 Ra 내지 Rd는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 메틸, 에틸, 프로필, iso-프로필, t-부틸, 페닐, 비페닐 등으로 이루어진 군에서 선택될 수 있다. 전술한 치환체인 알킬기, 아릴기는 전자 공여성 및 정공 수송성을 가짐으로써, 분자 내의 전자주게기(Electron Donating Group) 특성을 강화시킨다. 본 발명에서, Ra 내지 Rd는 각각 독립적으로 페닐기인 것이 바람직하며, 이때 페닐기의 결합 위치는 특별히 한정되지 않으며, 비제한적이다.In the compound represented by Chemical Formula 1 according to the present invention, R a to R d are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group of C 1 to C 40 and an aryl group of C 6 to C 60 . Selected from the group. More specifically, R a to R d are the same as or different from each other, and each independently may be selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, t-butyl, phenyl, biphenyl, and the like. . Alkyl and aryl groups, which are the aforementioned substituents, have electron donating and hole transporting properties, thereby enhancing the characteristics of the electron donating group in the molecule. In the present invention, R a to R d are each independently preferably a phenyl group, and the bonding position of the phenyl group is not particularly limited and is not limited.
본 발명에 따라 화학식 1로 표시되는 화합물은, 하기 화학식으로 이루어진 화합물 군으로 보다 구체화될 수 있다. 그러나 이에 특별히 한정되는 것은 아니다.The compound represented by the formula (1) according to the present invention can be more embodied in a compound group consisting of the following formula. However, this is not particularly limited.
본 발명에서 제2 호스트로 사용되는, 상기 화학식 2로 표시되는 화합물은 인돌계 기본 골격에 축합 탄소고리 또는 축합 헤테로환 모이어티, 바람직하게는 축합 헤테로환 모이어티가 연결되고, 여러 치환체에 의해 에너지 레벨이 조절됨으로써 넓은 에너지 밴드 갭(sky blue ~ red)을 가진다. 이에 따라, 화학식 2로 표시되는 화합물을 유기 전계 발광 소자의 유기물층의 제 2 호스트로 사용할 경우, 유기 전계 발광 소자의 발광(인광)특성이 개선됨과 동시에 전자 및/또는 정공 수송 능력, 발광 능력을 높일 수 있다.The compound represented by Formula 2, which is used as the second host in the present invention, is a condensed carbon ring or a condensed heterocyclic moiety, preferably a condensed heterocyclic moiety, connected to an indole-based skeleton, and is energized by various substituents. The level is adjusted to have a wide energy band gap (sky blue to red). Accordingly, when the compound represented by Formula 2 is used as the second host of the organic material layer of the organic light emitting device, the light emitting (phosphorescence) characteristics of the organic light emitting device are improved, and the electron and / or hole transporting ability and the light emitting ability are improved. Can be.
보다 구체적으로, 상기 화학식 2로 표시되는 화합물은 인돌계 기본골격에 다양한 방향족 환(aromatic ring)이 치환체로 결합되어 화합물의 분자량이 유의적으로 증대된다. 따라서, 유리전이온도(Tg)가 향상되고 이로 인해 종래 CBP보다 높은 열적 안정성을 가질 수 있다. 또한 인돌계 기본골격에 결합된 다양한 방향족 환 치환체로 인해 분자 전체가 바이폴라(bipolar)한 성격을 가지면서 정공과 전자의 결합력을 높일 수 있기 때문에, 종래 CBP에 비해 발광층의 인광 호스트 물질로서 우수한 특성을 나타낼 수 있다.More specifically, in the compound represented by Formula 2, various aromatic rings are bonded to the indole-based backbone as a substituent to significantly increase the molecular weight of the compound. Therefore, the glass transition temperature (Tg) is improved and thereby may have a higher thermal stability than the conventional CBP. In addition, due to the various aromatic ring substituents bound to the indole-based backbone, the whole molecule has a bipolar characteristic and can enhance the binding force between holes and electrons. Can be represented.
본 발명에 따른 화학식 2로 표시되는 화합물에서, X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택된다. In the compound represented by the formula (2) according to the present invention, X 1 in the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ) Is selected.
또한 Y1 내지 Y4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R1)이다. 이때 C(R1)이 복수 개인 경우 복수의 R1은 각각 동일하거나 상이할 수 있으며, 이들은 각각 인접한 기와 축합 고리를 형성할 수 있다. In addition, Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ). In this case, when there are a plurality of C (R 1 ), a plurality of R 1 may be the same or different, and each of them may form a condensed ring with an adjacent group.
X2 및 X3는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R2)이다. 이때 C(R2)이 복수 개인 경우 복수의 R2는 각각 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있다. X 2 and X 3 are the same as or different from each other, and are each independently N or C (R 2 ). In this case, when there are a plurality of C (R 2 ), a plurality of R 2 are the same or different, and they may form a condensed ring with an adjacent group.
본 발명에서 '인접(adjacent)한 기와 축합고리를 형성하는 것'은, 서로 인접하는 2개 이상 복수의 치환기끼리 결합하여 당 분야에 알려진 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 또는 축합 헤테로 방향족 고리를 형성하는 것을 의미한다. In the present invention, 'to form a condensed ring with an adjacent group (adjacent)', two or more adjacent plural substituents are bonded to each other condensed aliphatic ring, condensed aromatic ring, condensed heteroaliphatic ring, or condensation known in the art It means forming a heteroaromatic ring.
상기 화학식 2로 표시되는 화합물은 하기 A-1 내지 A-24로 보다 구체화될 수 있으나, 이에 한정되는 것은 아니다.The compound represented by Chemical Formula 2 may be more specific as A-1 to A-24, but is not limited thereto.
상기 A-1 내지 A-24에서, In the above A-1 to A-24,
R2, Y1 내지 Y4 및 Ar1 내지 Ar5는 전술한 화학식 2에 정의된 바와 동일하다. 이때 화합물의 물리적, 화학적 특성을 고려했을 때, A-1 내지 A-6인 경우가 바람직하다.R 2 , Y 1 to Y 4 and Ar 1 to Ar 5 are the same as defined in Formula 2 above. In this case, considering the physical and chemical properties of the compound, the case of A-1 to A-6 is preferable.
한편 본 발명의 화학식 2로 표시되는 화합물은, 화학식 2의 구조로 단독 사용되거나, 또는 상기 화학식 2가 하기 화학식 3 또는 화학식 4와 결합하여 축합 구조를 형성할 수 있다.Meanwhile, the compound represented by Chemical Formula 2 of the present invention may be used alone as the structure of Chemical Formula 2, or Chemical Formula 2 may be combined with the following Chemical Formula 3 or Chemical Formula 4 to form a condensation structure.
보다 구체적으로, 상기 화학식 2에서 Y1 내지 Y4가 복수 개의 C(R1)인 경우, Y1과 Y2, Y2와 Y3 또는 Y3와 Y4 중 하나는 하기 화학식 3과 축합 고리를 형성할 수 있다. 이때 복수의 R1은 각각 동일하거나 상이할 수 있다. 일례로, 화학식 2의 Y1 내지 Y4는 화학식 3의 X9와 X10과 결합할 수 있다. More specifically, when Y 1 to Y 4 in Formula 2 are a plurality of C (R 1 ), one of Y 1 and Y 2 , Y 2 and Y 3 or Y 3 and Y 4 is a condensed ring with Formula 3 Can be formed. In this case, a plurality of R 1 may be the same or different, respectively. For example, Y 1 to Y 4 of Chemical Formula 2 may be combined with X 9 and X 10 of Chemical Formula 3.
또한, 상기 화학식 2에서 X2 및 X3가 모두 C(R2)인 경우, 이때 복수의 R2는 하기 화학식 3 또는 화학식 4와 서로 결합하여 축합 고리를 형성할 수 있다. 바람직하게는 화학식 4와 결합하여 축합고리를 형성할 수 있다. 일례로, 화학식 2의 X2와 X3는 화학식 4의 Y11 내지 Y14와 결합하여 축합고리를 형성할 수 있다. In addition, when both X 2 and X 3 in the formula ( 2 ) is C (R 2 ), a plurality of R 2 may be combined with each of the following formula (3) or formula (4) to form a condensed ring. Preferably it may be combined with Formula 4 to form a condensed ring. For example, X 2 and X 3 of Formula 2 may combine with Y 11 to Y 14 of Formula 4 to form a condensed ring.
화학식 3 
Formula 3
화학식 4 
Formula 4
상기 화학식 3 및 화학식 4 에서,In Chemical Formulas 3 and 4,
Y5 내지 Y14은 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R3)이고, 이때 C(R3)가 복수 개인 경우 복수의 R3는 각각 동일하거나 상이하고, 이들은 상기 화학식 2와 결합하여 축합 고리(환)를 형성할 수 있고, Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), and in the case where there are a plurality of C (R 3 ), a plurality of R 3 are the same as or different from each other, and they are represented by Formula 2 above. To form a condensed ring (ring),
X4는 전술한 X1과 동일하고, 이때 복수의 Ar1 내지 Ar5은 각각 동일하거나 상이하다.X 4 is the same as X 1 described above, wherein a plurality of Ar 1 to Ar 5 are the same or different, respectively.
상기 화학식 2와 축합 고리를 비(非)형성하는 R3는 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C1~C40의 포스핀기, 치환 또는 비치환된 C1~C40의 포스핀옥사이드기 및 치환 또는 비치환된 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 또는 이들은 인접한 기와 결합하여 축합 고리를 형성할 수 있다. R 3 non-forming a condensed ring with Formula 2 is each independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C 1 ~ C 40 alkyl, substituted or Unsubstituted C 2 -C 40 alkenyl group, substituted or unsubstituted C 2 -C 40 alkynyl group, substituted or unsubstituted C 3 -C 40 cycloalkyl group, substituted or unsubstituted nuclear atom 3 to 40 heterocycloalkyl groups, substituted or unsubstituted C 6 to C 60 aryl groups, substituted or unsubstituted heteroaryl groups having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 alkyloxy groups , Substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 1 -C 40 alkylsilyl group, substituted or unsubstituted C 6 -C 60 arylsilyl group, substituted or unsubstituted a C 1 ~ C 40 alkyl boron group, a substituted or unsubstituted C 6 ~ C 60 aryl boron group, a substituted or unsubstituted C 1 ~ C 40 of the phosphine , Is selected from substituted or unsubstituted C 1 ~ phosphine oxide of a C 40 group, and a substituted or unsubstituted group consisting of a ring with an aryl amine of the C 6 ~ C 60, or they may combine adjacent groups may form a condensed ring .
상기 R3에서 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기가 치환될 경우는, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다.In R 3 , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, a phosphine oxide group, and aryl amine groups are each independently selected from deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C case be substituted 2 or an alkynyl group of C 40, C 3 ~ C 40 cycloalkyl group, a number of the aryl group, the nucleus of atoms of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ~ C 40 of from 5 to 40 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 1 ~ C 40 alkyl silyl group, C 6 ~ aryl silyl group of C 60, C 1 ~ C 40 group of an alkyl boron, C 6 a group - C 60 aryl boron, C 1 ~ C 40 of the phosphine group, at least one selected from the group consisting of C 1 ~ C 40 of the phosphine oxide group, and a C 6 ~ C 60 aryl amines Hwandoel can.
본 발명에서, 상기 화학식 2와 화학식 3이 축합하여 형성된 화합물은 하기 화학식 2a 내지 2f로 표시되는 화합물로 보다 구체화될 수 있다.In the present invention, the compound formed by condensation of Chemical Formula 2 and Chemical Formula 3 may be further embodied as a compound represented by Chemical Formulas 2a to 2f.
[화학식 2a][Formula 2a]
[화학식 2b][Formula 2b]
[화학식 2c][Formula 2c]
[화학식 2d][Formula 2d]
[화학식 2e][Formula 2e]
[화학식 2f][Formula 2f]
상기 화학식 2a 내지 2f에서, In Chemical Formulas 2a to 2f,
X1 내지 X4 및 Y1 내지 Y8 은 각각 화학식 2 및 화학식 3에서 정의한 바와 같다.X 1 to X 4 and Y 1 to Y 8 are the same as defined in Chemical Formula 2 and Chemical Formula 3, respectively.
보다 구체적으로, 축합 고리를 비(非)형성하는 Y1 내지 Y4는 N 또는 C(R1)이고, 이때 Y1 내지 Y4가 모두 C(R1)인 경우가 바람직하다. More particularly, Y 1 to Y 4 to form a condensed ring ratio (非) is N or C (R 1), wherein if the Y 1 to Y 4 are both C (R 1) is preferred.
또한 Y5 내지 Y8은 N 또는 C(R3)이고, 이때 Y5 내지 Y8이 모두 C(R3)인 경우가 바람직하다. 이때 복수의 R1 및 R3는 각각 동일하거나 상이하다.In addition, the Y 5 to Y 8 is a case of N or C (R 3) a, wherein Y 5 to Y 8 are both C (R 3) are preferred. In this case, a plurality of R 1 and R 3 are the same or different, respectively.
상기 화학식 2와 화학식 3이 축합된 본 발명의 화합물은 하기 화학식 B-1 내지 B-30으로 이루어진 화합물 군으로 보다 구체화될 수 있다. 그러나, 이에 특별히 한정되는 것은 아니다.Compounds of the present invention in which Formula 2 and Formula 3 are condensed may be more specifically formulated into a compound group consisting of Formulas B-1 to B-30. However, this is not particularly limited.
상기 화학식 B-1 내지 B-30에서, Ar1 및 R1 내지 R3는 전술한 화학식 2 및 화학식 3에서 정의한 바와 동일하다.In Formulas B-1 to B-30, Ar 1 and R 1 to R 3 are the same as defined in Formula 2 and Formula 3 above.
보다 구체적으로, Ar1은 치환 또는 비치환된 C6~C40의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기이며,More specifically, Ar 1 is a substituted or unsubstituted C 6 ~ C 40 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms,
R1 내지 R3은 각각 독립적으로 수소, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C40의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기인 경우가 바람직하다. R 1 to R 3 are each independently hydrogen, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, or a substituted or unsubstituted nuclear atom 5 to 40 It is preferable when it is a heteroaryl group of.
여기서, 상기 화학식 2 및 화학식 3이 축합하여 형성된 구조를 가지는 상기 화학식 B-1 내지 B-30은 1개 이상의 축합된 인돌 혹은 축합된 카바졸 모이어티를 포함한다. Here, Formulas B-1 to B-30 having a structure formed by condensation of Formulas 2 and 3 include one or more condensed indole or condensed carbazole moieties.
본 발명에서, 상기 화학식 2와 화학식 4가 축합하여 형성된 화합물은 하기 화학식 2g 내지 2n으로 표시되는 화합물로 보다 구체화될 수 있다.In the present invention, the compound formed by condensation of Chemical Formula 2 and Chemical Formula 4 may be further embodied as a compound represented by Chemical Formula 2g to 2n.
[화학식 2g][Formula 2g]
[화학식 2h][Formula 2h]
[화학식 2i][Formula 2i]
[화학식 2j][Formula 2j]
[화학식 2k][Formula 2k]
[화학식 2l][Formula 2l]
[화학식 2m][Formula 2m]
[화학식 2n][Formula 2n]
상기 화학식 2g 내지 2n 에서, X1, X4 및 Y1 내지 Y14 는 각각 전술한 화학식 2 및 화학식 4에서 정의한 바와 같다.In Formulas 2g to 2n, X 1 , X 4 and Y 1 to Y 14 are the same as defined in Formula 2 and Formula 4, respectively.
보다 구체적으로, X1 및 X4는 각각 독립적으로 O, S 또는 N(Ar1)인 것이 바람직하며, X1 및 X4가 모두 N(Ar1)인 것이 더욱 바람직하며, 이때 복수의 Ar1은 각각 동일하거나 상이하다.More specifically, X 1 and X 4 are each independently O, S or N (Ar 1 ), it is more preferable that both X 1 and X 4 is N (Ar 1 ), wherein a plurality of Ar 1 Are the same or different, respectively.
Y1 내지 Y4는 각각 독립적으로 N 또는 C(R1)이고, 이중 Y1 내지 Y4가 모두 C(R1)인 것이 바람직하며, 이때 복수의 R1은 각각 동일하거나 상이하다.Y 1 to Y 4 are each independently N or C (R 1 ), and preferably Y 1 to Y 4 are all C (R 1 ), wherein a plurality of R 1 are the same or different.
Y5 내지 Y14는 각각 독립적으로 N 또는 C(R3)이고, 이중 Y5 내지 Y14가 모두 C(R3)인 것이 바람직하며, 이때 복수의 R3은 동일하거나 상이하다.Y 5 to Y 14 are each independently N or C (R 3 ), and preferably Y 5 to Y 14 are all C (R 3 ), wherein a plurality of R 3 are the same or different.
여기서, Ar1 및 R1 내지 R3는 전술한 화학식 2 및 화학식 4에서 정의한 바와 동일하다.Here, Ar 1 and R 1 to R 3 are the same as defined in the above formula (2) and (4).
본 발명에서 유기 전계 발광 소자의 발광 효율, 구동 전압 및 수명 등의 특성을 고려할 때, 제2 호스트로 사용되는 화학식 2a 내지 화학식 2n 중 어느 하나로 표시되는 화합물은, X1 및 X4가 각각 독립적으로 N(Ar1) 또는 S인 것이 바람직하다. 즉, X1이 N(Ar1)이고 X4가 S이거나, X1이 S이고 X4가 N (Ar1)이거나, 또는 X1 및 X4가 모두 N(Ar1)인 것이 바람직하다.In consideration of characteristics such as luminous efficiency, driving voltage, and lifetime of the organic electroluminescent device in the present invention, the compound represented by any one of Formulas 2a to 2n used as the second host, X 1 and X 4 are each independently It is preferred that it is N (Ar 1 ) or S. That is, it is preferable that X 1 is N (Ar 1 ) and X 4 is S, X 1 is S and X 4 is N (Ar 1 ), or both X 1 and X 4 are N (Ar 1 ).
또한 상기 화학식 2a 내지 화학식 2n 로 표시되는 화합물에서, Ar1은 치환 또는 비치환된 C6~C60의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기인 것이 바람직하며, Ar2 내지 Ar5는 서로 동일하거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기(구체적으로, 메틸기) 또는 치환 또는 비치환된 C6~C60의 아릴기(구체적으로 페닐기)인 것이 바람직하다. In addition, in the compound represented by Formula 2a to Formula 2n, Ar 1 is preferably a substituted or unsubstituted C 6 ~ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, Ar 2 to Ar 5 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group (specifically, a methyl group) or a substituted or unsubstituted C 6 to C 60 aryl group (specifically Phenyl group) is preferable.
