WO2015174640A1 - Compound, organic optoelectronic element comprising same and display device thereof - Google Patents
Compound, organic optoelectronic element comprising same and display device thereof Download PDFInfo
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- WO2015174640A1 WO2015174640A1 PCT/KR2015/003678 KR2015003678W WO2015174640A1 WO 2015174640 A1 WO2015174640 A1 WO 2015174640A1 KR 2015003678 W KR2015003678 W KR 2015003678W WO 2015174640 A1 WO2015174640 A1 WO 2015174640A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 97
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 33
- 239000010410 layer Substances 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 46
- 239000012044 organic layer Substances 0.000 claims description 41
- -1 sulfamoylamino group Chemical group 0.000 claims description 27
- 230000005525 hole transport Effects 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 13
- 230000000903 blocking effect Effects 0.000 claims description 13
- 229910052805 deuterium Inorganic materials 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 9
- 150000007945 N-acyl ureas Chemical group 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 8
- 125000005264 aryl amine group Chemical group 0.000 claims description 8
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002910 aryl thiol group Chemical group 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 5
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000004419 alkynylene group Chemical group 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 150
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 96
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 68
- 230000015572 biosynthetic process Effects 0.000 description 49
- 238000003786 synthesis reaction Methods 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 239000012299 nitrogen atmosphere Substances 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000000706 filtrate Substances 0.000 description 34
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 34
- 235000019341 magnesium sulphate Nutrition 0.000 description 34
- 239000000203 mixture Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 29
- 239000012153 distilled water Substances 0.000 description 29
- 238000010898 silica gel chromatography Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 28
- 238000010992 reflux Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 238000005259 measurement Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 0 CC1C23*=CC(C(CCCCC=CC=*)C([C@]4C5CC(C)CCCC4)C4=*5C=C=CCCC4)=CCC2C13 Chemical compound CC1C23*=CC(C(CCCCC=CC=*)C([C@]4C5CC(C)CCCC4)C4=*5C=C=CCCC4)=CCC2C13 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 8
- 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 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- SPDPTFAJSFKAMT-UHFFFAOYSA-N 1-n-[4-[4-(n-[4-(3-methyl-n-(3-methylphenyl)anilino)phenyl]anilino)phenyl]phenyl]-4-n,4-n-bis(3-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 SPDPTFAJSFKAMT-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 108700039708 galantide Proteins 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 2
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 2
- GOXNHPQCCUVWRO-UHFFFAOYSA-N dibenzothiophen-4-ylboronic acid Chemical compound C12=CC=CC=C2SC2=C1C=CC=C2B(O)O GOXNHPQCCUVWRO-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
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- 108020004707 nucleic acids Proteins 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-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
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- PFFIDZXUXFLSSR-UHFFFAOYSA-N 1-methyl-N-[2-(4-methylpentan-2-yl)-3-thienyl]-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound S1C=CC(NC(=O)C=2C(=NN(C)C=2)C(F)(F)F)=C1C(C)CC(C)C PFFIDZXUXFLSSR-UHFFFAOYSA-N 0.000 description 1
- IVYAYAWSXINSEF-UHFFFAOYSA-N 1-tert-butylperylene Chemical group C1=CC(C=2C(C(C)(C)C)=CC=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 IVYAYAWSXINSEF-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RNEOFIVNTNLSEH-UHFFFAOYSA-N 2-bromo-1-benzofuran Chemical compound C1=CC=C2OC(Br)=CC2=C1 RNEOFIVNTNLSEH-UHFFFAOYSA-N 0.000 description 1
- IJICRIUYZZESMW-UHFFFAOYSA-N 2-bromodibenzothiophene Chemical compound C1=CC=C2C3=CC(Br)=CC=C3SC2=C1 IJICRIUYZZESMW-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
- YOZHUJDVYMRYDM-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-naphthalen-1-yl-n-phenylaniline Chemical compound C=1C=C(C=2C(=CC(NC=3C=CC=CC=3)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 YOZHUJDVYMRYDM-UHFFFAOYSA-N 0.000 description 1
- SYQQWGGBOQFINV-FBWHQHKGSA-N 4-[2-[(2s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-2-yl]ethoxy]-4-oxobutanoic acid Chemical compound C1CC2=CC(=O)[C@H](CCOC(=O)CCC(O)=O)C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 SYQQWGGBOQFINV-FBWHQHKGSA-N 0.000 description 1
- JLQQJJCUPBUCKI-PMERELPUSA-N 4-[[(3S)-9-(cyclohexylmethyl)-5-[4-(4-fluoro-2-methoxyphenyl)piperazin-1-yl]sulfonyl-3-methyl-1,5,9-triazacyclododec-1-yl]sulfonyl]-N,N-dimethylaniline Chemical compound C1=C(C=CC(=C1)S(=O)(=O)N1C[C@@H](CN(CCCN(CCC1)CC1CCCCC1)S(=O)(=O)N1CCN(CC1)C1=C(C=C(C=C1)F)OC)C)N(C)C JLQQJJCUPBUCKI-PMERELPUSA-N 0.000 description 1
- RAFPKRKWQYIVDC-UHFFFAOYSA-N 8-(4-bromophenyl)quinoline Chemical compound BrC1=CC=C(C=C1)C=1C=CC=C2C=CC=NC=12 RAFPKRKWQYIVDC-UHFFFAOYSA-N 0.000 description 1
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000012905 Brassica oleracea var viridis Nutrition 0.000 description 1
- ILEFZGNFDZBUEC-UHFFFAOYSA-N C(CCC)C(CCCP)(CCCC)CCCC Chemical compound C(CCC)C(CCCP)(CCCC)CCCC ILEFZGNFDZBUEC-UHFFFAOYSA-N 0.000 description 1
- WYEDZBWTEOBTFB-RXMQYKEDSA-N C[C@H]1[BrH]2(CC2)C1 Chemical compound C[C@H]1[BrH]2(CC2)C1 WYEDZBWTEOBTFB-RXMQYKEDSA-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
- 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
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 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
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004622 benzoxazinyl group Chemical group O1NC(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([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
- DSSBJZCMMKRJTF-UHFFFAOYSA-N dibenzofuran-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3OC2=C1 DSSBJZCMMKRJTF-UHFFFAOYSA-N 0.000 description 1
- CSLSCVHILGCSTE-UHFFFAOYSA-N dibenzothiophen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3SC2=C1 CSLSCVHILGCSTE-UHFFFAOYSA-N 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 125000001041 indolyl group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 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
- 230000007704 transition Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000004950 trifluoroalkyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 238000004017 vitrification 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- 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
- a compound, an organic optoelectronic device, and a display device are provided.
- Organic optoelectronic diodes are devices that can switch electrical energy and light energy.
- Organic optoelectronic devices can be divided into two types according to the principle of operation.
- One is an optoelectronic device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electric energy.
- It is a light emitting device that generates light energy from energy.
- Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting device, an organic solar cell and an organic photo conductor drum.
- organic light emitting diodes have attracted much attention recently as demand for flat panel displays increases.
- the organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material, and has a structure in which an organic layer is inserted between an anode and a cathode.
- the organic layer may include a light emitting layer and an auxiliary layer
- the auxiliary layer may include, for example, a hole injection layer for increasing efficiency and stability of the organic light emitting device.
- the performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and in particular, is affected by the organic material included in the organic layer.
- An organic optoelectronic device including the compound and a display device including the organic optoelectronic device are provided.
- L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted group A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C 1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or and unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, '
- R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 Alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
- Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C1 to C30 alkylthi group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstit
- R 2 and R 3 are represented by the following Chemical Formula 2 or the following Chemical Formula 3:
- X is 0 or S
- R a to R g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to
- C30 alkyl group substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted Or an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30
- Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C 1 to C30 alkylthio group, substituted or unsubstituted C6 to C30 arylthi group, substituted or unsubstitute
- the compound according to one embodiment of the present invention may be for an organic optoelectronic device.
- a display device including the organic optoelectronic device described above is provided. .
- FIG. 1 and 2 are cross-sectional views illustrating various embodiments of an organic light emitting diode according to an embodiment of the present invention.
- Figure 3 is a graph showing the results of measuring the PL wavelength of the compound according to an embodiment of the present invention.
- organic light emitting element 200 organic light emitting element
- substituted unless otherwise defined, at least one hydrogen of the substituent or compound is deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C10 such as C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group, etc.
- hetero means one to three hetero atoms selected from the group consisting of ⁇ , ⁇ , S, P and Si in one functional group, and the remainder is carbon unless otherwise defined. do.
- an "alkyl group” means an aliphatic hydrocarbon group.
- the alkyl group may be a "saturated alkyl group” that does not contain any double or triple bonds.
- the alkyl group may be an alkyl group of C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group.
- a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, and methyl, ethyl, propyl, iso-propyl, ⁇ -butyl, iso-butyl, sec -butyl and t-butyl Selected from the group consisting of:
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nucleosil group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means real skill.
- an "aryl group” means a substituent in which all elements of a cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic or fused ring polishes. It includes a click (ie, a ring that divides adjacent pairs of carbon atoms) functional groups.
- a “heterocyclic group” refers to a hetero atom selected from the group consisting of N, 0, S, P, and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. Containing at least one, and the rest being carbon.
- the heterocyclic group is a fused ring, the heterocyclic group It may contain one or more heteroatoms for all or each ring.
- the heterocyclic group is a higher concept encompassing the heteroaryl group.
- a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl group, substituted or unsubstituted
- Phenanthryl groups substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted P-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted Or unsubstituted chrysenyl group, substituted or unsubstituted
- Triphenylenyl group substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted Substituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group , Substituted or unsubstituted
- Thiadiazolyl group substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted Or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted A quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group,
- a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.
- a single bond refers to carbon or hetero atoms other than carbon.
- L is a single bond means that the substituents connected to L is directly connected to the central core. That is, in the present specification, a single bond refers to methylene or the like via carbon.
- the hole characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It refers to a property that facilitates the movement of the hole formed in the anode and movement in the light emitting layer.
- the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement.
- a compound according to one embodiment is described.
- a compound represented by the following Chemical Formula 1 may be provided.
- L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or unsubstituted A substituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,
- R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
- Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted A substituted C1 to C30 sulfonyl group, a substituted or unsubstituted C1 to C30 alkylthio group, a substituted or unsubstituted C6 to C30 arylthiol group, a
- R 2 and R 3 is at least one of the following general formula 2, or is represented by the following general formula (3): formula (2);
- X is 0 or S
- R a to R g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
- Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C 1 to C20 acylamino group, substituted or Unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiyl group, substituted or unsubstitute
- the compound according to the embodiment of the present invention is at least one of R 2 and R 3 is represented by the formula (2) or (3), thereby increasing the hole transport of the molecule to be applied to the hole transport layer and hole transport light emitting host of the organic optoelectronic device In this case, excellent efficiency can be obtained.
- the thin film when the thin film is applied to the organic optoelectronic device by increasing the vitrification transition temperature while improving the hole transporting properties compared to the compound of R 2 and R 3 are both aryl group, it can exhibit long life and high efficiency characteristics,
- the heat resistance against thermal decomposition is excellent, and thus the processability and device stability can be improved by the vacuum heating deposition method.
- Formula 1 may be specifically represented by any one of the following Formula 4 to Formula 12. [Formula 4] [Formula 5]
- ⁇ , ⁇ 1 and X 2 are each independently 0 or S,
- R 1 , R 2 , R 4 to R 7 , R a to R g , and R a 'to R g ' are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy Groups, substituted or unsubstituted C2 to C30
- L 1 to L 3 are as defined in Chemical Formula 1.
- R 2 and R 3 may each independently be selected from a substituted or unsubstituted C2 to C30 heterocyclic group or a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted phenyl group, substituted or Unsubstituted naphthalene group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted pyrenyl group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothio 3 ⁇ 4yl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted
- Benzothiophenyl group substituted or unsubstituted benzofuranyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted benzoquinolinyl group, substituted or unsubstituted benzoisoquinolineyl group, It may be selected from a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazineyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and the like.
- R 2 and R 3 are each independently selected from a substituted or unsubstituted group listed in Group I, and at least one of R 2 and R 3 is selected from a substituted or unsubstituted group listed in Group 1-1 below. Can be selected. '
- X and W are each independently 0 or S, and R and R 'are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof, and * is a point of attachment.
- R 1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, or these It can be a combination of.
- R 1 is a methyl group, an ethyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclonuclear group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naph A methyl group, a substituted or unsubstituted pyridyl group, Substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted quinolinyl group, or a combination thereof,
- a methyl group for example, a methyl group, an ethyl group, or one selected from the groups listed in the following group ⁇ .
- Formula 1, and R 4 to R 7 , R a to R g , and R a 'to R g of Formulas 4 to 12 are each independently hydrogen, deuterium, substituted or unsubstituted Or a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C2 to C12 heterocyclic group, or a substituted or unsubstituted C6 to C12 aryl group.
- R 4 to R 7 , R a to R g , and R a ′ to R 8 ′ in Formula 1, and Formulas 4 to 12 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group. Or a substituted or unsubstituted C6 to C12 aryl group.
- Formula 1, and L 1 to L 3 of Formulas 4 to 12 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroaryl It may be a Rengi ⁇
- L 1 to L 3 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substitution Or an unsubstituted pyrimidylene group, a substituted or unsubstituted benzofuranylene group, or a combination thereof,
- the above-mentioned compounds may be for organic optoelectronic devices.
- an organic optoelectronic device to which the above-described compound is applied will be described.
- the auxiliary caterpillar provides an organic optoelectronic device comprising the compound described above.
- the auxiliary layer may be a hole transport layer.
- the organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy. Examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.
- an organic optoelectronic device 100 includes an anode 120 and a cathode 1 10 facing each other, and an organic layer 105 positioned between the anode 120 and the cathode 1 10. ).
- the anode 120 may be made of, for example, a conductor having a high hole function, for example, to facilitate hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer.
- the anode 120 may be, for example, a metal such as nickel, platinum, vanadium, cream, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide ( ⁇ ),
- Metal oxides such as indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO and A1 or Sn0 2 and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not limited.
- the cathode 1 10 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example.
- the negative electrode 1 10 is made of, for example, metals such as magnesium, kale, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or the like. alloy; Multilayer structure materials such as LiF / AI, Li0 2 / Al, LiF / Ca, LiF / Al, and BaF 2 / Ca, but are not limited thereto.
- the organic layer 105 includes the light emitting layer 130.
- the light emitting layer 130 may include, for example, a compound alone, or may include two kinds in combination. Including two kinds in combination, for example
- the host can be, for example, a phosphorescent host or a fluorescent host.
- the dopant may be an inorganic, organic, organic or inorganic compound and may be selected from known dopants.
- the organic light emitting diode 200 further includes a hole auxiliary layer 140 in addition to the light emitting layer 230.
- the hole auxiliary layer 140 may further increase hole injection and / or hole mobility between the anode 120 and the emission layer 230 and block electrons.
- the hole auxiliary layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The aforementioned compound may be included in the hole auxiliary layer 140.
- the organic layer 105 of FIG. 1 or 2 may further include an electron injection layer, an electron transport layer, an auxiliary electron transport layer, a hole transport layer, an auxiliary hole transport layer, a hole injection layer, or a combination thereof.
- the compound described above may be included in the auxiliary hole transport layer.
- the emission layer 230 and the auxiliary hole transport layer may be adjacent to each other.
- the compounds of the present invention can be included in these organic layers.
- the organic light emitting diodes 100 and 200 form an anode or a cathode on a substrate, and then evaporation,
- Dry film formation methods such as sputtering, plasma plating and ion plating; or
- the organic layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode or an anode thereon.
- the aforementioned compounds can be included as fluorescent materials.
- the fluorescent material may have a maximum emission wavelength of 550 nm or less, and specifically, a maximum emission wavelength may appear in a range of 420 nm to 550 nm.
- HOMO level of the compound represented by Formula 1 may be more than 5.4eV 5.8eV.
- the triplet excitation energy (T1) of the compound represented by Formula 1 may be 2.4 eV or more and 2.7 eV or less.
- the organic light emitting diode described above may be applied to an organic light emitting diode display.
- Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
- the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 27 g (89% yield) of the target compound intermediate M-1 as a white solid.
- the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 19.2 g (yield 74%) of the target compound intermediate M-12 as a white solid.
- Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
- the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 17.9 g (yield 69%) of the target compound intermediate M-13 as a white solid. It was.
- each compound was dissolved in THF, and then PL (photoluminescence) wavelength was measured using HITACHI F-4500.
- the PL wavelength measurement results of the A-137 of Example 2 are shown in FIG. 3.
- the energy level of each material was calculated by the Gaussian 09 method using a supercomputer GAIA (IBM power 6), and the results are shown in Table 1 below.
- HOMO energy levels differ by more than 0.1 eV, which can affect device efficiency when used as a hole transport layer for organic optoelectronic devices.
- a glass substrate coated with a thin film of indium tin oxide (1500 ⁇ ) of 1500 A was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic washing with isopropyl alcohol, acetone, methane and the like, and then dried and transferred to a plasma cleaner, and then washed the substrate using oxygen plasma for 5 minutes and then transferred to a vacuum depositor.
- 4,4'-bisP ⁇ -[4- ⁇ N, N-bis (3-methylphenyl) amino ⁇ -phenyl] -N-phenylamino] biphenyl (DNTPD) was formed on the ⁇ substrate using the prepared ⁇ transparent electrode as an anode. Was vacuum deposited to form a hole injection layer having a thickness of 600A.
- HT-1 was then vacuum deposited to form a 250 A thick hole transport layer.
- a secondary hole transport layer having a thickness of 50A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer.
- 9,10-di- (2-naphthyl) anthracene (ADN) is used as a host on the auxiliary hole transport layer, and 3,2,5,8,1 l-tetra (tert-butyl) perylene (TBPe) is used as a dopant.
- ADN 9,10-di- (2-naphthyl) anthracene
- TBPe 3,2,5,8,1 l-tetra (tert-butyl) perylene
- Alq3 was vacuum deposited on the emission layer to form an electron transport layer having a thickness of 250 A.
- An organic light emitting device was manufactured by sequentially depositing LiF lOA and A1 1000A on the electron transport layer to form a cathode.
- the organic light emitting device has a structure having five organic thin layers, specifically
- Example 7 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 2 instead of Example 1.
- Example 7
- Example 8 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 3 instead of Example 1.
- Example 8
- Example ad-9 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 4 instead of Example 1.
- Example ad-9 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 4 instead of Example 1.
- An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-3 instead of Example 1. Due Diligence ad-10
- Example 5 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-6 instead of Example 1. Comparative Example 1
- An organic light emitting diode was manufactured according to the same method as Example 5 except for using HT-2 instead of compound A-5 of Example 1.
- the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V, and the measured current value was divided by the area to obtain a result.
- the luminance was measured using a luminance meter (Minolta Cs-I OOOA) while increasing the voltage from 0V to 10V to obtain a result. (3) Measurement of luminous efficiency
- the current efficiency (cd / A) of the same current density (10 mA / cm 2 ) was calculated using the luminance, current density and voltage measured from (1) and (2). (4) life measurement
- Examples 5 to 8 Examples ad-9 and ad-10 are significantly improved luminous efficiency compared to Comparative Examples 1 and 2, the lifetime is also equal or It can be seen that the improved characteristics are shown above.
- Examples 5-8, Examples ad-9 and ad-10 are at least 13% more efficient than Comparative Example 1, which does not use auxiliary HTL. Increased, with minimal compared to Comparative Example 2 using HT-2 as the secondary HTL.
- biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50 A.
- Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a 250 A thickness.
- An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing LiF lOA and AP000A on the electron transport layer to form a cathode.
- the organic light emitting device has a structure having five organic thin layers, specifically
- Example ad-11 An organic light emitting diode was manufactured according to the same method as Example 2 instead of Example 1.
- Example ad-13 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example 3 instead of Example 1.
- Example ad-14 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example 3 instead of Example 1.
- Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
- Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
- Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
- Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
- Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
- Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
- Example ad-17 Example ad-17
- Example ad-1 1 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-4 instead of Example 1. Comparative Example 3
- Example ad-1 instead of HT-1, ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine
- Example ad-1 N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine is substituted for HT-1.
- An organic light emitting diode was manufactured according to the same method except that [TCTA] was used. Comparative Example 5 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using HT-1 instead of Example 1.
- HT-1 and Alq3 used in the organic light emitting device fabrication are as described above, and the structure of NPB TCTA, CBP, Balq, Ir (ppy) 3 is as follows.
- the method of measuring the current density change, the brightness change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 3. Life measurement
- Examples ad-1 1 to ad-17 can be seen to exhibit improved characteristics in terms of luminous efficiency, driving voltage, life compared to Comparative Examples 3 to 5.
- Examples ad-1 1 to ad-17 showed an efficiency increase of at least 70% compared to Comparative Example 3 without the use of auxiliary HTL, the minimum compared to Comparative Example 5
- HT-1 was then vacuum deposited to form a 200 A thick hole transport layer.
- An auxiliary hole transport layer having a thickness of 100A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer.
- (4,4'- ⁇ , ⁇ '-dicarbazole) biphenyl [CBP] was used as a host on the auxiliary hole transport layer, and dopant bis (2-phenylquinoline) (acetylacetonate) iridium ( ⁇ ) [Ir (pq) 2 acac] to 5 wt% to form a 300 A thick light emitting layer by vacuum deposition.
- biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50A.
- Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a thickness of 250 A.
- An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing UF 10A and A 000 000 A on the electron transport layer to form a cathode.
- the organic light emitting device has a structure having six organic thin layers, specifically
- Example ad-20 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 2 instead of Example 1.
- Example ad-20 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 2 instead of Example 1.
- Example ad-18 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 4 instead of Example 1.
- Example ad-21 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-1 instead of Example 1.
- Example ad-22 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-1 instead of Example 1.
- Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
- Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
- Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
- Example ad-18 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-5 instead of Example 1. Comparative Example 6
- Example ad-18 ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] is used instead of HT-1, and ⁇ , ⁇ '-di is used instead of Example 1.
- An organic light emitting diode was manufactured according to the same method except that (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] was used. Comparative Example 7
- Example ad-18 ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] was used instead of HT-1, and Tris (4,4 ') was used instead of Example 1. , 4 "-(9-carbazolyl))-triphenylamine
- An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using HT-1 instead of Example 1.
- the structures of DNTPD, NPB, HT-1, TCTA, CBP, Balq, and Alq3 used in fabricating the organic light emitting diode are as described above, and the structure of Ir (pq) 2 acac is as follows.
- the method of measuring the current density change, the luminance change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 4 below. Life measurement
- the light was emitted at an initial luminance of 1,000 nit and over time.
- the decrease in luminance was measured as the T80 lifetime when the luminance was reduced to 80% of the initial luminance.
- Examples a d-18 to ad-23 showed at least an efficiency increase of at least 19% compared to Comparative Example 6 without the use of auxiliary HTL, and at least 8% increase in efficiency compared to Comparative Example 8. Compared with Comparative Example 4 using TCTA as the auxiliary HTL, the efficiency was higher and the T80 life was increased by at least 28%.
- the present invention is not limited to the above embodiments, but may be manufactured in various forms. Those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.
Abstract
The present invention relates to a compound represented by formula 1, an organic optoelectronic element comprising the same, and a display device comprising the organic optoelectronic element. Formula 1 and the description regarding the same are as defined in the specification.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
화합물, 이를 포함하는 유기 광전자 소자 및 표시장치 Compound, organic optoelectronic device and display device comprising same
【기술분야】 Technical Field
화합물, 유기 광전자 소자 및 표시장치에 관한 것이다. A compound, an organic optoelectronic device, and a display device are provided.
【배경기술】 Background Art
유기 광전자 소자 (organic optoelectronic diode)는 전기 에너지와 광 에너지를 상호 전환할 수 있는 소자이다. Organic optoelectronic diodes are devices that can switch electrical energy and light energy.
유기 광전자 소자는 동작 원리에 따라 크게 두 가지로 나눌 수 있다. 하나는 광 에너지에 의해 형성된 엑시톤 (exciton)이 전자와 정공으로 분리되고 상기 전자와 정공이 각각 다른 전극으로 전달되면서 전기 에너지를 발생하는 광전 소자이고， 다른 하나는 전극에 전압 또는 전류를 공급하여 전기 에너지로부터 광 에너지를 발생하는 발광 소자이다. Organic optoelectronic devices can be divided into two types according to the principle of operation. One is an optoelectronic device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electric energy. It is a light emitting device that generates light energy from energy.
유기 광전자 소자의 예로는 유기 광전 소자, 유기 발광 소자, 유기 태양 전지 및 유기 감광체 드럼 (organic photo conductor drum) 등을 들 수 있다. Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting device, an organic solar cell and an organic photo conductor drum.
이 중, 유기 발광 소자 (organic light emitting diode, OLED)는 근래 평판 표시 장치 (flat panel display device)의 수요 증가에 따라 크게 주목받고 있다. 상기 유기 발광 소자는 유기 발광 재료에 전류를 가하여 전기 에너지를 빛으로 전환시키는 소자로서, 통상 양극 (anode)과 음극 (cathode) 사이에 유기 층이 삽입된 구조로 Among these, organic light emitting diodes (OLEDs) have attracted much attention recently as demand for flat panel displays increases. The organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material, and has a structure in which an organic layer is inserted between an anode and a cathode.
이루어져 있다. 여기서 유기 층은 발광층과 선택적으로 보조층을 포함할 수 있으며， 상기 보조층은 예컨대 유기발광소자의 효율과 안정성을 높이기 위한 정공 주입 층, . 정공 수송 층, 전자 차단 층, 전자 수송 층， 전자 주입 층 및 정공 차단 층에서 선택된 적어도 1층을 포함할 수 있다ᅳ consist of. Herein, the organic layer may include a light emitting layer and an auxiliary layer, and the auxiliary layer may include, for example, a hole injection layer for increasing efficiency and stability of the organic light emitting device. And at least one layer selected from a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, and a hole blocking layer.
유기 발광 소자의 성능은 상기 유기 층의 특성에 의해 영향을 많이 받으며, 그 중에서도 상기 유기 층에 포함된 유기 재료에 의해 영향을 많이 받는다. The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and in particular, is affected by the organic material included in the organic layer.
특히 상기 유기 발광 소자가 대형 평판 표시 장치에 적용되기 위해서는 정공 및 전자의 이동성올 높이는 동시에 전기화학적 안정성을 높일 수 있는 유기 재료의 개발이 필요하다. In particular, in order for the organic light emitting diode to be applied to a large flat panel display, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing electrochemical stability.
【발명의 상세한 설명】 [Detailed Description of the Invention]
【기술적 과제】
고효율, 장수명 등의 특성을 가지는 유기 광전자 소자를 제공할 수 있는 화합물을 제공하는 것이다. [Technical problem] It is to provide a compound capable of providing an organic optoelectronic device having characteristics such as high efficiency and long life.
상기 화합물을 포함하는 유기 광전자 소자 및 상기 유기 광전자 소자를 포함하는 표시장치를 제공하는 것이다. An organic optoelectronic device including the compound and a display device including the organic optoelectronic device are provided.
【기술적 해결방법】 Technical Solution
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 제공한다. In one embodiment of the present invention, a compound represented by Chemical Formula 1 is provided.
L1 내지 L3은 각각 독립적으로, 단일 결합， 치환 또는 비치환된 C1 내지 C30 알킬렌기， 치환 또는 비치환된 C3 내지 C30 사이클로알킬렌기 , 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌아민기 , 치환 또는 비치환된 C 1 내지 C30 알콕실렌기, 치환 또는 비치환된 C1 내지 C30 아릴옥실렌기， 치환 또는 비치환된 C2 내지 C30 알케닐렌기, 치환 또는 비치환된 C2 내지 C30 알키닐렌기， 또는 이들의 조합이고， ' L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted group A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C 1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or and unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, '
R1 내지 R7은 각각 독립적으로, 수소， 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30쒜테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴아민기， 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기, 치환 또는 비치환된 C7 내지 C30 R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 Alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기， 치환 또는 비치환된 C1 내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기， 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기， 치환 또는 비치환된 C3 내지
C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기， 치환 또는 비치환된 C1 내지 C20 아실아미노기, 치환 또는 비치환된 C1 내지 C30 술포닐기， 치환 또는 비치환된 C1 내지 C30 알킬티을기, 치환 또는 비치환된 C6 내지 C30 아릴티올기, 치환 또는 비치환된 C1 내지 C30 우레이드기， 할로겐기, 할로겐 함유기, 시아노기, 히드록실기， 아미노기， 니트로기, 카르복실기, 페로세닐기, 또는 이들의 조합이고, Aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C1 to C30 alkylthi group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing group, cyano group, hydroxyl group, Amino group, nitro group, carboxyl group, ferrocenyl group, or a combination thereof,
R2 및 R3 중 적어도 하나는 하기 화학식 2 또는 하기 화학식 3으로 표시된다: 화학식 2] At least one of R 2 and R 3 is represented by the following Chemical Formula 2 or the following Chemical Formula 3:
상기 화학식 2 및 3에서, In Chemical Formulas 2 and 3,
*은 연결지점이고, * Is the connection point,
X는 0 또는 S 이고, X is 0 or S,
Ra 내지 Rg는 각각 독립적으로, 수소， 중수소， 치환 또는 비치환된 C1 내지R a to R g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to
C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐기， 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기, 치환 또는 비치환된 C7 내지 C30 C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted Or an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기， 치환 또는 비치환된 C1 내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기， 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지
C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기， 치환 또는 비치환된 C1 내지 C20 아실아미노기, 치환 또는 비치환된 C1 내지 C30 술포닐기， 치환 또는 비치환된 C 1 내지 C30 알킬티을기， 치환 또는 비치환된 C6 내지 C30 아릴티을기, 치환 또는 비치환된 C1 내지 C30 우레이드기， 할로겐기, 할로겐 함유기, 시아노기, 히드록실기, 아미노기， 니트로기, 카르복실기， 페로세닐기， 또는 이들의 조합이다. Aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C 1 to C30 alkylthio group, substituted or unsubstituted C6 to C30 arylthi group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing group, cyano group, hydroxyl group , Amino group, nitro group, carboxyl group, ferrocenyl group, or a combination thereof.
본 발명의 일구현예에 따른 화합물은 유기 광전자 소자용일 수 있다. The compound according to one embodiment of the present invention may be for an organic optoelectronic device.
본 발명의 다른 일 구현예에서는, 서로 마주하는 양극과 음극, 및 상기 양극과 상기 음극 사이에 위치하는 적어도 한 층의 유기층을 포함하고, 상기 유기층은， 발광층 및 정공 주입 층, 정공 수송 층， 전자 차단 층, 전자 수송 층, 전자 주입 층 및 정공 차단 층에서 선택된 적어도 하나의 보조층을 포함하고, 상기 보조층은 상기 화합물을 포함하는 유기 광전자 소자를 제공한다. In another embodiment of the present invention, an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, the organic layer is a light emitting layer and a hole injection layer, a hole transport layer, electrons At least one auxiliary layer selected from a blocking layer, an electron transport layer, an electron injection layer and a hole blocking layer, the auxiliary layer provides an organic optoelectronic device comprising the compound.
본 발명의 또 다른 일 구현예에서는, 전술한 유기 광전자 소자를 포함하는 표시장치를 제공한다. . In another embodiment of the present invention, a display device including the organic optoelectronic device described above is provided. .
【유리한 효과】 Advantageous Effects
고효율 장수명 유기 광전자 소자를 구현할 수 있다. High efficiency long life organic optoelectronic devices can be implemented.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1 및 도 2는 본 발명의 일 구현예에 따른 유기 발광 소자에 대한 다양한 구현예들을 나타내는 단면도이다. 1 and 2 are cross-sectional views illustrating various embodiments of an organic light emitting diode according to an embodiment of the present invention.
도 3은 본 발명의 일 구현예에 따른 화합물의 PL 파장 측정 결과를 나타낸 그래프이다. Figure 3 is a graph showing the results of measuring the PL wavelength of the compound according to an embodiment of the present invention.
<부호의 설명 > <Description of the sign>
100: 유기 발광 소자 200: 유기 발광 소자 100: organic light emitting element 200: organic light emitting element
105: 유기층 105: organic layer
1 10: 음극 1 10: cathode
120: 양극 120: anode
130: 발광층 230: 발광층 130: light emitting layer 230: light emitting layer
140: 정공 보조층 140: hole auxiliary layer
【발명을 실시를 위한 최선의 형태】 [The best form for carrying out invention]
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만， 이는 예시로서
제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is an example As is presented, the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.
본 명세서에서 "치환"이란 별도의 정의가 없는 한, 치환기 또는 화합물 중의 적어도 하나의 수소가 중수소， 할로겐기， 히드록시기， 아미노기， 치환 또는 비치환된 C1 내지 C30 아민기, 니트로기, 치환 또는 비치환된 C1 내지 C40 실릴기, C1 내지 C30 알킬기, C1 내지 C10 알킬실릴기, C3 내지 C30 시클로알킬기, C6 내지 C30 아릴기, C1 내지 C20 알콕시기， 플루오로기, 트리플루오로메틸기 등의 C1 내지 C10 트리플루오로알킬기 또는 시아노기로 치환된 것을 의미한다. In the present specification, "substituted", unless otherwise defined, at least one hydrogen of the substituent or compound is deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C10 such as C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group, etc. Mean substituted by a trifluoroalkyl group or a cyano group.
본'명세서에서 "헤테로"란 별도의 정의가 없는 한, 하나의 작용기 내에 Ν, Ο, S, P 및 Si로 이루어진 군에서 선택되는 헤테로 원자를 1 내지 3개 함유하고, 나머지는 탄소인 것을 의미한다. In the present specification, "hetero" means one to three hetero atoms selected from the group consisting of Ν, Ο, S, P and Si in one functional group, and the remainder is carbon unless otherwise defined. do.
본 명세서에서 "알킬 (alkyl)기"란 별도의 정의가 없는 한， 지방족 탄화수소기를 의미한다. 알킬기는 어떠한 이중결합이나 삼중결합을 포함하고 있지 않은 "포화 알킬 (saturated alkyl)기 "일 수 있다. As used herein, unless otherwise defined, an "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.
상기 알킬기는 C1 내지 C20인 알킬기일 수 있다. 보다 구체적으로 알킬기는 C1 내지 C10 알킬기 또는 C1 내지 C6 알킬기일 수도 있다. 예를 들어, C1 내지 C4 알킬기는 알킬쇄에 1 내지 4 개의 탄소원자가 포함되는 것을 의미하며, 메틸, 에틸, 프로필, 이소-프로필 , η-부틸， 이소-부틸， sec-부틸 및 t-부틸로 이루어진 군에서 선택됨을 나타낸다. The alkyl group may be an alkyl group of C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, and methyl, ethyl, propyl, iso-propyl, η-butyl, iso-butyl, sec -butyl and t-butyl Selected from the group consisting of:
상기 알킬기는 구체적인 예를 들어 메틸기， 에틸기, 프로필기， 이소프로필기， 부틸기, 이소부틸기, t-부틸기, 펜틸기, 핵실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로핵실기 등올 의미한다. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nucleosil group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means real skill.
본 명세서에서 "아릴 (aryl)기"는 환형인 치환기의 모든 원소가 p-오비탈을 가지고 있으며， 이들 P-오비탈이 공액 (conjugation)을 형성하고 있는 치환기를 의미하고， 모노시클릭 또는 융합 고리 폴리시클릭 (즉, 탄소원자들의 인접한 쌍들을 나눠 가지는 고리) 작용기를 포함한다. As used herein, an "aryl group" means a substituent in which all elements of a cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic or fused ring polishes. It includes a click (ie, a ring that divides adjacent pairs of carbon atoms) functional groups.
본 명세서에서 "헤테로고리기 (heterocyclic group)"는 아릴기, 시클로알킬기, 이들의 융합고리 또는 이들의 조합과 같은 고리 화합물 내에 N, 0, S, P 및 Si로 이루어진 군에서 선택되는 헤테로 원자를 적어도 한 개를 함유하고, 나머지는 탄소인 것올 의미한다. 상기 헤테로고리기가 융합고리인 경우, 상기 헤테로고리기
전체 또는 각각의 고리마다 헤테로 원자를 한 개 이상 포함할 수 있다. 따라서, 헤테로고리기는 헤테로아릴기를 포괄하는 상위개념이다. As used herein, a “heterocyclic group” refers to a hetero atom selected from the group consisting of N, 0, S, P, and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. Containing at least one, and the rest being carbon. When the heterocyclic group is a fused ring, the heterocyclic group It may contain one or more heteroatoms for all or each ring. Thus, the heterocyclic group is a higher concept encompassing the heteroaryl group.
보다 구체적으로， 치환 또는 비치환된 C6 내지 C30 아릴기 및 /또는 치환 또는 비치환된 C2 내지 C30 헤테로고리기는, 치환 또는 비치환된 페닐기， 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 안트라세닐기, 치환 또는 비치환된 More specifically, a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl group, substituted or unsubstituted
페난트릴렌기， 치환 또는 비치환된 나프타세닐기, 치환 또는 비치환된 피레닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 P-터페닐기, 치환 또는 비치환된 m-터페닐기 , 치환 또는 비치환된 크리세닐기 , 치환 또는 비치환된 Phenanthryl groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted P-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted Or unsubstituted chrysenyl group, substituted or unsubstituted
트리페닐레닐기, 치환 또는 비치환된 페릴레닐기, 치환 또는 비치환된 인데닐기， 치환 또는 비치환된 퓨라닐기, 치환 또는 비치환된 티오페닐기, 치환 또는 비치환된 피롤릴기, 치환 또는 비치환된 피라졸릴기, 치환 또는 비치환된 이미다졸일기， 치환 또는 비치환된 트리아졸일기, 치환 또는 비치환된 옥사졸일기, 치환 또는 비치환된 티아졸일기, 치환 또는 비치환된 옥사디아졸일기, 치환또는 비치환된 Triphenylenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted Substituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group , Substituted or unsubstituted
티아디아졸일기， 치환 또는 비치환된 피리딜기， 치환 또는 비치환된 피리미디닐기， 치환 또는 비치환된 피라지닐기， 치환 또는 비치환된 트리아지닐기, 치환 또는 비치환된 벤조퓨라닐기, 치환 또는 비치환된 벤조티오페닐기， 치환 또는 비치환된 벤즈이미다졸일기, 치환 또는 비치환된 인돌일기, 치환 또는 비치환된 퀴놀리닐기, 치환 또는 비치환된 이소퀴놀리닐기， 치환 또는 비치환된 퀴나졸리닐기, 치환 또는 비치환된 퀴녹살리닐기， 치환또는 비치환된 나프티리디닐기, 치환 또는 비치환된 벤즈옥사진일기, 치환또는 비치환된 벤즈티아진일기, 치환 또는 비치환된 Thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted Or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted A quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted
아크리디닐기, 치환 또는 비치환된 페나진일기, 치환 또는 비치환된 페노티아진일기, 치환 또는 비치환된 페녹사진일기, 치환 또는 비치환된 플루오레닐기， 치환 또는 비치환된 카바졸일기, 치환 또는 비치환된 디벤조퓨라닐기, 치환 또는 비치환된 디벤조티오페닐기, 이들의 조합 또는 이들의 조합이 융합된 형태일 수 있으나, 이에 제한되지는 않는다. Acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenothiazineyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted carbazolyl group, A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.
