KR20120116269A - Novel compounds for organic electronic material and organic electroluminescence device using the same - Google Patents
Novel compounds for organic electronic material and organic electroluminescence device using the same Download PDFInfo
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- KR20120116269A KR20120116269A KR1020110033910A KR20110033910A KR20120116269A KR 20120116269 A KR20120116269 A KR 20120116269A KR 1020110033910 A KR1020110033910 A KR 1020110033910A KR 20110033910 A KR20110033910 A KR 20110033910A KR 20120116269 A KR20120116269 A KR 20120116269A
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- KR
- South Korea
- Prior art keywords
- substituted
- unsubstituted
- compound
- alkyl
- organic
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 140
- 239000012776 electronic material Substances 0.000 title claims abstract description 22
- 238000005401 electroluminescence Methods 0.000 title abstract description 3
- 239000002019 doping agent Substances 0.000 claims abstract description 22
- 239000011368 organic material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 39
- -1 cyano, carbazolyl Chemical group 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 16
- 229910052805 deuterium Inorganic materials 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000005104 aryl silyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 125000002950 monocyclic group Chemical group 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000001769 aryl amino group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052717 sulfur Chemical group 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 2
- 125000005549 heteroarylene group Chemical group 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 125000006822 tri(C1-C30) alkylsilyl group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 125000005566 carbazolylene group Chemical group 0.000 claims 1
- 125000005584 chrysenylene group Chemical group 0.000 claims 1
- 125000005567 fluorenylene group Chemical group 0.000 claims 1
- 125000004957 naphthylene group Chemical group 0.000 claims 1
- 125000005565 oxadiazolylene group Chemical group 0.000 claims 1
- 125000005564 oxazolylene group Chemical group 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 125000005550 pyrazinylene group Chemical group 0.000 claims 1
- 125000005548 pyrenylene group Chemical group 0.000 claims 1
- 125000005551 pyridylene group Chemical group 0.000 claims 1
- 125000005576 pyrimidinylene group Chemical group 0.000 claims 1
- 125000006836 terphenylene group Chemical group 0.000 claims 1
- 125000005557 thiazolylene group Chemical group 0.000 claims 1
- 125000005730 thiophenylene group Chemical group 0.000 claims 1
- 125000005559 triazolylene group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 61
- 238000004519 manufacturing process Methods 0.000 abstract description 52
- 239000000463 material Substances 0.000 abstract description 40
- 239000012044 organic layer Substances 0.000 abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 13
- 239000008213 purified water Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 235000019439 ethyl acetate Nutrition 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- TUQSVSYUEBNNKQ-UHFFFAOYSA-N 2,4-dichloroquinazoline Chemical compound C1=CC=CC2=NC(Cl)=NC(Cl)=C21 TUQSVSYUEBNNKQ-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000001665 trituration Methods 0.000 description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 0 C*(cc1)cc(c2cc(-c3ccccc3)ccc22)c1[n]2-c1ccccc1 Chemical compound C*(cc1)cc(c2cc(-c3ccccc3)ccc22)c1[n]2-c1ccccc1 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- ASGMFNBUXDJWJJ-JLCFBVMHSA-N (1R,3R)-3-[[3-bromo-1-[4-(5-methyl-1,3,4-thiadiazol-2-yl)phenyl]pyrazolo[3,4-d]pyrimidin-6-yl]amino]-N,1-dimethylcyclopentane-1-carboxamide Chemical compound BrC1=NN(C2=NC(=NC=C21)N[C@H]1C[C@@](CC1)(C(=O)NC)C)C1=CC=C(C=C1)C=1SC(=NN=1)C ASGMFNBUXDJWJJ-JLCFBVMHSA-N 0.000 description 4
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 4
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 4
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 4
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 4
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229940126639 Compound 33 Drugs 0.000 description 4
- 229940127007 Compound 39 Drugs 0.000 description 4
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 229940126543 compound 14 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940125878 compound 36 Drugs 0.000 description 4
- 229940125807 compound 37 Drugs 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 3
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 3
- CEUHUKZKJZSAPU-UHFFFAOYSA-N NC(CCCC1)C1C(C1C=CC(c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)=CC1)[Mn] Chemical compound NC(CCCC1)C1C(C1C=CC(c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)=CC1)[Mn] CEUHUKZKJZSAPU-UHFFFAOYSA-N 0.000 description 3
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
- 150000004770 chalcogenides Chemical class 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- 229940126086 compound 21 Drugs 0.000 description 3
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 3
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 2
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-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
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006654 (C3-C12) heteroaryl group Chemical group 0.000 description 1
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- TWOIWLFSUGLFHY-UHFFFAOYSA-N 1,4-diphenylbenzimidazole Chemical compound C1=NC2=C(C=3C=CC=CC=3)C=CC=C2N1C1=CC=CC=C1 TWOIWLFSUGLFHY-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-M 4-phenylphenolate Chemical compound C1=CC([O-])=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-M 0.000 description 1
- ZCUPSHZNFJPULB-UHFFFAOYSA-N C(CC1)CC(C2C3)=C1NC2C=CC3c(cc1)cc2c1[o]c1ccccc21 Chemical compound C(CC1)CC(C2C3)=C1NC2C=CC3c(cc1)cc2c1[o]c1ccccc21 ZCUPSHZNFJPULB-UHFFFAOYSA-N 0.000 description 1
- UTKOSVNHQBEKNR-UHFFFAOYSA-N C(CC1)CC(C2C3)=C1NC2C=CC3c(cc1)cc2c1[s]c1ccccc21 Chemical compound C(CC1)CC(C2C3)=C1NC2C=CC3c(cc1)cc2c1[s]c1ccccc21 UTKOSVNHQBEKNR-UHFFFAOYSA-N 0.000 description 1
- SALKGZPYZJYHMX-UHFFFAOYSA-N C(CC1)CC2=C1NC1C=CC(c(cc3)cc4c3[s]c3ccccc43)=CC21 Chemical compound C(CC1)CC2=C1NC1C=CC(c(cc3)cc4c3[s]c3ccccc43)=CC21 SALKGZPYZJYHMX-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- HNYNOKDUWSXYIX-UHFFFAOYSA-N CC1(C)c(ccc(C2C=CC3NC(CCCC4)=C4C3C2)c2)c2-c2ccccc12 Chemical compound CC1(C)c(ccc(C2C=CC3NC(CCCC4)=C4C3C2)c2)c2-c2ccccc12 HNYNOKDUWSXYIX-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- YCAIECYQFONUCH-UHFFFAOYSA-N NC(CCCC1)C1C(C1C=CC(c(cc2)cc(c3ccc(CCC=C4)c4c33)c2[n]3-c2ccccc2)=CC1)[Mn] Chemical compound NC(CCCC1)C1C(C1C=CC(c(cc2)cc(c3ccc(CCC=C4)c4c33)c2[n]3-c2ccccc2)=CC1)[Mn] YCAIECYQFONUCH-UHFFFAOYSA-N 0.000 description 1
- QWKFYAGZLGBCIE-UHFFFAOYSA-N OC(C(BC=C1)=C1C1=COC=C1)=O Chemical compound OC(C(BC=C1)=C1C1=COC=C1)=O QWKFYAGZLGBCIE-UHFFFAOYSA-N 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- HSSPXXSSTKINGH-UHFFFAOYSA-L dilithium quinoline-2-carboxylate Chemical compound N1=C(C=CC2=CC=CC=C12)C(=O)[O-].[Li+].[Li+].N1=C(C=CC2=CC=CC=C12)C(=O)[O-] HSSPXXSSTKINGH-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical class [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 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 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl 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
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
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Abstract
Description
본 발명은 신규한 유기 전자재료용 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel compound for organic electronic materials and an organic electroluminescent device comprising the same.