특히 상기 Ar1은 하기 화학식 5로 표시되는 치환체이거나 또는 페닐기인 것이 바람직하다.In particular, Ar 1 is preferably a substituent represented by the following formula (5) or a phenyl group.
화학식 5 
Formula 5
상기 화학식 5에서,In Chemical Formula 5,
L은 단일결합, 치환 또는 비치환된 C6~C18의 아릴렌기 및 치환 또는 비치환된 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택되고,L is selected from the group consisting of a single bond, a substituted or unsubstituted C 6 ~ C 18 arylene group and a substituted or unsubstituted heteroarylene group having 5 to 18 nuclear atoms,
Z1 내지 Z5는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R11)이며, 이때 Z1 내지 Z5 중 적어도 하나는 N이고,Z 1 to Z 5 are the same as or different from each other, and each independently N or C (R 11 ), wherein at least one of Z 1 to Z 5 is N,
R11이 복수 개인 경우, 이들은 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 치환 또는 비치환된 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴아민기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴실릴기로 이루어진 군에서 선택되고, 또는 이들이 인접하는 기와 결합하여 축합 고리를 형성할 수 있으며,When there are a plurality of R 11 s , they are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted substituted or unsubstituted C 1 to C 40 alkyl group, substituted or Unsubstituted C 2 -C 40 alkenyl group, substituted or unsubstituted C 2 -C 40 alkynyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl groups, substituted or unsubstituted C 6 -C 60 aryloxy groups, substituted or unsubstituted C 1 -C 40 alkyloxy groups, substituted or unsubstituted C 3 -C 40 cycloalkyl groups, Substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 to C 60 arylamine group, substituted or unsubstituted C 1 to C 40 alkylsilyl group, substituted or unsubstituted a C 1 ~ C 40 alkyl group of boron, a substituted or unsubstituted C 6 ~ C 60 aryl boron group, a substituted or unsubstituted C 6 ~ C 60 aryl phosphine group, a substituted or unsubstituted C 6 ~ C 60 aryl phosphine oxide group, and a substituted or unsubstituted aryl silyl group of unsubstituted C 6 ~ C 60 of is selected from the group consisting, or they Can combine with adjacent groups to form a condensed ring,
상기 L 및 R11에서, 아릴렌기, 헤테로아릴렌기, 알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 시클로알킬기, 헤테로시클로알킬기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C40 60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환될 수 있으며, 이때 상기 치환기가 복수 개인 경우, 이들은 서로 동일하거나 또는 상이할 수 있다.In the above L and R 11 , arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl Group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 6 ~ C 60 Aryl group, Nuclear 5 to 60 heteroaryl group, C 6 ~ C 40 60 Aryloxy group, C 1 ~ C 40 Alkyl Oxy group, C 6 to C 60 arylamine group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 1 to C 40 alkylsilyl group, C 1 to C 40 alkyl a boron group, the group consisting of C 6 ~ C 60 aryl group of boron, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl group in the silyl It may be substituted or unsubstituted with one or more substituents selected, wherein when there are a plurality of the substituents, they may be the same or different from each other.
상기 화학식 5로 표시되는 치환체에서, L은 단일결합, 페닐렌기 또는 비페닐렌기인 것이 바람직하다. In the substituent represented by Formula 5, L is preferably a single bond, a phenylene group or a biphenylene group.
또한 *는 상기 화학식 2에 결합되는 부분을 의미하고, Z1 내지 Z5 중 둘 이상이 C(R11)일 경우, 복수의 R11은 서로 동일하거나 상이할 수 있다.In addition, * means a part bonded to the formula (2), when two or more of Z 1 to Z 5 is C (R 11 ), a plurality of R 11 may be the same or different from each other.
보다 구체적으로, 상기 화학식 5로 표시되는 치환체는 하기 C-1 내지 C-15로 표시되는 구조로 이루어진 치환체 군에서 선택되는 것이 바람직하다.More specifically, the substituent represented by the formula (5) is preferably selected from a substituent group consisting of a structure represented by the following C-1 to C-15.
상기 C-1 내지 C-15에서, In the above C-1 to C-15,
L 및 R11는 상기 화학식 5에서 정의한 바와 같고,L and R 11 are the same as defined in Formula 5,
R12는 수소, 중수소, 할로겐, 시아노기, 니트로기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴아민기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C6~C60의 아릴포스핀기, 치환 또는 비치환된 C6~C60의 아릴포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴실릴기로 이루어진 군에서 선택되고, 또는 이들이 인접하는 기와 결합하여 축합 고리를 형성할 수 있으며,R 12 is hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C 1 ~ C 40 alkyl group, substituted or unsubstituted C 2 ~ C 40 alkenyl group, substituted or unsubstituted C 2 ~ C 40 alkynyl group, substituted or unsubstituted C 3 to C 40 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryl group, Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 arylamine group, substituted or unsubstituted C 1 ~ C 40 Alkylsilyl group, substituted or unsubstituted C 1 ~ C 40 Alkyl boron group, substituted or unsubstituted C 6 ~ C 60 of the arylboronic group, a substituted or unsubstituted C 6 ~ C 60 aryl phosphine group, a substituted or unsubstituted C 6 ~ C 60 aryl ring of the phosphine oxide group, and a substituted or Unsubstituted C 6 ~ C 60 It is selected from the group consisting of arylsilyl groups, or they can be combined with adjacent groups to form a condensed ring,
n은 1 내지 4의 정수이다.n is an integer of 1-4.
상기 R12에서, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환될 수 있으며, 이때 치환기가 복수 개일 경우, 이들은 서로 동일하거나 상이할 수 있다.In R 12 , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group , Arylphosphine group, arylphosphine oxide group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 Alkynyl group, C 6 ~ C 60 Aryl group, Nuclear 5 to 60 heteroaryl group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryl Amine group, C 3 -C 40 cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C 1 -C 40 alkylsilyl group, C 1 -C 40 alkylboron group, C 6 -C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide of the group and a C 6 ~ value to 1 or more substituents chosen from the group consisting of C 60 aryl silyl Alternatively, if the beach may be unsubstituted, wherein the substituent is clear up a plurality, they may be the same or different from each other.
본 발명의 화학식 2a 내지 화학식 2n으로 표시되는 화합물에서, Ar1 내지 Ar5 및 R1 내지 R3는 각각 독립적으로 수소 또는 하기 치환체(작용기)로 이루어진 치환체 군(S1-S206)에서 선택될 수 있으나, 이에 특별히 한정되는 것은 아니다.In the compounds represented by Formulas 2a to 2n of the present invention, Ar 1 to Ar 5 and R 1 to R 3 may be each independently selected from a substituent group (S1-S206) consisting of hydrogen or the following substituents (functional groups). However, this is not particularly limited.
한편, 본 발명에서의 알킬은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있다.Meanwhile, alkyl in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl. Etc. can be mentioned.
본 발명에서의 알케닐(alkenyl)은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있다.Alkenyl in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl and allyl. ), Isopropenyl, 2-butenyl, and the like.
본 발명에서의 알키닐(alkynyl)은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있다.Alkynyl in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having at least one carbon-carbon triple bond, examples of which are ethynyl, 2- Propanyl (2-propynyl) etc. are mentioned.
본 발명에서의 아릴은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있다.Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are pendant or condensed with each other may also be included. Examples of such aryls include phenyl, naphthyl, phenanthryl, anthryl and the like.
본 발명에서의 헤테로아릴은 핵원자수 5 내지 40의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 아릴기와 축합된 형태도 포함할 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리, 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있다.Heteroaryl in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may also be included, and may also include a form condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like.
본 발명에서의 아릴옥시는 RO-로 표시되는 1가의 치환기로 상기 R은 탄소수 5 내지 60의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있다.Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
본 발명에서의 알킬옥시는 R'O-로 표시되는 1가의 치환기로 상기 R'는 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있다.Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means 1 to 40 alkyl, and includes a linear, branched or cyclic structure Interpret Examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서의 아릴아민은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
본 발명에서의 시클로알킬은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있다.Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
본 발명에서의 헤테로시클로알킬은 핵원자수 3 내지 40의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있다.Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Substituted with a hetero atom such as Se. Examples of such heterocycloalkyl include morpholine, piperazine and the like.
본 발명에서의 알킬실릴은 탄소수 1 내지 40의 알킬로 치환된 실릴이고, 아릴실릴은 탄소수 5 내지 40의 아릴로 치환된 실릴을 의미한다.Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 5 to 40 carbon atoms.
본 발명에서의 축합 고리는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
상기와 같이 구성되는 본 발명의 유기 전계 발광 소자는 복수 개의 유기물층 중 하나 이상이 상기 제 1 호스트와 제 2 호스트를 포함하여 소자로 주입되는 정공과 전자의 균형을 맞출 수 있기 때문에 고수명을 가질 수 있다. 여기서, 유기물층 제조시 제 1 호스트와 제 2 호스트의 혼합비율은 특별히 한정되지 않으며, 일례로 제 1 호스트와 제 2 호스트를 1:99 내지 99:1의 중량 비율로 혼합할 수 있다. 이때, 제 1 호스트의 사용 비율이 더 높은 것이 바람직하다.The organic electroluminescent device of the present invention configured as described above may have a long life because at least one of the plurality of organic material layers may balance holes and electrons injected into the device including the first host and the second host. have. Here, the mixing ratio of the first host and the second host is not particularly limited when the organic layer is manufactured. For example, the first host and the second host may be mixed in a weight ratio of 1:99 to 99: 1. At this time, it is preferable that the use ratio of the first host is higher.
본 발명의 유기 전계 발광 소자에서, 발광층은 단일 발광층일 수 있으며, 또는 복수 개의 발광층을 가져 이들의 혼합색을 구현할 수 있다. 보다 구체적으로, 본 발명에서는 정공수송층과 전자수송층 사이에 복수 개의 발광층을 순차적으로 적층하여 전압, 전류 인가시 이들의 혼합색을 구현할 수 있다. In the organic electroluminescent device of the present invention, the light emitting layer may be a single light emitting layer, or may have a plurality of light emitting layers to implement a mixed color thereof. More specifically, in the present invention, a plurality of light emitting layers may be sequentially stacked between the hole transport layer and the electron transport layer to implement a mixed color thereof when voltage and current are applied.
상기와 같이 정공수송층과 전자수송층 사이에 복수 개의 발광층 또는 이종 재료를 포함하는 복수 개 발광층을 직렬로 구비하는 본 발명의 스택형 유기 전계 발광 소자는 전압, 전류 인가시 혼합색을 구현하거나, 또는 복수 개의 발광층 수만큼 발광 효율을 증가시킬 수 있다.The stacked organic electroluminescent device of the present invention having a plurality of light emitting layers including a plurality of light emitting layers or heterogeneous materials in series between the hole transport layer and the electron transport layer as described above may realize a mixed color when voltage and current are applied or a plurality of light emitting layers. The light emission efficiency can be increased by the number of light emitting layers.
한편, 제 1 호스트와 제 2 호스트를 포함하는 본 발명의 유기물층은 발광층인 것이 바람직하며, 이때 본 발명의 발광층은 제 1 호스트 및 제 2 호스트와 함께 도펀트를 포함할 수 있다.On the other hand, the organic material layer of the present invention including the first host and the second host is preferably a light emitting layer, wherein the light emitting layer of the present invention may include a dopant together with the first host and the second host.
여기서, 상기 발광층에 포함되는 도펀트로 사용 가능한 물질은 당 업계에 알려진 통상적인 도펀트 성분을 제한 없이 사용할 수 있으며, 일례로 이리듐(Ir)을 포함하는 금속 착체 화합물을 사용하는 것이 바람직하다.Here, the material that can be used as the dopant included in the light emitting layer can be used without limitation conventional dopant components known in the art, it is preferable to use a metal complex compound containing iridium (Ir) as an example.
전술한 제 1 호스트, 제 2 호스트 및 도펀트를 포함하는 발광층을 제조하는 방법은 당 업계에 공지된 방법에 따라 특별한 제한 없이 제조될 수 있다. 이하, 상기 발광층을 제조하는 2가지 바람직한 실시형태를 하기에 예시하나, 이에 특별히 한정되는 것은 아니다. The method of manufacturing the light emitting layer including the first host, the second host, and the dopant described above may be manufactured without particular limitation in accordance with methods known in the art. Hereinafter, although two preferable embodiment which manufactures the said light emitting layer is illustrated below, it is not specifically limited to this.
상기 2가지 실시형태 중 첫번째 방법은, 제 1 호스트와 제 2 호스트를 각각 제 1 열원 및 제 2 열원에 위치시키고, 제 3 열원에 도펀트를 위치시켜 동시에 열을 가해 발광층을 형성하는 공증착 방법이다. A first method of the above two embodiments is a co-deposition method of placing a first host and a second host in a first heat source and a second heat source, respectively, and placing a dopant in a third heat source to simultaneously apply heat to form a light emitting layer. .
보다 구체적으로, 1×10-06 torr 이하의 진공도에서, 제1 열원에 정공이동도(Hole mobility)가 높고 정공 주입효율이 좋은 제 2 호스트를 위치시키고, 제2 열원에 전자이동도(Electron mobility)가 높고, 전자 주입효율이 좋은 제 2 호스트를 위치시켜, 제3열원의 도펀트와 초당 증발속도를 조절하여 적정비율로 공증착하는 방법이다. 이때 공증착되는 호스트의 개수는 발광층의 특성에 따라 2개 이상이 될 수 있다. More specifically, at a vacuum degree of 1 × 10 −06 torr or less, a second host having high hole mobility and good hole injection efficiency is placed in the first heat source, and electron mobility is located in the second heat source. A method of co-depositing at a proper ratio by placing a second host having a high c) and having a good electron injection efficiency and controlling a dopant of a third heat source and an evaporation rate per second. In this case, the number of co-deposited hosts may be two or more according to the characteristics of the light emitting layer.
상기 제 1 호스트, 제 2 호스트 및 도펀트의 사용량은 특별히 한정되지 않으며, 일례로 제 1 호스트와 제 2 호스트를 70~99 중량%, 도펀트를 1~30 중량%로 사용할 수 있다. 구체적으로, 제 1 호스트와 제 2 호스트를 80~95 중량%, 도펀트를 5~20 중량%로 사용하는 것이 바람직하다.The amount of the first host, the second host, and the dopant is not particularly limited. For example, the first host, the second host, and the first host and the second host may be 70 to 99% by weight and the dopant to 1 to 30% by weight. Specifically, it is preferable to use 80 to 95 wt% of the first host and the second host, and 5 to 20 wt% of the dopant.
상기 2가지 실시형태 중 두번째 방법은, 사용되는 열원의 개수를 줄이고, 형성과정을 간소화하고자, 발광층 형성에 사용되는 제 1 호스트 및 제 2 호스트를 적정비율로 혼합하여 하나의 열원에 위치시키고 열을 가해 발광층을 형성하는 공증착 방법이다. In the second of the two embodiments, in order to reduce the number of heat sources used and to simplify the formation process, the first host and the second host used for forming the light emitting layer are mixed at an appropriate ratio, placed in one heat source, and heat is removed. It is a co-deposition method which adds and forms a light emitting layer.
보다 구체적으로, 1 × 10-06 이하의 진공도에서 제 1 열원에 혼합된 호스트(제 1 호스트+제 2 호스트)를 위치시키고, 제 2 열원에 도펀트를 위치시켜 동시에 초당 증발속도를 조절하며 발광층을 형성시키는 방법이다. 이러한 두번째 방법은 1종 이상의 호스트를 사용할 경우 발생하는 혼합비율의 오차를 줄이고, 적은 수의 열원으로 발광층을 형성할 수 있다는 이점이 있다. More specifically, by placing the host (first host + second host) mixed in the first heat source at a vacuum degree of 1 × 10 -06 or less, and the dopant is placed in the second heat source at the same time to control the evaporation rate per second It is a method of forming. This second method has the advantage of reducing the mixing ratio error that occurs when using more than one host, and can form a light emitting layer with a small number of heat sources.
이때 상기 제 1 호스트, 제 2 호스트 및 도펀트의 사용량은 특별히 한정되지 않으며, 일례로 제 1 호스트와 제 2 호스트를 70~99 중량%, 도펀트를 1~30 중량% 범위로 사용할 수 있다. 구체적으로, 제 1 호스트와 제 2 호스트를 80~95 중량%, 도펀트를 5~20 중량%로 사용하는 것이 바람직하다.In this case, the amount of the first host, the second host, and the dopant is not particularly limited. For example, the first host, the second host, and the dopant may be used in a range of 70 to 99% by weight, and the dopant to 1 to 30% by weight. Specifically, it is preferable to use 80 to 95 wt% of the first host and the second host, and 5 to 20 wt% of the dopant.
본 발명의 유기 전계 발광 소자에 포함되는 양극으로 사용 가능한 물질은 특별히 한정되지 않으나, 비제한적인 예로 바나듐, 크롬, 구리, 아연, 금 등의 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO) 등의 금속 산화물; ZnO:Al, SnO2:Sb 등의 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤, 폴리아닐린 등의 전도성 고분자; 및 카본블랙 등을 들 수 있다.The material usable as the anode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And carbon black.
본 발명의 유기 전계 발광 소자에 포함되는 음극으로 사용 가능한 물질은 특별히 한정되지 않으나, 비제한적인 예로 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 납 등의 금속 또는 이들의 합금 및 LiF/Al,LiO2/Al 등의 다층 구조 물질 등을 들 수 있다.The material which can be used as the cathode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead Metals such as these, alloys thereof, and multilayered structure materials such as LiF / Al and LiO 2 / Al.
이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 비제한적인 예로 기판, 양극, 유기물층(정공주입층->정공수송층->발광층->전자수송층) 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 상기 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 제 1 호스트로 포함할 수 있다.The structure of the organic EL device of the present invention is not particularly limited, but a non-limiting example is a structure in which a substrate, an anode, an organic material layer (hole injection layer-> hole transport layer-> light emitting layer-> electron transport layer) and a cathode are sequentially stacked. Can be. In this case, at least one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1 as a first host.
한편, 상기 전자수송층 위에는 전자주입층이 추가로 적층될 수 있다. 또한, 본 발명에 따른 유기 전계 발광 소자의 구조는 양극 및 음극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.On the other hand, the electron injection layer may be further stacked on the electron transport layer. In addition, the structure of the organic EL device according to the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the anode and cathode and the organic material layer.