본 명세서에서, 단일 결합이란 탄소 또는 탄소 이외의 헤테로 원자를 In this specification, a single bond refers to carbon or hetero atoms other than carbon.
경유하지 않고 직접 연결되는 결합을 의미하는 것으로, 구체적으로 L이 단일 결합이라는 의미는 L과 연결되는 치환기가 중심 코어에 직접 연결되는 것을 의미한다. 즉， 본 명세서에서 단일 결합이란 탄소를 경유하는 메틸렌 등을 It means a bond that is directly connected without passing through, specifically, that L is a single bond means that the substituents connected to L is directly connected to the central core. That is, in the present specification, a single bond refers to methylene or the like via carbon.
의미하는 것이 아니다.
본 명세서에서, 정공 특성이란, 전기장 (electric field)을 가했을 때 전자를 공여하여 정공을 형성할 수 있는 특성을 말하는 것으로 , HOMO 준위를 따라 전도 특성을 가져 양극에서 형성된 정공의 발광층으로의 주입, 발광층에서 형성된 정공의 양극으로의 이동 및 발광층에서의 이동을 용이하게 하는 특성을 의미한다. It does not mean. In the present specification, the hole characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It refers to a property that facilitates the movement of the hole formed in the anode and movement in the light emitting layer.
또한 전자 특성이란, 전기장을 가했을 때 전자를 받을 수 있는 특성을 말하는 것으로, LUMO 준위를 따라 전도 특성을 가져 음극에서 형성된 전자의 발광층으로의 주입, 발광층에서 형성된 전자의 음극으로의 이동 및 발광층에서의 이동을 용이하게 하는 특성을 의미한다. 이하 일 구현예에 따른 화합물을 설명한다. In addition, the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement. Hereinafter, a compound according to one embodiment is described.
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 제공할 수 있다. In one embodiment of the present invention, a compound represented by the following Chemical Formula 1 may be provided.
상기 화학식 1에서， In Chemical Formula 1,
L1 내지 L3은 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌아민기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C1 내지 C30 아릴옥실렌기， 치환 또는 비치환된 C2 내지 C30 알케닐렌기, 치환 또는 비치환된 C2 내지 C30 알키닐렌기， 또는 이들의 조합이고, L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or unsubstituted A substituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,
R1 내지 R7은 각각 독립적으로, 수소， 중수소， 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기， 치환 또는 비치환된
C2 내지 C30 헤테아릴기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기, 치환 또는 비치환된 C7 내지 C30 R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기, 치환 또는 비치환된 C1 내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기， 치환 또는 비치환된 C1 내지 C20 아실아미노기, 치환 또는 비치환된 C1 내지 C30 술포닐기, 치환 또는 비치환된 C1 내지 C30 알킬티을기, 치환 또는 비치환된 C6 내지 C30 아릴티올기, 치환 또는 비치환된 C1 내지 C30 우레이드기, 할로겐기， 할로겐 함유기, 시아노기, 히드록실기, 아미노기， 니트로기, 카르복실기, 페로세닐기, 또는 이들의 조합이고, Aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted A substituted C1 to C30 sulfonyl group, a substituted or unsubstituted C1 to C30 alkylthio group, a substituted or unsubstituted C6 to C30 arylthiol group, a substituted or unsubstituted C1 to C30 ureide group, a halogen group, a halogen-containing group , Cyano group, hydroxyl group, amino group, nitro group, carboxyl group, ferrocenyl group, or a combination thereof,
R2 및 R3 중 적어도 하나는 하기 화학식 2 또는 하기 화학식 3으로 표시된다: 화학식 2] R 2 and R 3 is at least one of the following general formula 2, or is represented by the following general formula (3): formula (2);
[화학식 Formula
상기 화학식 2 및 3에서 In Chemical Formulas 2 and 3
*은 연결지점이고， * Is the connection point,
X는 0 또는 S 이고, X is 0 or S,
Ra 내지 Rg는 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30사이클로알킬기, 치환 또는 비치환된
C2 내지 C30 헤테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기 , 치환 또는 비치환된 C7 내지 C30 R a to R g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기, 치환 또는 비치환된 C1 내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기， 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기， 치환 또는 비치환된 C1 내지 C20 아실옥시기, 치환 또는 비치환된 C 1 내지 C20 아실아미노기, 치환 또는 비치환된 C1 내지 C30 술포닐기, 치환 또는 비치환된 C1 내지 C30 알킬티올기, 치환 또는 비치환된 C6 내지 C30 아릴티을기， 치환 또는 비치환된 C1 내지 C30 우레이드기, 할로겐기， 할로겐 함유기, 시아노기, 히드록실기, 아미노기, 니트로기, 카르복실기, 페로세닐기, 또는 이들의 조합이다. Aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C 1 to C20 acylamino group, substituted or Unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiyl group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing Group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, ferrocenyl group, or a combination thereof.
상기 본 발명의 일 구현예에 따른 화합물은 R2 및 R3 중 적어도 하나가 상기 화학식 2 또는 화학식 3으로 표시됨으로써, 분자의 정공 수송성을 증가 시켜 유기 광전자 소자의 정공 수송층 및 정공 수송성 발광 호스트로 적용할 경우 우수한 효율을 나타낼 수 있다. The compound according to the embodiment of the present invention is at least one of R 2 and R 3 is represented by the formula (2) or (3), thereby increasing the hole transport of the molecule to be applied to the hole transport layer and hole transport light emitting host of the organic optoelectronic device In this case, excellent efficiency can be obtained.
특히, R2 및 R3 가 모두 아릴기인 화합물에 비하여 정공 수송성을 향상 시키면서 유리화 전이 온도를 증가 시켜 유기 광전자 소자에 박막 적용할 경우 열적 안정성이 향상되어 장수명, 고효율 특성을 나타낼수 있고, In particular, when the thin film is applied to the organic optoelectronic device by increasing the vitrification transition temperature while improving the hole transporting properties compared to the compound of R 2 and R 3 are both aryl group, it can exhibit long life and high efficiency characteristics,
R2 및 R3 중 적어도 하나가 플루오레닐기인 화합물에 비하여 열분해에 대한 내열 안정성이 뛰어나 진공 가열 증착법으로 박막 형성시 보다 향상된 공정성과 소자 안정성을 확보할 수 있다. Compared with the compound having at least one of R 2 and R 3 is a fluorenyl group, the heat resistance against thermal decomposition is excellent, and thus the processability and device stability can be improved by the vacuum heating deposition method.
이에 따라 상기 화합물을 적용한 유기 광전자 소자의 고효율, 장수명의 장점 및 저전압에서 구동 가능한 특성을 조절할 수 있다. Accordingly, the advantages of high efficiency, long life, and low drive voltage of the organic optoelectronic device to which the compound is applied can be adjusted.
상기 화학식 1은 구체적으로 하기 화학식 4 내지 화학식 12 중 어느 하나로 표시될 수 있다.
[화학식 4] [화학식 5]
Formula 1 may be specifically represented by any one of the following Formula 4 to Formula 12. [Formula 4] [Formula 5]
[화학식 6] [화학식 7]
[Formula 6] [Formula 7]
[화학식 8] [화학식 9]
하^ [Formula 8] [Formula 9] Ha ^
상기 화학식 4 내지 12에서 In Chemical Formulas 4 to 12
Χ, Χ1 및 X2는 각각 독립적으로， 0 또는 S 이고, Χ, Χ 1 and X 2 are each independently 0 or S,
R1, R2, R4 내지 R7, Ra내지 Rg, 및 Ra' 내지 Rg '는 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C3 내지 C30 사이클로알킬기， 치환 또는 비치환된 C2 내지 C30 헤테로고리기， 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환 또는 비치환된 C2 내지 C30 R 1 , R 2 , R 4 to R 7 , R a to R g , and R a 'to R g ' are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy Groups, substituted or unsubstituted C2 to C30
알콕시카르보닐기， 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기， 치환 또는 비치환된 C7 내지 C30 아릴옥시카르보닐아미노기, 치환 또는 비치환된 C1
내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기, 치환 또는 비치환된 C1 내지 C20 아실아미노기， 치환 또는 비치환된 C1 내지 C30 술포닐기， 치환 또는 비치환된 C1 내지 C30 알킬티올기, 치환 또는 비치환된 C6 내지 C30 아릴티올기， 치환 또는 비치환된 C1 내지 C30 우레이드기, 할로겐기, 할로겐 함유기, 시아노기， 히드록실기, 아미노기, 니트로기, 카르복실기， 페로세닐기， 또는 이들의 조합이고, Alkoxycarbonyl group, substituted or unsubstituted C2 to C30 Alkoxycarbonylamino group, substituted or unsubstituted C7 to C30 aryloxycarbonylamino group, substituted or unsubstituted C1 To C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group, substituted or unsubstituted C3 to C40 silyloxy group , Substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted Substituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing group, cyano group, hydroxyl group, amino group, nitro group , Carboxyl group, ferrocenyl group, or a combination thereof,
L1 내지 L3은 상기 화학식 1에 정의된 바와 같다. L 1 to L 3 are as defined in Chemical Formula 1.
예컨대， 상기 R2 및 R3는 각각 독립적으로, 치환 또는 비치환된 C2 내지 C30 헤테로고리기 또는 치환 또는 비치환된 C6 내지 C30 아릴기에서 선택될 수 있으며, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 나프탈렌기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 트리페닐렌일기, 치환 또는 비치환된 안트라센일기, 치환 또는 비치환된 피렌일기， 치환 또는 비치환된 디벤조퓨란일기, 치환 또는 비치환된 디벤조티오 ¾일기， 치환 또는 비치환된 티오펜일기， 치환 또는 비치환된 퓨란일기, 치환 또는 비치환된 For example, R 2 and R 3 may each independently be selected from a substituted or unsubstituted C2 to C30 heterocyclic group or a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted phenyl group, substituted or Unsubstituted naphthalene group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted pyrenyl group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothio ¾yl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted
벤조티오펜일기, 치환 또는 비치환된 벤조퓨란일기， 치환 또는 비치환된 퀴놀린일기, 치환 또는 비치환된 이소퀴놀린일기, 치환 또는 비치환된 벤조퀴놀린일기, 치환 또는 비치환된 벤조이소퀴놀린일기, 치환 또는 비치환된 피리딘일기, 치환 또는 비치환된 피리미딘일기, 치환 또는 비치환된 트리아진일기, 치환 또는 비치환된 플루오렌일기, 치환 또는 비치환된 카바졸일기 등에서 선택된 것일 수 있다. Benzothiophenyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted benzoquinolinyl group, substituted or unsubstituted benzoisoquinolineyl group, It may be selected from a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazineyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and the like.
예컨대， 상기 R2 및 R3는 각각 독립적으로 하기 그룹 I에 나열된 치환 또는 비치환된 기에서 선택되고, R2 및 R3 중 적어도 하나는 하기 그룹 1 -1에 나열된 치환 또는 비치환된 기에서 선택될 수 있다. ' For example, R 2 and R 3 are each independently selected from a substituted or unsubstituted group listed in Group I, and at least one of R 2 and R 3 is selected from a substituted or unsubstituted group listed in Group 1-1 below. Can be selected. '
[그룹 I ]
[Group I]
[그룹 1 -1] [Group 1 -1]
상기 그룹 I 및 1 -1에서, In groups I and 1-1,
X 및 W는 각각 독립적으로， 0 또는 S이고， R 및 R'은 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 헤테로고리기, 또는 이들의 조합이고, *는 연결 지점이다. X and W are each independently 0 or S, and R and R 'are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof, and * is a point of attachment.
상기 R1은 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C3 내지 C30 사이클로알킬기， 치환 또는 비치환된 C2 내지 C30 헤테아릴기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 이들의 조합일 수 있다. R 1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, or these It can be a combination of.
구체적으로, 상기 R1은 메틸기, 에틸기， 치환 또는 비치환된 사이클로펜틸기, 치환 또는 비치환된 사이클로핵실기， 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 피리딜기,
치환 또는 비치환된 퓨라닐기, 치환 또는 비치환된 티오페닐기, 치환 또는 비치환된 퀴놀리닐기, 또는 이들의 조합일 수 있고, Specifically, R 1 is a methyl group, an ethyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclonuclear group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naph A methyl group, a substituted or unsubstituted pyridyl group, Substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted quinolinyl group, or a combination thereof,
예컨대 메틸기, 에틸기， 또는 하기 그룹 Π에 나열된 기에서 선택된 하나일 수 있다. For example, a methyl group, an ethyl group, or one selected from the groups listed in the following group Π.
[그룹 Π ] [Group Π]
본 발명의 일예에서, 상기 화학식 1, 및 화학식 4 내지 12의 R4 내지 R7, Ra 내지 Rg, 및 Ra' 내지 Rg '는 각각 독립적으로， 수소, 중수소, 치환 또는 비치환된 C1 내자 C10 알킬기, 치환 또는 비치환된 C3 내지 C12 사이클로알킬기, 치환 또는 비치환된 C2 내지 C12 헤테로고리기, 또는 치환 또는 비치환된 C6 내지 C12 아릴기일 수 있다. In one embodiment of the present invention, Formula 1, and R 4 to R 7 , R a to R g , and R a 'to R g of Formulas 4 to 12 are each independently hydrogen, deuterium, substituted or unsubstituted Or a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C2 to C12 heterocyclic group, or a substituted or unsubstituted C6 to C12 aryl group.
또한, 상기 화학식 1, 및 화학식 4 내지 12의 R4 내지 R7, Ra 내지 Rg, 및 Ra' 내지 R8'는 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C10 알킬기 또는 치환 또는 비치환된 C6 내지 C12 아릴기일 수 있다. In addition, R 4 to R 7 , R a to R g , and R a ′ to R 8 ′ in Formula 1, and Formulas 4 to 12 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group. Or a substituted or unsubstituted C6 to C12 aryl group.
본 발명의 일예에서, 상기 화학식 1, 및 화학식 4 내지 12의 L1 내지 L3은 각각 독립적으로 단일 결합, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기일 수 있다ᅳ In one embodiment of the present invention, Formula 1, and L 1 to L 3 of Formulas 4 to 12 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroaryl It may be a Rengi ᅳ
상기 L1 내지 L3은각각 독립적으로,단일결합, 치환 또는 비치환된 페닐렌기， 치환 또는 비치환된 바이페닐렌기 , 치환 또는 비치환된 나프틸렌기 , 치환 또는 비치환된 피리딜렌기， 치환 또는 비치환된 피리미딜렌기, 치환 또는 비치환된 벤조퓨라닐렌기, 또는 이들의 조합일 수 있고， L 1 to L 3 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substitution Or an unsubstituted pyrimidylene group, a substituted or unsubstituted benzofuranylene group, or a combination thereof,
예컨대 단일결합, 또는 하기 그룹 m에 나열된 치환 또는 비치환된 기에서
For example in single bonds or substituted or unsubstituted groups listed in group m below
[A-9] [A- 10] [A-ll] [A- 12]
[A-9] [A-10] [A-ll] [A-12]
Izt7-V] [ -v] iz - ] [it7-v]
Izt7-V] [-v] iz-] [it 7 -v]
[9ε-ν] [ζ£-ν] [ -ν] [εε-ν]
[9ε-ν] [ζ £ -ν] [-ν] [εε-ν]
[ζί-γ] [ιε-ν] [οε-ν] [6ζ-ν] [ζί-γ] [ιε-ν] [οε-ν] [6ζ-ν]
LI LI
.9C00/ST0ZaM/X3d 0l79l7.l/Sl0Z OAV
.9C00 / ST0ZaM / X3d 0l79l7.l / Sl0Z OAV
[ -V] [£9-V] Z9-V] [I9-V]
[-V] [£ 9-V] Z9-V] [I9-V]
[9S-v] [gg-v] [ -v] [«-v]
[9S-v] [gg-v] [-v] [«-v]
[^g-v] [ig-v] [os-v] [6t-v]
[^ gv] [ig-v] [os-v] [6t-v]
[ -ν] [LP-Y] [917-V] [ -v] [-ν] [LP-Y] [917-V] [-v]
8181
.9C00/ST0ZaM/X3d 0l79l7.l/Sl0Z OAV
[A-65] [A-66] [A-67] [A-68]
.9C00 / ST0ZaM / X3d 0l79l7.l / Sl0Z OAV [A-65] [A-66] [A-67] [A-68]
-69] [A-70] [A-71] [A-72]
[69] [A-70] [A-71] [A-72]
[A-77] [A-78] [A-79] [A-80] [A-77] [A-78] [A-79] [A-80]
[A-85] [A-86] [A-87] [A-88]
[A-85] [A-86] [A-87] [A-88]
-94] [A-95] [A-96]
-94] [A-95] [A-96]
[A-97] [A-98] [A-99] [A- 100]
[A-97] [A-98] [A-99] [A-100]
.9C00/ST0ZaM/X3d Ol79l7.l/SlOZ OAV
.9C00 / ST0ZaM / X3d Ol79l7.l / SlOZ OAV
O 03ssAV O 0 3ssA V
ΙΠν:- t6UlV C8U:-V u:v----- Ι Πν: - t6 U l V C8 U: -V u: v -----
v:-23 kv:! 7 _:ΐν S-.-- v : -23 kv :! 7 _ : ΐ ν S -.--
_:8JV _i.lv (9H ΕςΗν:----
_ : 8 J V _i. l v ( 9H Ες Ην : ----
//:/ O/-9soSSSMl>d OSSJSSZAV // : / O / -9 s oS SSM l> d O SSJSSZAV
(89ΐ【횩【991|\9£1V-- I (89 ΐ hyok - - 99 1 | \ 9 £ 1 V-- I
_:9nv【쏙】 V【횩 V t£v--
_ : 9nv 【쏙】 V 【횩 V t £ v--
083 _:6v t8u:v-:V---
083 _ : 6v t 8u : v- : V ---
[A-181] [A- 182] [A-183] [A- 184] [A-181] [A-182] [A-183] [A-184]
[A-193] [A- 194] [A- 195] [A- 196]
[A-193] [A-194] [A-195] [A-196]
!:1 tAl225 t 1>226A2-2TA228---
!: 1 t A l 225 t 1 > 226A2-2TA228 ---
t≤ t:-A2 ()>214A251-A216---
( tu ΕΑ254>624A247Α248---, t≤ t: -A2 () > 2 1 4A25 1 -A2 1 6 --- ( t u Ε Α254> 624A247Α248 ---,
; _η C≤Α23>238>392A24----
; _η C ≤Α23>238> 392A24 ----
t>257>258A259>260--,- t> 257> 258A259> 260-,-
( _:≤9Α24Α25>251>252----
31 ( _ : ≤9Α24Α25> 25 1 > 252 ---- 31
[C-5] [C-6] [C-7]
[C-5] [C-6] [C-7]
-25] [C-26] -27] [C-28]
-25] [C-26] -27] [C-28]
-33] [C-34] [C-35] [C-36]
-33] [C-34] [C-35] [C-36]
[C-41] [C-42] [C-43] [C-44]
[C-41] [C-42] [C-43] [C-44]
-65] [C-66] [C-67] [C-68]
-65] [C-66] [C-67] [C-68]
[C-69] [C-70] [C-71] [C-72]
[C-69] [C-70] [C-71] [C-72]
-4]
-4]
6t .9C00/ST0ZaM/X3d
상술한 화합물은 유기 광전자 소자용일 수 있다. 이하， 상술한 화합물을 적용한 유기 광전자 소자를 설명한다. 6t .9C00 / ST0ZaM / X3d The above-mentioned compounds may be for organic optoelectronic devices. Hereinafter, an organic optoelectronic device to which the above-described compound is applied will be described.