표시 소자 중, 전기 발광 소자(electroluminescence device: EL device)는 자체 발광형 표시 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다. 1987년 이스트만 코닥(Eastman Kodak)사는 발광층 형성용 재료로서 저분자인 방향족 디아민과 알루미늄 착물을 이용하고 있는 유기 EL 소자를 처음으로 개발하였다[Appl. Phys. Lett. 51, 913, 1987].Among the display elements, an electroluminescence device (EL device) is a self-luminous display element and has advantages of wide viewing angle, excellent contrast, and fast response speed. In 1987, Eastman Kodak developed for the first time an organic EL device using a low molecular weight aromatic diamine and an aluminum complex as a material for forming a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].
OLED에서 발광 효율을 결정하는 가장 중요한 요인은 발광 재료이다. 발광 재료로는 현재까지 형광 재료가 널리 사용되고 있으나, 전기발광의 메커니즘 상 인광 재료의 개발은 이론적으로 4배까지 발광 효율을 개선시킬 수 있는 가장 좋은 방법 중 하나이다. 현재까지 이리듐(III)착물 계열이 인광 발광 재료로 널리 알려져 있으며, 각 RGB 별로는 (acac)Ir(btp)2, Ir(ppy)3 및 Firpic 등의 재료가 알려져 있다. 특히, 최근 일본, 구미에서 많은 인광 재료들이 연구되고 있다.The most important factor determining the luminous efficiency in OLEDs is the luminous material. Fluorescent materials are widely used as the light emitting materials to date, but the development of phosphorescent materials is one of the best ways to improve the luminous efficiency theoretically up to 4 times. To date, iridium (III) complexes are widely known as phosphorescent materials, and for each RGB, materials such as (acac) Ir (btp) 2 , Ir (ppy) 3, and Firpic are known. In particular, many phosphorescent materials have recently been studied in Japan and Europe.
인광 발광체의 호스트 재료로는 현재까지 CBP가 가장 널리 알려져 있고, BCP 및 BAlq 등의 정공차단층을 적용한 고효율의 OLED가 공지되어 있으며, 일본의 파이오니어 등에서는 BAlq 유도체를 호스트로 이용해 고성능의 OLED를 개발한 바 있다.CBP is the most widely known host material for phosphorescent emitters. To date, high-efficiency OLEDs with hole blocking layers such as BCP and BAlq have been known. In Japan, Pioneer has developed high-performance OLEDs using BAlq derivatives as hosts. I've done it.
그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮고 열적 안정성이 매우 좋지 않아서, 진공 하에서 고온 증착 공정을 거칠 때, 물질이 변하는 단점을 갖고 있다. OLED에서 전력효율 = [(π/전압) × 전류효율]의 관계에 있으므로 전력 효율은 전압에 반비례하고, 따라서 OLED의 소비 전력을 낮으려면 전력 효율을 높여야 한다. 실제 인광 발광 재료를 사용한 OLED는 형광 발광 재료를 사용한 OLED에 비해 전류 효율(cd/A)이 상당히 높으나, 인광 발광 재료의 호스트로 사용되던 BAlq 또는 CBP와 같은 종래재료의 경우, 형광재료를 사용한 OLED에 비해 구동 전압이 높아서 전력 효율(lm/w)면에서 큰 이점이 없었다. 또한, OLED 소자에 사용할 경우 수명 측면에서도 만족스럽지 못하였다.However, existing materials have advantages in terms of luminescence properties, but the glass transition temperature is low and the thermal stability is not very good, so that the material changes when undergoing a high temperature deposition process under vacuum. In the relationship of power efficiency = [(π / voltage) × current efficiency] in OLED, power efficiency is inversely proportional to voltage. Therefore, to lower the power consumption of OLED, power efficiency must be increased. In fact, OLEDs using phosphorescent materials have considerably higher current efficiency (cd / A) than OLEDs using fluorescent materials, but in the case of conventional materials such as BAlq or CBP used as a host of phosphorescent materials, OLEDs using fluorescent materials Compared with the higher driving voltage, there was no significant advantage in terms of power efficiency (lm / w). In addition, when used in OLED devices, it was not satisfactory in terms of lifetime.
한편, 국제특허공보 제WO 2006/049013호에는 축합 이환기를 골격으로 하는 유기 전기 발광 소재용 화합물을 언급하고 있다. 그러나, 상기 문헌에는 카바졸 골격의 9번, 3번위치에 각각 방향족 고리가 융합된 헤테로시클로알킬 또는 시클로알킬이 치환된 질소 함유 축합 이환기 및 방향족 고리가 융합된 헤테로시클로알킬 또는 시클로알킬기를 모두 겸비한 화합물을 개시하고 있지 않다. On the other hand, International Patent Publication No. WO 2006/049013 mentions a compound for an organic electroluminescent material having a condensed bicyclic group as a skeleton. However, this document combines both a heterocycloalkyl or a cycloalkyl-substituted nitrogen-containing condensed bicyclic group in which the aromatic ring is fused at positions 9 and 3 of the carbazole skeleton, and a heterocycloalkyl or cycloalkyl group in which the aromatic ring is fused. No compound is disclosed.
따라서 본 발명의 목적은 첫째로, 상기한 문제점들을 해결하기 위하여 기존의 재료보다 발광 효율 및 소자 수명이 좋으며, 적절한 색좌표를 갖는 우수한 골격의 유기 전자재료용 화합물을 제공하는 것이며 둘째로, 상기 유기 전자재료용 화합물을 발광 재료로서 채용하는 고효율 및 장수명의 유기 전계 발광 소자를 제공하는 것이다. Accordingly, an object of the present invention is to firstly provide a compound for organic electronic material having a good skeleton having an excellent luminous efficiency and device life, and having an appropriate color coordinate, in order to solve the above problems. It is to provide a high efficiency and long life organic electroluminescent element employing a compound for a material as a light emitting material.
본 발명은 하기 화학식 1로 표시되는 유기 전자재료용 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로서, 본 발명에 따른 유기 전자재료용 화합물은 기존 재료에 비해 발광 효율이 좋고 재료의 수명특성이 뛰어나 소자의 구동수명이 매우 우수할 뿐만 아니라 전력효율의 상승을 유도하여 소비전력이 개선된 OLED 소자를 제조할 수 있는 장점이 있다.The present invention relates to a compound for an organic electronic material represented by the following formula (1) and an organic electroluminescent device comprising the same, the compound for an organic electronic material according to the present invention has better luminous efficiency and excellent life characteristics of the material than the conventional material The driving life of the device is very excellent and there is an advantage of manufacturing an OLED device with improved power consumption by inducing an increase in power efficiency.
[화학식 1] [Formula 1]
상기 화학식 1에서,In Formula 1,
L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환된 (C5-C30)헤테로아릴렌, 치환 또는 비치환된 (C6-C30)아릴렌, 치환 또는 비치환된 (C6-C30)시클로알킬렌이고;L 1 and L 2 are each independently a single bond, substituted or unsubstituted (C5-C30) heteroarylene, substituted or unsubstituted (C6-C30) arylene, substituted or unsubstituted (C6-C30) cyclo Alkylene;
X1은 CH 또는 N이며;X 1 is CH or N;
Y1 및 Y2는 각각 독립적으로 -O-, -S-, -CR8R9- 또는 -NR10-이고;Y 1 and Y 2 are each independently —O—, —S—, —CR 8 R 9 —, or —NR 10 —;
R1 내지 R10은 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아르(C1-C30)알킬, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 5원 내지 7원의 헤테로시클로알킬이거나 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 (C3-C30)시클로알킬, -NR21R22, -SiR23R24R25, -SR26, -OR27, (C2-C30)알케닐, (C2-C30)알키닐, 시아노, 니트로 또는 히드록시이거나 인접한 치환체와 융합고리를 포함하거나 포함하지 않는 치환 또는 비치환된 (C3-C30)알킬렌 또는 치환 또는 비치환된 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있고, 상기 형성된 지환족 고리 및 단일환 또는 다환의 방향족 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있으며;R 1 to R 10 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, cycloalkyl At least one fused substituted or unsubstituted (C6-C30) aryl, a 5 to 7 membered heterocycloalkyl fused at least one substituted or unsubstituted aromatic ring, or at least one fused substituted or unsubstituted aromatic ring (C3-C30) cycloalkyl, -NR 21 R 22 , -SiR 23 R 24 R 25 , -SR 26 , -OR 27, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, Substituted or unsubstituted (C3-C30) alkylene or substituted or unsubstituted (C3-C30) with or without nitro or hydroxy or with a fused ring with adjacent substituents May be linked to alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, wherein the carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring are one or more selected from nitrogen, oxygen, and sulfur May be substituted with a heteroatom;
상기 R21 내지 R27은 상기 R1 내지 R10의 정의와 동일하며,R 21 to R 27 are the same as the definitions of R 1 to R 10 ,
a, b, e, g는 각각 독립적으로 1 내지 4의 정수이며, a, b, g, e가 2이상의 정수인 경우 동일하거나 상이할수 있고; a, b, e and g are each independently integers of 1 to 4, and may be the same or different when a, b, g and e are integers of 2 or more;
c, d, f는 각각 독립적으로 1 내지 3의 정수이며, c, d, f가 2이상의 정수인 경우 동일하거나 상이할수 있고; c, d and f are each independently integers of 1 to 3, and may be the same or different when c, d and f are integers of 2 or more;
상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.The heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.