본 발명의 유기 전계 발광 소자는 상기 유기물층 중 1층 이상(예컨대, 발광층)이 상기 제 1 호스트와 제 2 호스트를 포함하도록 형성하는 것을 제외하고는, 당 업계에 알려진 통상적인 물질 및 방법을 이용하여 다른 유기물층을 형성할 수 있다.The organic electroluminescent device of the present invention uses conventional materials and methods known in the art, except that at least one layer (eg, the light emitting layer) of the organic material layer is formed to include the first host and the second host. Another organic material layer can be formed.
한편, 본 발명의 유기 전계 발광 소자 제조시 사용되는 기판은 특별히 한정되지 않으나, 비제한적인 예로 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등을 들 수 있다. The substrate used in the manufacture of the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
이하 본 발명을 실시예를 통하여 상세히 설명하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples.
[준비예 1] IC-1의 합성Preparation Example 1 Synthesis of IC-1
<단계 1> 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
질소 기류 하에서 5-bromo-1H-indole (25 g, 0.128 mol), 4,4,4',4',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (48.58 g, 0.191 mol), Pd(dppf)Cl2 (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) 및 1,4-dioxane (500 ml)를 혼합하고 130℃에서 12시간 동안 교반하였다.5-bromo-1H-indole (25 g, 0.128 mol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3) under nitrogen stream , 2-dioxaborolane) (48.58 g, 0.191 mol), Pd (dppf) Cl 2 (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) and 1,4-dioxane (500 ml) were mixed and 130 ° C Stir at 12 h.
반응이 종결된 후 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 10:1 (v/v))로 정제하여 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22.32 g, 수율 72%)을 얻었다. After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO 4 , purified by column chromatography (Hexane: EA = 10: 1 (v / v)), and purified by 5- (4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl) -1H-indole (22.32 g, yield 72%) was obtained.
1H-NMR: δ 1.24 (s, 12H), 6.45 (d, 1H), 7.27 (d, 1H), 7.42 (d, 1H), 7.52 (d, 1H), 7.95 (s, 1H), 8.21 (s, 1H) 1 H-NMR: δ 1.24 (s, 12H), 6.45 (d, 1H), 7.27 (d, 1H), 7.42 (d, 1H), 7.52 (d, 1H), 7.95 (s, 1H), 8.21 ( s, 1 H)
<단계 2> 5-(2-nitrophenyl)-1H-indole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -1H-indole
질소 기류 하에서 1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol)과 상기 <단계 1>에서 얻은 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22 g, 90.49 mmol), NaOH (9.05 g, 226.24 mmol) 및 THF/H2O(400 ml/200 ml)를 혼합한 다음, 40℃에서 Pd(PPh3)4(4.36 g, 5 mol%)를 넣고 80℃에서 12시간 동안 교반하였다. 1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol) under nitrogen stream and 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) obtained in <Step 1> above -1H-indole (22 g, 90.49 mmol), NaOH (9.05 g, 226.24 mmol) and THF / H 2 O (400 ml / 200 ml) were mixed and then Pd (PPh 3 ) 4 (4.36 g) at 40 ° C. , 5 mol%) was added and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 3:1 (v/v))로 정제하여 5-(2-nitrophenyl)-1H-indole (11.32 g, 수율 63%)을 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1H-indole (11.32 g, 63% yield).
1H-NMR: δ 6.47 (d, 1H), 7.25 (d, 1H), 7.44 (d, 1H), 7.53 (d, 1H), 7.65 (t, 1H), 7.86 (t, 1H), 7.95 (s, 1H), 8.00 (d, 1H), 8.09 (t, 1H), 8.20 (s, 1H) 1 H-NMR: δ 6.47 (d, 1H), 7.25 (d, 1H), 7.44 (d, 1H), 7.53 (d, 1H), 7.65 (t, 1H), 7.86 (t, 1H), 7.95 ( s, 1H), 8.00 (d, 1H), 8.09 (t, 1H), 8.20 (s, 1H)
<단계 3> 5-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indole
질소 기류 하에서 상기 <단계 2>에서 얻은 5-(2-nitrophenyl)-1H-indole (11 g, 46.17 mmol), iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K2CO3 (6.38 g, 46.17 mmol), Na2SO4 (6.56 g, 46.17 mmol), nitrobenzene (200 ml)를 혼합하고 190℃에서 12시간 동안 교반하였다. 5- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol), iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K 2 obtained in the above <Step 2> under a nitrogen stream CO 3 (6.38 g, 46.17 mmol), Na 2 SO 4 (6.56 g, 46.17 mmol) and nitrobenzene (200 ml) were mixed and stirred at 190 ° C. for 12 h.
반응 종결 후 nitrobenzene을 제거하고 메틸렌클로라이드로 유기층을 분리하여 MgSO4를 사용하여 물을 제거하였다. 물이 제거된 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 3:1 (v/v))로 정제하여 5-(2-nitrophenyl)-1-phenyl-1H-indole (10.30 g, 수율 71%)을 얻었다. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO 4 . The solvent was removed from the organic layer, which was freed of water, and then purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1-phenyl-1H-indole (10.30 g, yield). 71%).
1H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.45 (m, 3H), 7.55 (m, 4H), 7.63 (t, 1H), 7.84 (t, 1H), 7.93 (s, 1H), 8.01 (d, 1H), 8.11 (t, 1H) 1 H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.45 (m, 3H), 7.55 (m, 4H), 7.63 (t, 1H), 7.84 (t, 1H), 7.93 ( s, 1H), 8.01 (d, 1H), 8.11 (t, 1H)
<단계 4> IC-1의 합성Step 4 Synthesis of IC-1
질소 기류 하에서 상기 <단계 3>에서 얻은 5-(2-nitrophenyl)-1-phenyl-1H-indole (5 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) 및 1,2-dichlorobenzene (50 ml)를 혼합하고 12시간 동안 교반하였다.5- (2-nitrophenyl) -1-phenyl-1H-indole (5 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) and 1,2-dichlorobenzene (50 ml) obtained in <Step 3> under a nitrogen stream. ) Was mixed and stirred for 12 hours.
반응 종료 후 1,2-dichlorobenzene를 제거하고 디클로로메탄으로 추출하였다. 얻어진 유기층에 대해 MgSO4로 물을 제거하고, 컬럼크로마토그래피 (Hexane:MC=3:1 (v/v))로 정제하여 IC-1 (2.38 g, 수율 53%)을 얻었다. After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. Water was removed with MgSO 4 and the resulting organic layer was purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to obtain IC-1 (2.38 g, yield 53%).
1H-NMR: δ 6.99 (d, 1H), 7.12 (t, 1H), 7.27 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.50 (d, 1H), 7.60 (m, 5H), 7.85 (d, 1H), 8.02 (d, 1H), 10.59 (s, 1H) 1 H-NMR: δ 6.99 (d, 1H), 7.12 (t, 1H), 7.27 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.50 (d, 1H), 7.60 ( m, 5H), 7.85 (d, 1H), 8.02 (d, 1H), 10.59 (s, 1H)
[준비예 2] IC-2의 합성Preparation Example 2 Synthesis of IC-2
<단계 1> 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indazole 의 합성<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole
5-bromo-1H-indole 대신 5-bromo-1H-indazole (25.22 g, 0.128 mol) 을 사용하는 것을 제외하고는, 상기 준비예 1의 단계 1과 동일한 방법으로 합성하여 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indazole (22.49 g, 수율 72%)을 얻었다. Except for using 5-bromo-1H-indazole (25.22 g, 0.128 mol) instead of 5-bromo-1H-indole, it was synthesized in the same manner as in Step 1 of Preparation Example 1 5- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole (22.49 g, yield 72%) was obtained.
1H-NMR: δ 1.24 (s, 12H), 7.60 (d, 1H), 8.15 (m, 2H), 8.34 (d, 1H), 12.34 (s, 1H) 1 H-NMR: δ 1.24 (s, 12H), 7.60 (d, 1H), 8.15 (m, 2H), 8.34 (d, 1H), 12.34 (s, 1H)
<단계 2> 5-(2-nitrophenyl)-1H-indazole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -1H-indazole
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indazole (22.09 g, 90.49 mmol)을 사용한 것을 제외하고는, 상기 준비예 1의 단계 2와 동일한 방법으로 합성하여, 5-(2-nitrophenyl)-1H-indazole (13.64 g, 수율 63%)을 얻었다. 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan 2- (yl) -1H-indazole (22.09 g, 90.49 mmol) was synthesized in the same manner as in Step 2 of Preparation Example 1, except that 5- (2-nitrophenyl) -1H-indazole (13.64 g, yield 63%) was obtained.
1H-NMR: δ 7.64 (m, 2H), 7.90 (m, 1H), 8.05 (m, 3H), 8.21 (s, 1H), 8.38(d, 1H), 12.24(s, 1H) 1 H-NMR: δ 7.64 (m, 2H), 7.90 (m, 1H), 8.05 (m, 3H), 8.21 (s, 1H), 8.38 (d, 1H), 12.24 (s, 1H)
<단계 3> 5-(2-nitrophenyl)-1-phenyl-1H-indazole의 합성<Step 3> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indazole
5-(2-nitrophenyl)-1H-indole 대신 5-(2-nitrophenyl)-1H-indazole (11.04 g, 46.17 mmol)을 사용한 것을 제외하고는, 상기 준비예 1의 단계 3과 동일한 방법으로 합성하여, 5-(2-nitrophenyl)-1-phenyl-1H-indazole (10.34 g, 수율 71%)을 얻었다. Synthesis was carried out in the same manner as in Step 3 of Preparation Example 1, except that 5- (2-nitrophenyl) -1H-indazole (11.04 g, 46.17 mmol) was used instead of 5- (2-nitrophenyl) -1H-indole. , 5- (2-nitrophenyl) -1-phenyl-1H-indazole (10.34 g, yield 71%) was obtained.
1H-NMR: δ 7.48 (t, 1H), 7.62 (m, 6H), 7.90 (m, 1H), 8.05 (m, 3H), 8.37 (m, 2H) 1 H-NMR: δ 7.48 (t, 1H), 7.62 (m, 6H), 7.90 (m, 1H), 8.05 (m, 3H), 8.37 (m, 2H)
<단계 4> IC-2의 합성Step 4 Synthesis of IC-2
5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 5-(2-nitrophenyl)-1-phenyl-1H-indazole (5.01 g, 15.91 mmol)을 사용한 것을 제외하고는, 상기 준비예 1의 단계 4와 동일한 방법으로 합성하여, IC-2 (2.39 g, 수율 53%)을 얻었다. Preparation Example 1, except that 5- (2-nitrophenyl) -1-phenyl-1H-indazole (5.01 g, 15.91 mmol) was used instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole. Synthesis was carried out in the same manner as in Step 4, to obtain IC-2 (2.39 g, 53% yield).
1H-NMR: δ 7.29 (t, 1H), 7.45 (m, 3H), 7.60 (m, 5H), 8.12 (d, 1H), 8.33 (d, 2H), 10.09 (s, 1H) 1 H-NMR: δ 7.29 (t, 1H), 7.45 (m, 3H), 7.60 (m, 5H), 8.12 (d, 1H), 8.33 (d, 2H), 10.09 (s, 1H)
[준비예 3] IC-3의 합성Preparation Example 3 Synthesis of IC-3
<단계1> <Step 1>
NN
-(2,4-Dibromophenyl)benzamide의 합성Synthesis of-(2,4-Dibromophenyl) benzamide
반응기에 2,4-dibromoaniline (25.09 g, 0.1 mol) 을 투입하고, methylene chloride (100 ml)를 가한 후 교반하였다. 반응기에 benzoyl chloride (11.6 mL, 0.1mol), pyridine (1.62 mL, 0.02 mol)을 적가하고 혼합하고 상온에서 2시간 동안 교반하였다.2,4-dibromoaniline (25.09 g, 0.1 mol) was added to the reactor, and methylene chloride (100 ml) was added thereto, followed by stirring. Benzoyl chloride (11.6 mL, 0.1mol) and pyridine (1.62 mL, 0.02 mol) were added dropwise to the reactor, mixed and stirred for 2 hours at room temperature.
반응이 종결된 후 메틸렌클로라이드로 추출한 다음 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 4:1 (v/v))로 정제하여 N-(2,4-dibromophenyl)benzamide (25.1 g, 수율 71%)를 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride and then water was removed with MgSO 4 , and purified by column chromatography (Hexane: EA = 4: 1 (v / v)) to obtain N- (2,4-dibromophenyl) benzamide ( 25.1 g, yield 71%) was obtained.
1H-NMR: δ 7.52 (d, 1H), 7.59 (d, 1H), 7.63 (dd, 2H), 7.70 (t, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 9.15 (b, 1H) 1 H-NMR: δ 7.52 (d, 1H), 7.59 (d, 1H), 7.63 (dd, 2H), 7.70 (t, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 9.15 ( b, 1H)
<단계2> 6-Bromo-2-phenylbenzo[<Step 2> 6-Bromo-2-phenylbenzo [
dd
]oxazole의 합성] oxazole synthesis
질소 기류 하에서 N-(2,4-dibromophenyl)benzamide (25.1 g, 71.0 mmol), K2CO3 (19.6g, 142 mmol) 및 DMSO (710 ml)를 혼합하고 140℃에서 1.5시간 동안 교반하였다.N- (2,4-dibromophenyl) benzamide (25.1 g, 71.0 mmol), K 2 CO 3 (19.6 g, 142 mmol) and DMSO (710 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 h.
반응이 종결된 후 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 9:1 (v/v))로 정제하여 6-bromo-2-phenylbenzo[d]oxazole (14.8 g, 수율 76%)을 얻었다. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO 4 , and purified by column chromatography (Hexane: EA = 9: 1 (v / v)) to obtain 6-bromo-2-phenylbenzo [d] oxazole ( 14.8 g, yield 76%).
1H-NMR: δ 7.41 (t, 1H) 7.43 (s, 1H), 7.51 (m, 3H), 7.60 (d, 1H), 8.05 (d, 2H) 1 H-NMR: δ 7.41 (t, 1H) 7.43 (s, 1H), 7.51 (m, 3H), 7.60 (d, 1H), 8.05 (d, 2H)
<단계3> 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]oxazole 의 합성<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole
질소 기류 하에서 6-bromo-2-phenylbenzo[d]oxazole (14.8 g, 54.0 mmol), 4,4,4',4',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (15.1 g, 59.4 mmol), Pd(dppf)Cl2 (6.24 g, 5.40 mmol), KOAc (15.25 g, 0.162 mol) 및 1,4-Dioxane (280 ml)를 혼합하고 130℃에서 12시간 동안 교반하였다.6-bromo-2-phenylbenzo [d] oxazole (14.8 g, 54.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (15.1 g, 59.4 mmol), Pd (dppf) Cl 2 (6.24 g, 5.40 mmol), KOAc (15.25 g, 0.162 mol) and 1,4-Dioxane (280 ml) Mix and stir at 130 ° C. for 12 h.
반응이 종결된 후 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 7:1 (v/v))로 정제하여 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]oxazole (13.35 g, 수율 77%)을 얻었다. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO 4 , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to 2-phenyl-6- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (13.35 g, yield 77%) was obtained.
1H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H) , 7.75 (s, 1H), 8.05 (d, 2H) 1 H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H), 7.75 (s, 1H), 8.05 (d , 2H)
<단계 4> 6-(2-nitrophenyl)-2-phenylbenzo[d]oxazole 의 합성Step 4 Synthesis of 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole
질소 기류 하에서 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]oxazole (13.35 g, 41.58 mmol), 1-bromo-2-nitrobenzene (9.24 g, 45.74 mmol), Pd(PPh3)4 (2.4 g, 2.08 mmol), K2CO3 (14.37 g, 0.104 mol), 1,4-dioxane/H2O (40 ml/10 ml)를 혼합하고 120℃에서 4시간 동안 교반하였다.2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (13.35 g, 41.58 mmol), 1-bromo-2 under nitrogen stream -nitrobenzene (9.24 g, 45.74 mmol), Pd (PPh 3 ) 4 (2.4 g, 2.08 mmol), K 2 CO 3 (14.37 g, 0.104 mol), 1,4-dioxane / H 2 O (40 ml / 10 ml) were mixed and stirred at 120 ° C. for 4 hours.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 7:1 (v/v))로 정제하여 6-(2-nitrophenyl)-2-phenylbenzo[d]oxazole (11.05 g, 수율 84%)을 얻었다. After the reaction was terminated and extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole (11.05 g, yield 84%). Got.
1H-NMR: δ 7.41-7.51 (m, 4H), 7.67-7.68 (m, 2H), 7.79 (d, 1H), 7.90 (dd, 1H), 8.00-8.05 (m, 4H) 1 H-NMR: δ 7.41-7.51 (m, 4H), 7.67-7.68 (m, 2H), 7.79 (d, 1H), 7.90 (dd, 1H), 8.00-8.05 (m, 4H)
<단계 5> IC-3의 합성Step 5 Synthesis of IC-3
질소 기류 하에서 6-(2-nitrophenyl)-2-phenylbenzo[d]oxazole (11.05 g, 34.9 mmol)과 triphenylphosphine (27.46 g, 104.7 mmol), 1,2-dichlorobenzene 150 ml를 넣은 후 12시간 교반하였다.6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole (11.05 g, 34.9 mmol), triphenylphosphine (27.46 g, 104.7 mmol), and 1,2-dichlorobenzene (150 ml) were added under nitrogen stream, followed by stirring for 12 hours.
반응 종료 후 1,2-dichlorobenzene를 제거하고 디클로로메탄으로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 4:1 (v/v))로 정제하여 목적 화합물인 IC-3 (5.56g, 수율 56 %)을 획득하였다. After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO 4 was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain the title compound IC-3 (5.56g, 56% yield).
1H-NMR : δ 7.23-7.29 (m, 2H), 7.41-7.51 (m, 4H), 7.63 (d, 1H), 8.05-8.12 (m, 4H), 10.1 (b, 1H) 1 H-NMR: δ 7.23-7.29 (m, 2H), 7.41-7.51 (m, 4H), 7.63 (d, 1H), 8.05-8.12 (m, 4H), 10.1 (b, 1H)
[준비예 4] IC-4의 합성 Preparation Example 4 Synthesis of IC-4
<단계 1> <Step 1>
N-N-
(2,4-dibromophenyl)benzothioamide의 합성Synthesis of (2,4-dibromophenyl) benzothioamide
반응기에 준비예 3의 <단계 1>에서 얻은 N-(2,4-dibromophenyl)benzamide (26.62 g, 0.075 mol) 을 투입하고, toluene (300 ml)를 가한 후 교반하였다. 반응기에 Lawesson's reagent (22.92 g, 0.053 mol)를 적가한 다음 혼합하고, 110 ℃에서 4시간 동안 교반하였다. N- (2,4-dibromophenyl) benzamide (26.62 g, 0.075 mol) obtained in <Step 1> of Preparation Example 3 was added to the reactor, toluene (300 ml) was added thereto, followed by stirring. Lawesson's reagent (22.92 g, 0.053 mol) was added dropwise to the reactor, followed by mixing and stirring at 110 ° C. for 4 hours.