본 발명의 다른 일 구현예에서는, 서로 마주하는 양극과 음극, 및 상기 양극과 상기 음극 사이에 위치하는 적어도 한 층의 유기층을 포함하고, 상기 유기층은 발광층, 그리고 정공 주입 층, 정공 수송 층, 전자 차단 층, 전자 수송 층， 전자 주입 층 및 정공 차단 층에서 선택된 적어도 하나의 보조층을 포함하고, 상기 보조충은 전술한 화합물을 포함하는 유기 광전자 소자를 제공한다. In another embodiment of the present invention, an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, the organic layer is a light emitting layer, and a hole injection layer, a hole transport layer, electrons At least one auxiliary layer selected from a blocking layer, an electron transport layer, an electron injection layer, and a hole blocking layer, the auxiliary caterpillar provides an organic optoelectronic device comprising the compound described above.
구체적으로, 상기 보조층은 정공 수송 층일 수 있다. Specifically, the auxiliary layer may be a hole transport layer.
상기 유기 광전자 소자는 전기 에너지와 광 에너지를 상호 전환할 수 있는 소자이면 특별히 한정되지 않으며, 예컨대 유기 광전 소자， 유기 발광 소자, 유기 태양 전지 및 유기 감광체 드럼 등을 들 수 있다. The organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy. Examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.
여기서는 유기 광전자 소자의 일 예인 유기 발광 소자를 도면을 참고하여 설명한다. Herein, an organic light emitting diode as an example of an organic optoelectronic device will be described with reference to the drawings.
도 1 및 도 2는 일 구현예에 따른 유기 발광 소자를 보여주는 단면도이다. 도 1을 참고하면, 일 구현예에 따른 유기 광전자 소자 (100)는 서로 마주하는 양극 (120)과 음극 (1 10), 그리고 양극 (120)과 음극 (1 10) 사이에 위치하는 유기층 (105)을 포함한다. 1 and 2 are cross-sectional views illustrating an organic light emitting diode according to an embodiment. Referring to FIG. 1, an organic optoelectronic device 100 according to an embodiment includes an anode 120 and a cathode 1 10 facing each other, and an organic layer 105 positioned between the anode 120 and the cathode 1 10. ).
양극 (120)은 예컨대 정공 주입이 원활하도톡 일 함수가 높은 도전체로 만들어질 수 있으며, 예컨대 금속, 금속 산화물 및 /또는 도전성 고분자로 만들어질 수 있다. 양극 (120)은 예컨대 니켈, 백금, 바나듐, 크름， 구리， 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물， 인듐산화물, 인듐주석산화물 (ΠΌ), The anode 120 may be made of, for example, a conductor having a high hole function, for example, to facilitate hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 may be, for example, a metal such as nickel, platinum, vanadium, cream, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide (ΠΌ),
인듐아연산화물 (IZO)과 같은 금속 산화물; ZnO와 A1 또는 Sn02와 Sb와 같은 금속과 산화물의 조합; 폴리 (3-메틸티오펜), 폴리 (3,4- (에틸렌 -1 ,2- 디옥시)티오펜 )(polyehtylenedioxythiophene: PEDT), 폴리피를 및 폴리아닐린과 같은 도전성 고분자 등을 들 수 있으나， 이에 한정되는 것은 아니다. Metal oxides such as indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO and A1 or Sn0 2 and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not limited.
음극 (1 10)은 예컨대 전자 주입이 원활하도록 일 함수가 낮은 도전체로 만들어질 수 있으며， 예컨대 금속， 금속 산화물 및 /또는 도전성 고분자로 만들어질 수 있다. 음극 (1 10)은 예컨대 마그네슘, 칼슴, 나트륨, 칼륨， 타이타늄, 인듐， 이트륨, 리튬, 가돌리늄, 알루미늄, 은， 주석, 납, 세슘, 바륨 등과 같은 금속 또는 이들의
합금; LiF/AI, Li02/Al, LiF/Ca, LiF/Al 및 BaF2/Ca과 같은 다층 구조 물질을 들 수 있으나, 이에 한정되는 것은 아니다. The cathode 1 10 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example. The negative electrode 1 10 is made of, for example, metals such as magnesium, kale, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or the like. alloy; Multilayer structure materials such as LiF / AI, Li0 2 / Al, LiF / Ca, LiF / Al, and BaF 2 / Ca, but are not limited thereto.
유기층 (105)은 발광층 (130)을 포함한다. The organic layer 105 includes the light emitting layer 130.
발광층 (130)은 예컨대 화합물을 단독으로 포함할 수도 있고 두 종류를 흔합하여 포함할 수도 있다. 두 종류를 흔합하여 포함하는 경우, 예컨대 The light emitting layer 130 may include, for example, a compound alone, or may include two kinds in combination. Including two kinds in combination, for example
호스트 (host)와 도편트 (dopant)의 형태로 포함될 수 있다. 상기 호스트는 예컨대 인광 호스트 또는 형광 호스트일 수 있다. It can be included in the form of a host and a dopant. The host can be, for example, a phosphorescent host or a fluorescent host.
도편트는 무기, 유기, 유무기 화합물일 수 있으며 공지된 도편트 중에서 선택될 수 있다. The dopant may be an inorganic, organic, organic or inorganic compound and may be selected from known dopants.
도 2를 참고하면, 유기 발광 소자 (200)는 발광층 (230) 외에 정공 보조층 (140)을 더 포함한다. 정공 보조층 (140)은 양극 (120)과 발광층 (230) 사이의 정공 주입 및 /또는 정공 이동성을 더욱 높이고 전자를 차단할 수 있다. 정공 보조층 (140)은 예컨대 정공 수송충, 정공 주입층 및 /또는 전자 차단층일 수 있으며， 적어도 1충을 포함할 수 있다. 전술한 화합물은 정공 보조층 (140)에 포함될 수 있다. Referring to FIG. 2, the organic light emitting diode 200 further includes a hole auxiliary layer 140 in addition to the light emitting layer 230. The hole auxiliary layer 140 may further increase hole injection and / or hole mobility between the anode 120 and the emission layer 230 and block electrons. The hole auxiliary layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The aforementioned compound may be included in the hole auxiliary layer 140.
도 1 또는 도 2의 유기층 (105)는 도시하지는 않았지만, 전자주입층, 전자수송층, 보조전자수송층, 정공수송층, 보조정공수송층, 정공주입층 또는 이들의 조합층을 추가로 더 포함할 수 있다. 전술한 화합물은 보조정공수송층에 포함될 수 있다. Although not shown, the organic layer 105 of FIG. 1 or 2 may further include an electron injection layer, an electron transport layer, an auxiliary electron transport layer, a hole transport layer, an auxiliary hole transport layer, a hole injection layer, or a combination thereof. The compound described above may be included in the auxiliary hole transport layer.
상기 발광층 (230)과 상기 보조정공수송층은 인접하여 위치할 수 있다. 본 발명의 화합물은 이들 유기층에 포함될 수 있다. 유기 발광 소자 (100, 200)는 기판 위에 양극 또는 음극을 형성한 후， 진공증착법 (evaporation), The emission layer 230 and the auxiliary hole transport layer may be adjacent to each other. The compounds of the present invention can be included in these organic layers. The organic light emitting diodes 100 and 200 form an anode or a cathode on a substrate, and then evaporation,
스퍼터링 (sputtering), 플라즈마 도금 및 이온도금과 같은 건식성막법 ; 또는 Dry film formation methods such as sputtering, plasma plating and ion plating; or
스핀코팅 (spin coating), 침지법 (dipping), 유동코팅법 (flow coating)과 같은 습식성막법 등으로 유기층을 형성한 후, 그 위에 음극 또는 양극을 형성하여 제조할 수 있다. 전술한 화합물은 형광 재료로서 포함될 수 있다. The organic layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode or an anode thereon. The aforementioned compounds can be included as fluorescent materials.
상기 형광 재료는 최대 발광 파장이 550 nm이하일 수 있고, 구체적으로는 420nm 내지 550 nm의 범위에서 최대 발광 파장이 나타날 수 있다. The fluorescent material may have a maximum emission wavelength of 550 nm or less, and specifically, a maximum emission wavelength may appear in a range of 420 nm to 550 nm.
상기 화학식 1로 표시되는 화합물의 HOMO 준위는 5.4eV 이상 5.8eV 이하일 수 있다.
상기 화학식 1로 표시되는 화합물의 3증항 여기에너지 (T1)는 2.4eV 이상 2.7eV 이하일 수 있다. HOMO level of the compound represented by Formula 1 may be more than 5.4eV 5.8eV. The triplet excitation energy (T1) of the compound represented by Formula 1 may be 2.4 eV or more and 2.7 eV or less.
상술한 유기 발광 소자는 유기 발광 표시 장치에 적용될 수 있다. The organic light emitting diode described above may be applied to an organic light emitting diode display.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
이하에서는 본 발명의 구체적인 실시예들올 제시한다. 다만, 하기에 기재된 실시예들은 본 발명을 구체적으로 예시하거나 설명하기 위한 것에 불과하며， 이로서 본 발명이 제한되어서는 아니된다. The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.
이하, 실시예 및 합성예에서 사용된 출발물질 및 반웅물질은 특별한 언급이 없는 한, Sigrfia-Aldrich 社, TCI 社 또는 시중에서 구입하여 사용하거나 공지의 방법으로 제조하였다. Hereinafter, starting materials and reaction materials used in Examples and Synthesis Examples were purchased from Sigrfia-Aldrich, TCI or commercially available or manufactured by known methods, unless otherwise specified.
(화합물의 제조) Preparation of Compound
본 발명의 화합물의 보다 구체적인 예로서 제시된 화합물을 하기 단계를 통해 합성하였다. Compounds given as more specific examples of the compounds of the present invention were synthesized through the following steps.
합성예 1 : 중간체 M-1의 합성 Synthesis Example 1 Synthesis of Intermediate M-1
등근 바닥 플라스크에 4-디벤조퓨란보론산 20g(94.3mmol), 1-브로모 -4- 아이오도벤젠 26.7g (94.3mmol)을 넣고 를루엔 (313ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 1 17ml를 첨가 시키고 교반 하였다. 20 g (94.3 mmol) of 4-dibenzofuranboronic acid and 26.7 g (94.3 mmol) of 1-bromo-4- iodobenzene were added to the back bottom flask and dissolved by adding toluene (313 ml), followed by dissolving 19.5 g of potassium carbonate ( 141.5 mmol) and 17 ml of an aqueous solution 1 were added thereto, followed by stirring.
여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 질소분위기 하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슴 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
생성물을 n-핵산 / 디클로로메탄 (9:1 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-1을 흰색 고체로 27g (수율 89%)올 수득 하였다. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 27 g (89% yield) of the target compound intermediate M-1 as a white solid.
LC-Mass (이론치： 322.00g/mol, 측정치 : M+ = 322.09g/mol, M+2 = 324.04g/mol)
LC-Mass (Theoretical value: 322.00g / mol, Measured value: M + = 322.09g / mol, M + 2 = 324.04g / mol)
M-2 M-2
등근 바닥 플라스크에 4-디벤조티오펜보론산 21.5g(94.3mmol), 1-브로모 -4- 아이오도벤젠 26.7g (94.3mmol)을 넣고 를루엔 (313ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 1 17ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 1.09g( 94mmol)을 가한 후 21.5 g (94.3 mmol) of 4-dibenzothiophenboronic acid and 26.7 g (94.3 mmol) of 1-bromo-4-iodobenzene were added to the back bottom flask and dissolved by adding toluene (313 ml), followed by potassium carbonate 19.5. 17 ml of an aqueous solution in which g (141.5 mmol) was dissolved were added and stirred. Tetrakistriphenylphosphinepalladium 1.09g (94mmol) was added to
질소분위기하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슘 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (9: 1 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-2를 흰색 고체로 29g (수율 91%)을 수득 하였다. It was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 29g (yield 91%) of the target compound intermediate M-2 as a white solid.
LC-Mass (이론치： 337.98g/mol, 측정치 : M+ = 338.04g/mol, M+2 = 340.1 lg/mol) LC-Mass (Theoretical value: 337.98 g / mol, Measured value: M + = 338.04 g / mol, M + 2 = 340.1 lg / mol)
등근 바닥 플라스크에 4-클로로페닐보론산 14.7g(94.3mmol), 2- 브로모디벤조퓨란 23.3g (94.3mmol)을 넣고 를루엔 (313ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 1 17ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 1.09g( 94mmol)을 가한 후 14.7 g (94.3 mmol) of 4-chlorophenylboronic acid and 23.3 g (94.3 mmol) of 2-bromobenzofuran were added to the back bottom flask, followed by dissolution by addition of toluene (313 ml) and potassium carbonate 19.5 g (141.5 mmol). 17 ml of dissolved aqueous solution 1 was added and stirred. Tetrakistriphenylphosphinepalladium 1.09g (94mmol) was added to
질소분위기하에서 12시간 동안 환류 교반 하였다. 반응 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슴 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (9: 1 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-3를 흰색 고체로 23.9g (수율 91%)을 수득 하였다. It was stirred under reflux for 12 hours under a nitrogen atmosphere. After the completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n -nucleic acid / dichloromethane (9: 1 volume ratio) to give 23.9 g (yield 91%) of the target compound intermediate M-3 as a white solid.
LC-Mass (이론치： 278.05g/mol, 측정치 : M+ = 278.12g/mol, M+2 = 280.13g/mol)
합성예 4: 중간체 M-4의 합성
LC-Mass (Theoretical value: 278.05 g / mol, Measured value: M + = 278.12 g / mol, M + 2 = 280.13 g / mol) Synthesis Example 4 Synthesis of Intermediate M-4
등근 바닥 플라스크에 4-클로로페닐보론산 14.7g(94.3mmol), 2- 브로모디벤조티오펜 24.8g (94.3mmol)을 넣고 를루엔 (313ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (14L5mmol)을 녹인 수용액 1 17ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 14.7 g (94.3 mmol) of 4-chlorophenylboronic acid and 24.8 g (94.3 mmol) of 2-bromodibenzothiophene were added to the back-bottom flask and dissolved with toluene (313 ml), followed by dissolving 19.5 g (14 L5 mmol) of potassium carbonate. 17 ml of dissolved aqueous solution 1 was added and stirred. After adding 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium,
질소분위기하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슘 설페이트로 건조 및 여과하고 여과액올 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (9: 1 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-4를 흰색 고체로 25.6g (수율 92%)을 수득 하였다. It was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 25.6 g (yield 92%) of the target compound Intermediate M-4 as a white solid.
LC-Mass (이론치： 294.03g/mol, 측정치 : M+ = 294.16g/mol, M+2 = 296.13g/mol) 합성예 5: 증간체 M-5의 합성 LC-Mass (Theoretical value: 294.03 g / mol, Measured value: M + = 294.16 g / mol, M + 2 = 296.13 g / mol) Synthesis Example 5: Synthesis of Intermediate M-5
ExsctiM ass: 259.11 ExsctiM ass: 259.11
259.3 .
259.3.
M -5 M -5
둥근 바닥 플라스크에 4-디벤조퓨란보론산 20g(94.3mmol), 4- 브로모아닐린 16.2g (94.3mmoI)을 넣고 톨루엔 (300ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)올 녹인 수용액 117ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 20 g (94.3 mmol) of 4-dibenzofuranboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to a round bottom flask, toluene (300 ml) was added to dissolve and 19.5 g (141.5 mmol) of potassium carbonate was dissolved. 117 ml was added and stirred. After adding 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium,
질소분위기하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슴 설페이트';로 건조 및 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (9:1 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-5을 흰색 고체로 17.4g (수율 71%)을 수득 하였다. It was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, and the extract was dried over Magnesium sulfate ' and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 17.4 g (yield 71%) of the target compound Intermediate M-5 as a white solid.
LC-Mass (이론치 : 259.1g/mol, 측정치: M+ = 259.21g/mol)
합성예 6: 중간체 M-6의 합성 LC-Mass (Theoretical value: 259.1 g / mol, Measured value: M + = 259.21 g / mol) Synthesis Example 6 Synthesis of Intermediate M-6
Exact Mass. 411.16 Exact Mass. 411.16
등근바닥플라스크에 4-브로모바이페닐 (30.9mmol)과 중간체 M- 5 9.6g(37.08mmol), 소디움 t-부톡사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반응 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 6를 흰색 고체로 l Llg을 수득하였다. 합성예 7: 중간체 M-7의 합성 4-bromobiphenyl (30.9 mmol), intermediate M-5, 9.6 g (37.08 mmol), and sodium t-butoxide 5.35 g (55.6 mmol) were added to the back bottom flask, and 155 ml of toluene was added and dissolved. 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-butyl-butylphosphine were added in this order, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give l Llg of the target compound Intermediate M-6 as a white solid. Synthesis Example 7 Synthesis of Intermediate M-7
BcacUvtes : 5M. 7 BcacUvtes: 5M. 7
등근바닥플라스크에 증간체 M-1 10g(30.9mmol)과 중간체 M-5 9.6g(37.08mmol), 소디움 t_부특사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반응 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 ' 크로마토그래피로 정제하여 목적 화합물인 중간체 M-7를 흰색 고체로 l L2g (수율 72%)을 수득하였다. Deunggeun in the bottom flask was put into a simplified authentication M-1 10g (30.9mmol) and intermediate M-5 9.6g (37.08mmol), sodium t _ buteuk side 5.35g (55.6mmol) was dissolved was added to 155ml toluene. 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were sequentially added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column ' chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give l L2g (yield 72%) of the target compound Intermediate M-7 as a white solid.
LC-Mass (이론치 : 501.17g/mol, 측정치: M+ = 501.31g/mol)
합성예 8: 중간체 M-8의 합성 LC-Mass (Theoretical value: 501.17 g / mol, Measured value: M + = 501.31 g / mol) Synthesis Example 8 Synthesis of Intermediate M-8
가열 감압 건조한 등근 바닥 플라스크에 1,4-디브로모벤젠 56.2g(238.1mmol)을 넣고 무수 디에틸에테르 (500ml)을 가하여 용해 시키고 -780C로 냉각한 후 56.2g (238.1mmol) of 1,4-dibromobenzene was added to a heated bottom-bottom flask, dissolved in diethyl ether (500ml), and cooled to -78 0 C.