본 발명에 기재된 「알킬」, 「알콕시」 및 그 외 「알킬」부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하고, 「시클로알킬」은 단일 고리계 뿐만 아니라 치환 또는 비치환된 아다만틸 또는 치환 또는 비치환된 (C7-C30)바이시클로알킬과 같은 여러 고리계 탄화수소도 포함한다. 본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로서 페닐, 나프틸, 비페닐, 터페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴, 트리페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등이 있다. 상기 나프틸은 1-나프틸 및 2-나프틸을 포함하며, 안트릴은 1-안트릴, 2-안트릴 및 9-안트릴을 포함하며, 플루오레닐은 1-플루오레닐, 2-플루오레닐, 3-플루오레닐, 4-플루오레닐 및 9-플루오레닐을 모두 포함한다. 본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P(=O), Si 및 P로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연결된 형태도 포함한다. 상기 헤테로아릴기는 고리내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적인 예로서 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴, 다이벤조퓨란닐, 다이벤조싸이오페닐 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 들수 있다.Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, and "cycloalkyl" is not only a monocyclic system but also substituted or unsubstituted adamantyl Or several ring-based hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. "Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like. There is this. Said naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. "Heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Means an aryl group, 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, Monocyclic heteroaryl such as tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoiso Thiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnaolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenantri Polycyclic heteroaryls such as dinyl, benzodioxyl, dibenzofuranyl, dibenzothiophenyl and their corresponding N-oxides (e.g. pyridyl N-oxides, quinolyl N-oxides), Quaternary salts;
또한, 본 발명에 기재되어 있는 '(C1-C30)알킬'기는 바람직하게는 (C1-C20)알킬이고, 더 바람직하게는 (C1-C10)알킬이며, '(C6-C30)아릴'기는 바람직하게는 (C6-C20)아릴이고, 더 바람직하게는 (C6-C12)아릴이다. '(C3-C30)헤테로아릴'기는 바람직하게는 (C3-C20)헤테로아릴이고, 더 바람직하게는 (C3-C12)헤테로아릴이다. '(C3-C30)시클로알킬'기는 바람직하게는 (C3-C20)시클로알킬이고, 더 바람직하게는 (C3-C7)시클로알킬이다. '(C2-C30)알케닐 또는 알키닐'기는 바람직하게는 (C2-C20)알케닐 또는 알키닐이고, 더 바람직하게는 (C2-C10)알케닐 또는 알키닐이다.Further, the '(C1-C30) alkyl' group described in the present invention is preferably (C1-C20) alkyl, more preferably (C1-C10) alkyl, and the '(C6-C30) aryl' group is preferred. Preferably (C6-C20) aryl, more preferably (C6-C12) aryl. The '(C3-C30) heteroaryl' group is preferably (C3-C20) heteroaryl, more preferably (C3-C12) heteroaryl. The '(C3-C30) cycloalkyl' group is preferably (C3-C20) cycloalkyl, more preferably (C3-C7) cycloalkyl. The '(C2-C30) alkenyl or alkynyl' group is preferably (C2-C20) alkenyl or alkynyl, more preferably (C2-C10) alkenyl or alkynyl.
또한 본 발명에 기재되어 있는 "치환 또는 비치환"이라는 기재에서 '치환'은 비치환된 치환기에 더 치환되는 경우를 뜻하며, 상기 L1 및 L2, R1 내지 R10 및 R21 내지 R27에 더 치환되는 치환기는 서로 독립적으로 중수소, 할로겐, (C1-C30)알킬, 할로겐이 치환된 (C1-C30)알킬, (C6-C30)아릴, (C5-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C5-C30)헤테로아릴, (C3-C30)시클로알킬, 헤테로시클로알킬, (C1-C30)알킬실릴, (C6-C30)아릴실릴, (C1-C30)알킬(C6-C30)아릴실릴, (C2-C30)알케닐, (C6-C30)알키닐, 시아노, 카바졸릴, (C1-C30)알킬아미노, (C6-C30)아릴아미노, (C1-C30)알킬(C6-C30)아릴아미노, (C6-C30)아릴보로닐, (C1-C30)알킬보로닐, (C1-C30)알킬(C6-C30)아릴보로닐, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, 카르보닐, 카르복실, 니트로 또는 히드록시로 이루어진 군으로부터 선택되는 하나 이상인 것을 의미한다.In addition, in the description of "substituted or unsubstituted" described in the present invention, 'substituted' means a case where it is further substituted with an unsubstituted substituent, the L 1 and L 2, R 1 to R 10 and R 21 to R 27 Substituents further substituted with each other independently are deuterium, halogen, (C1-C30) alkyl, halogen-substituted (C1-C30) alkyl, (C6-C30) aryl, (C5-C30) heteroaryl, (C6-C30 Aryl-substituted (C5-C30) heteroaryl, (C3-C30) cycloalkyl, heterocycloalkyl, (C1-C30) alkylsilyl, (C6-C30) arylsilyl, (C1-C30) alkyl (C6- C30) arylsilyl, (C2-C30) alkenyl, (C6-C30) alkynyl, cyano, carbazolyl, (C1-C30) alkylamino, (C6-C30) arylamino, (C1-C30) alkyl ( C6-C30) arylamino, (C6-C30) arylboronyl, (C1-C30) alkylboronyl, (C1-C30) alkyl (C6-C30) arylboronyl, (C6-C30) At least one selected from the group consisting of C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carbonyl, carboxyl, nitro or hydroxy It means.
더욱 구체적으로 상기 
본 발명에 따른 유기 전자재료용 화합물로는 대표적으로 하기의 화합물을 들 수 있다.Typical compounds for organic electronic materials according to the present invention include the following compounds.
본 발명에 따른 유기 전자재료용 화합물은 하기 반응식에 나타난 바와 같이 제조될 수 있다.The compound for an organic electronic material according to the present invention can be prepared as shown in the following scheme.
상기 반응식 1에서, R1 내지 R7, Y1 내지 Y2, X1, L1 내지 L2 , a, b, c, d, e, f 및 g는 화학식 1에서의 정의와 동일하고, X는 할로겐이다.In Scheme 1, R 1 to R 7 , Y 1 to Y 2 , X 1 , L 1 To L 2 , a, b, c, d, e, f and g are as defined in Formula 1, and X is halogen.
또한, 본 발명은 유기 전계 발광 소자를 제공하며, 본 발명에 따른 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극 및 제2전극 사이에 개재되는 1층 이상의 유기물층을 갖는 유기 전계 발광 소자에 있어서, 상기 유기물층은 상기 화학식 1의 화합물을 하나 이상 포함한다. 또한 상기 유기물층은 발광층을 포함하고, 이 발광층에서 상기 화학식 1의 화합물을 호스트 물질로 사용할 수 있다. In addition, the present invention provides an organic electroluminescent device, the organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one compound represented by Chemical Formula 1. The organic material layer may include a light emitting layer, and the compound of Formula 1 may be used as a host material in the light emitting layer.