반응이 종결된 후 메틸렌클로라이드로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 7:1 (v/v))로 정제하여 N-(2,4-dibromophenyl)benzothioamide (26.35 g, 수율 95%)를 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride and then water was removed with MgSO 4 , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to obtain N- (2,4-dibromophenyl) benzothioamide ( 26.35 g, yield 95%).
1H-NMR: δ 6.41 (d, 1H), 7.29 (d, 1H), 7.44-7.45 (m, 3H), 7.75 (s, 1H), 7.98 (d, 2H), 8.59 (b, 1H) 1 H-NMR: δ 6.41 (d, 1H), 7.29 (d, 1H), 7.44-7.45 (m, 3H), 7.75 (s, 1H), 7.98 (d, 2H), 8.59 (b, 1H)
<단계 2> 6-bromo-2-phenylbenzo[d]thiazole 의 합성<Step 2> Synthesis of 6-bromo-2-phenylbenzo [d] thiazole
질소 기류 하에서 상기 준비예 8의 <단계 1>에서 얻은 N-(2,4-dibromophenyl)benzothioamide (26.35 g, 71.0 mmol), K2CO3 (19.63 g, 142 mmol) 및 DMSO (710 ml)를 혼합하고 140 ℃에서 1.5시간 동안 교반하였다. N- (2,4-dibromophenyl) benzothioamide (26.35 g, 71.0 mmol), K 2 CO 3 (19.63 g, 142 mmol) and DMSO (710 ml) obtained in <Step 1> of Preparation Example 8 under nitrogen stream were prepared. Mix and stir at 140 ° C. for 1.5 h.
반응이 종결된 후 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 10:1 (v/v))로 정제하여 6-bromo-2-phenylbenzo[d]thiazole (15.66 g, 수율 76%)을 얻었다. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO 4 , and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 6-bromo-2-phenylbenzo [d] thiazole ( 15.66 g, yield 76%) was obtained.
1H-NMR: δ 7.41 (t, 1H) 7.51 (dd, 2H), 7.64 (d, 1H), 7.72 (d, 1H), 8.03 (d, 2H), 8.83 (s, 1H) 1 H-NMR: δ 7.41 (t, 1H) 7.51 (dd, 2H), 7.64 (d, 1H), 7.72 (d, 1H), 8.03 (d, 2H), 8.83 (s, 1H)
<단계 3> 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]thiazole 의 합성<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole
6-bromo-2-phenylbenzo[d]oxazole 대신 6-bromo-2-phenylbenzo[d]thiazole (15.66 g, 54.0 mmol) 을 사용한 것을 제외하고는, 상기 준비예 3의 단계 3과 동일한 방법으로 합성하여, 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]thiazole (14.02 g, 수율 77%)을 얻었다. 6-bromo-2-phenylbenzo [d] thiazole (15.66 g, 54.0 mmol) was used instead of 6-bromo-2-phenylbenzo [d] oxazole, and was synthesized in the same manner as in Step 3 of Preparation Example 3 above. , 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (14.02 g, yield 77%) was obtained.
1H-NMR: δ 1.24 (s, 12H) 7.38 (d, 1H), 7.41 (t, 1H), 7.51 (dd, 2H), 7.75 (d, 1H), 7.95 (s, 1H), 8.03 (d, 2H) 1 H-NMR: δ 1.24 (s, 12H) 7.38 (d, 1H), 7.41 (t, 1H), 7.51 (dd, 2H), 7.75 (d, 1H), 7.95 (s, 1H), 8.03 (d , 2H)
<단계 4> 6-(2-nitrophenyl)-2-phenylbenzo[d]thiazole 의 합성Step 4 Synthesis of 6- (2-nitrophenyl) -2-phenylbenzo [d] thiazole
2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]oxazole 대신 2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]thiazole (14.02 g, 41.57 mmol)을 사용한 것을 제외하고는, 상기 준비예 3의 단계 4와 동일한 방법으로 합성하여, 6-(2-nitrophenyl)-2-phenylbenzo[d]thiazole (11.61 g, 수율 84%)을 얻었다. 2-phenyl-6- (4,4,5,5- instead of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole Except for using tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (14.02 g, 41.57 mmol), and synthesized in the same manner as in Step 4 of Preparation Example 3, 6- ( 2-nitrophenyl) -2-phenylbenzo [d] thiazole (11.61 g, yield 84%) was obtained.
1H-NMR: δ 7.41-7.51 (m, 3H), 7.67 (dd, 1H), 7.77-7.90 (m, 3H), 8.00-8.05 (m, 4H), 8.34 (s, 1H) 1 H-NMR: δ 7.41-7.51 (m, 3H), 7.67 (dd, 1H), 7.77-7.90 (m, 3H), 8.00-8.05 (m, 4H), 8.34 (s, 1H)
<단계 5> 화합물 IC-4의 합성Step 5 Synthesis of Compound IC-4
6-(2-nitrophenyl)-2-phenylbenzo[d]oxazole 대신 6-(2-nitrophenyl)-2-phenylbenzo[d]thiazole (11.61 g, 34.9 mmol)을 사용한 것을 제외하고는, 상기 합성예 3의 단계 5와 동일한 방법으로 합성하여 화합물 IC-4 (5.56 g, 수율 53 %)을 획득하였다. Synthesis Example 3, except that 6- (2-nitrophenyl) -2-phenylbenzo [d] thiazole (11.61 g, 34.9 mmol) was used instead of 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole. Synthesis was carried out in the same manner as in Step 5 to obtain Compound IC-4 (5.56 g, 53% yield).
1H-NMR : δ 7.29 (dd, 1H), 7.41-7.63 (m, 6H), 7.75 (d, 1H), 8.03-8.12 (m, 3H), 10.1 (b, 1H) 1 H-NMR: δ 7.29 (dd, 1H), 7.41-7.63 (m, 6H), 7.75 (d, 1H), 8.03-8.12 (m, 3H), 10.1 (b, 1H)
[준비예 5] IC-5의 합성.Preparation Example 5 Synthesis of IC-5.
<단계 1> 5-(2-nitrophenyl)-1H-benzo[d]imidazole의 합성.Step 1 Synthesis of 5- (2-nitrophenyl) -1H-benzo [d] imidazole.
질소 기류 하에서 6.5 g (32.98 mmol)의 5-bromo-1H-benzo[d]imidazole, 6.6g (39.58 mmol)의 2-nitrophenylboronic acid, 3.9 g (98.96 mmol)의 NaOH과 150 ml/50 ml의 THF/H2O를 넣고 교반하였다. 40℃에서 1.14 g (0.98mmol)의 Pd(PPh3)4를 넣고 80℃에서 12시간 동안 환류 교반하였다. 반응 종결 후 디클로로메탄으로 추출하고 유기층을 MgSO4로 건조 후 감압여과 하였다. 여과된 유기층을 감압증류 한 뒤 컬럼 크로마토그래피를 이용하여 목적 화합물인 5-(2-nitrophenyl)-1H-benzo[d]imidazole 5.2 g (yield: 66 %)을 획득하였다. 6.5 g (32.98 mmol) of 5-bromo-1H-benzo [d] imidazole under nitrogen stream, 6.6 g (39.58 mmol) of 2-nitrophenylboronic acid, 3.9 g (98.96 mmol) of NaOH and 150 ml / 50 ml of THF / H 2 O was added and stirred. 1.14 g (0.98 mmol) of Pd (PPh 3 ) 4 was added at 40 ° C., and the mixture was stirred under reflux at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with dichloromethane and the organic layer was dried over MgSO 4 and filtered under reduced pressure. After distilling under reduced pressure on the filtered organic layer, 5.2 g (yield: 66%) of 5- (2-nitrophenyl) -1H-benzo [d] imidazole as a target compound was obtained by column chromatography.
1H-NMR : δ 7.68 (m, 2H), 8.02 (m, 5H), 8.14 (s, 1H), 8.45 (s, 1H) 1 H-NMR: δ 7.68 (m, 2H), 8.02 (m, 5H), 8.14 (s, 1H), 8.45 (s, 1H)
<단계 2> 5-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 2> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indole
5-(2-nitrophenyl)-1H-indole 대신 5-(2-nitrophenyl)-1H-benzo[d]imidazole (5.2 g, 21.75 mmol)를 사용한 것을 제외하고는, 상기 준비예 1의 단계 3과 동일한 방법으로 합성하여 5-(2-nitrophenyl)-1-phenyl-1H-benzo[d]imidazole (6.84 g, 수율 71%)을 얻었다. Same as step 3 of Preparation Example 1, except that 5- (2-nitrophenyl) -1H-benzo [d] imidazole (5.2 g, 21.75 mmol) was used instead of 5- (2-nitrophenyl) -1H-indole. The synthesis was carried out to obtain 5- (2-nitrophenyl) -1-phenyl-1H-benzo [d] imidazole (6.84 g, 71% yield).
1H-NMR: δ 7.55 (m, 6H), 7.98 (m, 2H), 8.05 (m, 4H), 8.32 (d, 1H) 1 H-NMR: δ 7.55 (m, 6H), 7.98 (m, 2H), 8.05 (m, 4H), 8.32 (d, 1H)
<단계 3> IC-5의 합성Step 3 Synthesis of IC-5
5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 5-(2-nitrophenyl)-1-phenyl-1H-benzo[d]imidazole (6.84 g, 21.73 mmol)을 사용하는 것을 제외하고는, 상기 준비예 1의 단계 4와 동일한 방법으로 합성하여 IC-5 (1.8 g, 수율 40 %)를 획득하였다.Except for using 5- (2-nitrophenyl) -1-phenyl-1H-benzo [d] imidazole (6.84 g, 21.73 mmol) instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole, Synthesis was carried out in the same manner as in Step 4 of Preparation Example 1, to obtain IC-5 (1.8 g, yield 40%).
1H-NMR : δ 7.31 (t, 1H), 7.55 (m, 3H), 7.87 (d, 1H), 8.15 (m, 2H), 8.43 (s, 1H), 10.23(s, 1H) 1 H-NMR: δ 7.31 (t, 1H), 7.55 (m, 3H), 7.87 (d, 1H), 8.15 (m, 2H), 8.43 (s, 1H), 10.23 (s, 1H)
[준비예 6] IC-6의 합성Preparation Example 6 Synthesis of IC-6
<단계 1> 5-(5-bromo-2-nitrophenyl)-1H-indole의 합성<Step 1> Synthesis of 5- (5-bromo-2-nitrophenyl) -1H-indole
1-bromo-2-nitrobenzene 대신 2,4-dibromo-1-nitrobenzene을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 2>와 동일한 과정을 수행하여 5-(5-bromo-2-nitrophenyl)-1H-indole을 얻었다.Except for using 2,4-dibromo-1-nitrobenzene instead of 1-bromo-2-nitrobenzene, the same procedure as in <Step 2> of Preparation Example 1 was carried out to 5- (5-bromo-2-nitrophenyl ) -1H-indole was obtained.
1H NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.45 (d, 1H), 7.55 (d, 1H), 7.64 (d, 1H), 7.85 (d, 1H), 7.96 (s, 1H), 8.13 (s, 1H), 8.21 (s, 1H) 1 H NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.45 (d, 1H), 7.55 (d, 1H), 7.64 (d, 1H), 7.85 (d, 1H), 7.96 (s , 1H), 8.13 (s, 1H), 8.21 (s, 1H)
<단계 2> 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 2> Synthesis of 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole
5-(2-nitrophenyl)-1H-indole 대신 상기 <단계 1>에서 얻은 5-(5-bromo-2-nitrophenyl)-1H-indole 을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 3>과 동일한 과정을 수행하여 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.<Step 3 of Preparation Example 1, except that 5- (5-bromo-2-nitrophenyl) -1H-indole obtained in <Step 1> was used instead of 5- (2-nitrophenyl) -1H-indole. > The same process as in to obtain 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole.
1H NMR: δ 6.44 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 4H), 7.65 (d, 1H), 7.86 (d, 1H), 7.95 (s, 1H), 8.11 (s, 1H) 1 H NMR: δ 6.44 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 4H), 7.65 (d, 1H), 7.86 (d, 1H), 7.95 (s , 1H), 8.11 (s, 1H)
<단계 3> 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 의 합성<Step 3> Synthesis of 7-bromo-3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole
5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 상기 <단계 2>에서 얻은 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole을 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>와 동일한 과정을 수행하여 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 을 얻었다.Except for using 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole, 7-bromo-3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole was obtained in the same manner as in <Step 4> of Preparation Example 1.
1H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.38 (m, 2H), 7.45 (d, 1H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 (d, 1H), 7.85 (d, 1H), 8.10 (s, 1H), 8.23 (s, 1H) 1 H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.38 (m, 2H), 7.45 (d, 1H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 ( d, 1H), 7.85 (d, 1H), 8.10 (s, 1H), 8.23 (s, 1H)
<단계 4> IC-6의 합성Step 4 Synthesis of IC-6
5-(2-nitrophenyl)-1H-indole 대신 상기 <단계 3>에서 얻은 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 을 사용한 것을 제외하고는, 상기 준비예 1의 단계 3과 동일한 방법으로 IC-6을 얻었다. Preparation Example except that 7-bromo-3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole obtained in <Step 3> was used instead of 5- (2-nitrophenyl) -1H-indole IC-6 was obtained by the same method as Step 3 of 1.
1H NMR: δ 6.52(d, 1H), 7.25 (d, 1H), 7.54 (m, 11H), 7.72 (s, 1H), 7.88 (d, 1H), 7.95(m, 2H) 1 H NMR: δ 6.52 (d, 1H), 7.25 (d, 1H), 7.54 (m, 11H), 7.72 (s, 1H), 7.88 (d, 1H), 7.95 (m, 2H)
[준비예 7] IC-7의 합성Preparation Example 7 Synthesis of IC-7
<단계 1> 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole의 합성Step 1 Synthesis of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole
5-bromo-1H-indole 대신 6-bromo-1H-indole를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 1>과 동일한 과정을 수행하여 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole을 얻었다.Except for using 6-bromo-1H-indole instead of 5-bromo-1H-indole, 6- (4,4,5,5-tetramethyl was carried out in the same manner as in <Step 1> of Preparation Example 1 -1,3,2-dioxaborolan-2-yl) -1H-indole was obtained.
1H-NMR: δ 1.25 (s, 12H), 6.52 (d, 1H), 7.16 (d, 1H), 7.21 (d, 1H), 7.49 (d, 1H), 7.53 (s, 1H), 8.15 (s, 1H) 1 H-NMR: δ 1.25 (s, 12H), 6.52 (d, 1H), 7.16 (d, 1H), 7.21 (d, 1H), 7.49 (d, 1H), 7.53 (s, 1H), 8.15 ( s, 1 H)
<단계 2> 6-(2-nitrophenyl)-1H-indole의 합성Step 2 Synthesis of 6- (2-nitrophenyl) -1H-indole
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 대신 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 2>와 동일한 과정을 수행하여 6-(2-nitrophenyl)-1H-indole을 얻었다.5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole instead of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan Except for using 2-yl) -1H-indole, 6- (2-nitrophenyl) -1H-indole was obtained in the same manner as in <Step 2> of Preparation Example 1.
1H-NMR: δ 6.57 (d, 1H), 7.07 (d, 1H), 7.24 (d, 1H), 7.35 (s, 1H), 7.43 (t, 1H), 7.50 (d, 1H), 7.58 (t, 1H), 7.66 (d, 1H), 7.78 (d, 1H), 8.19 (s, 1H) 1 H-NMR: δ 6.57 (d, 1H), 7.07 (d, 1H), 7.24 (d, 1H), 7.35 (s, 1H), 7.43 (t, 1H), 7.50 (d, 1H), 7.58 ( t, 1H), 7.66 (d, 1H), 7.78 (d, 1H), 8.19 (s, 1H)
<단계 3> 6-(2-nitrophenyl)-1-phenyl-1H-indole의 합성<Step 3> Synthesis of 6- (2-nitrophenyl) -1-phenyl-1H-indole
5-(2-nitrophenyl)-1H-indole 대신 6-(2-nitrophenyl)-1H-indole를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 3>과 동일한 과정을 수행하여 6-(2-nitrophenyl)-1-phenyl-1H-indole을 얻었다.Except for using 6- (2-nitrophenyl) -1H-indole instead of 5- (2-nitrophenyl) -1H-indole, 6- (2 -nitrophenyl) -1-phenyl-1H-indole was obtained.
1H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.35 (s, 1H), 7.43 (d, 1H), 7.51 (m, 3H), 7.56 (m, 2H), 7.62 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H) 1 H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.35 (s, 1H), 7.43 (d, 1H), 7.51 (m, 3H), 7.56 ( m, 2H), 7.62 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H)
<단계 4> IC-7의 합성Step 4 Synthesis of IC-7
5-(2-nitrophenyl)-1-phenyl-1H-indole 대신 6-(2-nitrophenyl)-1-phenyl-1H-indole를 사용하는 것을 제외하고는, 상기 준비예 1의 <단계 4>과 동일한 과정을 수행하여 PC-2을 얻었다.Except for using 6- (2-nitrophenyl) -1-phenyl-1H-indole instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole, the same as in <Step 4> of Preparation Example 1 The procedure was followed to obtain PC-2.