질소분위기하에서 교반 하였다. 여기에 2.5M n-부틸리튬 노르말 핵산 용액 The mixture was stirred under a nitrogen atmosphere. 2.5M n-butyllithium normal nucleic acid solution
100ml(250mmol)을 천천히 가한 후 -780C, 질소분위기하에서 2시간 동안 교반 하였다. 여기에 무수 테트라하이드로퓨란 100ml에 녹인 9-플루오렌온 41g(226mmol)을 천천히 가한 후 상온, 질소분위기하에서 8시간 동안 교반 하였다. 반응액을 0oC로 넁각하고 여기에 1.0M 염암모늄크로라이드수용액 250ml를 가하고 디에틸에테르로 추출 후 유기층올 마그네슘 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 잔사를 10% 에틸아세테이트 /노르말 -핵산 용액으로 실리카겔 칼럼 크로마토그래피로 100 ml (250 mmol) was added slowly, followed by stirring for 2 hours under -78 0 C and a nitrogen atmosphere. Here, 41 g (226 mmol) of 9-fluorenone dissolved in 100 ml of anhydrous tetrahydrofuran was slowly added, followed by stirring at room temperature and nitrogen atmosphere for 8 hours. The reaction solution was stirred at 0 ° C., and 250 ml of 1.0M aqueous ammonium chloride solution was added thereto, followed by extraction with diethyl ether. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography with 10% ethyl acetate / normal-nucleic acid solution.
분라하여목적 화합물인 중간체 M-8을 70g (수율 92%)을 수득 하였다. Isolation yielded 70 g (yield 92%) of intermediate compound M-8.
LC-Mass (이론치： 336.01g/mol, 측정치 : M+ = 336.17g/mol) 합성예 9: 중간체 M-9의 합성 LC-Mass (Theoretical value: 336.01 g / mol, Measured value: M + = 336.17 g / mol) Synthesis Example 9: Synthesis of Intermediate M-9
등근바닥플라스크에 중간체 M-8 6그 4g(200mmol)을 넣고 벤젠 534mL를가하여 용해 시켰다.여기에 트리플루오로메탄설폰산 30g(200mmol)을 천천히 가한 후 질소 분위기 하에서 24시간 동안 환류 교반 시킨다ᅳ 반응 종료 후 반웅액에 1.0M 4 g (200 mmol) of Intermediate M-8 6g (200 mmol) were added to the back bottom flask, and 534 mL of benzene was added thereto. Then, 30 g (200 mmol) of trifluoromethanesulfonic acid was slowly added thereto, followed by stirring under reflux for 24 hours under a nitrogen atmosphere. 1.0M at the end of the reaction
탄산수소나트륨 수용액 240ml를 천천히 가하고에틸아세테이트와 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (9: 1부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 M-9를 27.8g (수율 35%)을 수득하였다. 240 ml of aqueous sodium hydrogen carbonate solution was slowly added, followed by extraction with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 27.8 g (yield 35%) of the target compound M-9.
LC-Mass (이론치： 396.05.13g/mol, 측정치 : M+ = 396.14g/mol)
합성예 10: 중간 M- 10의 합성 LC-Mass (Theoretical value: 396.05.13 g / mol, Measured value: M + = 396.14 g / mol) Synthesis Example 10 Synthesis of Intermediate M-10
가열 감압 건조한 등근 바닥 플라스크에 1 ,3-디브로모밴젠 56.2g(238.1mmol)을 넣고 무수 디에틸에테르 (500ml)을 가하여 용해 시키고 -780C로 넁각한 후 56.2 g (238.1 mmol) of 1,3-dibromovanzene was added to a dry bottomed flask, heated and decompressed, and dissolved by adding anhydrous diethyl ether (500 ml), and then cooled to -78 0 C.
질소분위기하에서 교반 하였다. 여기에 2.5M n-부틸리튬 노르말 핵산 용액 The mixture was stirred under a nitrogen atmosphere. 2.5M n-butyllithium normal nucleic acid solution
100ml(250mmol)을 천천히 가한 후 -780C, 질소분위기하에서 2시간 동안 교반 하였다. 여기에 무수 테트라하이드로퓨란 100ml에 녹인 9-플루오렌온 41 g(226mmol)을 천천히 가한 후 상온, 질소분위기하에서 8시간 동안 교반 하였다. 반응액을 0oC로 넁각하고 여기에 1.0M 염암모늄크로라이드수용액 250ml를 가하고 디에틸에테르로 추출 후 유기층을 마그네슴 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 잔사를 10% 에틸아세테이트 /노르말 -핵산 용액으로 실리카겔 칼럼 크로마토그래피로 100 ml (250 mmol) was added slowly, followed by stirring for 2 hours under -78 0 C and a nitrogen atmosphere. Here, 41 g (226 mmol) of 9-fluorenone dissolved in 100 ml of anhydrous tetrahydrofuran was slowly added, followed by stirring at room temperature and nitrogen atmosphere for 8 hours. The reaction solution was washed with 0 ° C., and 250 ml of 1.0M aqueous ammonium chloride solution was added thereto, followed by extraction with diethyl ether. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography with 10% ethyl acetate / normal-nucleic acid solution.
분리하여목적 화합물인 중간체 M-10을 65g (수율 85%)올 수득 하였다. Isolation yielded 65 g (yield 85%) of intermediate compound M-10.
LC-Mass (이론치： 336.01 g/mol, 측정치 : M+ = 336.21 g/mol) 합성예 1 1 : 중간체 M-1 1의 합성 LC-Mass (Theoretical value: 336.01 g / mol, Measured value: M + = 336.21 g / mol) Synthesis Example 1 1: Synthesis of Intermediate M-1 1
탄산수소나트륨 수용액 214ml를 천천히 가하고에틸아세테이트과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (9: 1부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 M- U을 30.4g (수율 43%)을 수득하였다.
LC-Mass (이론치： 396.05.13g/mol, 측정치 : M+ = 396.19g/mol) 합성예 12: 중간체 M-12의 합성 214 ml of aqueous sodium hydrogen carbonate solution was slowly added, followed by extraction with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 30.4 g (yield 43%) of the target compound M-U. LC-Mass (Theoretical value: 396.05.13 g / mol, Measured value: M + = 396.19 g / mol) Synthesis Example 12 Synthesis of Intermediate M-12
등근 바닥 플라스크에 4-디벤조티오펜보론산 21.5g(94.3mmol), 4- 브로모아닐린 16.2g (94.3mmol)을 넣고 를루엔 (300ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 1 17ml를 첨가 시키고 교반 하였다ᅳ 여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 질소분위기 하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슴 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 21.5 g (94.3 mmol) of 4-dibenzothiophenboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to the back bottom flask and dissolved by adding toluene (300 ml) and potassium carbonate 19.5 g (141.5 mmol). 17 ml of an aqueous solution 1 was added thereto, followed by stirring. Tetrakistriphenylphosphine palladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
생성물을 n-핵산 / 디클로로메탄 (7:3 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-12를 흰색 고체로 19.2g (수율 74%)을 수득 하였다. ,The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 19.2 g (yield 74%) of the target compound intermediate M-12 as a white solid. ,
LC-Mass (이론치 : 275.08g/mol, 측정치: M+ = 275.14g/mol) 합성예 13: 중간체 M-13의 합성 LC-Mass (Theoretical value: 275.08 g / mol, Measured value: M + = 275.14 g / mol) Synthesis Example 13: Synthesis of Intermediate M-13
등근 바닥 플라스크에 2-디벤조티오펜보론산 21.5g(94.3mmol), 4- 브로모아닐린 16.2g (94.3mmoI)을 넣고 롤루엔 (300ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 117ml를 첨가 시키고 교반 하였다. 21.5 g (94.3 mmol) of 2-dibenzothiophenboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to the back bottom flask, followed by dissolving by adding toluene (300 ml) and potassium carbonate 19.5 g (141.5 mmol). 117 ml of dissolved aqueous solution was added and stirred.
여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 질소분위기 하에서 12시간 동안 환류 교반 하였다. 반응 종료 후 에틸아세테이트로 추출 후 추출액을 마그네슘 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
생성물을 n-핵산 / 디클로로메탄 (7:3 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-13을 흰색 고체로 17.9g (수율 69%)을 수득
하였다. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 17.9 g (yield 69%) of the target compound intermediate M-13 as a white solid. It was.
LC-Mass (이론치： 275.08g/mol, 측정치 : M+ = 275.21g/mol) 합성예 14: 중간체 M-14의 합성
LC-Mass (Theoretical value: 275.08 g / mol, Measured value: M + = 275.21 g / mol) Synthesis Example 14 Synthesis of Intermediate M-14
둥근 바닥 플라스크에 2-디벤조퓨란보론산 20g(94.3mmol), 4- 브로모아닐린 16.2g (94.3mmol)을 넣고 를루엔 (300ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 117ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 1.09g(0.94mmol)을 가한 후 질소분위기 하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출 후 추출액을 마그네습 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (7:3 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-14를 흰색 고체로 17.4g (수율 71%)을 수득 하였다. 20 g (94.3 mmol) of 2-dibenzofuranboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to a round-bottomed flask, dissolved by adding toluene (300 ml) and dissolved in 19.5 g (141.5 mmol) of potassium carbonate. 117 ml of aqueous solution was added and stirred. Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 17.4 g (yield 71%) of the target compound intermediate M-14 as a white solid.
LC-Mass (이론치 : 259.1/mol, 측정치: M+ = 259.12g/mol) 합성예 15: 중간체 M-15의 합성 LC-Mass (Theoretical value: 259.1 / mol, Measured value: M + = 259.12 g / mol) Synthesis Example 15 Synthesis of Intermediate M-15
등근 바닥 플라스크에 4-(9H-카바졸 -9-일)페닐보론산 27.1g(94.3mmol), 4- 브로모아닐린 16.2g (94.3mmol)을 넣고 를루엔 (300ml)을 가하여 용해 시킨 후 탄산칼륨 19.5g (141.5mmol)을 녹인 수용액 117ml를 첨가 시키고 교반 하였다. 여기에 테트라키스트리페닐포스핀팔라듐 L09g(0.94mmol)을 가한 후 질소분위기 하에서 12시간 동안 환류 교반 하였다. 반웅 종료 후 에틸아세테이트로 추출후 추출액을 마그네슘 설페이트로 건조 및 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 / 디클로로메탄 (7:3 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M-15를 흰색 고체로 23 g (수율 74%)을 수득
하였다ᅳ 27.1 g (94.3 mmol) of 4- (9H-carbazol-9-yl) phenylboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to the back bottom flask, followed by dissolution by addition of toluene (300 ml). 117 ml of an aqueous solution of 19.5 g (141.5 mmol) of potassium was added and stirred. Tetrakistriphenylphosphinepalladium L09g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 23 g (74% yield) of the target compound Intermediate M-15 as a white solid. ᅳ
LC-Mass (이론치 : 334.15g/mol, 측정치: M+ = 334.23g/nK)l) -16의 합성
LC-Mass (Theoretical value: 334.15 g / mol, Measured value: M + = 334.23 g / nK) l) -16 Synthesis
등근바닥플라스크에 4-브로모바이페닐 7.2g(30.9mmol)과 중간체 M-12 10.2g (37.08mmol), 소디움 t-부톡사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 7.2 g (30.9 mmol) of 4-bromobiphenyl, 10.2 g (37.08 mmol) of intermediate M-12, and 5.35 g (55.6 mmol) of sodium t-butoxide were added to the back bottom flask, and 155 ml of toluene was added to dissolve it. Here, Pd (dba) 2 0.178g (0.31 mmol) and tri-tertiary-butylphosphine
0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70°C에서 교반 시킨다. 반웅 종료 후 틀루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 16을 흰색 고체로 10g (수율 : 76%)을 수득하였다. 0.125 g (0.62 mmol) was added sequentially, followed by stirring at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n -nucleic acid / dichloromethane (7: 3 volume ratio) to give 10 g (yield: 76%) of the target compound Intermediate M-16 as a white solid.
LC-Mass (이론치： 427.14g/mol, 측정치 : M+ = 427.25g/mol) 합성예 17: 중간체 M-17의 합성
LC-Mass (Theoretical value: 427.14 g / mol, Measured value: M + = 427.25 g / mol) Synthesis Example 17 Synthesis of Intermediate M-17
둥근바닥플라스크에 3-브로모바이페닐 7.2g(30.9mmol)과 중간체 M-5 9.6g (37.08mmol), 소디움 t-부록사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g ( 31mmol)과 트리-터셔리 -부틸포스핀 7.2 g (30.9 mmol) of 3-bromobiphenyl, 9.6 g (37.08 mmol) of intermediate M-5 and 5.35 g (55.6 mmol) of sodium t-boxide were added to a round bottom flask, and 155 ml of toluene was added to dissolve it. Pd (dba) 2 0.178g (31mmol) and tri-tertiary-butylphosphine
0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70°C에서 교반 '시킨다. 반옹 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 ¾럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 17을 흰색 고체로 9.7g (수율 : 76%)을 수득하였다. 0.125 g (0.62 mmol) was added sequentially, followed by stirring at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 9.7 g (yield: 76%) of the target compound intermediate M-17 as a white solid.
LC-Mass (이론치 : 41 U6g/mol, 측정치: M+ = 41 1.24g/mol)
합성예 18: 중간체 M-18의 합성 LC-Mass (Theoretical value: 41 U6g / mol, Measured value: M + = 41 1.24g / mol) Synthesis Example 18 Synthesis of Intermediate M-18
둥근바닥플라스크에 4-브로모바이페닐 7.2g (30.9mmol)과 중간체 M-13 10.2g (37.08mmol), 소디음 t-부톡사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 7.2 g (30.9 mmol) of 4-bromobiphenyl, 10.2 g (37.08 mmol) of Intermediate M-13, and 5.35 g (55.6 mmol) of sodium t-butoxide were added to a round bottom flask, and 155 ml of toluene was added to dissolve it. Here, Pd (dba) 2 0.178g (0.31 mmol) and tri-tertiary-butylphosphine
O. I25g(0.62mmoI)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70°C에서 교반 시킨다. 반웅 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카-겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 18을 흰색 고체로 9.8g (수율 : 74%)을 수득하였다. O. I25g (0.62mmoI) is added sequentially and stirred at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica-gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 9.8 g (yield: 74%) of the target compound Intermediate M-18 as a white solid.
LC-Mass (이론치： 427.14g/mol, 측정치 : M+ = 427.2 lg/mol) 합성예 19: 중간체 M-19의 합성 LC-Mass (Theoretical value: 427.1 4 g / mol, Measured value: M + = 427.2 lg / mol) Synthesis Example 19: Synthesis of Intermediate M-19
둥근바닥플라스크에 1-브로모나프탈렌 6.4g (30.9mmol)과 중간체 M-14 9.6g (37.08mmol), 소디음 t-부특사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.3 hnmol)과 트리-터셔리 -부틸포스핀 In a round bottom flask, 6.4 g (30.9 mmol) of 1-bromonaphthalene, 9.6 g (37.08 mmol) of the intermediate M-14, and 5.35 g (55.6 mmol) of sodium t-butoxide were added and dissolved in 155 ml of toluene. Here, Pd (dba) 2 0.178g (0.3 hnmol) and tri-tertiary-butylphosphine
0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70 °C에서 교반 시킨다. 반웅 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 19를 흰색 고체로 9.2g (수율 : 77%)을 수득하였다ᅳ 0.125 g (0.62 mmol) was added sequentially, followed by stirring at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 9.2 g (yield: 77%) of the target compound Intermediate M-19 as a white solid.
LC-Mass (이론치 : 385.15g/mol, 측정치: M+ = 385.28g/mol)
합성예 20 : 중간체 M-20의 합성 LC-Mass (Theoretical value: 385.15 g / mol, Measured value: M + = 385.28 g / mol) Synthesis Example 20 Synthesis of Intermediate M-20
등근바닥플라스크에 4-브로모바이페닐 7.2g(30.9mmol)과 중간체 M- 15 12.4g(37.08mmol), 소디움 t-부톡사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 ( 78g (0.31mmoI)과 트리-터셔리 -부틸포스핀 0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70 °C에서 교반 시킨다. 반웅 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 20을 흰색 고체로 10.5g (수율 : 70%)을 수득하였다. 7.2 g (30.9 mmol) of 4-bromobiphenyl, 12.4 g (37.08 mmol) of Intermediate M-15, and 5.35 g (55.6 mmol) of sodium t-butoxide were added to the back bottom flask and 155 ml of toluene was added to dissolve it. Add Pd (dba) 2 (78g (0.31mmoI) and 0.125g (0.62mmol) of tri-tertiary-butylphosphine in this order and stir at 70 ° C for 8 hours under nitrogen atmosphere. After extraction with distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure.The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 by volume) to obtain the target compound, intermediate M-. 20 was obtained as a white solid (10.5 g, yield: 70%).
LC-Mass (이론치： 486.2 lg/mol, 측정치 : M+ = 486.2 lg/mol) 합성예 21： 중간체 M-21의 합성 LC-Mass (Theoretical value: 486.2 lg / mol, Measured value: M + = 486.2 lg / mol) Synthesis Example 21: Synthesis of Intermediate M-21
등근바닥플라스크에 증간체 M-1 1 12.3g(30.9mmol)과 중간체 M-5 9.6g Intermediate M-1 1 12.3 g (30.9 mmol) and intermediate M-5 9.6 g
(37.08mmol), 소디움 t-부특사이드 5.35g(55.6mmol)을 넣고 틀루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 (37.08 mmol) and 5.35 g (55.6 mmol) of sodium t-butoxide were added and 155 ml of toluene was added to dissolve it. Here, Pd (dba) 2 0.178g (0.31 mmol) and tri-tertiary-butylphosphine
0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70 °C에서 교반 시킨다. 반응 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슴 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 0.125 g (0.62 mmol) was added sequentially, followed by stirring at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. Product to n -nucleic acid / dichloromethane (7: 3
부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 21을 흰색 고체로 12.5g (수율 : 70%)을 수득하였다. Volume ratio) to give 12.5 g (yield: 70%) of the target compound, Intermediate M-21, as a white solid.
LC-Mass (이론치： 575.22g/mol, 측정치 : M+ = 575.24g/mol)
합성예 22： 중간체 M-22의 합성 LC-Mass (Theoretical value: 575.22 g / mol, Measured value: M + = 575.24 g / mol) Synthesis Example 22 Synthesis of Intermediate M-22
둥근바닥플라스크에 중간체 M-9 12.3g(30.9mmol)과 중간체 M-12 10.2g 12.3 g (30.9 mmol) of intermediate M-9 and 10.2 g of intermediate M-12 in a round bottom flask
(37.08mmol), 소디움 t-부특사이드 5.35g(55.6mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.178g (0.31mmol)과 트리-터셔리 -부틸포스핀 (37.08 mmol) and 5.35 g (55.6 mmol) of sodium t-butoxide were added, and 155 ml of toluene was added to dissolve it. Here, Pd (dba) 2 0.178g (0.31 mmol) and tri-tertiary-butylphosphine
0.125g(0.62mmol)을 차례로 넣은 후 질소 분위기 하에서 8시간 동안 70 °C에서 교반 시킨다. 반응 종료 후 를루엔과 증류수로 추출 후 유기층을 마그네슴 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (7:3 부피비) 으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 중간체 M- 22를 흰색 고체로 13.2g (수율 : 72%)을 수득하였다. 0.125 g (0.62 mmol) was added sequentially, followed by stirring at 70 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 13.2 g (yield: 72%) of the target compound Intermediate M-22 as a white solid.
LC-Mass (이론치 : 591.2g/mol, 측정치: M+ = 591.31g/mol) 1: 화합물 A-5의 합성 LC-Mass (Theoretical value: 591.2 g / mol, Measured value: M + = 591.31 g / mol) 1: Synthesis of Compound A-5
등근바닥플라스크에 중간체 M-9 7.95g(20mmol)과 중간체 M-6 8.23g(20mmol), 소디움 t_부톡사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-5를 13.5g (수율 93%)을 수득하였다. Deunggeun in the bottom flask of the intermediate M-9 7.95g (20mmol) and Intermediate M-6 8.23g (20mmol), sodium t-butoxide _ 2.9g (30mmol) was dissolved was added to 155ml toluene. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.5 g (yield 93%) of the target compound A-5.