또한 본 발명에 따른 호스트와 함께 사용되는 유기 전계 발광 소자용 인광 도판트에는 대표적으로 하기 화학식 2의 화합물이 있다. In addition, a phosphorescent dopant for an organic electroluminescent device used with a host according to the present invention typically includes a compound represented by the following Chemical Formula 2.
[화학식 2][Formula 2]
MM 1One LL 101101 LL 102102 LL 103103
상기 화학식 2에서,In Formula 2,
M1은 Ir, Pt, Pd, Os으로 이루어진 군으로부터 선택되고;M 1 is selected from the group consisting of Ir, Pt, Pd, Os;
리간드 L101, L102 및 L103 는 서로 독립적으로 하기 구조로부터 선택된다.The ligands L 101 , L 102 and L 103 are independently selected from the following structures.
R201 내지 R203은 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬, (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴 또는 할로겐이고;R 201 to R 203 independently represent hydrogen, deuterium, (C 1 -C 30) alkyl in which the halogen is optionally substituted (C 1 -C 30) alkyl, (C 6 -C 30) aryl or halogen in which the (C 1 -C 30) alkyl is optionally substituted;
R204 내지 R219는 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C1-C30)알콕시, 치환 또는 비치환된(C3-C30)시클로알킬, 치환 또는 비치환된(C2-C30)알케닐, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된 모노 또는 치환 또는 비치환된 디-(C1-C30)알킬아미노, 치환 또는 비치환된 모노 또는 디-(C6-C30)아릴아미노, SF5, 치환 또는 비치환된 트리(C1-C30)알킬실릴, 치환 또는 비치환된 디(C1-C30)알킬(C6-C30)아릴실릴, 치환 또는 비치환된 트리(C6-C30)아릴실릴, 시아노 또는 할로겐이고;R 204 to R 219 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, Substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted mono or substituted or unsubstituted di- (C1-C30) alkylamino, substituted or unsubstituted Substituted mono or di- (C6-C30) arylamino, SF 5 , substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl , Substituted or unsubstituted tri (C6-C30) arylsilyl, cyano or halogen;
R220 내지 R223는 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬 또는 (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴이고;R 220 to R 223 are each independently hydrogen, deuterium, (C1-C30) alkyl with or without halogen, or (C6-C30) aryl with or without (C1-C30) alkyl;
R224 및 R225는 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이거나, R224와 R225는 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성하며; R 224 and R 225 are independently of each other hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R 224 and R 225 contain fused rings Linked with (C3-C12) alkylene or (C3-C12) alkenylene with or without formation to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
R226은 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된(C5-C30)헤테로아릴 또는 할로겐이고;R 226 is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C5-C30) heteroaryl or halogen;
R227 내지 R229은 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이고;R 227 to R 229 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen;
Q는 
구체적으로 상기 화학식 2의 도판트 화합물로서 다음과 같은 화합물을 사용하는 것이 바람직하다. Specifically, it is preferable to use the following compounds as the dopant compound of Chemical Formula 2.
본 발명의 유기 전계 발광 소자는 화학식 1의 화합물을 포함하고, 이와 동시에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 화합물을 포함할 수 있다. The organic electroluminescent device of the present invention includes a compound of Formula 1, and at the same time may include one or more compounds selected from the group consisting of arylamine-based compounds or styrylarylamine-based compounds.
또한, 본 발명의 유기 전계 발광 소자에 있어서, 유기물층에 상기 화학식 1의 화합물 이외에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체화합물을 더 포함할 수도 있고,나아가 상기 유기물층은 발광층 및 전하생성층을 더 포함할 수 있다.In addition, in the organic electroluminescent device of the present invention, the organic material layer is selected from the group consisting of Group 1, Group 2, Group 4, Period 5 transition metals, Lanthanide series metals and organic metals of d-transition elements in addition to the compound of Formula 1 One or more metal or complex compounds may be further included. Furthermore, the organic material layer may further include a light emitting layer and a charge generating layer.
또한, 상기 유기물층은 상기 유기 전자재료용 화합물 이외에 청색, 적색 또는 녹색 발광 화합물을 포함하는 유기발광층 하나 이상을 동시에 포함하여 백색 발광을 하는 유기 전계 발광 소자를 형성할 수 있다. In addition, the organic material layer may include one or more organic light emitting layers including blue, red, or green light emitting compounds in addition to the compound for organic electronic materials to form an organic light emitting device that emits white light.
본 발명의 유기 전계 발광 소자에 있어서, 한 쌍의 전극의 적어도 한쪽의 내측표면에, 칼코제나이드(chalcogenide)층, 할로겐화 금속층 및 금속 산화물층으로부터 선택되는 일층(이하, 이들을 "표면층"이라고 지칭함) 이상을 배치하는 것이 바람직하다. 구체적으로는, 발광 매체층 측의 양극 표면에 규소 및 알루미늄의 금속의 칼코제나이드(산화물을 포함한다)층을, 또한 발광매체층 측의 음극 표면에 할로겐화 금속층 또는 금속 산화물층을 배치하는 것이 바람직하다. 이것에 의해 구동의 안정화를 얻을 수 있다. 상기 칼코제나이드의 바람직한 예로는 SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON 또는 SiAlON 등이 있고, 할로겐화 금속의 바람직한 예로는 LiF, MgF2, CaF2, 불화 희토류 금속 등이 있으며, 금속 산화물의 바람직한 예로는 Cs2O, Li2O, MgO, SrO, BaO, CaO 등이 있다.In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Preferred examples of the chalcogenide include SiO X (1 ≦ X ≦ 2 ), AlO X (1 ≦ X ≦ 1.5), SiON or SiAlON, and preferred examples of the halogenated metal include LiF, MgF 2 , CaF 2 , and fluoride. Rare earth metals and the like, and preferred examples of the metal oxides include Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, and the like.
또한, 본 발명의 유기 전계 발광 소자에 있어서, 이렇게 제작된 한 쌍의 전극의 적어도 한쪽의 표면에 전자 전달 화합물과 환원성 도판트의 혼합 영역 또는 정공 전달 화합물과 산화성 도판트의 혼합 영역을 배치하는 것도 바람직하다. 이러한 방식에 의해 전자 전달 화합물이 음이온으로 환원되므로 혼합 영역으로부터 발광 매체에 전자를 주입 및 전달하기 용이해진다. 또한, 정공 전달 화합물은 산화되어 양이온으로 되므로 혼합 영역으로부터 발광 매체에 정공을 주입 및 전달하기 용이해진다. 바람직한 산화성 도판트로서는 각종 루이스산 및 억셉터(acceptor) 화합물을 들 수 있고, 바람직한 환원성 도판트로는 알칼리 금속, 알칼리 금속 화합물, 알칼리 토류 금속, 희토류 금속 및 이들의 혼합물을 들 수 있다. 또한 환원성 도판트층을 전하생성층으로 사용하여 두 개 이상의 발광층을 가진 백색 유기 전계 발광소자를 제작할 수 있다.In addition, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transport compound and the oxidative dopant is disposed on at least one surface of the pair of electrodes thus fabricated desirable. In this way, the electron transfer compound is reduced to an anion, thereby facilitating injection and transfer of electrons from the mixed region to the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. In addition, a white organic electroluminescent device having two or more light emitting layers may be manufactured using a reducing dopant layer as a charge generating layer.
본 발명에 따른 유기 전자재료용 화합물은 발광 효율이 좋고 재료의 수명특성이 뛰어나 소자의 구동수명이 매우 우수한 OLED 소자를 제조할 수 있는 장점이 있다. The compound for an organic electronic material according to the present invention has an advantage of manufacturing an OLED device having excellent luminous efficiency and excellent lifespan characteristics of the device, and having excellent driving life of the device.
이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 들어 본 발명에 따른 유기 전자 재료용 화합물, 이의 제조방법 및 소자의 발광특성을 설명한다.Hereinafter, a compound for an organic electronic material according to the present invention, a method for preparing the same, and a light emitting property of a device will be described with reference to a representative compound of the present invention for a detailed understanding of the present invention.