1H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.23 (t, 1H), 7.42 (d, 1H), 7.50 (m, 3H), 7.57 (m, 2H), 7.63 (m, 2H), 7.86 (d, 1H), 8.03 (d, 1H), 9.81 (s, 1H) 1 H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.23 (t, 1H), 7.42 (d, 1H), 7.50 (m, 3H), 7.57 (m, 2H), 7.63 ( m, 2H), 7.86 (d, 1H), 8.03 (d, 1H), 9.81 (s, 1H)
[준비예 8] 화합물 IC-8 의 합성Preparation Example 8 Synthesis of Compound IC-8
<단계 1> 5-phenyl-5H-dibenzo[b,f]azepine 의 합성<Step 1> Synthesis of 5-phenyl-5H-dibenzo [b, f] azepine
질소 기류 하에서 5H-dibenzo[b,f]azepine (10 g, 51.75 mmol), iodobenzene (12.67 g, 62.10 mmol), Cu (1.64 g, 25.87 mmol), K2CO3 (14.30 g, 103.5mmol) 및 nitrobenzene (100 ml)를 혼합하고, 210 ℃에서 12시간 동안 교반하였다.5H-dibenzo [b, f] azepine (10 g, 51.75 mmol), iodobenzene (12.67 g, 62.10 mmol), Cu (1.64 g, 25.87 mmol), K 2 CO 3 (14.30 g, 103.5 mmol) under a nitrogen stream and nitrobenzene (100 ml) was mixed and stirred at 210 ° C. for 12 h.
반응이 종결된 후 에틸아세테이트로 유기층을 추출한 다음 농축하고, 에탄올로 재결정하여 5-phenyl-5H-dibenzo[b,f]azepine (10.04 g, 수율 72%)을 얻었다. After completion of the reaction, the organic layer was extracted with ethyl acetate, concentrated and recrystallized with ethanol to give 5-phenyl-5H-dibenzo [b, f] azepine (10.04 g, yield 72%).
1H-NMR: δ 6.63-6.81 (m, 3H), 6.92 (d, 1H), 6.98 (d, 1H), 7.20 (d, 2H), 7.26-7.45 (m, 8H) 1 H-NMR: δ 6.63-6.81 (m, 3H), 6.92 (d, 1H), 6.98 (d, 1H), 7.20 (d, 2H), 7.26-7.45 (m, 8H)
<단계 2> 6-phenyl-6,10b-dihydro-1aH-dibenzo[b,f]oxireno[2,3-d]azepine 의 합성<Step 2> Synthesis of 6-phenyl-6,10b-dihydro-1aH-dibenzo [b, f] oxireno [2,3-d] azepine
질소 기류 하에서 준비예 2의 <단계 1>에서 얻은 5-phenyl-5H-dibenzo[b,f]azepine (10.04 g, 37.26 mmol), meta-chloroperoxybenzoic acid (7.72 g, 44.71 mmol), silica (20.07 g), NaOCl (20.07 g), acetonitrile (100 ml)를 혼합하고, 80 ℃에서 2시간 동안 교반하였다.5-phenyl-5H-dibenzo [b, f] azepine (10.04 g, 37.26 mmol), meta- chloroperoxybenzoic acid (7.72 g, 44.71 mmol), silica (20.07 g) obtained in <Step 1> of Preparation Example 2 under nitrogen stream ), NaOCl (20.07 g), acetonitrile (100 ml) were mixed and stirred at 80 ° C. for 2 hours.
반응이 종결된 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 에탄올로 재결정하여 6-phenyl-6,10b-dihydro-1aH-dibenzo[b,f]oxireno[2,3-d]azepine (8.40 g, 수율 79%)을 얻었다. After the reaction was terminated, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and recrystallized with ethanol to obtain 6-phenyl-6,10b-dihydro-1aH-dibenzo [b, f] oxireno [2,3-d] azepine (8.40 g, 79% yield).
1H-NMR: δ 4.31 (s, 2H), 6.63-6.81 (m, 3H), 7.24-7.53 (m, 10H) 1 H-NMR: δ 4.31 (s, 2H), 6.63-6.81 (m, 3H), 7.24-7.53 (m, 10H)
<단계 3> 5-phenyl-5H-dibenzo[b,f]azepin-10(11H)-one 의 합성<Step 3> Synthesis of 5-phenyl-5H-dibenzo [b, f] azepin-10 (11H) -one
질소 기류 하에서 준비예 2의 <단계 2>에서 얻은 6-phenyl-6,10b-dihydro-1aH-dibenzo[b,f]oxireno[2,3-d]azepine (8.40 g, 29.43 mmol), lithium iodide (4.73 g, 35.32 mmol) 및 chloroform (84 ml)를 혼합하고, 60 ℃에서 1시간 동안 교반하였다.6-phenyl-6,10b-dihydro-1aH-dibenzo [b, f] oxireno [2,3-d] azepine (8.40 g, 29.43 mmol) obtained in <Step 2> of Preparation Example 2 under nitrogen stream, lithium iodide (4.73 g, 35.32 mmol) and chloroform (84 ml) were mixed and stirred at 60 ° C for 1 hour.
반응이 종결된 후 에틸아세테이트로 유기층을 추출한 다음, MgSO4로 수분을 제거하고, 에탄올에서 재결정하여 5-phenyl-5H-dibenzo[b,f]azepin-10(11H)-one (6.80 g, 수율 81%)을 얻었다. After completion of the reaction, the organic layer was extracted with ethyl acetate, and then water was removed with MgSO 4 and recrystallized from ethanol to 5-phenyl-5H-dibenzo [b, f] azepin-10 (11H) -one (6.80 g, yield 81%).
1H-NMR: δ 3.42 (d, 1H), 4.21 (d, 1H), 6.62-6.74 (m, 3H), 7.25-7.40 (m, 7H), 7.51-7.59 (m, 2H), 8.10 (d, 1H) 1 H-NMR: δ 3.42 (d, 1H), 4.21 (d, 1H), 6.62-6.74 (m, 3H), 7.25-7.40 (m, 7H), 7.51-7.59 (m, 2H), 8.10 (d , 1H)
<단계 4> 화합물 IC-8의 합성Step 4 Synthesis of Compound IC-8
질소 기류 하에서 준비예 2의 <단계 3>에서 얻은 5-phenyl-5H-dibenzo[b,f]azepin-10(11H)-one (6.80 g, 23.84 mmol)과 phenylhydrazine (2.84 g, 26.23 mmol), 및 acetic acid (70 ml)를 혼합한 후, 120 ℃에서 12시간 교반하였다.5-phenyl-5H-dibenzo [b, f] azepin-10 (11H) -one (6.80 g, 23.84 mmol) and phenylhydrazine obtained in <Step 3> of Preparation Example 2 under nitrogen stream (2.84 g, 26.23 mmol), and acetic acid (70 ml) were mixed and stirred at 120 ° C for 12 hours.
반응 종료 후 디클로로메탄으로 유기층을 추출한 다음, MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 3:1 (v/v))로 정제하여 화합물 IC-8 (6.07 g, 수율 71 %)을 획득하였다. After completion of the reaction, the organic layer was extracted with dichloromethane, MgSO 4 was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to obtain the compound IC-8 (6.07 g, 71% yield).
IC-9 의 1H-NMR : δ 6.63-6.69 (m, 4H), 6.81-6.87 (m, 3H), 7.08-7.20 (m, 6H), 7.44-7.56 (m, 3H), 8.83 (d, 1H), 11.36 (b, 1H) 1 H-NMR of IC-9: δ 6.63-6.69 (m, 4H), 6.81-6.87 (m, 3H), 7.08-7.20 (m, 6H), 7.44-7.56 (m, 3H), 8.83 (d, 1H), 11.36 (b, 1H)
[준비예 9] IIC-1 의 합성Preparation Example 9 Synthesis of IIC-1
<단계 1> IIC-1의 합성Step 1 Synthesis of IIC-1
질소 기류 하에서 3-Bromo-9H-carbazole (27.8 g, 113 mmol), (9H-carbazol-3-yl)boronic acid (23.8 g, 113 mmol), K2CO3 (46.8g, 339 mmol) 및 THF/H2O(400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (6.53 g, 5.65 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. In a nitrogen atmosphere 3-Bromo-9H-carbazole ( 27.8 g, 113 mmol), (9H-carbazol-3-yl) boronic acid (23.8 g, 113 mmol), K 2 CO 3 (46.8g, 339 mmol) and THF / H 2 O (400 ml / 100 ml) was mixed, Pd (PPh 3 ) 4 (6.53 g, 5.65 mmol) was added and stirred at 80 ℃ for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 IIC-1 (30 g, 수율 80%)을 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-1 (30 g, yield 80%).
IIC-1의 1H-NMR: δ 7.29-7.50 (m, 5H), 7.94(d, 1H), 8.01(s, 1H), 10.1(s, 1H) 1 H-NMR of IIC-1: δ 7.29-7.50 (m, 5H), 7.94 (d, 1H), 8.01 (s, 1H), 10.1 (s, 1H)
[준비예 10] IIC-2 의 합성Preparation Example 10 Synthesis of IIC-2
<단계 1> IIC-2의 합성Step 1 Synthesis of IIC-2
질소 기류 하에서 3-Bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (6-phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K2CO3 (32.0g, 232 mmol) 및 THF/H2O(400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4 (4.47 g, 3.86 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-Bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (6-phenyl-9H-carbazol-3-yl) boronic acid (22.2 g, 77.4 mmol), K 2 CO 3 ( 32.0 g, 232 mmol) and THF / H 2 O (400 ml / 100 ml) were mixed, and then Pd (PPh 3 ) 4 (4.47 g, 3.86 mmol) was added thereto and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 IIC-2 (30 g, 수율 80%)을 얻었다. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-2 (30 g, yield 80%).
IIC-2의 1H-NMR: δ 7.29-7.50 (m, 10H), 7.92(s, 1H), 8.00(s, 1H), 10.1(s, 1H) 1 H-NMR of IIC-2: δ 7.29-7.50 (m, 10H), 7.92 (s, 1H), 8.00 (s, 1H), 10.1 (s, 1H)
[준비예 11] IIC-3 의 합성Preparation Example 11 Synthesis of IIC-3
<단계 1> 3-bromo-6,9-diphenyl-9H-carbazole의 합성<Step 1> Synthesis of 3-bromo-6,9-diphenyl-9H-carbazole
질소 기류 하에서 3-bromo-6-phenyl-9H-carbazole (35.9 g, 111 mmol), iodobenzene (22.7 g, 111 mmol), Pd(OAc)2 (1.25 g, 5.57 mmol), NaO(t-Bu) (21.4 g, 223 mmol), P(t-Bu)3 (50wt%) (4.51 g, 11.1 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 3-bromo-6,9-diphenyl-9H-carbazole (31.7g, 60%)을 얻었다.3-bromo-6-phenyl-9H-carbazole (35.9 g, 111 mmol), iodobenzene (22.7 g, 111 mmol), Pd (OAc) 2 (1.25 g, 5.57 mmol), NaO (t-Bu) under nitrogen stream (21.4 g, 223 mmol), P (t-Bu) 3 (50 wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 and purified by column chromatography to give the target compound 3-bromo-6,9-diphenyl-9H-carbazole (31.7g, 60%).
1H-NMR: δ 7.07-7.35(m, 14H), 7.92(s, 1H), 7.98 (s, 1H) 1 H-NMR: δ 7.07-7.35 (m, 14H), 7.92 (s, 1H), 7.98 (s, 1H)
<단계 2> IIC-3의 합성Step 2 Synthesis of IIC-3
질소 기류 하에서 3-bromo-6,9-diphenyl-9H-carbazole (26.6 g, 66.9 mmol), (6-phenyl-9H-carbazol-3-yl)boronic acid (19.2 g, 66.9 mmol), K2CO3 (27.7 g, 200 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4(3.86 g, 3.34 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-bromo-6,9-diphenyl-9H-carbazole (26.6 g, 66.9 mmol), (6-phenyl-9H-carbazol-3-yl) boronic acid (19.2 g, 66.9 mmol), K 2 CO under nitrogen stream 3 (27.7 g, 200 mmol) and THF / H 2 O (400 ml / 100 ml) were mixed, and then Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 IIC-3 (30 g, 수율 80%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-3 (30 g, yield 80%).
1H-NMR : δ 7.05-7.33(m, 15H), 7.38-7.42(m, 8H), 7.92(s, 1H), 7.94(s, 1H), 8.00(s, 1H), 8.03(s, 1H), 10.3(s, 1H) 1 H-NMR: δ 7.05-7.33 (m, 15H), 7.38-7.42 (m, 8H), 7.92 (s, 1H), 7.94 (s, 1H), 8.00 (s, 1H), 8.03 (s, 1H ), 10.3 (s, 1 H)
[준비예 12] IIC-4의 합성Preparation Example 12 Synthesis of IIC-4
<단계 1> IIC-4의 합성Step 1 Synthesis of IIC-4
질소 기류 하에서 3-bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid (22.2 g, 77.4 mmol), K2CO3 (32.1 g, 232 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4(4.47 g, 3.87 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 3-bromo-6-phenyl-9H-carbazole (24.9 g, 77.4 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (22.2 g, 77.4 mmol), K 2 CO 3 ( 32.1 g, 232 mmol) and THF / H 2 O (400 ml / 100 ml) were mixed, and then Pd (PPh 3 ) 4 (4.47 g, 3.87 mmol) was added thereto and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 IIC-4 (30 g, 수율 80%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain IIC-4 (30 g, yield 80%).
1H-NMR : δ 7.03-7.29(m, 10H), 7.38-7.42(m, 9H), 7.94(s, 1H), 7.96(s, 1H), 7.98(s, 1H), 8.01(s, 1H), 10.2(s, 1H) 1 H-NMR: δ 7.03-7.29 (m, 10H), 7.38-7.42 (m, 9H), 7.94 (s, 1H), 7.96 (s, 1H), 7.98 (s, 1H), 8.01 (s, 1H ), 10.2 (s, 1H)
[준비예 13] IIC-5 의 합성Preparation Example 13 Synthesis of IIC-5
<단계 1> 9-(biphenyl-3-yl)-3-bromo-9H-carbazole의 합성Step 1 Synthesis of 9- (biphenyl-3-yl) -3-bromo-9H-carbazole
질소 기류 하에서 3-iodobiphenyl (39.7 g, 111 mmol), 3-bromo-9H-carbazole (27.4 g, 111 mmol), Pd(OAc)2 (1.25 g, 5.57 mmol), NaO(t-Bu) (21.4 g, 223 mmol), P(t-Bu)3 (50wt%) (4.51 g, 11.1 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 9-(biphenyl-3-yl)-3-bromo-9H-carbazole (26.9g, 61%)을 얻었다.3-iodobiphenyl (39.7 g, 111 mmol), 3-bromo-9H-carbazole (27.4 g, 111 mmol), Pd (OAc) 2 (1.25 g, 5.57 mmol), NaO (t-Bu) (21.4 under nitrogen stream g, 223 mmol), P (t-Bu) 3 (50 wt%) (4.51 g, 11.1 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate, and then water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound 9- (biphenyl-3-yl) -3-bromo-9H-carbazole (26.9g, 61% )
1H-NMR: δ 7.25-7.52(m, 12H), 7.94(d, 1H), 8.07 (m, 2H), 8.55 (d, 1H) 1 H-NMR: δ 7.25-7.52 (m, 12H), 7.94 (d, 1H), 8.07 (m, 2H), 8.55 (d, 1H)
<단계 2> IIC-5의 합성Step 2 Synthesis of IIC-5
질소 기류 하에서 9-(biphenyl-3-yl)-3-bromo-9H-carbazole (26.9g, 67.7mmol), (9H-carbazol-3-yl)boronic acid (14.1 g, 66.9 mmol), K2CO3 (27.7 g, 200 mmol) 및 THF/H2O (400 ml/100 ml)를 혼합한 다음, Pd(PPh3)4(3.86 g, 3.34 mmol)를 넣고 80℃에서 12시간 동안 교반하였다. 9- (biphenyl-3-yl) -3-bromo-9H-carbazole (26.9g, 67.7mmol), (9H-carbazol-3-yl) boronic acid (14.1 g, 66.9 mmol), K 2 CO under nitrogen stream 3 (27.7 g, 200 mmol) and THF / H 2 O (400 ml / 100 ml) were mixed, and then Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:MC = 5:1 (v/v))로 정제하여 IIC-5 (24.6 g, 수율 75%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to give IIC-5 (24.6 g, yield 75%).
1H-NMR : δ 7.29(t, 2H), 7.46-7.69(m, 13H), 7.77(s, 2H), 7.87-8.18(m, 6H), 10.1(s, 1H) 1 H-NMR: δ 7.29 (t, 2H), 7.46-7.69 (m, 13H), 7.77 (s, 2H), 7.87-8.18 (m, 6H), 10.1 (s, 1H)
[합성예 1] C-1의 합성Synthesis Example 1 Synthesis of C-1
질소 기류 하에서 IIC-1 (5 g, 15.0 mmol), 4-bromo-1,1'-biphenyl (7.01 g, 30.1 mmol), Pd(OAc)2 (338 mg, 1.50 mmol), NaO(t-Bu) (5.78 g, 60.2 mmol), P(t-Bu)3 (50wt%) (1.22 g, 3.01 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 C-1 (6.70 g, 70%)을 얻었다.IIC-1 (5 g, 15.0 mmol), 4-bromo-1,1'-biphenyl (7.01 g, 30.1 mmol), Pd (OAc) 2 (338 mg, 1.50 mmol), NaO (t-Bu) under nitrogen stream ) (5.78 g, 60.2 mmol), P (t-Bu) 3 (50 wt%) (1.22 g, 3.01 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 and purified by column chromatography to give the target compound C-1 (6.70 g, 70%).
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 2] C-2의 합성Synthesis Example 2 Synthesis of C-2
4-bromo-1,1'-biphenyl 대신 3-bromo-1,1'-biphenyl (7.02 g, 30.1 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 C-2 (6.70 g, 수율 70%)를 얻었다.Except for using 3-bromo-1,1'-biphenyl (7.02 g, 30.1 mmol) instead of 4-bromo-1,1'-biphenyl, the same procedure as in Synthesis Example 1 was carried out to C -2 (6.70 g, yield 70%) was obtained.
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 3] C-3의 합성Synthesis Example 3 Synthesis of C-3
질소 기류 하에서 IIC-2 (5 g, 10.3 mmol), Iodobenzene (4.21 g, 20.6 mmol), Pd(OAc)2 (232 mg, 1.03 mmol), NaO(t-Bu) (3.96 g, 41.2 mmol), P(t-Bu)3 (50wt%) (836 mg, 2.06 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 C-3 (4.60 g, 70%)을 얻었다.Under nitrogen stream IIC-2 (5 g, 10.3 mmol), Iodobenzene (4.21 g, 20.6 mmol), Pd (OAc) 2 (232 mg, 1.03 mmol), NaO (t-Bu) (3.96 g, 41.2 mmol), mixture of P (t-Bu) 3 ( 50wt%) (836 mg, 2.06 mmol) and Toluene (100 ml) and stirred at 110 ℃ for 12 hours. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to give the target compound C-3 (4.60 g, 70%).