LC-Mass (이론치： 727.29g/mol, 측정치 : M+ = 727.34g/mol)
LC-Mass (Theoretical value: 727.29 g / mol, Measured value: M + = 727.34 g / mol)
등근바닥플라스크에 중간체 M-1 1 7.95g(20mmol)과 중간체 M-6 8.23g(20mmol), 소디움 t-부톡사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-137을 13.2g (수율 91%)을 수득하였다. 7.95g (20mmol) of intermediate M-1 1, 8.23g (20mmol) of intermediate M-6 and 2.9g (30mmol) of sodium t-butoxide were added to the back bottom flask and 155ml of toluene was added to dissolve it. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the organic layer was extracted with toluene and distilled water, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n -nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.2 g (yield 91%) of the target compound A-137.
LC-Mass (이론치： 727.29g/mol, 측정치 : M+ = 727.3 lg/mol) LC-Mass (Theoretical value: 727.29 g / mol, Measured value: M + = 727.3 lg / mol)
등근바닥플라스크에 중간체 M-9 7.95g(20mmol)과 중간체 M-7 10g(20mmol) 소디움 t-부록사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 7.95g (20mmol) of Intermediate M-9 and 10g (20mmol) of sodium t-boxide (2.9mmol) were added to the back bottom flask and 155ml of toluene was added to dissolve it.
여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페아트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 B-1을 15.1g (수율 92%)을 수득하였다. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) in this order and stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 15.1 g (yield 92%) of the target compound B-1.
LC-Mass (이론치： 817.30g/mol, 측정치 : M+ = 817.36g/mol)
실시예 4: 화합물 B-13의 합성 LC-Mass (Theoretical value: 817.30 g / mol, Measured value: M + = 817.36 g / mol) Example 4: Synthesis of Compound B-13
등근바닥플라스크에 중간체 M-1 1 7.95g(20mmol)과 중간체 M-7 10g(20mmol): 소디움 t-부톡사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 ().1 15g ( 2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 B-13을 14.7g (수율 90%)을 수득하였다. 7.95g (20mmol) of Intermediate M-1 1 and 10g (20mmol) of Intermediate M-7 : Sodium t-butoxide 2.9g (30mmol) were added to the back bottom flask and 155ml of toluene was added and dissolved. 15 g ( 2 mmol) of Pd (dba) 2 () .1 and 0.101 g (0.5 mmol) of tri-tertiary-butylphosphine are sequentially added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 14.7 g (yield 90%) of the target compound B-13.
LC-Mass (이론치 : 817.30g/mol, 측정치: M+ = 817.38g/mol) 실시예 ad-1: 화합물 A-6의 합성 LC-Mass (Theoretical value: 817.30 g / mol, Measured value: M + = 817.38 g / mol) Example ad-1: Synthesis of Compound A-6
등근바닥플라스크에 중간체 M-9 7.95g(20mmol)과 중간체 M-16 8.6g(20mmol), 소디움 t-부특사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층올 마그네슴 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-6을 13.8g (수율 93%)을 수득하였다. 7.95g (20mmol) of Intermediate M-9, 8.6g (20mmol) of Intermediate M-16 and 2.9g (30mmol) of sodium t-butoxide were added to the back bottom flask and 155ml of toluene was added and dissolved. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, dried over an organic layer of magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.8 g (yield 93%) of the target compound A-6.
LC-Mass (이론치 : 743.26g/mol, 측정치: M+ = 743.12g/mol)
LC-Mass (Theoretical value: 743.26 g / mol, Measured value: M + = 743.12 g / mol)
둥근바닥플라스크에 중간체 M-1 1 7.95g(20mmol)과 중간체 M-16 8.6g(20mmol), 소디움 t-부록사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 7.95 g (20 mmol) of intermediate M-1 1, 8.6 g (20 mmol) of intermediate M-16 and 2.9 g (30 mmol) of sodium t-boxide were added to a round bottom flask, and 155 ml of toluene was added to dissolve it.
여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다ᅳ 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the organic layer was extracted with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column with n-nucleic acid / dichloromethane (8: 2 by volume).
크로마토그래피로 정제하여 목적 화합물인 A-138을 14g (수율 94%)을 수득하였다. Purification by chromatography gave 14 g (yield 94%) of the target compound, A-138.
LC-Mass (이론치 : 743.26g/mol, 측정치: M+ = 743.29g/mol) ad-3 : 화합물 A-147의 합성 LC-Mass (Theoretical value: 743.26 g / mol, Measured value: M + = 743.29 g / mol) ad-3: Synthesis of Compound A-147
등근바닥플라스크에 중간체 M-1 1 7.95g(20mmol)과 중간체 M-17 8.22g(20mmol): 소디움 t-부톡사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 7.95g (20mmol) of Intermediate M-1 1 and 8.22g (20mmol) of Intermediate M-17 : 2.9g (30mmol) of sodium t-butoxide were added and dissolved in 155ml of toluene.
여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8 :2 부피비)으로 실리카 겔 컬럼 Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. Silica gel column with n -nucleic acid / dichloromethane (8: 2 volume ratio)
크로마토그래피로 정제하여 목적 화합물인 A-147을 13.2g (수율 91%)을 수득하였다. Purification by chromatography gave 13.2 g (yield 91%) of the target compound A-147.
LC-Mass (이론치： 727.29g/mol, 측정치 : M+ = 727.34g/mol)
실시예 ad-4: 화합물 A-50의 합성 LC-Mass (Theoretical value: 727.29 g / mol, Measured value: M + = 727.34 g / mol) Example ad-4: Synthesis of Compound A-50
등근바닥플라스크에 중간체 M-9 7.95g(20mmol)과 중간체 M-18 8.6g(20mmol), 소디움 t-부특사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)올 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물올 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-50을 13.7g (수율 92%)을 수득하였다. 7.95g (20mmol) of Intermediate M-9, 8.6g (20mmol) of Intermediate M-18 and 2.9g (30mmol) of sodium t -butoxide were added to the back bottom flask and 155ml of toluene was added to dissolve it. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) ol were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.7 g (yield 92%) of the target compound A-50.
LC-Mass (이론치 : 743.26g/mol, 측정치: M+ = 743.18g/mol) 실시예 ad-5: 화합물 A-47의 합성 LC-Mass (Theoretical value: 743.26 g / mol, Measured value: M + = 743.18 g / mol) Example ad-5: Synthesis of Compound A-47
등근바닥플라스크에 증간체 M-9 7.95g(20mmol)과 중간체 M-19 7.7g(20mmol), 소디움 t-부특사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-47을 13.3g (수율 95%)을 수득하였다. 7.95 g (20 mmol) of Intermediate M-9, 7.7 g (20 mmol) of Intermediate M-19, and 2.9 g (30 mmol) of sodium t-butoxide were added to the back bottom flask and 155 ml of toluene was added and dissolved. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.3 g (yield 95%) of the target compound A-47.
LC-Mass (이론치 : 701.27g/mol, 측정치: M+ = 701.15g/mol)
실시예 ad-6: 화합물 C-37의 합성 LC-Mass (Theoretical value: 701.27 g / mol, Measured value: M + = 701.15 g / mol) Example ad-6: Synthesis of Compound C-37
등근바닥플라스크에 증간체 M-1 1 7.95g(20mmol)과 중간체 M-20 9.7g(20mmol), 소디움 tᅳ부특사이드 2.9g(30mmol)을 넣고 틀루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반웅 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 7.95g (20mmol) of Intermediate M-1 1, 9.7g (20mmol) of Intermediate M-20 and 2.9g (30mmol) of sodium t- butbuside were added to the back bottom flask and 155ml of toluene was added to dissolve it. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. Silica gel column with n-nucleic acid / dichloromethane (8: 2 volume ratio)
크로마토그래피로 정제하여 목적 화합물인 C-37을 14.6g (수율 91%)을 수득하였다. Purification by chromatography gave 14.6 g (91% yield) of the target compound C-37.
LC-Mass (이론치： 802.23g/mol, 측정치 : M+ = 803g/mol) 실시예 ad-7: 화합물 A-173의 합성 LC-Mass (Theoretical value: 802.23 g / mol, Measured value: M + = 803 g / mol) Example ad-7 Synthesis of Compound A-173
등근바닥플라스크에 중간체 M-21 1 1.5g(20mmol)과 중간체 2-클로로 -4,6- 디페닐피리미딘 5.3g(20mmol), 탄산세슘 9.8g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리-터셔리 -부틸포스핀 1.5 g (20 mmol) of intermediate M-21 1, 5.3 g (20 mmol) of intermediate 2-chloro-4,6-diphenylpyrimidine, and 9.8 g (30 mmol) of cesium carbonate were added to the back bottom flask, and 155 ml of toluene was added to dissolve it. . Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine
으 101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반응 종료 를루엔과 증류수로 추출 후 유기층올 마그네슘 설페이트로 건조， 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-173을 14.5g (수율 After adding 101g (0.5mmol) in order and stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with toluene and distilled water, dried over magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 14.5 g of the target compound A-173 (yield)
90%)을 수득하였다. 90%) was obtained.
LC-Mass (이론치： 805.3 lg/mol, 측정치 : M+ = 805.23g/mol)
LC-Mass (Theoretical value: 805.3 lg / mol, Measured value: M + = 805.23 g / mol)
등근바닥플라스크에 중간체 M-22 1 1.8g (20mmol)과 8-(4- 브로모페닐)퀴놀린 5.7g(20mm'ol), 소디움 t-부록사이드 2.9g(30mmol)을 넣고 를루엔 155ml을 가하여 용해 시켰다. 여기에 Pd(dba)2 0.1 15g (0.2mmol)과 트리 -터셔리- 부틸포스핀 0.101g(0.5mmol)을 차례로 넣은 후 질소 분위기 하에서 4시간 동안 환류 교반 시킨다. 반응 종료 를루엔과 증류수로 추출 후 유기층을 마그네슘 설페이트로 건조, 여과하고 여과액을 감압 농축하였다. 생성물을 n-핵산 /디클로로메탄 (8:2 부피비)으로 실리카 겔 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-40을 14.5g (수율 91%)을 수득하였다. To the back bottom flask, add 1.8 g (20 mmol) of intermediate M-22 1, 5.7 g (20 mm ' ol) of 8- (4-bromophenyl) quinoline, and 2.9 g (30 mmol) of sodium t-boxide, add 155 ml of toluene. Dissolved. Pd (dba) 2 0.1 15g (0.2mmol) and tri-tertiary-butylphosphine 0.101g (0.5mmol) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. Reaction completion After extraction with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (8: 2 volume ratio) to give 14.5 g (91% yield) of the target compound A-40.
LC-Mass (이론치： 794.28g/mol, 측정치 M+ = 794.35g/mol) LC-Mass (Theoretical value: 794.28 g / mol, Measured value M + = 794.35 g / mol)
(제조된 화합물의 분석 및 특성 측정) (Analysis and Characterization of Prepared Compounds)
1. 형광 특성 분석 1. Fluorescence Characterization
상기 실시예 1 내지 4 의 형광 특성을 측정하기 위해서 각 화합물을 THF에 녹인 후 HITACHI F-4500을 이용하여 PL(photoluminescence) 파장을 측정하였다. 상기 실시예 2의 A-137에 대한 PL 파장 측정 결과를 도 3에 나타내었다. In order to measure the fluorescence characteristics of Examples 1 to 4, each compound was dissolved in THF, and then PL (photoluminescence) wavelength was measured using HITACHI F-4500. The PL wavelength measurement results of the A-137 of Example 2 are shown in FIG. 3.
2. 전기화학적 특성 분석 2. Electrochemical Characterization
슈퍼컴퓨터 GAIA (IBM power 6)를 사용하여 Gaussian 09 방법으로 각 재료의 에너지 준위를 계산하여, 그 결과를 하기 표 1에 나타냈다. The energy level of each material was calculated by the Gaussian 09 method using a supercomputer GAIA (IBM power 6), and the results are shown in Table 1 below.
[표 1] TABLE 1
실험 화합물 HOMO (eV) LUMO (eV) Tl (eV) SI (eV) 실시예 1 A-5 -4.84 -1.12 2.70 3.30 실시예 2 A-137 -4.88 -1.12 2.70 3.33
실시예 3 B-1 -4.84 -1.17 2.65 3.24 실시예 4 B-13 -4.84 -1.15 2.65 3.25 Experimental Compound HOMO (eV) LUMO (eV) Tl (eV) SI (eV) Example 1 A-5 -4.84 -1.12 2.70 3.30 Example 2 A-137 -4.88 -1.12 2.70 3.33 Example 3 B-1 -4.84 -1.17 2.65 3.24 Example 4 B-13 -4.84 -1.15 2.65 3.25
HT-1 -4.70 -0.91 2.64 3.33 비교예 HT-1 -4.70 -0.91 2.64 3.33 Comparative Example
HT-2 -4.74 -0.87 2.77 3.46 상기 표 1에서 알 수 있듯이, HT-2 -4.74 -0.87 2.77 3.46 As can be seen from Table 1,
실시예 1 내지 4에서 합성된 화합물인 경우, 비교예 화합물과 비교하여 In the case of the compound synthesized in Examples 1 to 4,
HOMO에너지 레벨이 O. l eV이상 차이가 나 유기 광전자 소자의 정공 수송층으로 사용될 경우 소자 효율에 영향을 줄 수 있다. HOMO energy levels differ by more than 0.1 eV, which can affect device efficiency when used as a hole transport layer for organic optoelectronic devices.
(유기발광소자의 제작) (Production of organic light emitting device)
실시예 5: 청색 유기 발광소자의 제조 Example 5 Fabrication of Blue Organic Light Emitting Diode
ΠΌ (Indium tin oxide)가 1500A의 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올， 아세톤, 메탄을 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 진공 층착기로 기판을 이송하였다. 이렇게 준비된 ΠΌ 투명 전극올 양극으로 사용하여 ΠΌ 기판 상부에 4,4'-bisP^-[4-{N,N-bis(3-methylphenyl)amino}-phenyl]-N-phenylamino]biphenyl (DNTPD)를 진공 증착하여 600A두께의 정공 주입층을 형성하였다. 이어서 HT-1을 진공 증착으로 250A 두께의 정공 수송층을 형성하였다. 상기 정공수송층 상부에 실시예 1에서 제조된 화합물을 사용하여 진공 증착으로 50A 두께의 보조 정공 수송층을 형성하였다. 상기 보조 정공 수송층 상부에 9,10-di-(2-naphthyl)anthracene(ADN)을 호스트로 사용하고 도판트로 2,5,8,1 l-tetra(tert-butyl)perylene(TBPe)를 3중량0 /0로 도핑하여 진공 증착으로 250 A 두께의 발광층을 형성하였다. A glass substrate coated with a thin film of indium tin oxide (1500Ό) of 1500 A was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic washing with isopropyl alcohol, acetone, methane and the like, and then dried and transferred to a plasma cleaner, and then washed the substrate using oxygen plasma for 5 minutes and then transferred to a vacuum depositor. 4,4'-bisP ^-[4- {N, N-bis (3-methylphenyl) amino} -phenyl] -N-phenylamino] biphenyl (DNTPD) was formed on the ΠΌ substrate using the prepared ΠΌ transparent electrode as an anode. Was vacuum deposited to form a hole injection layer having a thickness of 600A. HT-1 was then vacuum deposited to form a 250 A thick hole transport layer. A secondary hole transport layer having a thickness of 50A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer. 9,10-di- (2-naphthyl) anthracene (ADN) is used as a host on the auxiliary hole transport layer, and 3,2,5,8,1 l-tetra (tert-butyl) perylene (TBPe) is used as a dopant. by doping with 0/0 by vacuum deposition to form a light emitting layer of 250 a thickness.
그 후 상기 발광층 상부에 Alq3를 진공 증착하여 250A 두께의 전자수송층을 형성하였다ᅳ 상기 전자수송층 상부에 LiF lOA과 A1 1000A을 순차적으로 진공 증착하여 음극을 형성함으로써 유기발광소자를 제조하였다. After that, Alq3 was vacuum deposited on the emission layer to form an electron transport layer having a thickness of 250 A. An organic light emitting device was manufactured by sequentially depositing LiF lOA and A1 1000A on the electron transport layer to form a cathode.
상기 유기발광소자는 5층의 유기박막층을 가지는 구조로 되어 있으며, 구체적으로 The organic light emitting device has a structure having five organic thin layers, specifically
Al( 1000 A )/LiF( 10 A )/Alq3 (250 A )/EML[ ADN :TBPe=97 : 3 ] (250 A)/보조정공수송층(
50A)/ HT-1(250A)/DNTPD (600A)/ITO(1500A)의 구조로 제작하였다. 실시예 6 Al (1000 A) / LiF (10 A) / Alq3 (250 A) / EML [ADN: TBPe = 97: 3] (250 A) / adjusted air transport layer ( 50A) / HT-1 (250A) / DNTPD (600A) / ITO (1500A). Example 6
상기 실시예 5에서, 실시예 1 대신 실시예 2를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 7 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 2 instead of Example 1. Example 7
상기 실시예 5에서， 실시예 1 대신 실시예 3을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 8 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 3 instead of Example 1. Example 8
상기 실시예 5에서, 실시예 1 대신 실시예 4를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-9 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 4 instead of Example 1. Example ad-9
상기 실시예 5에서, 실시예 1 대신 실시예 ad-3을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실사예 ad-10 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-3 instead of Example 1. Due Diligence ad-10
상기 실시예 5에서， 실시예 1 대신 실시예 ad-6을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 1 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-6 instead of Example 1. Comparative Example 1
실시예 1의 화합물 A-5 대신 HT-1올 사용한 것을 제외하고는 실시예 5와 동일한 방법으로 유기발광소자를 제조하였다. 비교예 2 An organic light emitting diode was manufactured according to the same method as Example 5 except for using HT-1 instead of compound A-5 of Example 1. Comparative Example 2
실시예 1의 화합물 A-5 대신 HT-2를 사용한 것을 제외하고는 실시예 5와 동일한 방법으로 유기발광소자를 제조하였다. 상기 유기발광소자 제작에 사용된 DNTPD, HT-l , HT-2, Alq3, ADN, TBPe 의
T/KR2015/003678 An organic light emitting diode was manufactured according to the same method as Example 5 except for using HT-2 instead of compound A-5 of Example 1. DNTPD, HT-l, HT-2, Alq 3 , ADN, TBPe used in the organic light emitting device fabrication T / KR2015 / 003678
62 구조는 62 structure is
(청색 유기발광소자의 성능 측정) (Performance Measurement of Blue Organic Light Emitting Diode)
실시예 5 내지 8， 실시예 ad-9 및 ad-10, 그리고 비교예 1 내지 2 에 따른 유기발광소자의 전압에 따른 전류밀도 변화, 휘도 변화, 발광효율, 및 수명을 측정하였다. The current density change, luminance change, luminous efficiency, and lifetime of the organic light emitting diode according to Examples 5 to 8, Examples ad-9 and ad-10, and Comparative Examples 1 to 2 were measured.
구체적인 측정방법은 하기와 같고, 그 결과는 표 2와 같다. Specific measurement methods are as follows, and the results are shown in Table 2.