[제조예 1] 화합물 2의 제조Preparation Example 1 Preparation of Compound 2
화합물 compound 1-11-1 의 제조Manufacturing
9-phenyl-9H-carbazol-3-ylboronic acid (14g, 48.76mmol), 3-bromo-9H-carbazole (10g, 40.63mmol), K2CO3(13.5g, 97.52mmol), Pd(PPh3)4 (2.35g, 2.03mmol)을 Toluene 200mL, EtOH 50mL, 정제수 50mL 에 투입 후 95℃에서 3시간 동안 교반 하였다. 반응 종결 후 실온으로 냉각 한 뒤 정치하여 수층을 제거 하였다. 유층은 농축 후 MC로 trituration 한 후 여과하여 화합물 1-1(12g, 72%)을 얻었다. 9-phenyl-9H-carbazol-3-ylboronic acid (14g, 48.76mmol), 3-bromo-9H-carbazole (10g, 40.63mmol), K 2 CO 3 (13.5g, 97.52mmol), Pd (PPh 3 ) 4 (2.35 g, 2.03 mmol) was added to 200 mL of Toluene, 50 mL of EtOH, and 50 mL of purified water, followed by stirring at 95 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and left to stand to remove the aqueous layer. The oil layer was concentrated, triturated with MC, and filtered to obtain compound 1-1 (12 g, 72%).
화합물 compound 1-21-2 의 제조Manufacturing
2,4-dichloroquinazoline (30 g, 151 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (15.6 g, 75.3 mmol), Pd(PPh3)4 (2.6 g, 2.3 mmol), Na2CO3 (16g,150mmol)을 Toluene (300ml), 증류수 (75 ml)에 녹인 후 90℃로 2시간 동안 교반하였다. 유기층을 감압증류한 후 MeOH로 trituration 하였다. 얻어진 고체를 MC에 녹여 silica filter한 후 MC와 헥산으로 trituration하여 화합물 1-2(9.3g, 51.4 %)를 얻었다. 2,4-dichloroquinazoline (30 g, 151 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (15.6 g, 75.3 mmol), Pd (PPh 3 ) 4 (2.6 g, 2.3 mmol), Na 2 CO 3 (16g, 150mmol) was dissolved in Toluene (300ml) and distilled water (75ml) and stirred at 90 ° C for 2 hours. The organic layer was distilled under reduced pressure and triturated with MeOH. The obtained solid was dissolved in MC, silica filtered, and triturated with MC and hexane to obtain compound 1-2 (9.3 g, 51.4%).
화합물 compound 22 의 제조Manufacturing
화합물 1-1 (5.3 g, 14.7mmol), 화합물 1-2 (6.4 g, 15.8 mmol)을 DMF 80mL에 현탁한 뒤 60% NaH (948 mg, 22mmol)를 상온에서 투입 하였다. 12시간 동안 교반하였다. 정제수(1L) 투입 후 감압여과하였다. 얻어진 고체를 MeOH/EA로 trituration 하고 MC로 녹여 silica filter한 후 MC/n-Hexane 으로 trituration하여 화합물 2(1.9g, 16.8%)을 얻었다.Compound 1-1 (5.3 g, 14.7 mmol) and compound 1-2 (6.4 g, 15.8 mmol) were suspended in 80 mL of DMF, and 60% NaH (948 mg, 22 mmol) was added at room temperature. Stir for 12 hours. Purified water (1L) and filtered under reduced pressure. The obtained solid was triturated with MeOH / EA, dissolved in MC, silica filtered, and triturated with MC / n-Hexane to obtain Compound 2 (1.9 g, 16.8%).
MS/FAB found 778, calculated 777.91MS / FAB found 778, calculated 777.91
[제조예 2] 화합물 13의 제조Preparation Example 2 Preparation of Compound 13
화합물 compound 2-12-1 의 제조Manufacturing
2,4-디클로로퀴나졸린 50 g (251 mmol) 과 디벤조[b,d]퓨란-4-일보로산 53.2 g (251 mmol)을 톨루엔 1 L, 물 200 mL 혼합용액에 녹인 후 테트라키스트리페닐포스핀 팔라듐 14.5 g (12.5 mmol)과 탄산나트륨 80 g (755 mmol)을 첨가하여 준다. 이 혼합물을 80℃에서 20시간 동안 교반하여 준다. 반응 혼합물을 상온으로 시키고 염화암모늄 수용액 200 mL로 반응을 종결 시킨 시킨 후 에틸아세테이트 1 L 로 추출한 후, 수층은 다시 디클로로메탄 1 L로 추출한다. 유기층을 무수황산마그네슘으로 건조하고, 유기용매는 감압하에서 제거하였다. 얻어진 고체는 실리카겔 로 여과 후 용매는 감압하에서 제게하였다. 얻어진 고체를 EtOAc 100 mL 로 씻어주어 화합물 2-1 (50 g, 74%)을 얻었다.50 g (251 mmol) of 2,4-dichloroquinazoline and 53.2 g (251 mmol) of dibenzo [ b , d ] furan-4-ylborolic acid were dissolved in a mixed solution of 1 L of toluene and 200 mL of water, followed by tetrakistri. 14.5 g (12.5 mmol) of phenylphosphine palladium and 80 g (755 mmol) of sodium carbonate are added. The mixture is stirred at 80 ° C. for 20 hours. The reaction mixture was cooled to room temperature, the reaction was terminated with 200 mL of aqueous ammonium chloride solution, extracted with 1 L of ethyl acetate, and the aqueous layer was extracted with 1 L of dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was filtered through silica gel, and the solvent was removed under reduced pressure. The obtained solid was washed with 100 mL of EtOAc to give compound 2-1 (50 g, 74%).
화합물 compound 1313 의 제조Manufacturing
화합물 1-1 50 g (122 mmol) 을 DMF에 녹인 후 60% NaH 5.9 (148 mmol) 을 천천히 첨가하여 준다. 이 반응 혼합물을 상온에서 1시간동안 교반한 후 화합물 2-1 51 g (147 mmol)을 첨가한다. 전체 반응 혼합물을 상온에서 20 시간 교반하여 준다. 반응 혼합물에 얼음물을 천천히 적가하여 반응을 종결 시킨 후 생성된 고체를 여과하여 얻는다. 얻어진 고체를 물 1 L로 세척하고, MeOH 1 L로 세척하여 준다. 고체를 건조한 후 후 CHCl34L에 녹인 후 실리카겔 여과를 하여 무기물을 제거 하였다. 얻어진 용액은 감압하에서 용매를 제거 하여 고체를 얻었다. 얻어진 고체는 DMF 에서 재결정하여 목적화합물 13 (50 g, 58%) 을 얻었다.50 g (122 mmol) of Compound 1-1 was dissolved in DMF, and 60% NaH 5.9 (148 mmol) was slowly added thereto. The reaction mixture is stirred for 1 hour at room temperature and then 51 g (147 mmol) of compound 2-1 are added. The whole reaction mixture is stirred at room temperature for 20 hours. Ice water is slowly added dropwise to the reaction mixture to terminate the reaction, and the resulting solid is filtered off. The solid obtained is washed with 1 L of water and washed with 1 L of MeOH. After drying the solid was dissolved in 4L CHCl 3 and the silica gel was filtered to remove the inorganic matter. The obtained solution removed the solvent under reduced pressure to obtain a solid. The obtained solid was recrystallized in DMF to obtain the target compound 13 (50 g, 58%).