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 4] C-4의 합성Synthesis Example 4 Synthesis of C-4
4-bromo-1,1'-biphenyl 대신 5'-bromo-1,1':3',1''-terphenyl (9.30 g, 30.1 mmol)을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 C-4 (8.31 g, 수율 70%)을 얻었다.Same as Synthesis Example 1, except that 5'-bromo-1,1 ': 3', 1 ''-terphenyl (9.30 g, 30.1 mmol) was used instead of 4-bromo-1,1'-biphenyl. The process was carried out to obtain the title compound C-4 (8.31 g, yield 70%).
Mass (이론치: 788.97 g/mol, 측정치: 788 g/mol)Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)
[합성예 5] C-5의 합성Synthesis Example 5 Synthesis of C-5
질소 기류 하에서 IIC-3 (5 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 C-5 (4.45 g, 70%)을 얻었다.IIC-3 (5 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) 2 (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) (1.71 g, 17.8 mmol), P (t-Bu) 3 (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 and purified by column chromatography to give the target compound C-5 (4.45 g, 70%).
Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 6] C-6의 합성Synthesis Example 6 Synthesis of C-6
질소 기류 하에서 IIC-4 (4.31 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 C-6 (4.60 g, 수율 70%)를 얻었다.IIC-4 (4.31 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) 2 (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) a (1.71 g, 17.8 mmol), P (t-Bu) 3 (50wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ℃ for 12 hours. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 and purified by column chromatography to give the target compound C-6 (4.60 g, yield 70%).
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 7] C-7의 합성Synthesis Example 7 Synthesis of C-7
질소 기류 하에서 IIC-5 (4.31 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd(OAc)2 (100 mg, 0.446 mmol), NaO(t-Bu) (1.71 g, 17.8 mmol), P(t-Bu)3 (50wt%) (361 mg, 0.892 mmol) 및 Toluene (100 ml)를 혼합하고 110℃ 에서 12시간 동안 교반하였다. 반응이 종결된 후 에틸아세테이트로 추출한 다음, MgSO4로 수분을 제거하고, 컬럼크로마토그래피로 정제하여 목적 화합물 C-7 (3.68 g, 수율 65%)를 얻었다.IIC-5 (4.31 g, 8.92 mmol), 4-bromo-1,1'-biphenyl (2.08 g, 8.92 mmol), Pd (OAc) 2 (100 mg, 0.446 mmol), NaO (t-Bu) under nitrogen stream ) (1.71 g, 17.8 mmol), P (t-Bu) 3 (50 wt%) (361 mg, 0.892 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After the reaction was terminated and extracted with ethyl acetate, water was removed with MgSO 4 and purified by column chromatography to give the target compound C-7 (3.68 g, yield 65%).
Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 8] Com-1의 합성Synthesis Example 8 Synthesis of Com-1
질소 기류 하에서 IC-1 (3 g, 10.63 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (4.38 g, 12.75 mmol), Pd(OAc)2 (0.12 g, 5 mol%), NaO(t-bu) (2.04 g, 21.25 mmol), P(t-bu)3 (0.21 g, 1.06 mmol) 및 Toluene (100 ml)을 혼합하고 110℃에서 12시간 동안 교반하였다.IC-1 (3 g, 10.63 mmol), 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (4.38 g, 12.75 mmol), Pd (OAc) 2 (0.12) under nitrogen stream g, 5 mol%), NaO (t-bu) (2.04 g, 21.25 mmol), P (t-bu) 3 (0.21 g, 1.06 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 hours. Stirred.
반응이 종결된 후 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고, 컬럼크로마토그래피 (Hexane:EA = 2:1 (v/v))로 정제하여 목적 화합물인 Com-1 (4.89 g, 수율 78 %)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate and then water was removed with MgSO 4 , and purified by column chromatography (Hexane: EA = 2: 1 (v / v)) to obtain the title compound Com-1 (4.89 g, yield 78 %) Was obtained.
GC-Mass (이론치: 589.23 g/mol, 측정치: 589 g/mol)GC-Mass (Theoretical value: 589.23 g / mol, Measured value: 589 g / mol)
[합성예 9] Com-2의 합성Synthesis Example 9 Synthesis of Com-2
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (4.36 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-2(4.68 g, 수율 75 %)를 얻었다.Except for using 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (4.36 g, 12.75 mmol) instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine, Com-2 (4.68 g, yield 75%) was obtained by the same procedure as in Synthesis example 8.
GC-Mass (이론치: 588.23 g/mol, 측정치: 588 g/mol)GC-Mass (Theoretical value: 588.23 g / mol, Measured value: 588 g / mol)
[합성예 10] Com-3의 합성Synthesis Example 10 Synthesis of Com-3
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3-chlorophenyl)-4,6-diphenylpyridine (4.34 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-3(4.36 g, 수율 70 %)를 얻었다.Except for using 2- (3-chlorophenyl) -4,6-diphenylpyridine (4.34 g, 12.75 mmol) instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine, Com-3 (4.36 g, yield 70%) as a target compound was obtained in the same manner as in Synthesis example 8.
GC-Mass (이론치: 587.23 g/mol, 측정치: 587 g/mol)GC-Mass (Theoretical value: 587.23 g / mol, Measured value: 587 g / mol)
[합성예 11] Com-4의 합성Synthesis Example 11 Synthesis of Com-4
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3-chloro-5-methylphenyl)-4,6-diphenyl-1,3,5-triazine (4.55 g, 12.75 mmol)을 사용한 것을 제외하고는 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-4(4.81 g, 수율 75 %)를 얻었다.2- (3-chloro-5-methylphenyl) -4,6-diphenyl-1,3,5-triazine (4.55 g instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine , 12.75 mmol) was obtained in the same manner as in Synthesis Example 8 to obtain Com-4 (4.81 g, yield 75%) as a target compound.
GC-Mass (이론치: 603.24 g/mol, 측정치: 603 g/mol)GC-Mass (Theoretical value: 603.24 g / mol, Measured value: 603 g / mol)
[합성예 12] Com-5의 합성Synthesis Example 12 Synthesis of Com-5
IC-1 대신 IC-7 (3 g, 10.63 mmol)를 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-5(4.81 g, 수율 75 %)를 얻었다.Except for using IC-7 (3 g, 10.63 mmol) instead of IC-1, the same process as in Synthesis Example 8 was carried out to obtain the title compound Com-5 (4.81 g, yield 75%).
GC-Mass (이론치: 589.23 g/mol, 측정치: 589 g/mol)GC-Mass (Theoretical value: 589.23 g / mol, Measured value: 589 g / mol)
[합성예 13] Com-6의 합성Synthesis Example 13 Synthesis of Com-6
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenyl-1,3,5-triazine (3.40 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-6(3.98 g, 수율 73 %)를 얻었다.Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (3.40 g, 12.75 mmol) instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Then, Com-6 (3.98 g, yield 73%) was obtained by the same procedure as in Synthesis Example 8.
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[합성예 14] Com-7의 합성Synthesis Example 14 Synthesis of Com-7
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenylpyrimidine (3.40 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-7(3.81 g, 수율 70 %)를 얻었다.Synthesis Example 8 except that 2-chloro-4,6-diphenylpyrimidine (3.40 g, 12.75 mmol) was used instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine. The same procedure was followed to obtain the title compound Com-7 (3.81 g, yield 70%).
GC-Mass (이론치: 512.20 g/mol, 측정치: 512 g/mol)GC-Mass (Theoretical value: 512.20 g / mol, Measured value: 512 g / mol)
[합성예 15] Com-8의 합성Synthesis Example 15 Synthesis of Com-8
2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenylpyridine (3.38 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-8(4.07 g, 수율 75 %)를 얻었다.Except for using 2-chloro-4,6-diphenylpyridine (3.38 g, 12.75 mmol) instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine, The same procedure was followed to obtain the title compound Com-8 (4.07 g, yield 75%).
GC-Mass (이론치: 511.20 g/mol, 측정치: 511 g/mol)GC-Mass (Theoretical value: 511.20 g / mol, Measured value: 511 g / mol)
[합성예 16] Com-9의 합성Synthesis Example 16 Synthesis of Com-9
IC-1 대신 IC-7 (3 g, 10.63 mmol)를 사용하고, 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenyl-1,3,5-triazine (3.38 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-9(3.92 g, 수율 72 %)를 얻었다.Use IC-7 (3 g, 10.63 mmol) instead of IC-1, 2-chloro-4,6-diphenyl- instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Except for using 1,3,5-triazine (3.38 g, 12.75 mmol), the same procedure as in Synthesis Example 8 was carried out to obtain Com-9 (3.92 g, yield 72%).
GC-Mass (이론치: 513.20 g/mol, 측정치: 513 g/mol)GC-Mass (Theoretical value: 513.20 g / mol, Measured value: 513 g / mol)
[합성예 17] Com-10의 합성Synthesis Example 17 Synthesis of Com-10
IC-1 대신 IC-2 (3 g, 10.63 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-10(4.39 g, 수율 70 %)를 얻었다.Except for using IC-2 (3 g, 10.63 mmol) instead of IC-1, the same procedure as in Synthesis Example 8 was carried out to obtain the title compound Com-10 (4.39 g, yield 70%).
GC-Mass (이론치: 590.22 g/mol, 측정치: 590 g/mol)GC-Mass (Theoretical value: 590.22 g / mol, Measured value: 590 g / mol)
[합성예 18] Com-11의 합성Synthesis Example 18 Synthesis of Com-11
IC-1 대신 IC-3 (3.02 g, 10.63 mmol) 을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-11(4.39 g, 수율 70 %)를 얻었다.Except for using IC-3 (3.02 g, 10.63 mmol) instead of IC-1, the same procedure as in Synthesis Example 8 was carried out to obtain the title compound Com-11 (4.39 g, yield 70%).
GC-Mass (이론치: 591.21 g/mol, 측정치: 591 g/mol)GC-Mass (Theoretical value: 591.21 g / mol, Measured value: 591 g / mol)
[합성예 19] Com-12의 합성Synthesis Example 19 Synthesis of Com-12
IC-1 대신 IC-4 (3.18 g, 10.63 mmol) 을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-12(4.39 g, 수율 68 %)를 얻었다.Except for using IC-4 (3.18 g, 10.63 mmol) instead of IC-1, the same procedure as in Synthesis Example 8 was carried out to obtain the title compound Com-12 (4.39 g, yield 68%).
GC-Mass (이론치: 607.18 g/mol, 측정치: 607 g/mol)GC-Mass (Theoretical value: 607.18 g / mol, Measured value: 607 g / mol)
[합성예 20] Com-13의 합성Synthesis Example 20 Synthesis of Com-13
IC-1 대신 IC-5 (3 g, 10.63 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenyltriazine (3.40 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 방법으로 합성하여 목적 화합물인 Com-13 (3.87 g, 수율 71 %)을 얻었다.IC-5 (3 g, 10.63 mmol) instead of IC-1, 2-chloro-4,6-diphenyltriazine (3.40 g, instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine 12.75 mmol) was synthesized in the same manner as in Synthesis Example 8 to obtain Com-13 (3.87 g, 71% yield) of the title compound.
GC-Mass (이론치: 514.19 g/mol, 측정치: 514 g/mol)GC-Mass (Theoretical value: 514.19 g / mol, Measured value: 514 g / mol)
[합성예 21] Com-14의 합성Synthesis Example 21 Synthesis of Com-14
질소 기류 하에서 준비예 6에서 제조된 화합물인 IC-6 (3.20 g, 7.31 mmol), 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (3.81 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd(PPh3)4 (0.25 g, 0.21 mmol) 및 1,4-dioxane, H2O (30 ml, 8 ml)를 혼합하고 100℃에서 12시간 동안 교반하였다. 반응 종결 후 에틸아세테이트로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 Com-14 (2.67 g, 수율 55%)를 얻었다. IC-6 (3.20 g, 7.31 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-), which are the compounds prepared in Preparation Example 6 under nitrogen stream dioxaborolan-2-yl) phenyl) -1,3,5-triazine (3.81 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3 ) 4 (0.25 g, 0.21 mmol) and 1,4 -dioxane, H 2 O (30 ml, 8 ml) was mixed and stirred at 100 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate and filtered with MgSO 4 . After removing the solvent of the organic layer filtered to obtain the target compound Com-14 (2.67 g, 55% yield) using column chromatography.
GC-Mass (이론치: 665.26 g/mol, 측정치: 665 g/mol)GC-Mass (Theoretical value: 665.26 g / mol, Measured value: 665 g / mol)
[합성예 22] Com-15의 합성Synthesis Example 22 Synthesis of Com-15
질소 기류 하에서 준비예 8에서 합성된 화합물 IC-8 (2.4 g, 6.7 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol), Pd(OAc)2 (0.08 g, 0.34 mmol), P(t-Bu)3 (0.16 ml, 0.67 mmol), NaO(t-Bu) (1.29 g, 13.4 mmol) 및 toluene (70 ml)를 혼합하고, 110 ℃ 에서 5시간 동안 교반하였다. 반응이 종결된 후 toluenen을 농축하고, 고체염을 필터링한 후, 재결정으로 정제하여 화합물 Com-15 (3.3 g, 수율 73%)를 얻었다.Compound IC-8 (2.4 g, 6.7 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) synthesized in Preparation Example 8 under nitrogen stream, Pd (OAc) 2 (0.08 g, 0.34 mmol), P ( t -Bu) 3 (0.16 ml, 0.67 mmol), NaO ( t -Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed And stirred at 110 ° C. for 5 hours. After the reaction was completed, toluenen was concentrated, the solid salt was filtered, and then purified by recrystallization to obtain a compound Com-15 (3.3 g, 73% yield).
Mass (이론치: 665.26, 측정치: 665 g/mol)Mass (Theoretical value: 665.26, Measured value: 665 g / mol)
[합성예 23] Com-16의 합성Synthesis Example 23 Synthesis of Com-16
IC-1 대신 IC-3 (3.02 g, 10.63 mmol)를 사용하고, 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine 대신 2-(3'-chlorobiphenyl-3-yl)-4,6-diphenyl-1,3,5-triazine (5.34 g, 12.75 mmol)을 사용한 것을 제외하고는, 상기 합성예 8과 동일한 과정을 수행하여 목적 화합물인 Com-16 (4.89g, 수율 69%)를 얻었다.Use IC-3 (3.02 g, 10.63 mmol) instead of IC-1 and 2- (3'-chlorobiphenyl-3- instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Except for using yl) -4,6-diphenyl-1,3,5-triazine (5.34 g, 12.75 mmol), the same procedure as in Synthesis Example 8 was performed to obtain Com-16 (4.89 g, Yield 69%).
GC-Mass (이론치: 667.24 g/mol, 측정치: 667 g/mol)GC-Mass (Theoretical value: 667.24 g / mol, Measured value: 667 g / mol)
[실시예 1 내지 78] 유기 전계 발광 소자의 제조Examples 1 to 78 Fabrication of Organic Electroluminescent Device
ITO(Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.The glass substrate coated with ITO (Indium tin oxide) with a thickness of 1500Å was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then wash the substrate using UV for 5 minutes The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 기판 위에, C-1 내지 C-7을 제 1호스트로, 상기 Com-1 내지 Com-16으로 표시되는 화합물을 각각 제 2호스트로 이용하여, m-MTDATA(60 nm) / TCTA(80 nm) / 90%의 제1 호스트와 제2 호스트 + 10 % Ir(ppy)3(300nm) / BCP(10 nm) / Alq3(30 nm) / LiF(1 nm) / Al(200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.M-MTDATA (60 nm) using the C-1 to C-7 as the first host and the compounds represented by the Com-1 to Com-16 as the second host, respectively, on the prepared ITO transparent substrate. / TCTA (80 nm) / 90% of the first and second host + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al ( 200 nm) was laminated in order to fabricate an organic EL device.
이때, 사용된 m-MTDATA, TCTA, Ir(ppy)3 및 BCP의 구조는 하기와 같으며, 제1 호스트와 제2 호스트의 혼합비율은 7:3으로 하였다.At this time, the structures of m-MTDATA, TCTA, Ir (ppy) 3 and BCP used are as follows, and the mixing ratio of the first host and the second host is 7: 3.
[실시예 79 내지 81] 유기 전계 발광 소자의 제조Examples 79 to 81 Fabrication of Organic Electroluminescent Device
실시예 1과 같이 준비된 ITO 투명 기판 위에, 상기 C-3을 제1 호스트로, 상기 Com-1로 표시되는 화합물을 제2 호스트로 이용하여, m-MTDATA(60 nm) / TCTA(80 nm) / 90%의 제1 호스트와 제2 호스트 + 10 % Ir(ppy)3(300nm) / BCP(10 nm) / Alq3(30 nm) / LiF(1 nm) / Al(200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.Example 1 On the prepared ITO transparent substrate, m-MTDATA (60 nm) / TCTA (80 nm) / 90% of C-3 as the first host and the compound represented by the Com-1 as the second host Organic electroluminescence by stacking the first host and the second host + 10% Ir (ppy) 3 (300nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) The device was produced.
이때, 사용된 m-MTDATA, TCTA, Ir(ppy)3, BCP의 구조는 상기 실시예 1과 같고, 제1 호스트와 제2 호스트의 혼합비율은 하기 표 1과 같이 조정하였다.At this time, the structure of m-MTDATA, TCTA, Ir (ppy) 3 , BCP used is the same as in Example 1, the mixing ratio of the first host and the second host was adjusted as shown in Table 1.
[비교예 1] 유기 전계 발광 소자의 제조Comparative Example 1 Fabrication of Organic Electroluminescent Device
발광층 형성시 90%의 CBP + 10 % Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다. 이때, 사용된 CBP의 구조는 하기와 같다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 90% CBP + 10% Ir (ppy) 3 was used to form the emission layer. At this time, the structure of the CBP used is as follows.
[비교예 2] 유기 전계 발광 소자의 제조Comparative Example 2 Fabrication of Organic Electroluminescent Device
발광층 형성시 90%의 제2 호스트(Com-1) + 10 % Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다.An organic EL device was manufactured in the same manner as in Example 1, except that 90% of the second host (Com-1) + 10% Ir (ppy) 3 was used to form the emission layer.
[비교예 3] 유기 전계 발광 소자의 제조Comparative Example 3 Fabrication of Organic Electroluminescent Device
발광층 형성시 90%의 제1 호스트(C-3) + 10 % Ir(ppy)3를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다.An organic EL device was manufactured in the same manner as in Example 1, except that 90% of the first host (C-3) + 10% Ir (ppy) 3 was used to form the emission layer.