(1) 전압변화에 따른 전류밀도의 변화 측정 (1) Measurement of change in current density according to voltage change
제조된 유기발광소자에 대해, 전압을 0V 부터 10V까지 상승시키면서 전류- 전압계 (Keithley 2400)를 이용하여 단위소자에 흐르는 전류값올 측정하고, 측정된 전류값을 면적으로 나누어 결과를 얻었다. For the organic light emitting device manufactured, the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V, and the measured current value was divided by the area to obtain a result.
(2) 전압변화에 따른 휘도변화 측정 (2) Measurement of luminance change according to voltage change
제조된 유기발광소자에 대해, 전압을 0V 부터 10V까지 상승시키면서 휘도계 (Minolta Cs-I OOOA)를 이용하여 그 때의 휘도를 측정하여 결과를 얻었다. (3) 발광효율 측정 For the organic light emitting device manufactured, the luminance was measured using a luminance meter (Minolta Cs-I OOOA) while increasing the voltage from 0V to 10V to obtain a result. (3) Measurement of luminous efficiency
상기 (1) 및 (2)로부터 측정된 휘도와 전류밀도 및 전압을 이용하여 동일 전류밀도 (10 mA/cm2)의 전류 효율 (cd/A) 을 계산하였다.
(4) 수명 측정 The current efficiency (cd / A) of the same current density (10 mA / cm 2 ) was calculated using the luminance, current density and voltage measured from (1) and (2). (4) life measurement
제조된 유기발광소자에 대해 폴라로닉스 수명 측정 시스템을 사용하여 실시예 5 내지 8, 실시예 ad-9 및 ad-10, 그리고 비교예 1 및 2의 청색 유기 발광 소자의 경우에는 초기 휘도 l ,000nit로 발광시키고 시간 경과에 따른 휘도의 감소를 측정하여 초기 휘도 대비 1/2로 휘도가 감소된 시점을 반감수명으로 하여 In the case of the blue organic light emitting diodes of Examples 5 to 8, Examples ad-9 and ad-10, and Comparative Examples 1 and 2, using the Polaronics Lifetime Measurement System for the manufactured organic light emitting diodes, Light emission and measure the decrease in luminance over time.
측정하였다. Measured.
[표 2] TABLE 2
전류밀도: 10mA/cm: 상기 표 2 에서 알 수 있듯이, 실시예 5 내지 8, 실시예 ad-9 및 ad-10은 비교예 1 및 2에 비해 발광효율이 크게 개선되고, 수명 역시 동등하거나 그 이상으로 개선된 특성을 보이는 것을 알 수 있다. 특히 실시예 5 내지 8， 실시예 ad- 9 및 ad- 10은 보조 HTL을 사용하지 않은 비교예 1에 비해 최소 13% 이상의 효율
증가를 나타 내었으며, 보조 HTL로 HT-2를 사용한 비교예 2에 비해 최소 Current density: 10 mA / cm : As can be seen in Table 2, Examples 5 to 8, Examples ad-9 and ad-10 are significantly improved luminous efficiency compared to Comparative Examples 1 and 2, the lifetime is also equal or It can be seen that the improved characteristics are shown above. In particular, Examples 5-8, Examples ad-9 and ad-10 are at least 13% more efficient than Comparative Example 1, which does not use auxiliary HTL. Increased, with minimal compared to Comparative Example 2 using HT-2 as the secondary HTL.
20%이상의 반감 수명이 증가하는 효과를 나타 내었다. 실시예 ad-ll: 녹색 유기 발광소자의 제조 The half life of more than 20% was increased. Example ad-ll: Fabrication of Green Organic Light Emitting Diode
ΠΌ (Indium tin oxide)가 1500A의 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄을 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 진공 증착기로 기판을 이송하였다. 이렇게 준비된 ΠΌ 투명 전극을 양극으로 사용하여 ΠΌ 기판 상부에 HT-1을 진공 증착하여 700A두께의 정공 주입 및 수송층올 형성하였다. 이어서 실시예 1에서 제조된 화합물올 사용하여,진공 증착으로 100A 두께의 보조 정공 수송층을 형성하였다. 상기 보조 정공 수송층 상부에 (4,4'-Ν,Ν'-디카바졸)비페닐 [CBP]를 호스트로 사용하고 도판트로 트리스 (2-페닐피리딘)이리듐 (ΠΙ) [Ir(ppy)3]를 5중량 %로 도핑하여 진공 증착으로 300A 두께의 발광층을 형성하였다. Glass substrates coated with ΠΌ (Indium tin oxide) to a thickness of 1500A were washed by distilled water ultrasonically. After the washing of distilled water, ultrasonic washing with isopropyl alcohol, acetone, methane and the like, dried and transferred to a plasma cleaner, and then washed the substrate using oxygen plasma for 5 minutes and then transferred to a vacuum evaporator. HT-1 was vacuum deposited on the ΠΌ substrate using the πΌ transparent electrode thus prepared as an anode to form a hole injection and transport layer having a thickness of 700A. Subsequently, the compound hole prepared in Example 1 was used to form an auxiliary hole transport layer having a thickness of 100 A by vacuum deposition. (4,4'-Ν, Ν'-dicarbazole) biphenyl [CBP] was used as a host on the auxiliary hole transport layer, and doptro tris (2-phenylpyridine) iridium (ΠΙ) [Ir (ppy) 3 ] Was doped to 5% by weight to form a light emitting layer of 300A thickness by vacuum deposition.
그 후 상기 발광층 상부에 비페녹시 -비스 (8-히드록시퀴놀린)알루미늄 [Balq]을 진공 증착하여 50 A 두께의 정공저지층을 형성하였다. 상기 정공 저지층 상부에 트리스 (8-히드록시퀴놀린)알루미늄 [Alq3]을 진공 증착하여 250 A두께의 Thereafter, biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50 A. Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a 250 A thickness.
전자수송층을 형성하고 상기 전자수송층 상부에 LiF lOA과 ΑΠ000Α을 순차적으로 진공 증착하여 음극을 형성함으로써 유기발광소자를 제조하였다. An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing LiF lOA and AP000A on the electron transport layer to form a cathode.
상기 유기발광소자는 5층의 유기박막층을 가지는 구조로 되어 있으며, 구체적으로 The organic light emitting device has a structure having five organic thin layers, specifically
Al( 1000 A )/LiF( 10 A )/Alq3 (250 A )/Balq(50 A )/EML[CBP :Ir(ppy)^^ Al (1000 A) / LiF (10 A) / Alq3 (250 A) / Balq (50 A) / EML [CBP: Ir (ppy) ^^
조 ΗΤ (100Α)/ΗΤ-1(700Α)/ΠΌ(1500Α)의 구조로 제작하였다. 실시예 ad-12 It was prepared in the structure of crude ΗΤ (100Α) / ΗΤ-1 (700Α) / ΠΌ (1500Α). Example ad-12
상기 실시예 ad-l l에서, 실시예 1대신 실시예 2를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-13
상기 실시예 ad-1 1에서, 실시예 1대신 실시예 3을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-14 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example 2 instead of Example 1. Example ad-13 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example 3 instead of Example 1. Example ad-14
상기 실시예 ad-1 1에서, 실시예 1대신 실시예 ad-l을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1. Example ad-15
상기 실시예 ad-1 1에서, 실시예 1대신 실시예 ad-2를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-l 6 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-2 instead of Example 1. Example ad-l 6
상기 실시예 ad-11에서, 실시예 1대신 실시예 ad-3을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1. Example ad-17
상기 실시예 ad-1 1에서, 실시예 1대신 실시예 ad-4를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 3 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-4 instead of Example 1. Comparative Example 3
상기 실시예 ad-1 1에서， HT-1 대신 Ν,Ν'-디 (1-나프틸) -Ν,Ν'-디페닐벤지딘 In Example ad-1 1, instead of HT-1, Ν, Ν'-di (1-naphthyl) -Ν, Ν'-diphenylbenzidine
[ΝΡΒ]를 사용하고, 실시예 1 대신 -디(1-나프틸)- -디페닐벤지딘[1^1 ]를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 4 An organic light emitting diode was manufactured according to the same method except that [ΝΡΒ] was used and -di (1-naphthyl)--diphenylbenzidine [1 ^ 1] was used instead of Example 1. Comparative Example 4
상기 실시예 ad-1 1에서, HT-1 대신 Ν,Ν'-디 (1-나프틸) -Ν,Ν'-디페닐벤지딘 In Example ad-1 1, N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine is substituted for HT-1.
[ΝΡΒ]를 사용하고, 실시예 1 대신 트리스 (4,4'，4"-(9-카르바졸릴)) -트리페닐아민 Tris (4,4 ', 4 "-(9-carbazolyl))-triphenylamine instead of Example 1, using [ΝΡΒ]
[TCTA]을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 5
상기 실시예 ad-11에서, 실시예 1 대신 HT-1올 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 상기 유기발광소자 제작에 사용된 HT-1 및 Alq3는 전술한 바와 같고， NPB TCTA, CBP, Balq, Ir(ppy)3의 구조는 아래와 같다. An organic light emitting diode was manufactured according to the same method except that [TCTA] was used. Comparative Example 5 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using HT-1 instead of Example 1. HT-1 and Alq3 used in the organic light emitting device fabrication are as described above, and the structure of NPB TCTA, CBP, Balq, Ir (ppy) 3 is as follows.
(녹색 유기발광소자의 성능 측정) (Performance Measurement of Green Organic Light Emitting Diode)
실시예 ad-11 내지 ad-17, 및 비교예 3 내지 5에 따른 유기발광소자의 전압에 따른 전류밀도 변화， 휘도 변화, 발광효율, 및 수명을 측정하였다. The current density change, luminance change, luminous efficiency, and lifetime of the organic light emitting diodes according to Examples ad-11 to ad-17 and Comparative Examples 3 to 5 were measured.
전압에 따른 전류밀도 변화, 휘도 변화, 및 발광효율의 측정방법은 상기 청색 유기발광소자에서의 방법과 동일하고, 수명 측정방법은 하기와 같으며, 그 결과는 표 3과 같다. 수명 측정 The method of measuring the current density change, the brightness change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 3. Life measurement
제조된 유기발광소자에 대해 폴라로닉스 수명 측정 시스템을 사용하여 실시예 ad-11 내지 ad-17과 비교예 3 내지 5의 녹색 유기 발광 소자의 경우에는
초기 휘도 3,000nit로 발광시키고 시간 경과에 따른 휘도의 감소를 측정하여 초기 휘도 대비 1/2로 휘도가 감소된 시점을 반감수명으로 하여 측정하였다. In the case of the green organic light emitting diodes of Examples ad-11 to ad-17 and Comparative Examples 3 to 5 using a polarization lifetime measurement system for the manufactured organic light emitting diodes The luminance was emitted at an initial luminance of 3,000 nits, and the decrease in luminance over time was measured, and the half life was measured when the luminance was reduced to 1/2 of the initial luminance.
[표 3] TABLE 3
20%이상의 효율 증가를 나타내었다. 보조 HTL로 TCTA를 사용한 비교예 4에 비해서도 보다 높은 효율을 나타내었으며 최소 30%이상의 반감 수명이 증가하는 효과를 나타내었다. 실시예 ad-18: 적색 유기 발광소자의 제조 It showed an efficiency increase of more than 20%. Compared with Comparative Example 4 using TCTA as the auxiliary HTL, the efficiency was higher and the half life of at least 30% was increased. Example ad-18 Preparation of Red Organic Light-Emitting Device
ΠΌ (Indium tin oxide)가 1500A의 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 진공 층착기로 기판을
이송하였다. 이렇게 준비된 ΠΌ 투명 전극을 양극으로 사용하여 ΠΌ 기판 상부에 4,4'-bis[N-[4- {N,N-bis(3 -methylphenyl)amino } -phenyl]-N-phenylamino]biphenyl [DNTPD]를 진공 증착하여 600A두께의 정공 주입층을 형성하였다. 이어서 HT-1을 진공 증착으로 200 A 두께의 정공 수송층을 형성하였다. 상기 정공수송층 상부에 실시예 1에서 제조된 화합물을 사용하여 진공 증착으로 100A 두께의 보조 정공 수송층을 형성하였다. 상기 보조 정공 수송층 상부에 (4,4'-Ν,Ν'-디카바졸)비페닐 [CBP]를 호스트로 사용하고 도판트로 비스 (2-페닐퀴놀린) (아세틸아세토네이트)이리듐 (ΙΠ) [Ir(pq)2acac]를 5중량 %로 도핑하여 진공 증착으로 300 A 두께의 발광층을 Glass substrates coated with ΠΌ (Indium tin oxide) to a thickness of 1500A were washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma. Transferred. 4,4'-bis [N- [4- {N, N-bis (3 -methylphenyl) amino} -phenyl] -N-phenylamino] biphenyl [DNTPD] was prepared on the ΠΌ substrate using the prepared ΠΌ transparent electrode as an anode. ] Was vacuum-deposited to form a hole injection layer of 600 A thickness. HT-1 was then vacuum deposited to form a 200 A thick hole transport layer. An auxiliary hole transport layer having a thickness of 100A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer. (4,4'-Ν, Ν'-dicarbazole) biphenyl [CBP] was used as a host on the auxiliary hole transport layer, and dopant bis (2-phenylquinoline) (acetylacetonate) iridium (ΙΠ) [Ir (pq) 2 acac] to 5 wt% to form a 300 A thick light emitting layer by vacuum deposition.
형성하였다. Formed.
그 후 상기 발광층 상부에 비페녹시 -비스 (8-히드록시퀴놀린)알루미늄 [Balq]을 진공 증착하여 50A 두께의 정공저지층을 형성하였다. 상기 정공 저지층 상부에 트리스 (8-히드록시퀴놀린)알루미늄 [Alq3]을 진공 증착하여 250A두께의 Thereafter, biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50A. Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a thickness of 250 A.
전자수송층을 형성하고 상기 전자수송층 상부에 UF 10A과 ΑΠ 000 A을 순차적으로 진공 증착하여 음극을 형성함으로써 유기발광소자를 제조하였다. An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing UF 10A and A 000 000 A on the electron transport layer to form a cathode.
상기 유기발광소자는 6층의 유기박막층을 가지는 구조로 되어 있으며 , 구체적으로 The organic light emitting device has a structure having six organic thin layers, specifically
Al(1000A)/LiF(10A)/Alq3(250A)/Balq(50A)/EML[CBP: Ir(pq)2acac 제작하였다. 실시예 ad-19 Al (1000A) / LiF (10A) / Alq3 (250A) / Balq (50A) / EML [CBP: Ir (pq) 2 acac were produced. Example ad-19
상기 실시예 ad-18에서, 실시예 1대신 실시예 2를사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-20 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 2 instead of Example 1. Example ad-20
상기 실시예 ad-18에서， 실시예 1대신 실시예 4를사용한 점을 제외하고 동일한 방법으로 유기발광소자를.제조하였다. 실시예 ad-21
상기 실시예 ad-18에서， 실시예 1대신 실시예 ad-1올사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-22 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 4 instead of Example 1. Example ad-21 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-1 instead of Example 1. Example ad-22
상기 실시예 ad-18에서， 실시예 1대신 실시예 ad-3을사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 실시예 ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1. Example ad-23
상기 실시예 ad-18에서， 실시예 1대신 실시예 ad-5를사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 6 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-5 instead of Example 1. Comparative Example 6
상기 실시예 ad-18에서， HT-1 대신 Ν,Ν'-디 (1-나프틸) -Ν,Ν'-디페닐벤지딘 [ΝΡΒ]를 사용하고, 실시예 1 대신 Ν,Ν'-디 (1-나프틸) -Ν,Ν'-디페닐벤지딘 [ΝΡΒ]를 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 7 In Example ad-18, Ν, Ν'-di (1-naphthyl) -Ν, Ν'-diphenylbenzidine [ΝΡΒ] is used instead of HT-1, and Ν, Ν'-di is used instead of Example 1. An organic light emitting diode was manufactured according to the same method except that (1-naphthyl) -Ν, Ν'-diphenylbenzidine [ΝΡΒ] was used. Comparative Example 7
상기 실시예 ad-18에서, HT-1 대신 Ν,Ν'-디 (1-나프틸) -Ν,Ν'-디페닐벤지딘 [ΝΡΒ]를 사용하고, 실시예 1 대신 트리스 (4,4'，4"-(9-카르바졸릴)) -트리페닐아민 In Example ad-18, Ν, Ν'-di (1-naphthyl) -Ν, Ν'-diphenylbenzidine [ΝΡΒ] was used instead of HT-1, and Tris (4,4 ') was used instead of Example 1. , 4 "-(9-carbazolyl))-triphenylamine
[TCTA]을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 비교예 8 An organic light emitting diode was manufactured according to the same method except that [TCTA] was used. Comparative Example 8
상기 실시예 ad-18에서, 실시예 1 대신 HT-1을 사용한 점을 제외하고는 동일한 방법으로 유기발광소자를 제조하였다. 상기 유기발광소자 제작에 사용된 DNTPD, NPB, HT-1, TCTA, CBP, Balq, 및 Alq3의 구조는 전술한 바와 같고， Ir(pq)2acac의 구조는 아래와 같다.
An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using HT-1 instead of Example 1. The structures of DNTPD, NPB, HT-1, TCTA, CBP, Balq, and Alq3 used in fabricating the organic light emitting diode are as described above, and the structure of Ir (pq) 2 acac is as follows.
lr(pq)2acac lr (pq) 2 acac
(적색 유기발광소자의 성능 측정) (Performance Measurement of Red Organic Light Emitting Diode)
실시예 ad-18 내지 ad-23, 및 비교예 6 내지 8에 따른 유기발광소자의 전압에 따른 전류밀도 변화, 휘도 변화, 발광효율, 및 수명을 측정하였다. The current density change, luminance change, luminous efficiency, and lifetime of the organic light emitting diode according to Examples ad-18 to ad-23 and Comparative Examples 6 to 8 were measured.
전압에 따른 전류밀도 변화, 휘도 변화, 및 발광효율의 측정방법은 상기 청색 유기발광소자에서의 방법과 동일하고， 수명 측정방법은 하기와 같으며, 그 결과는 표 4와 같다. 수명 측정 The method of measuring the current density change, the luminance change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 4 below. Life measurement
제조된 유기발광소자에 대해 폴라로닉스 수명 측정 시스템을 사용하여 실시예 ad-18 내지 ad-23과 비교예 6 내지 8의 적색 유기 발광 소자의 경우에는 초기 휘도 l,000nit로 발광시키고 시간 경과에 따른 휘도의 감소를 측정하여 초기 휘도 대비 80%로 휘도가 감소된 시점을 T80 수명으로 하여 측정하였다. In the case of the red organic light emitting diodes of Examples ad-18 to ad-23 and Comparative Examples 6 to 8 using a polarization lifetime measurement system for the manufactured organic light emitting diodes, the light was emitted at an initial luminance of 1,000 nit and over time. The decrease in luminance was measured as the T80 lifetime when the luminance was reduced to 80% of the initial luminance.