MS/FAB found 703, calculated 702.80MS / FAB found 703, calculated 702.80
[제조예 3] 화합물 14의 제조Preparation Example 3 Preparation of Compound 14
화합물 compound 3-13-1 의 제조Manufacturing
2,4-디클로로퀴나졸린 50 g (251 mmol) 과 디벤조[b,d]티오펜-4-일보로산 57.3 g (251 mmol)을 톨루엔 1 L, 물 200 mL 혼합용액에 녹인 후 테트라키스트리페닐포스핀 팔라듐 14.5 g (12.5 mmol)과 탄산나트륨 80 g (755 mmol)을 첨가하여 준다. 이 혼합물을 80℃에서 20시간 동안 교반하여 준다. 반응 혼합물을 상온으로 시키고 염화암모늄 수용액 200 mL로 반응을 종결 시킨 시킨 후 에틸아세테이트 1 L 로 추출한 후, 수층은 다시 디클로로메탄 1 L로 추출한다. 유기층을 무수황산마그네슘으로 건조하고, 유기용매는 감압하에서 제거하였다. 얻어진 고체는 실리카겔 로 여과 후 용매는 감압하에서 제게하였다. 얻어진 고체를 EtOAc 100 mL 로 씻어주어 화합물 3-1 (50 g, 60%)을 얻었다.50 g (251 mmol) of 2,4-dichloroquinazoline and 57.3 g (251 mmol) of dibenzo [ b , d ] thiophen-4-ylborolic acid were dissolved in a mixed solution of 1 L of toluene and 200 mL of water, followed by tetrakis Add 14.5 g (12.5 mmol) of triphenylphosphine palladium and 80 g (755 mmol) of sodium carbonate. The mixture is stirred at 80 ° C. for 20 hours. The reaction mixture was cooled to room temperature, the reaction was terminated with 200 mL of aqueous ammonium chloride solution, extracted with 1 L of ethyl acetate, and the aqueous layer was extracted with 1 L of dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was filtered through silica gel, and the solvent was removed under reduced pressure. The obtained solid was washed with 100 mL of EtOAc to obtain compound 3-1 (50 g, 60%).
화합물 compound 1414 의 제조Manufacturing
화합물 1-1 50 g (122 mmol) 을 DMF에 녹인 후 60% NaH 5.9 (148 mmol) 을 천천히 첨가하여 준다. 이 반응 혼합물을 상온에서 1시간동안 교반한 후 화합물 3-1 51 g (147 mmol)을 첨가한다. 전체 반응 혼합물을 상온에서 20 시간 교반하여 준다. 반응 혼합물에 얼음물을 천천히 적가하여 반응을 종결 시킨 후 생성된 고체를 여과하여 얻는다. 얻어진 고체를 물 1 L로 세척하고, MeOH 1 L로 세척하여 준다. 고체를 건조한 후 CHCl3 4L에 녹인 후 실리카겔 여과를 하여 무기물을 제거 하였다. 얻어진 용액은 감압하에서 용매를 제거 하여 고체를 얻었다. 얻어진 고체는 DMF 에서 재결정하여 목적화합물 14 (50 g, 57%) 을 얻었다.50 g (122 mmol) of Compound 1-1 was dissolved in DMF, and 60% NaH 5.9 (148 mmol) was slowly added thereto. The reaction mixture is stirred at room temperature for 1 hour and then 51 g (147 mmol) of compound 3-1 are added. The whole reaction mixture is stirred at room temperature for 20 hours. Ice water is slowly added dropwise to the reaction mixture to terminate the reaction, and the resulting solid is filtered off. The solid obtained is washed with 1 L of water and washed with 1 L of MeOH. CHCl 3 after drying solid After dissolving in 4L silica gel filtration to remove the inorganic material. The obtained solution removed the solvent under reduced pressure to obtain a solid. The obtained solid was recrystallized in DMF to obtain the target compound 14 (50 g, 57%).
MS/FAB found 729 calculated 718.87MS / FAB found 729 calculated 718.87
[제조예 4] 화합물 20의 제조Preparation Example 4 Preparation of Compound 20
화합물 compound 4-14-1 의 제조Manufacturing
dibenzo[b,d]furan-4-ylboronic acid(19 g, 89.6 mmol), bromobenzene (18.4ml, 138 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol), Na2CO3(23.2g,219mmol)을 Toluene(375ml), EtOH (75ml), 증류수(75 ml)에 녹인 후 90℃로 4시간 동안 교반하였다. 유기층을 감압증류한 후 MC와 헥산으로 column하여 화합물 4-1 (17g, 77 %)을 얻었다.dibenzo [b, d] furan-4-ylboronic acid (19 g, 89.6 mmol), bromobenzene (18.4ml, 138 mmol), Pd (PPh 3 ) 4 (2.9 g, 2.5 mmol), Na 2 CO 3 (23.2g , 219 mmol) was dissolved in Toluene (375 ml), EtOH (75 ml) and distilled water (75 ml) and stirred at 90 ° C. for 4 hours. After distilling the organic layer under reduced pressure, Compound 4-1 (17 g, 77%) was obtained by column chromatography with MC and hexane.
화합물compound 4-2 4-2 의 제조Manufacturing
화합물 4-1(17g, 65.3mmol)을 THF(500ml)에 녹이고 -78℃에서 2.5 M n-BuLi in Hexane (52.2 ml, 130 mmol)을 첨가한 후 한 시간 동안 교반하였다. B(Oi-Pr)3(21.8ml,195mmol)을 천천히 첨가하여 2시간 동안 교반하였다. 2M HCl을 첨가하여 quenching 한 후 증류수와 EA로 추출하였다. MC와 Hex으로 재결정하여 화합물 4-2 (6.4g, 33 %)를 얻었다. Compound 4-1 (17 g, 65.3 mmol) was dissolved in THF (500 ml), 2.5 M n-BuLi in Hexane (52.2 ml, 130 mmol) was added at -78 ° C, and the mixture was stirred for an hour. B (Oi-Pr) 3 (21.8 ml, 195 mmol) was added slowly and stirred for 2 hours. 2M HCl was added and quenched, followed by extraction with distilled water and EA. Recrystallization from MC and Hex gave Compound 4-2 (6.4 g, 33%).
화합물 compound 4-34-3 의 제조Manufacturing
화합물 4-2(4.9 g, 24.4 mmol), 2,4-dichloroquinazoline (6.4 g, 22.2 mmol), Pd(PPh3)4(1.1 g, 2.5 mmol), Na2CO37.1g,66.6mmol)을 Toluene(300ml), 증류수(75 ml)에 녹인 후 90℃로 2시간 동안 교반하였다. 유기층을 감압증류한 후 MeOH로 trituration 하였다. 얻어진 고체를 MC에 녹여 silica filter한 후 MC와 헥산으로 trituration하여 화합물 4-3 (4.1g, 45 %)을 얻었다.Compound 4-2 (4.9 g, 24.4 mmol), 2,4-dichloroquinazoline (6.4 g, 22.2 mmol), Pd (PPh 3 ) 4 (1.1 g, 2.5 mmol), Na 2 CO 3 7.1 g, 66.6 mmol) Toluene (300ml) and dissolved in distilled water (75ml) and stirred at 90 ℃ for 2 hours. The organic layer was distilled under reduced pressure and triturated with MeOH. The obtained solid was dissolved in MC, silica filtered, and triturated with MC and hexane to obtain compound 4-3 (4.1g, 45%).
화합물 compound 2020 의 제조Manufacturing
화합물 4-3 (4.5g, 10.9mmol), 화합물 1-1 (4.1 g, 9.9 mmol)을 DMF 80mL에 현탁한 뒤 60% NaH (594mg, 14.8mmol)를 상온에서 투입 하였다. 12시간 동안 교반하였다. 정제수(1L) 투입 후 감압여과하였다. 얻어진 고체를 MeOH/EA로 trituration 하고 DMF로 trituration한 후 EA/THF로 trituration하였다. MC로 녹여 silica filter한 후 MeOH/ EA로 trituration하여 목적화합물 20 (3.4g,44 %)를 얻었다.Compound 4-3 (4.5 g, 10.9 mmol) and compound 1-1 (4.1 g, 9.9 mmol) were suspended in 80 mL of DMF, and 60% NaH (594 mg, 14.8 mmol) was added at room temperature. Stir for 12 hours. Purified water (1L) and filtered under reduced pressure. The obtained solid was triturated with MeOH / EA, triturated with DMF, and triturated with EA / THF. After melting with MC and silica filter, trituration with MeOH / EA gave target compound 20 (3.4g, 44%).