[실험예]Experimental Example
상기 실시예 1 내지 81 및 비교예 1~3에서 제조된 각각의 유기 전계 발광 소자에 대하여 전류밀도 10mA/㎠에서의 구동전압과 전류효율을 측정하였고, 그 결과를 하기 표 1에 나타내었다.For each of the organic EL devices manufactured in Examples 1 to 81 and Comparative Examples 1 to 3, the driving voltage and the current efficiency at the current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.
표 1
Table 1
| 샘플 | 호스트 사용비율 | 구동 전압 (V) | 전류효율 (cd/A) |
| 실시예 1 | 70% C-1 + 30% Com-1 | 6.10 | 42.9 |
| 실시예 2 | 70% C-1 + 30% Com-2 | 6.15 | 42.8 |
| 실시예 3 | 70% C-1 + 30% Com-3 | 6.15 | 42.8 |
| 실시예 4 | 70% C-1 + 30% Com-4 | 6.10 | 42.9 |
| 실시예 5 | 70% C-1 + 30% Com-5 | 6.10 | 42.5 |
| 실시예 6 | 70% C-1 + 30% Com-6 | 6.25 | 42.6 |
| 실시예 7 | 70% C-1 + 30% Com-7 | 6.15 | 42.5 |
| 실시예 8 | 70% C-1 + 30% Com-8 | 6.20 | 42.9 |
| 실시예 9 | 70% C-1 + 30% Com-9 | 6.25 | 43.0 |
| 실시예 10 | 70% C-1 + 30% Com-10 | 6.20 | 42.7 |
| 실시예 11 | 70% C-1 + 30% Com-11 | 6.25 | 42.9 |
| 실시예 12 | 70% C-1 + 30% Com-12 | 6.35 | 42.5 |
| 실시예 13 | 70% C-1 + 30% Com-13 | 6.30 | 43.2 |
| 실시예 14 | 70% C-1 + 30% Com-14 | 6.10 | 43.0 |
| 실시예 15 | 70% C-1 + 30% Com-15 | 6.25 | 42.9 |
| 실시예 16 | 70% C-2 + 30% Com-1 | 6.25 | 43.1 |
| 실시예 17 | 70% C-2 + 30% Com-2 | 6.20 | 42.9 |
| 실시예 18 | 70% C-2 + 30% Com-3 | 6.25 | 42.8 |
| 실시예 19 | 70% C-2 + 30% Com-4 | 6.25 | 42.8 |
| 실시예 20 | 70% C-2 + 30% Com-5 | 6.40 | 42.9 |
| 실시예 21 | 70% C-2 + 30% Com-6 | 6.50 | 42.5 |
| 실시예 22 | 70% C-2 + 30% Com-7 | 6.55 | 42.6 |
| 실시예 23 | 70% C-2 + 30% Com-8 | 6.55 | 42.5 |
| 실시예 24 | 70% C-2 + 30% Com-9 | 6.40 | 42.9 |
| 실시예 25 | 70% C-2 + 30% Com-10 | 6.45 | 43.0 |
| 실시예 26 | 70% C-2 + 30% Com-11 | 6.90 | 42.7 |
| 실시예 27 | 70% C-2 + 30% Com-12 | 6.95 | 42.9 |
| 실시예 28 | 70% C-2 + 30% Com-13 | 6.95 | 42.5 |
| 실시예 29 | 70% C-2 + 30% Com-14 | 6.90 | 43.2 |
| 실시예 30 | 70% C-2 + 30% Com-15 | 6.90 | 43.0 |
| 실시예 31 | 70% C-3 + 30% Com-1 | 6.95 | 42.9 |
| 실시예 32 | 70% C-3 + 30% Com-2 | 6.00 | 43.3 |
| 실시예 33 | 70% C-3 + 30% Com-3 | 6.05 | 43.0 |
| 실시예 34 | 70% C-3 + 30% Com-4 | 6.15 | 42.8 |
| 실시예 35 | 70% C-3 + 30% Com-5 | 6.10 | 42.9 |
| 실시예 36 | 70% C-3 + 30% Com-6 | 6.00 | 43.0 |
| 실시예 37 | 70% C-3 + 30% Com-7 | 6.20 | 43.2 |
| 실시예 38 | 70% C-3 + 30% Com-8 | 6.10 | 43.0 |
| 실시예 39 | 70% C-3 + 30% Com-9 | 6.15 | 42.7 |
| 실시예 40 | 70% C-3 + 30% Com-10 | 6.25 | 42.5 |
| 실시예 41 | 70% C-3 + 30% Com-11 | 6.20 | 42.3 |
| 실시예 42 | 70% C-3 + 30% Com-12 | 6.25 | 42.4 |
| 실시예 43 | 70% C-3 + 30% Com-13 | 6.30 | 43.0 |
| 실시예 44 | 70% C-3 + 30% Com-14 | 6.30 | 43.8 |
| 실시예 45 | 70% C-3 + 30% Com-15 | 6.40 | 43.7 |
| 실시예 46 | 70% C-4 + 30% Com-1 | 6.95 | 43.1 |
| 실시예 47 | 70% C-4 + 30% Com-2 | 6.50 | 42.0 |
| 실시예 48 | 70% C-4 + 30% Com-3 | 6.45 | 42.8 |
| 실시예 49 | 70% C-4 + 30% Com-4 | 6.45 | 42.8 |
| 실시예 50 | 70% C-4 + 30% Com-5 | 6.40 | 42.0 |
| 실시예 51 | 70% C-4 + 30% Com-6 | 6.50 | 42.5 |
| 실시예 52 | 70% C-4 + 30% Com-7 | 6.55 | 42.3 |
| 실시예 53 | 70% C-4 + 30% Com-8 | 6.55 | 42.5 |
| 실시예 54 | 70% C-4 + 30% Com-9 | 6.40 | 42.9 |
| 실시예 55 | 70% C-4 + 30% Com-10 | 6.45 | 43.0 |
| 실시예 56 | 70% C-4 + 30% Com-11 | 6.30 | 42.7 |
| 실시예 57 | 70% C-4 + 30% Com-12 | 6.35 | 42.6 |
| 실시예 58 | 70% C-4 + 30% Com-13 | 6.35 | 42.5 |
| 실시예 59 | 70% C-4 + 30% Com-14 | 6.30 | 42.8 |
| 실시예 60 | 70% C-4 + 30% Com-15 | 6.30 | 43.0 |
| 실시예 61 | 70% C-5 + 30% Com-1 | 6.50 | 42.5 |
| 실시예 62 | 70% C-6 + 30% Com-1 | 6.45 | 42.8 |
| 실시예 63 | 70% C-7 + 30% Com-1 | 6.05 | 43.9 |
| 실시예 64 | 70% C-7 + 30% Com-2 | 6.10 | 42.9 |
| 실시예 65 | 70% C-7 + 30% Com-3 | 6.20 | 42.5 |
| 실시예 66 | 70% C-7 + 30% Com-4 | 6.15 | 42.6 |
| 실시예 67 | 70% C-7 + 30% Com-5 | 6.15 | 42.5 |
| 실시예 68 | 70% C-7 + 30% Com-6 | 6.20 | 42.9 |
| 실시예 69 | 70% C-7 + 30% Com-7 | 6.25 | 43.0 |
| 실시예 70 | 70% C-7 + 30% Com-8 | 6.20 | 42.7 |
| 실시예 71 | 70% C-7 + 30% Com-9 | 6.25 | 42.9 |
| 실시예 72 | 70% C-7 + 30% Com-10 | 6.35 | 42.5 |
| 실시예 73 | 70% C-7 + 30% Com-11 | 6.20 | 43.2 |
| 실시예 74 | 70% C-7 + 30% Com-12 | 6.30 | 43.0 |
| 실시예 75 | 70% C-7 + 30% Com-13 | 6.35 | 42.9 |
| 실시예 76 | 70% C-7 + 30% Com-14 | 6.20 | 42.0 |
| 실시예 77 | 70% C-7 + 30% Com-15 | 6.15 | 42.1 |
| 실시예 78 | 70% C-3 + 30% Com-16 | 6.20 | 42.9 |
| 실시예 79 | 80% C-3 + 20% Com-1 | 6.45 | 41.1 |
| 실시예 80 | 60% C-3 + 40% Com-1 | 6.20 | 42.9 |
| 실시예 81 | 50% C-3 + 50% Com-1 | 6.35 | 42.7 |
| 비교예 1 | CBP | 6.93 | 38.2 |
| 비교예 2 | Com-1 | 6.55 | 41.0 |
| 비교예 3 | C-3 | 6.40 | 35.2 |
| Sample | Host Usage Rate | Driving voltage (V) | Current efficiency (cd / A) |
| Example 1 | 70% C-1 + 30% Com-1 | 6.10 | 42.9 |
| Example 2 | 70% C-1 + 30% Com-2 | 6.15 | 42.8 |
| Example 3 | 70% C-1 + 30% Com-3 | 6.15 | 42.8 |
| Example 4 | 70% C-1 + 30% Com-4 | 6.10 | 42.9 |
| Example 5 | 70% C-1 + 30% Com-5 | 6.10 | 42.5 |
| Example 6 | 70% C-1 + 30% Com-6 | 6.25 | 42.6 |
| Example 7 | 70% C-1 + 30% Com-7 | 6.15 | 42.5 |
| Example 8 | 70% C-1 + 30% Com-8 | 6.20 | 42.9 |
| Example 9 | 70% C-1 + 30% Com-9 | 6.25 | 43.0 |
| Example 10 | 70% C-1 + 30% Com-10 | 6.20 | 42.7 |
| Example 11 | 70% C-1 + 30% Com-11 | 6.25 | 42.9 |
| Example 12 | 70% C-1 + 30% Com-12 | 6.35 | 42.5 |
| Example 13 | 70% C-1 + 30% Com-13 | 6.30 | 43.2 |
| Example 14 | 70% C-1 + 30% Com-14 | 6.10 | 43.0 |
| Example 15 | 70% C-1 + 30% Com-15 | 6.25 | 42.9 |
| Example 16 | 70% C-2 + 30% Com-1 | 6.25 | 43.1 |
| Example 17 | 70% C-2 + 30% Com-2 | 6.20 | 42.9 |
| Example 18 | 70% C-2 + 30% Com-3 | 6.25 | 42.8 |
| Example 19 | 70% C-2 + 30% Com-4 | 6.25 | 42.8 |
| Example 20 | 70% C-2 + 30% Com-5 | 6.40 | 42.9 |
| Example 21 | 70% C-2 + 30% Com-6 | 6.50 | 42.5 |
| Example 22 | 70% C-2 + 30% Com-7 | 6.55 | 42.6 |
| Example 23 | 70% C-2 + 30% Com-8 | 6.55 | 42.5 |
| Example 24 | 70% C-2 + 30% Com-9 | 6.40 | 42.9 |
| Example 25 | 70% C-2 + 30% Com-10 | 6.45 | 43.0 |
| Example 26 | 70% C-2 + 30% Com-11 | 6.90 | 42.7 |
| Example 27 | 70% C-2 + 30% Com-12 | 6.95 | 42.9 |
| Example 28 | 70% C-2 + 30% Com-13 | 6.95 | 42.5 |
| Example 29 | 70% C-2 + 30% Com-14 | 6.90 | 43.2 |
| Example 30 | 70% C-2 + 30% Com-15 | 6.90 | 43.0 |
| Example 31 | 70% C-3 + 30% Com-1 | 6.95 | 42.9 |
| Example 32 | 70% C-3 + 30% Com-2 | 6.00 | 43.3 |
| Example 33 | 70% C-3 + 30% Com-3 | 6.05 | 43.0 |
| Example 34 | 70% C-3 + 30% Com-4 | 6.15 | 42.8 |
| Example 35 | 70% C-3 + 30% Com-5 | 6.10 | 42.9 |
| Example 36 | 70% C-3 + 30% Com-6 | 6.00 | 43.0 |
| Example 37 | 70% C-3 + 30% Com-7 | 6.20 | 43.2 |
| Example 38 | 70% C-3 + 30% Com-8 | 6.10 | 43.0 |
| Example 39 | 70% C-3 + 30% Com-9 | 6.15 | 42.7 |
| Example 40 | 70% C-3 + 30% Com-10 | 6.25 | 42.5 |
| Example 41 | 70% C-3 + 30% Com-11 | 6.20 | 42.3 |
| Example 42 | 70% C-3 + 30% Com-12 | 6.25 | 42.4 |
| Example 43 | 70% C-3 + 30% Com-13 | 6.30 | 43.0 |
| Example 44 | 70% C-3 + 30% Com-14 | 6.30 | 43.8 |
| Example 45 | 70% C-3 + 30% Com-15 | 6.40 | 43.7 |
| Example 46 | 70% C-4 + 30% Com-1 | 6.95 | 43.1 |
| Example 47 | 70% C-4 + 30% Com-2 | 6.50 | 42.0 |
| Example 48 | 70% C-4 + 30% Com-3 | 6.45 | 42.8 |
| Example 49 | 70% C-4 + 30% Com-4 | 6.45 | 42.8 |
| Example 50 | 70% C-4 + 30% Com-5 | 6.40 | 42.0 |
| Example 51 | 70% C-4 + 30% Com-6 | 6.50 | 42.5 |
| Example 52 | 70% C-4 + 30% Com-7 | 6.55 | 42.3 |
| Example 53 | 70% C-4 + 30% Com-8 | 6.55 | 42.5 |
| Example 54 | 70% C-4 + 30% Com-9 | 6.40 | 42.9 |
| Example 55 | 70% C-4 + 30% Com-10 | 6.45 | 43.0 |
| Example 56 | 70% C-4 + 30% Com-11 | 6.30 | 42.7 |
| Example 57 | 70% C-4 + 30% Com-12 | 6.35 | 42.6 |
| Example 58 | 70% C-4 + 30% Com-13 | 6.35 | 42.5 |
| Example 59 | 70% C-4 + 30% Com-14 | 6.30 | 42.8 |
| Example 60 | 70% C-4 + 30% Com-15 | 6.30 | 43.0 |
| Example 61 | 70% C-5 + 30% Com-1 | 6.50 | 42.5 |
| Example 62 | 70% C-6 + 30% Com-1 | 6.45 | 42.8 |
| Example 63 | 70% C-7 + 30% Com-1 | 6.05 | 43.9 |
| Example 64 | 70% C-7 + 30% Com-2 | 6.10 | 42.9 |
| Example 65 | 70% C-7 + 30% Com-3 | 6.20 | 42.5 |
| Example 66 | 70% C-7 + 30% Com-4 | 6.15 | 42.6 |
| Example 67 | 70% C-7 + 30% Com-5 | 6.15 | 42.5 |
| Example 68 | 70% C-7 + 30% Com-6 | 6.20 | 42.9 |
| Example 69 | 70% C-7 + 30% Com-7 | 6.25 | 43.0 |
| Example 70 | 70% C-7 + 30% Com-8 | 6.20 | 42.7 |
| Example 71 | 70% C-7 + 30% Com-9 | 6.25 | 42.9 |
| Example 72 | 70% C-7 + 30% Com-10 | 6.35 | 42.5 |
| Example 73 | 70% C-7 + 30% Com-11 | 6.20 | 43.2 |
| Example 74 | 70% C-7 + 30% Com-12 | 6.30 | 43.0 |
| Example 75 | 70% C-7 + 30% Com-13 | 6.35 | 42.9 |
| Example 76 | 70% C-7 + 30% Com-14 | 6.20 | 42.0 |
| Example 77 | 70% C-7 + 30% Com-15 | 6.15 | 42.1 |
| Example 78 | 70% C-3 + 30% Com-16 | 6.20 | 42.9 |
| Example 79 | 80% C-3 + 20% Com-1 | 6.45 | 41.1 |
| Example 80 | 60% C-3 + 40% Com-1 | 6.20 | 42.9 |
| Example 81 | 50% C-3 + 50% Com-1 | 6.35 | 42.7 |
| Comparative Example 1 | CBP | 6.93 | 38.2 |
| Comparative Example 2 | Com-1 | 6.55 | 41.0 |
| Comparative Example 3 | C-3 | 6.40 | 35.2 |
상기 표 1을 살펴보면, 제1 호스트와 제2 호스트를 포함하는 발광층을 사용하는 실시예 1 내지 81의 유기 전계 발광 소자는 종래 CBP 를 사용하는 비교예 1; 또는 Com-1과 C-3을 각각 단독 호스트 물질로 포함하는 발광층을 사용한 비교예 2 및 비교예 3의 유기 전계 발광 소자에 비해서, 보다 전류효율 및 구동전압 면에서 우수한 성능을 나타내는 것을 확인할 수 있었다.Referring to Table 1, the organic electroluminescent device of Examples 1 to 81 using the light emitting layer including the first host and the second host is Comparative Example 1 using a conventional CBP; Or compared with the organic electroluminescent device of Comparative Example 2 and Comparative Example 3 using the light emitting layer containing Com-1 and C-3 as a single host material, it was confirmed that the excellent performance in terms of current efficiency and driving voltage. .