[표 4] 구동전압 발광효율 ELpeak T80수명 (h) 소자 HTL 보조 HTL [Table 4] Driving Voltage Luminous Efficiency ELpeak T80 Life (h) Device HTL Auxiliary HTL
(V) (cd/A) (nm) @1000nit 실시예 ad-18 HT-1 A-5 8.1 17.9 600 890 실시예 ad-19 HT-1 A-137 8.3 18.3 600 910 실시예 ad-20 HT-1 B-13 8.4 18.5 600 870 실시예 ad-21 HT-1 A-6 8.3 18.1 600 890 실시예 ad-22 HT-1 A-147 8.4 18.9 600 880 실시예 ad-23 HT-1 A-47 8.0 18.2 600 830 비교예 6 NPB NPB 8.7 15.1 600 720
비교예 7 NPB TCTA 9.1 17.3 600 650 비교예 8 HT-1 HT-1 8.4 16.6 600 800 상기 표 4 에서 알 수 있듯이, 실시예 ad-18 내지 ad-23은 비교예 6 내지 8에 비해 발광 효율, 구동 전압, 수명 측면에서 개선된 특성을 보이는 것을 알 수 있다. 특히 실시예 ad-18 내지 ad-23은 보조 HTL을 사용하지 않은 비교예 6에 비해 최소 19% 이상의 효율 증가를 나타내었으며， 비교예 8에 비해 최소 8%이상의 효율 증가를 나타내었다. 보조 HTL로 TCTA를 사용한 비교예 4에 비해서도 보다 높은 효율을 나타내었으며 최소 28%이상의 T80 수명이 증가하는 효과를 나타내었다 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.
(V) (cd / A) (nm) @ 1000nit Example ad-18 HT-1 A-5 8.1 17.9 600 890 Example ad-19 HT-1 A-137 8.3 18.3 600 910 Example ad-20 HT- 1 B-13 8.4 18.5 600 870 Example ad-21 HT-1 A-6 8.3 18.1 600 890 Example ad-22 HT-1 A-147 8.4 18.9 600 880 Example ad-23 HT-1 A-47 8.0 18.2 600 830 Comparative example 6 NPB NPB 8.7 15.1 600 720 Comparative Example 7 NPB TCTA 9.1 17.3 600 650 Comparative Example 8 HT-1 HT-1 8.4 16.6 600 800 As can be seen from Table 4, Examples ad-18 to ad-23 are luminous efficiency, compared to Comparative Examples 6 to 8, It can be seen that the improved characteristics in terms of driving voltage and lifetime. In particular, Examples a d-18 to ad-23 showed at least an efficiency increase of at least 19% compared to Comparative Example 6 without the use of auxiliary HTL, and at least 8% increase in efficiency compared to Comparative Example 8. Compared with Comparative Example 4 using TCTA as the auxiliary HTL, the efficiency was higher and the T80 life was increased by at least 28%. The present invention is not limited to the above embodiments, but may be manufactured in various forms. Those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.
Claims
【청구의 범위】 [Range of request]
【청구항 1 ] [Claim 1]
하기 화학식 1로 표시되는 화합물: Compound represented by the following formula (1):
상기 화학식 1에서 In Chemical Formula 1
L1 내지 L3은 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C1 내지 C30 알킬렌기， 치환 또는 비치환된 C3 내지 C30 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기， 치환 또는 비치환된 C2 내지 C30 해테로아릴렌기， 치환 또는 비치환된 C6 내지 C30 아릴렌아민기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C1 내지 C30 아릴옥실렌기, 치환 또는 비치환된 C2 내지 C30 알케닐렌기， 치환 또는 비치환된 C2 내지 C30 알키닐렌기, 또는 이들의 조합이고, L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted group A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,
R1 내지 R7은 각각 독립적으로, 수소, 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기， 치환 또는 비치환된 C2 내지 C30 헤테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환 또는 비치환된 C2 내지 C30.알콕시카르보닐기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기, 치환 또는 비치환된 C7 내지 C30 R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기, 치환 또는 비치환된 ci 내지 C30 술파모일아미노기， 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기， 치환 또는 비치환된 C1 내지 C20 아실옥시기， 치환 또는 비치환된 C1 내지 C20 아실아미노기 , 치환 또는
비치환된 CI 내지 C30 술포닐기, 치환 또는 비치환된 C1 내지 C30 알킬티올기, 치환 또는 비치환된 C6 내지 C30 아릴티올기, 치환 또는 비치환된 C1 내지 C30 우레이드기， 할로겐기, 할로겐 함유기, 시아노기, 히드록실기, 아미노기, 니트로기, 카르복실기， 페로세닐기， 또는 이들의 조합이고, Aryloxycarbonylamino group, substituted or unsubstituted ci to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or Unsubstituted CI to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing Group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, ferrocenyl group, or a combination thereof,
R2 R3 중 적어도 하나는 하기 화학식 2 또는 하기 화학식 3으로 표시된다: At least one of R 2 R 3 is represented by the following Chemical Formula 2 or the following Chemical Formula 3:
[화학식 Formula
상기 화학식 2 및 3에서, In Chemical Formulas 2 and 3,
*은 연결지점이고, * Is the connection point,
X는 0 또는 S 이고, X is 0 or S,
Ra 내지 Rg는 각각 독립적으로, 수소, 중수소， 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐기， 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기, 치환 또는 비치환된 C7 내지 C30 R a to R g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted Substituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxycarbonyl group, substituted or unsubstituted C2 to C30 Alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
아릴옥시카르보닐아미노기, 치환 또는 비치환된 C1 내지 C30 술파모일아미노기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기, 치환 또는 비치환된 C1 내지 C20 아실아미노기, 치환 또는
비치환된 CI 내지 C30 술포닐기, 치환 또는 비치환된 C1 내지 C30 알킬티올기, 치환 또는 비치환된 C6 내지 C30 아릴티올기, 치환 또는 비치환된 C1 내지 C30 우레이드기, 할로겐기, 할로겐 함유기, 시아노기, 히드록실기, 아미노기, 니트로기, 카르복실기, 페로세닐기， 또는 아들의 조합이다. Aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or Unsubstituted CI to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen containing Group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, ferrocenyl group, or a combination of sons.
【청구항 2】 [Claim 2]
제 1항에 있어서， The method of claim 1,
상기 화학식 1은 하기 화학식 4 내지 화학식 12 중 어느 하나로 표시되는 화합물: Formula 1 is a compound represented by any one of the following formula 4 to formula 12:
4] [화학식 5] 4] [Formula 5]
[화학식 6] [화학식 7] [Formula 6] [Formula 7 ]
상기 화학식 4 내지 12에서
Χ, Χ1 및 X2는 각각 독립적으로, 0 또는 S 이고, In Chemical Formulas 4 to 12 Χ, Χ 1 and X 2 are each independently 0 or S,
L1 내지 L3은 각각 독립적으로, 단일 결합, 치환 또는 비치환된 C1 내지 C30 알킬렌기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬렌기, 치환 또는 비치환된 C6 내지 C30 아릴렌기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기， 치환 또는 비치환된 C6 내지 C30 아릴렌아민기, 치환 또는 비치환된 C1 내지 C30 알콕실렌기, 치환 또는 비치환된 C1 내지 C30 아릴옥실렌기, 치환 또는 비치환된 C2 내지 C30 알케닐렌기, 치환 또는 비치환된 C2 내지 C30 알키닐렌기， 또는 이들의 조합이고， L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted group A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or unsubstituted A substituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,
R1, R2, R4 내지 R7, Ra 내지 Rg, 및 Ra' 내지 Rg'는 각각 독립적으로， 수소， 중수소, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로고리기， 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C6 내지 C30 아릴아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C2 내지 C30 R 1 , R 2 , R 4 to R 7 , R a to R g , and R a 'to R g' are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy Groups, substituted or unsubstituted C2 to C30
알콕시카르보닐기, 치환 또는 비치환된 C2 내지 C30 알콕시카르보닐아미노기 , 치환 또는 비치환된 C7 내지 C30 아릴옥시카르보닐아미노기, 치환 또는 비치환된 C1 내지 C30 술파모일아미노기， 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기， 치환 또는 비치환된 C3 내지 C40 실릴기, 치환 또는 비치환된 C3 내지 C40 실릴옥시기, 치환 또는 비치환된 C1 내지 C30 아실기, 치환 또는 비치환된 C1 내지 C20 아실옥시기, 치환 또는 비치환된 C1 내지 C20 아실아미노기， 치환 또는 비치환된 C1 내지 C30 술포닐기， 치환 또는 비치환된 C1 내지 C30 알킬티을기, 치환 또는 비치환된 C6 내지 C30 아릴티을기, 치환 또는 비치환된 C1 내지 C30 우레이드기, 할로겐기, 할로겐 함유기, 시아노기， 히드록실기, 아미노기， 니트로기, 카르복실기, 페로세닐기, 또는 이들의 조합이다. Alkoxycarbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30 aryloxycarbonylamino group, substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 Alkenyl groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C3 to C40 silyl groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted or unsubstituted C1 to C30 acyl groups, substituted or Unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthi group, substituted or unsubstituted C6 To C30 arylthiyl group, substituted or unsubstituted C1 to C30 ureide group, halogen group, halogen-containing group, cyano group, hydroxyl group, amino group, nitro group, carboxyl group, ferro Group, or a combination thereof.
【청구항 3 ] [Claim 3]
거 1 1항에 있어서, The method of claim 1,
상기 R2 및 R3는 각각 독립적으로 하기 그룹 I에 나열된 치환 또는 R 2 and R 3 are each independently a substituent listed in Group I or
비치환된 기에서 선택되고, Selected from unsubstituted groups,
R2 및 R3 중 적어도 하나는 하기 그룹 1 -1에 나열된 치환 또는 비치환된 기에서 선택된 하나인 화합물:
[그룹 I At least one of R 2 and R 3 is one selected from the substituted or unsubstituted groups listed in Group 1-1 below: [Group I
상기 그룹 I 및 1 -1에서， In groups I and 1-1,
X 및 W는 각각 독립적으로， 0 또는 S이고， X and W are each independently 0 or S,
R 및 R'은 각각 독립적으로 수소， 중수소， 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 헤테로고리기, 또는 이들의 조합이고, R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof ,
*는 연결 지점이다. * Is the connection point.
【청구항 4】
제 1항에 있어서, [Claim 4] The method of claim 1,
상기 R1은 치환'또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로고리기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 이들의 조합인 화합물. Wherein R 1 represents a substituted 'or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1-C30 heterocyclic group, a substituted or unsubstituted unsubstituted C6 to C30 aryl group, or Compounds which are combinations of these.
【청구항 5】 [Claim 5]
거 U항에 있어서, In U,
상기 R1은 메틸기, 에틸기, 치환 또는 비치환된 사이클로펜틸기, 치환 또는 비치환된 사이클로핵실기, 치환 또는 비치환된 페닐기， 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 피리딜기, 치환 또는 비치환된 퓨라닐기, 치환 또는 비치환된 티오페닐기, 치환 또는 비치환된 R 1 is a methyl group, an ethyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclonuclear group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substitution Or unsubstituted pyridyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted
퀴놀리닐기， 또는 이들의 조합인 화합물. A quinolinyl group, or a combination thereof.
【청구항 6] [Claim 6]
제 1항에 있어서， The method of claim 1,
상기 R1은 메틸기, 에틸기, 또는 하기 그룹 Π에 나열된 기에서 선택된 하나인 화합물:R 1 is a compound selected from a methyl group, an ethyl group, or a group listed in the following group Π:
그룹 Π ] Group Π]
상기 그룹 Π에서, In the group Π,
*는 연결 지점이다. * Is the connection point.
【청구항 7] [Claim 7]
제 1항에 있어서, The method of claim 1,
상기 L1 내지 L3은각각 독립적으로，단일결합, 치환 또는 비치환된 페닐렌기, 치환 또는 비치환된 바이페닐렌기, 치환 또는 비치환된 나프틸렌기, 치환 또는
비치환된 피리딜렌기, 치환 또는 비치환된 피리미딜렌기, 치환 또는 비치환된 벤조퓨라닐렌기， 또는 이들의 조합인 화합물. L 1 to L 3 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or A compound which is an unsubstituted pyridylene group, a substituted or unsubstituted pyrimidylene group, a substituted or unsubstituted benzofuranylene group, or a combination thereof.
【청구항 8】 [Claim 8]
제 1항에 있어서, The method of claim 1,
상기 L1 내지 L3은각각 독립적으로,단일결합, 또는 하기 그룹 m에 나열된 치환 또는 비치환된 기에서 선택된 하나인 화합물: Wherein L 1 to L 3 are each independently a single bond or one selected from substituted or unsubstituted groups listed in group m:
[그룹 m]
[Group m]
상기 그룹 in에서, In the group in,
*는 연결 지점이다. * Is the connection point.
【청구항 9】 [Claim 9]
게 1항에 있어서， According to claim 1,
상기 화학식 1로 표시되는 화합물은 하기 화학식 A-5 내지 A-32, A-49 내^ A-76, A-137 내지 A-164, 및 B-1 내지 B-24에서 선택된 하나인 화합물: Compound represented by Formula 1 is a compound selected from the following formula A-5 to A-32, A-49 ^ A-76, A-137 to A-164, and B-1 to B-24:
[A-5] [A-6] [A-7] [A-8] [A-5] [A-6] [A-7] [A-8]
-v] [£i- [ -v] [ -v] -v] [£ i- [-v] [-v]
[9ΐ-ν] [g i-v] [w-v] [π-ν] [9ΐ-ν] [g i-v] [w-v] [π-ν]
[ζ\-γ] [π-ν] [οι-ν] [6-ν] [ζ \ -γ] [π-ν] [οι-ν] [6-ν]
0808
.9C00/ST0ZaM/X3d 01?9ΐ7 .ΐ/£ΐΟΖ OAV
-25] -26] [A-27] [A-28]
.9C00 / ST0ZaM / X3d 01? 9ΐ7 .ΐ / £ ΐΟΖ OAV -25] -26] [A-27] [A-28]
-32]
-32]
[A-49] [A-50] [A-51] [A-52]
[A-49] [A-50] [A-51] [A-52]
[A-53] [A-54] [A-55] [A-56]
82
[A-53] [A-54] [A-55] [A-56] 82
_:Ov kn:-v8£5χ ιπνι--- _ : O v k n : -v 8 £ 5χ ι πν ι ---
//:/ O 8/-9soSSSMl>d OSSJSSZAV // : / O 8 / -9 s oS SSMl> d O SSJSSZAV
85
85
【청구항 10] [Claim 10]
제 1항에 있어서, The method of claim 1,
상기 화학식 1로 표시되는 화합물은 하기 화학식 C-1 내지 C-48 D-1 내지 D- 8, D-17 내지 D-24, 및 E-1 내지 E-4, E-9 내지 E-16에서 선택된 하나인 화합물: Compound represented by Formula 1 is represented by the following formula C-1 to C-48 D-1 to D-8, D-17 to D-24, and E-1 to E-4, E-9 to E-16 One selected compound:
-1] [C-2] [C-3] [C-4] -1] [C-2] [C-3] [C-4]
[C-9] [C-10] [C-l l] [C-12] [C-9] [C-10] [C-l l] [C-12]
-D] [9trO] [ξ -D] -D] [9trO] [ξ -D]
-D] ii -D] [ZP-D] [Tt-3]
-D] ii -D] [ZP-D] [Tt-3]
[017- ] [6i-D] [8£-3] [Li-D] [017-] [6i-D] [8 £ -3] [Li-D]
-D] ζΖ-D] [εε-3]
-D] ζΖ-D] [εε-3]
[ZZ-D] [\Z-D] [οε- ] [6Z-D] [ZZ-D] [\ Z-D] [οε-] [6Z-D]
8888
.9C00/ST0ZaM/X3d Ol79l7.l/SlOZ OAV
.9C00 / ST0ZaM / X3d Ol79l7.l / SlOZ OAV
-9] [E-10] [E-l l] [E-12] -9] [E-10] [E-l l] [E-12]
【청구항 11】 [Claim 11]
게 1항 내지 제 10항 중 어느 한 항에 따른 화합물은 유기 광전자 소자용^ 화합물. The compound according to any one of claims 1 to 10 is for an organic optoelectronic device ^ compound.
【청구항 12】 . [Claim 12].
서로 마주하는 양극과 음극, 및 An anode and a cathode facing each other, and
상기 양극과 상기 음극 사이에 위치하는 적어도 한 층의 유기층을 포함하고 상기 유기층은, At least one organic layer positioned between the anode and the cathode, wherein the organic layer is
발광층, 및 Light emitting layer, and
정공 주입층, 정공 수송충, 전자 차단층, 전자 수송층, 전자 주입층 및 정공 차단층에서 선택된 적어도 하나의 보조층을 포함하고, At least one auxiliary layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer and a hole blocking layer,
상기 보조층은 상기 제 1항 내지 제 10항 중 어느 한 항에 따른 화합물을 포함하는 유기 광전자 소자. The auxiliary layer is an organic optoelectronic device comprising a compound according to any one of claims 1 to 10.
【청구항 13】 [Claim 13]
제 12항에 있어서， The method of claim 12,
상기 보조층은 발광층에 인접한 보조정공수송층을 더 포함하고, The auxiliary layer further includes an auxiliary hole transport layer adjacent to the light emitting layer,
상기 보조정공수송층은 상기 게 1항 내지 제 10항 중 어느 한 항에 따른 화합물을 포함하는 유기 광전자 소자. The auxiliary hole transport layer is an organic optoelectronic device comprising a compound according to any one of claims 1 to 10.
【청구항 14】 [Claim 14]
제 12항에 있어서，
상기 화합물은 형광 재료로서 포함되는 유기 광전자 소자. The method of claim 12, The compound is an organic optoelectronic device included as a fluorescent material.
【청구항 15】 [Claim 15]
제 14항에 있어서, The method of claim 14,
상기 형광 재료는 최대 발광 파장이 550 nm이하인 유기 광전자 소자. The fluorescent material is an organic optoelectronic device having a maximum emission wavelength of 550 nm or less.
【청구항 16】 [Claim 16]
제 1항에 있어서, The method of claim 1,
상기 화학식 1로 표시되는 화합물의 HOMO 준위는 5.4eV 이상 5.8eV 이하인 유기광전자소자. HOMO level of the compound represented by the formula (1) is more than 5.4eV 5.8eV organic optoelectronic device.
【청구항 17】 [Claim 17]
제 1항에 있어서, The method of claim 1,
상기 화학식 1로 표시되는 화합물의 3중항 여기에너지 (T1 )는 2.4eV 이상 2.7eV 이하인 것인 유기광전자소자. The triplet excitation energy (T1) of the compound represented by Formula 1 is 2.4eV or more and 2.7eV or less.
[청구항 18】 [Claim 18]
제 12항에 따른 유기 광전자 소자를 포함하는 표시장치 .
A display device comprising the organic optoelectronic device of claim 12.
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| CN201580019167.5A CN106164061B (en) | 2014-05-13 | 2015-04-13 | Compound for organic photoelectric device, and display device |
| EP15791911.9A EP3144301B1 (en) | 2014-05-13 | 2015-04-13 | Compound, organic optoelectronic element comprising same and display device thereof |
| US15/117,753 US11563179B2 (en) | 2014-05-13 | 2015-04-13 | Compound, organic optoelectronic element comprising same and display device thereof |
| JP2016566263A JP6575969B2 (en) | 2014-05-13 | 2015-04-13 | Compound, organic optoelectronic device including the same, and display |
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| KR20140057324 | 2014-05-13 | ||
| KR10-2014-0057324 | 2014-05-13 | ||
| KR10-2015-0051095 | 2015-04-10 | ||
| KR1020150051095A KR101931250B1 (en) | 2014-05-13 | 2015-04-10 | Compound, organic optoelectric device and display device |
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| WO2015174640A1 true WO2015174640A1 (en) | 2015-11-19 |
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| JP2017109992A (en) * | 2015-12-15 | 2017-06-22 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Amine compound and organic electroluminescent element comprising the same |
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