MS/FAB found 779, calculated 778.90MS / FAB found 779, calculated 778.90
[제조예 5] 화합물 21의 제조Preparation Example 5 Preparation of Compound 21
화합물 compound 5-15-1 의 제조Manufacturing
dibenzo[b,d]thiophen-4-ylboronic acid(20 g, 87.7 mmol), bromobenzene (18.4ml, 175 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol), Na2CO3(23.2g,219mmol)을 Toluene(375ml), EtOH (75ml), 증류수(75 ml)에 녹인 후 90℃로 4시간 동안 교반하였다. 유기층을 감압증류한 후 MC와 헥산으로 column하여 화합물 화합물 5-1 (17g, 75 %)을 얻었다.dibenzo [b, d] thiophen-4-ylboronic acid (20 g, 87.7 mmol), bromobenzene (18.4 ml, 175 mmol), Pd (PPh 3 ) 4 (2.9 g, 2.5 mmol), Na 2 CO 3 (23.2 g , 219 mmol) was dissolved in Toluene (375 ml), EtOH (75 ml) and distilled water (75 ml) and stirred at 90 ° C. for 4 hours. The organic layer was distilled under reduced pressure and then columned with MC and hexane to obtain compound compound 5-1 (17g, 75%).
화합물 compound 5-25-2 의 제조Manufacturing
화합물 5-1(17g, 65.3mmol)을 THF(500ml)에 녹이고 -78℃에서 2.5 M n-BuLi in Hexane (52.2 ml, 130 mmol)을 첨가한 후 한 시간 동안 교반하였다. B(Oi-Pr)3(21.8ml,195mmol)을 천천히 첨가하여 2시간 동안 교반하였다. 2M HCl을 첨가하여 quenching 한 후 증류수와 EA로 추출하였다. MC와 Hex으로 재결정하여 화합물 5-2 (11.5g, 60 %)를 얻었다. Compound 5-1 (17 g, 65.3 mmol) was dissolved in THF (500 ml), 2.5 M n-BuLi in Hexane (52.2 ml, 130 mmol) was added at -78 ° C, and the mixture was stirred for an hour. B (Oi-Pr) 3 (21.8 ml, 195 mmol) was added slowly and stirred for 2 hours. 2M HCl was added and quenched, followed by extraction with distilled water and EA. Recrystallization with MC and Hex gave compound 5-2 (11.5 g, 60%).
화합물 compound 5-35-3 의 제조Manufacturing
화합물 5-2(8.3 g, 41.5 mmol), 2,4-dichloroquinazoline (11.5 g, 37.8 mmol), Pd(PPh3)4(2.2 g, 2.5 mmol), Na2CO312g,113mmol)을 Toluene(300ml), 증류수(75 ml)에 녹인 후 90℃로 2시간 동안 교반하였다. 유기층을 감압증류한 후 MeOH로 trituration 하였다. 얻어진 고체를 MC에 녹여 silica filter한 후 MC와 헥산으로 trituration하여 화합물 5-3 (10g, 68 %)을 얻었다.Compound 5-2 (8.3 g, 41.5 mmol), 2,4-dichloroquinazoline (11.5 g, 37.8 mmol), Pd (PPh 3 ) 4 (2.2 g, 2.5 mmol), Na 2 CO 3 12 g, 113 mmol) was added to Toluene ( 300 ml), dissolved in distilled water (75 ml) and stirred at 90 ℃ for 2 hours. The organic layer was distilled under reduced pressure and triturated with MeOH. The obtained solid was dissolved in MC, filtered through silica, and triturated with MC and hexane to obtain compound 5-3 (10 g, 68%).
화합물 compound 2121 의 제조Manufacturing
화합물 5-3 (5g, 11.8mmol), 화합물 1-1 (4.8 g, 11.8 mmol)을 DMF 80mL에 현탁한 뒤 60% NaH (881mg, 22mmol)를 상온에서 투입 하였다. 12시간 동안 교반하였다. 정제수(1L) 투입 후 감압여과하였다. 얻어진 고체를 MeOH/EA로 trituration 하고 DMF로 trituration한 후 EA/THF로 trituration하였다. MC로 녹여 silica filter한 후 MeOH/ EA로 trituration하여 HP336 (4.8g, 51 %)를 얻다.Compound 5-3 (5 g, 11.8 mmol) and compound 1-1 (4.8 g, 11.8 mmol) were suspended in 80 mL of DMF, and 60% NaH (881 mg, 22 mmol) was added at room temperature. Stir for 12 hours. Purified water (1L) and filtered under reduced pressure. The obtained solid was triturated with MeOH / EA, triturated with DMF, and triturated with EA / THF. After dissolving with MC and silica filter, trituration with MeOH / EA gave HP336 (4.8g, 51%).
MS/FAB found 795, calculated 794.96 MS / FAB found 795, calculated 794.96
[제조예 6] 화합물 33의 제조Preparation Example 6 Preparation of Compound 33
화합물compound 6-1 6-1 의 제조Manufacturing
dibenzo[b,d]furan-4-ylboronic acid (20g, 94.34mmol), 1-bromo-4-iodobenzene (53.4g, 188.68mmol), Pd(PPh3)4(5.45g,4.72mmol), K2CO3(39.1g,283.01mmol)을 Toluene 900mL, EtOH 200mL, 정제수 200mL에 투입 후 75℃에서 3시간 동안 교반하였다. 반응 종결 후 정치 하여 수층 제거 후 유층은 농축 하였다. 실리카 컬럼 정제하여 화합물 6-1 (17g, 56%)을 얻었다. dibenzo [b, d] furan-4-ylboronic acid (20g, 94.34mmol), 1-bromo-4-iodobenzene (53.4g, 188.68mmol), Pd (PPh 3 ) 4 (5.45g, 4.72mmol), K 2 CO 3 (39.1 g, 283.01 mmol) was added to 900 mL of Toluene, 200 mL of EtOH, and 200 mL of purified water, followed by stirring at 75 ° C. for 3 hours. After completion of the reaction, the mixture was left to stand and the oil layer was concentrated after removing the aqueous layer. Silica column purification gave compound 6-1 (17 g, 56%).
화합물 compound 6-26-2 의 제조Manufacturing
화합물 6-1 (17g, 52.6mmol)을 THF(400ml)에 녹이고 -78℃에서 2.5 M n-BuLi in Hexane (31.5 ml, 78.9 mmol)을 첨가한 후 한 시간 동안 교반하였다. B(Oi-propy)3(24.1ml,105.2mmol)을 천천히 첨가하여 12시간 동안 교반하였다. 반응 종결 후 정제수 20mL를 천천히 적가 하고 EA/NH4Cl aq. 로 추출 하였다. 유층은 농축 후 MC/Hexane으로 trituration 후 여과 하여 화합물 6-2 (14.5g, 96%)을 얻었다. Compound 6-1 (17 g, 52.6 mmol) was dissolved in THF (400 ml), 2.5 M n-BuLi in Hexane (31.5 ml, 78.9 mmol) was added at -78 ° C, and the mixture was stirred for an hour. B (Oi-propy) 3 (24.1 ml, 105.2 mmol) was added slowly and stirred for 12 hours. After completion of the reaction, 20 mL of purified water was slowly added dropwise and EA / NH 4 Cl aq. Extracted with. The oil layer was concentrated, triturated with MC / Hexane, and filtered to obtain compound 6-2 (14.5 g, 96%).