Claims (10)
- 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며,anode; cathode; And one or more organic material layers interposed between the anode and the cathode,상기 1층 이상의 유기물층 중 적어도 하나는 제1 호스트와 제2 호스트를 포함하고,At least one of the one or more organic material layers includes a first host and a second host,상기 제1 호스트는 하기 화학식 1로 표시되는 화합물이며, The first host is a compound represented by the following formula (1),상기 제2 호스트는 하기 화학식 2로 표시되는 화합물인 것을 특징으로 하는 유기 전계 발광 소자:The second host is an organic electroluminescent device, characterized in that the compound represented by the formula (2):[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,Ra 내지 Rd는 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1~C40의 알킬기, 및 치환 또는 비치환된 C6~C60의 아릴기로 이루어진 군에서 선택되고,R a to R d are the same as or different from each other, and each independently, a group consisting of hydrogen, deuterium, a substituted or unsubstituted C 1 to C 40 alkyl group, and a substituted or unsubstituted C 6 to C 60 aryl group Is selected from,[화학식 2] [Formula 2]
상기 화학식 2에서,In Chemical Formula 2,X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고,X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),Y1 내지 Y4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 이때 C(R1)이 복수 개인 경우 복수의 R1은 각각 동일하거나 상이하며, 이들은 각각 인접한 기와 축합 고리를 형성할 수 있고;Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), and when there are a plurality of C (R 1 ), a plurality of R 1 are the same or different, and each of them is adjacent to an adjacent group. Can form condensed rings;X2 및 X3는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R2)이고, 이때 C(R2)가 복수 개인 경우 복수의 R2는 각각 동일하거나 상이하며, 이들은 인접한 기와 축합 고리를 형성할 수 있고;X 2 and X 3 are the same or different from each other, and each independently represents N, or a C (R 2), wherein C (R 2) a plurality of R 2, if multiple individuals are the same or different from each other, all of which are adjacent tile condensation May form a ring;상기 R1 내지 R2 및 Ar1 내지 Ar5는 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C1~C40의 포스핀기, 치환 또는 비치환된 C1~C40의 포스핀옥사이드기 및 치환 또는 비치환된 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C 1 to C 40 An alkyl group, a substituted or unsubstituted C 2 -C 40 alkenyl group, a substituted or unsubstituted C 2 -C 40 alkynyl group, a substituted or unsubstituted C 3 -C 40 cycloalkyl group, a substituted or unsubstituted nucleus Heterocycloalkyl group having 3 to 40 atoms, substituted or unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 An alkyloxy group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 1 -C 40 alkylsilyl group, a substituted or unsubstituted C 6 -C 60 arylsilyl group, Substituted or unsubstituted C 1 to C 40 alkylboron group, substituted or unsubstituted C 6 to C 60 arylboron group, substituted or unsubstituted C Is selected from 1 ~ C 40 of the phosphine group, a substituted or unsubstituted C 1 ~ C 40 phosphine oxide group, and the group consisting of a substituted or unsubstituted C 6 ~ C 60 aryl amine,상기 Ra 내지 Rd, R1 내지 R2 및 Ar1 내지 Ar5에서, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기가 치환될 경우는, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다.In the R a to R d , R 1 to R 2 and Ar 1 to Ar 5 , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, When an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group and an arylamine group are substituted, each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 a ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, a nuclear atoms, 3 to 40 hetero cycloalkyl group, C 6 ~ C 40 of the An aryl group, a heteroaryl group having 5 to 40 nuclear atoms, an alkyloxy group of C 1 to C 40 , an aryloxy group of C 6 to C 60 , an alkylsilyl group of C 1 to C 40 , and a C 6 to C 60 group aryl silyl group, a C 1 ~ C 40 group of an alkyl boron, C 6 ~ C 60 aryl boron group, a C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ C 60 of the With arylamine groups It may be substituted with one or more selected from the group consisting of. - 제 1항에 있어서,The method of claim 1,상기 Ra 내지 Rd는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 메틸기, t-부틸기, 및 페닐기로 이루어진 군에서 선택되는 것을 특징으로 하는 유기 전계 발광 소자.R a to R d are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, methyl group, t-butyl group, and phenyl group.
- 제1항에 있어서,The method of claim 1,상기 제 1 호스트는 하기 화합물로 이루어진 화합물 군에서 선택되는 것을 특징으로 하는 유기 전계 발광 소자:The organic light emitting device, characterized in that the first host is selected from the group consisting of compounds:
- 제 1항에 있어서,The method of claim 1,상기 화학식 2로 표시되는 화합물은 하기 화학식 A-1 내지 A-24으로 이루어진 화합물 군에서 선택되는 것을 특징으로 하는 유기 전계 발광 소자.Compound represented by the formula (2) is an organic electroluminescent device, characterized in that selected from the group consisting of the formula A-1 to A-24.
상기 A-1 내지 A-24에서, In the above A-1 to A-24,R2, Y1 내지 Y4 및 Ar1 내지 Ar5는 제1항에서 정의된 바와 동일하다.R 2 , Y 1 to Y 4 and Ar 1 to Ar 5 are the same as defined in claim 1 . - 제 1항에 있어서,The method of claim 1,상기 화학식 2에서, X2 및 X3가 모두 C(R2)인 경우, 복수의 R2는 하기 화학식 3 또는 화학식 4와 결합하여 축합 고리를 형성하는 것을 특징으로 하는 유기 전계 발광 소자.In Chemical Formula 2, when X 2 and X 3 are both C (R 2 ), a plurality of R 2 is combined with the following Chemical Formula 3 or Chemical Formula 4 to form a condensed ring.[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 화학식 3 및 화학식 4 에서,In Chemical Formulas 3 and 4,X4는 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, X 4 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),Ar1 내지 Ar5는 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C1~C40의 포스핀기, 치환 또는 비치환된 C1~C40의 포스핀옥사이드기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,Ar 1 to Ar 5 are the same as or different from each other, and each independently, hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 ~ C 40 alkenyl group, a substituted or unsubstituted C 2 ~ C 40 of the alkynyl group, a substituted or unsubstituted C 3 ~ C 40 cycloalkyl group, a substituted or unsubstituted nucleus of atoms of 3 to 40 hetero Cycloalkyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 -C 40 alkyloxy group, substituted or Unsubstituted C 6 to C 60 aryloxy group, substituted or unsubstituted C 1 to C 40 alkylsilyl group, substituted or unsubstituted C 6 to C 60 arylsilyl group, substituted or unsubstituted C 1 An alkylboron group of -C 40 , a substituted or unsubstituted C 6 -C 60 arylboron group, a substituted or unsubstituted C 1 -C 40 phosphine group, A substituted or unsubstituted C 1 to C 40 phosphine oxide group, and a substituted or unsubstituted C 6 to C 60 arylamine group,Y5 내지 Y14은 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R3)이고, 이때 C(R3)가 복수 개인 경우 복수의 R3는 각각 동일하거나 상이하며, 상기 화학식 2와 축합 고리를 형성할 수 있고, Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), wherein when there are a plurality of C (R 3 ), a plurality of R 3 are the same as or different from each other. Can form condensed rings,상기 화학식 2와 축합 고리를 비(非)형성하는 R3는 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 치환 또는 비치환된 C1~C40의 알킬보론기, 치환 또는 비치환된 C6~C60의 아릴보론기, 치환 또는 비치환된 C1~C40의 포스핀기, 치환 또는 비치환된 C1~C40의 포스핀옥사이드기 및 치환 또는 비치환된 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 또는 이들은 인접한 기와 결합하여 축합 고리를 형성할 수 있으며,R 3 non-forming a condensed ring with Formula 2 is independently hydrogen, deuterium, halogen, cyano, nitro, amino, substituted or unsubstituted C 1 ~ C 40 alkyl, substituted or unsubstituted A substituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 to C 40 alkynyl group, a substituted or unsubstituted C 3 to C 40 cycloalkyl group, a substituted or unsubstituted nuclear atom 3 to 40 Heterocycloalkyl group, substituted or unsubstituted C 6 ~ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ~ C 40 alkyloxy group, Substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 1 -C 40 alkylsilyl group, substituted or unsubstituted C 6 -C 60 arylsilyl group, substituted or unsubstituted C 1 ~ C 40 alkyl boron group, a substituted or unsubstituted C 6 ~ C 60 aryl boron group, a substituted or unsubstituted C 1 ~ C 40 of the phosphine , Is selected from substituted or unsubstituted C 1 ~ C 40 phosphine oxide group, and the group consisting of a substituted or unsubstituted C 6 ~ C 60 aryl amine, or they combine adjacent groups may form a fused ring, and ,상기 Ar1 내지 Ar5, 및 R3에서, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기가 치환될 경우는, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다.In Ar 1 to Ar 5 , and R 3 , an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, When an alkyl boron group, an aryl boron group, a phosphine group, a phosphine oxide group and an arylamine group are substituted, they are each independently deuterium, a halogen group, a cyano group, a nitro group, an amino group, an alkyl group of C 1 to C 40 , and C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to in the 40 heteroaryl groups, C 1 to C 40 alkyloxy groups, C 6 to C 60 aryloxy groups, C 1 to C 40 alkylsilyl groups, C 6 to C 60 arylsilyl groups, C 1 to C 40 alkyl group of boron, C 6 ~ C 60 aryl group of boron, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ selected from the group consisting of an arylamine C in 60 It may be substituted with one or more. - 제 5항에 있어서,The method of claim 5,상기 화학식 2와 화학식 3, 또는 화학식 2와 화학식 4가 결합하여 축합된 화합물은 하기 화학식 2a 내지 화학식 2n 중 어느 하나로 표시되는 것을 특징으로 하는 유기 전계 발광 소자.The compound of Formula 2 and Formula 3, or Formula 2 and Formula 4 combined and condensed is represented by any one of the following Formulas 2a to 2n.[화학식 2a][Formula 2a]
[화학식 2b][Formula 2b]
[화학식 2c][Formula 2c]
[화학식 2d][Formula 2d]
[화학식 2e][Formula 2e]
[화학식 2f][Formula 2f]
[화학식 2g][Formula 2g]
[화학식 2h][Formula 2h]
[화학식 2i][Formula 2i]
[화학식 2j][Formula 2j]
[화학식 2k][Formula 2k]
[화학식 2l][Formula 2l]
[화학식 2m][Formula 2m]
[화학식 2n][Formula 2n]
상기 화학식 2a 내지 2n에서, In Chemical Formulas 2a to 2n,X1 내지 X4 및 Y1 내지 Y14는 제4항에서 정의된 바와 동일하다. X 1 to X 4 and Y 1 to Y 14 are the same as defined in claim 4. - 제6항에 있어서, The method of claim 6,상기 X1 및 X4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N(Ar1) 또는 S이며, X 1 and X 4 are the same as or different from each other, and each independently N (Ar 1 ) or S,Ar1은 치환 또는 비치환된 C6~C60의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기이며, Ar 1 is a substituted or unsubstituted C 6 ~ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms,상기 아릴기 및 헤테로아릴기가 치환될 경우는, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환되는 것을 특징으로 하는 화합물.When the aryl group and heteroaryl group are substituted, each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 to C 40 Alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 of the phosphine oxide group, and a C 6 ~ compound being substituted by at least one selected from the group consisting of C 60 arylamines.
- 제1항에 있어서, The method of claim 1,상기 제1 호스트와 제2 호스트의 혼합 비율은 1~99 : 99~1 중량 범위인 것을 특징으로 하는 유기 전계 발광 소자.The mixing ratio of the first host and the second host is an organic electroluminescent device, characterized in that 1 ~ 99: 99 ~ 1 weight range.
- 제1항에 있어서,The method of claim 1,상기 제1 호스트와 제2 호스트를 포함하는 유기물층은 인광 발광층인 것을 특징으로 하는 유기 전계 발광 소자.The organic material layer including the first host and the second host is a phosphorescent light emitting layer.
- 제9항에 있어서, The method of claim 9,상기 발광층은 도펀트를 포함하되, 상기 도펀트는 금속 착체 화합물인 것을 특징으로 하는 유기 전계 발광 소자.The light emitting layer includes a dopant, wherein the dopant is a metal complex compound.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160012409A (en) * | 2014-07-24 | 2016-02-03 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
| US20160322583A1 (en) * | 2013-12-27 | 2016-11-03 | Doosan Corporation | Organic electroluminescent device |
| EP3185331A1 (en) * | 2015-12-22 | 2017-06-28 | Samsung Display Co., Ltd. | Organic light-emitting device |
| EP3188277A1 (en) * | 2015-12-29 | 2017-07-05 | Samsung Display Co., Ltd. | Organic light-emitting device |
| CN107275496A (en) * | 2016-04-07 | 2017-10-20 | 三星显示有限公司 | Organic luminescent device |
| US10230053B2 (en) * | 2015-01-30 | 2019-03-12 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US10280171B2 (en) | 2016-05-31 | 2019-05-07 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| EP3643761A1 (en) | 2018-10-25 | 2020-04-29 | Idemitsu Kosan Co., Ltd. | Composition, organic electroluminescence device material, composition film, organic electroluminescence device, and electronic device |
| CN111406060A (en) * | 2018-02-02 | 2020-07-10 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting element comprising same |
| US10954243B2 (en) | 2018-05-02 | 2021-03-23 | Navire Pharma, Inc. | Substituted heterocyclic inhibitors of PTPN11 |
| US11104675B2 (en) | 2018-08-10 | 2021-08-31 | Navire Pharma, Inc. | PTPN11 inhibitors |
| US11168093B2 (en) | 2018-12-21 | 2021-11-09 | Celgene Corporation | Thienopyridine inhibitors of RIPK2 |
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| CN115043852A (en) * | 2022-07-26 | 2022-09-13 | 武汉天马微电子有限公司 | Benzoxazole derivative and electroluminescent application thereof |
| US11466017B2 (en) | 2011-03-10 | 2022-10-11 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| US11617290B2 (en) | 2015-12-22 | 2023-03-28 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US11696496B2 (en) | 2015-12-22 | 2023-07-04 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US11937500B2 (en) | 2015-12-22 | 2024-03-19 | Samsung Display Co., Ltd. | Organic light-emitting device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11075343B2 (en) | 2016-01-18 | 2021-07-27 | Sfc Co., Ltd. | Organic light emitting compounds and organic light emitting devices including the same |
| KR102507368B1 (en) * | 2017-12-14 | 2023-03-08 | 솔루스첨단소재 주식회사 | Organic compound and organic electroluminescent device using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011155507A1 (en) * | 2010-06-08 | 2011-12-15 | 出光興産株式会社 | Organic electroluminescence element |
| WO2013085339A2 (en) * | 2011-12-07 | 2013-06-13 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent device using same |
| WO2013122364A2 (en) * | 2012-02-13 | 2013-08-22 | 덕산하이메탈(주) | Compound for organic electrical element, organic electrical element comprising same, and electronic device therewith |
| WO2014065498A1 (en) * | 2012-10-24 | 2014-05-01 | 주식회사 두산 | Organic electroluminescent device |
-
2014
- 2014-06-09 KR KR1020140069538A patent/KR101998435B1/en active IP Right Grant
-
2015
- 2015-05-21 WO PCT/KR2015/005080 patent/WO2015190718A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011155507A1 (en) * | 2010-06-08 | 2011-12-15 | 出光興産株式会社 | Organic electroluminescence element |
| WO2013085339A2 (en) * | 2011-12-07 | 2013-06-13 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent device using same |
| WO2013122364A2 (en) * | 2012-02-13 | 2013-08-22 | 덕산하이메탈(주) | Compound for organic electrical element, organic electrical element comprising same, and electronic device therewith |
| WO2014065498A1 (en) * | 2012-10-24 | 2014-05-01 | 주식회사 두산 | Organic electroluminescent device |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11466017B2 (en) | 2011-03-10 | 2022-10-11 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| US20160322583A1 (en) * | 2013-12-27 | 2016-11-03 | Doosan Corporation | Organic electroluminescent device |
| US11588109B2 (en) | 2013-12-27 | 2023-02-21 | Solus Advanced Materials Co., Ltd. | Organic electroluminescent device |
| US10573822B2 (en) * | 2013-12-27 | 2020-02-25 | Doosan Corporation | Organic electroluminescent device |
| WO2016013894A3 (en) * | 2014-07-24 | 2016-08-04 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising same |
| KR102238282B1 (en) | 2014-07-24 | 2021-04-08 | 솔루스첨단소재 주식회사 | Organic compounds and organic electro luminescence device comprising the same |
| KR20160012409A (en) * | 2014-07-24 | 2016-02-03 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
| US10230053B2 (en) * | 2015-01-30 | 2019-03-12 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US11617290B2 (en) | 2015-12-22 | 2023-03-28 | Samsung Display Co., Ltd. | Organic light-emitting device |
| EP3185331A1 (en) * | 2015-12-22 | 2017-06-28 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US11937500B2 (en) | 2015-12-22 | 2024-03-19 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US11696496B2 (en) | 2015-12-22 | 2023-07-04 | Samsung Display Co., Ltd. | Organic light-emitting device |
| EP3188277A1 (en) * | 2015-12-29 | 2017-07-05 | Samsung Display Co., Ltd. | Organic light-emitting device |
| CN112670425A (en) * | 2015-12-29 | 2021-04-16 | 三星显示有限公司 | Organic light emitting device |
| CN106935715A (en) * | 2015-12-29 | 2017-07-07 | 三星显示有限公司 | Organic light emitting apparatus |
| US11678498B2 (en) | 2016-04-07 | 2023-06-13 | Samsung Display Co., Ltd. | Organic light-emitting device |
| CN107275496A (en) * | 2016-04-07 | 2017-10-20 | 三星显示有限公司 | Organic luminescent device |
| CN107275496B (en) * | 2016-04-07 | 2022-04-15 | 三星显示有限公司 | Organic light emitting device |
| US10280171B2 (en) | 2016-05-31 | 2019-05-07 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| US10851110B2 (en) | 2016-05-31 | 2020-12-01 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| US11840536B2 (en) | 2016-05-31 | 2023-12-12 | Board Of Regents, The University Of Texas System | Heterocyclic inhibitors of PTPN11 |
| CN111406060B (en) * | 2018-02-02 | 2023-02-03 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting element comprising same |
| CN111406060A (en) * | 2018-02-02 | 2020-07-10 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting element comprising same |
| US10954243B2 (en) | 2018-05-02 | 2021-03-23 | Navire Pharma, Inc. | Substituted heterocyclic inhibitors of PTPN11 |
| US11932643B2 (en) | 2018-05-02 | 2024-03-19 | Navire Pharma, Inc. | Substituted heterocyclic inhibitors of PTPN11 |
| US11104675B2 (en) | 2018-08-10 | 2021-08-31 | Navire Pharma, Inc. | PTPN11 inhibitors |
| US11945815B2 (en) | 2018-08-10 | 2024-04-02 | Navire Pharma, Inc. | PTPN11 inhibitors |
| EP3643761A1 (en) | 2018-10-25 | 2020-04-29 | Idemitsu Kosan Co., Ltd. | Composition, organic electroluminescence device material, composition film, organic electroluminescence device, and electronic device |
| US11168093B2 (en) | 2018-12-21 | 2021-11-09 | Celgene Corporation | Thienopyridine inhibitors of RIPK2 |
| WO2022178693A1 (en) * | 2021-02-23 | 2022-09-01 | 苏州大学 | Method for preparing benzothiazole compound by using n-(2-bromophenyl)thioamide under promotion of visible light |
| CN115043852A (en) * | 2022-07-26 | 2022-09-13 | 武汉天马微电子有限公司 | Benzoxazole derivative and electroluminescent application thereof |
| CN115043852B (en) * | 2022-07-26 | 2023-12-29 | 武汉天马微电子有限公司 | Benzoxazole derivative and electroluminescent application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101998435B1 (en) | 2019-07-09 |
| KR20150141045A (en) | 2015-12-17 |
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