화합물 compound 6-36-3 의 제조Manufacturing
화합물 6-2 (14.5g, 50.33mmol), 2,4-dichloroquinazoline (11.5g, 50.33mmol), Na2CO3(20.9g,150.99mmol), Pd(PPh3)4(2.9g,2.52mmol)을 Toluene 300mL, EtOH 75mL, 정제수 75mL 에 투입 후 77℃에서 12시간 동안 교반 하였다. 반응 종결 후 실온으로 냉각 한 뒤 정치하여 수층을 제거 하였다. 유층은 농축 후 THF/MeOH로 trituration 한 후 여과하여 건조 하였다. 건조 화합물에 Chloroform 3L에 녹인 뒤 실리카 필터를 실시 하고 여액은 농축 한 뒤 EA 로 Trituration을 진행하여 화합물 6-3(3.8g, 19%)을 얻었다.Compound 6-2 (14.5g, 50.33mmol), 2,4-dichloroquinazoline (11.5g, 50.33mmol), Na 2 CO 3 (20.9g, 150.99mmol), Pd (PPh 3 ) 4 (2.9g, 2.52mmol) Toluene was added to 300mL, EtOH 75mL, and purified water 75mL, and stirred at 77 ° C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and left to stand to remove the aqueous layer. The oil layer was concentrated, triturated with THF / MeOH, filtered and dried. After dissolving in Chloroform 3L to the dry compound, the silica filter was concentrated, the filtrate was concentrated and then subjected to Trituration with EA to give compound 6-3 (3.8g, 19%).
화합물 compound 3333 의 제조Manufacturing
화합물 1-1 (3.8g, 9.34mmol), 화합물 6-3 (3.8g, 9.34mmol)을 DMF 80mL에 현탁한 뒤 60% NaH (1.12g, 28.02mL)를 상온에서 투입 하였다. 12시간 동안 교반하였다. 정제수(1L) 투입 후 감압여과하였다. 얻어진 고체를 MeOH/EA로 trituration 하고 DMF로 trituration한 후 EA/THF로 trituration하였다. MC로 녹여 silica filter한 후 MeOH/ EA로 trituration하여 목적화합물 33 (2.9g, 40 %)를 얻었다.Compound 1-1 (3.8 g, 9.34 mmol) and compound 6-3 (3.8 g, 9.34 mmol) were suspended in 80 mL of DMF, and 60% NaH (1.12 g, 28.02 mL) was added at room temperature. Stir for 12 hours. Purified water (1L) and filtered under reduced pressure. The obtained solid was triturated with MeOH / EA, triturated with DMF, and triturated with EA / THF. After melting with MC and silica filter, trituration with MeOH / EA gave target compound 33 (2.9g, 40%).
MS/FAB found 779, calculated 778.90MS / FAB found 779, calculated 778.90
[제조예 7] 화합물 34의 제조Preparation Example 7 Preparation of Compound 34
화합물 compound 7-17-1 의 제조Manufacturing
2000mL 둥근 바닥 플라스크에 1-bromo-4-iodobenzene (49.6g, 0.17mol), benzo[b,d]thiophen-4-ylboronic acid (20g, 0.087mol), Pd(PPh3)4 (5.0g, 0.044mol), Na2CO3 (18.5g, 0.18mol), Toluene(880ml), H2O (200ml)을 넣은 후 80℃ 12시간 교반하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후 흡착 Column으로 흰색 고체, 화합물 7-1 (21.2g, 71 %) 을 얻었다.In a 2000 mL round bottom flask, 1-bromo-4-iodobenzene (49.6g, 0.17mol), benzo [b, d] thiophen-4-ylboronic acid (20g, 0.087mol), Pd (PPh 3 ) 4 (5.0g, 0.044 mol), Na 2 CO 3 (18.5g, 0.18mol), Toluene (880ml), H 2 O (200ml) was added and stirred at 80 ℃ 12 hours. After completion of the reaction, the mixture was extracted using Ethyl Acetate, and the organic layer was dried over MgSO 4 , filtered, and then the solvent was removed under reduced pressure. A white solid, Compound 7-1 (21.2g, 71%) was obtained by an adsorption column.
화합물 compound 7-27-2 의 제조Manufacturing
무수 조건의 2000ml 둥근 바닥 플라스크에 dry 한 THF (1000ml), 화합물 7-1 (21.4g, 0.06mol) 을 넣은 후 질소하에서 교반하면서 -78℃ 에서 n-BuLi (37ml, 2.25M solution in hexane) 을 천천히 넣어주었다. -78℃ 에서 1시간 교반하고, -78℃ 에서 B(O-iPr)3(29ml,0.13mol)을 천천히 넣은 후 상온으로 온도를 올려 12시간 반응하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후, Column하여 흰색 고체, 화합물 7-2 (15.5g, 81%)를 얻었다.Put dry THF (1000 ml) and compound 7-1 (21.4 g, 0.06 mol) in a 2000 ml round bottom flask with anhydrous conditions, and n-BuLi (37 ml, 2.25 M solution in hexane) at -78 ° C while stirring under nitrogen. I put it slowly. After stirring at -78 ° C for 1 hour, slowly adding B (O-iPr) 3 (29ml, 0.13mol) at -78 ° C, the temperature was raised to room temperature and reacted for 12 hours. After completion of the reaction, the mixture was extracted using Ethyl Acetate, and the organic layer was dried over MgSO 4 , filtered, and then the solvent was removed under reduced pressure, followed by column to obtain a white solid, Compound 7-2 (15.5g, 81%).
화합물 compound 7-37-3 의 제조Manufacturing
250ml 둥근 바닥 플라스크에 2,4-dichloroquinazoline (12.2g, 0.06mol), 화합물 7-2 (15.5g, 0.051mol), Pd(PPh3)4 (2.94g, 0.0025mol), Na2CO3 (16.2g, 0.153mol), Toluene (250ml), H2O (70ml), EtOH (40ml)을 넣은 후 80℃ 12시간 교반하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후 재결정으로 화합물 7-3 (14g, 65 %) 을 얻었다.2,4-dichloroquinazoline (12.2g, 0.06mol), Compound 7-2 (15.5g, 0.051mol), Pd (PPh 3 ) 4 (2.94g, 0.0025mol), Na 2 CO 3 (16.2) in 250ml round bottom flask g, 0.153mol), Toluene (250ml), H 2 O (70ml), EtOH (40ml) were added thereto, and the mixture was stirred at 80 ° C for 12 hours. After completion of the reaction, the mixture was extracted with Ethyl Acetate, and the organic layer was dried over MgSO 4 , filtered, and then the solvent was removed under reduced pressure, and then compound 7-3 (14g, 65%) was obtained by recrystallization.
화합물 compound 3434 의 제조Manufacturing
무수 조건의 250ml 둥근 바닥 플라스크에 NaH 60% (0.62g, 0.0154mol)과 DMF (60ml)을 넣는다. 화합물 1-1 (4.83g, 0.012mol)을 DMF (30ml)에 녹여 NaH 둥근바닥 플라스크에 넣는다. 한시간 교반 후, 화합물 7-3 (5g, 0.012mol)을 DMF (30ml)에 녹여 플라스크에 넣는다. 12시간 교반 후, 노란 고체를 filter하고, MeOH washing, THF Trituration, DMF Trituration하여 목적 화합물 34 (4.2g, 45%)을 얻는다.In a 250 ml round bottom flask with anhydrous conditions add 60% NaH (0.62 g, 0.0154 mol) and DMF (60 ml). Compound 1-1 (4.83 g, 0.012 mol) is dissolved in DMF (30 ml) and placed in a NaH round bottom flask. After stirring for an hour, Compound 7-3 (5 g, 0.012 mol) is dissolved in DMF (30 ml) and placed in a flask. After stirring for 12 hours, the yellow solid was filtered, MeOH washing, THF trituration, and DMF trituration to obtain the target compound 34 (4.2 g, 45%).
MS/FAB found 795, calculated 794.96MS / FAB found 795, calculated 794.96
[제조예 8] 화합물 36의 제조Preparation Example 8 Preparation of Compound 36
화합물 compound 8-18-1 의 제조Manufacturing
dibenzo[b,d]furan-4-ylboronic acid(20g, 94.34mmol), 1,3-dibromobenzene(22.3g, 94.34mmol), Pd(PPh3)4(5.45g,4.72mmol), K2CO3(39.1g,283.01mmol)을 Toluene 800mL, EtOH 200mL, 정제수 200mL에 투입 후 75℃에서 3시간 동안 교반하였다. 반응 종결 후 정치 하여 수층 제거 후 유층은 농축 하였다. 실리카 컬럼 정제하여 화합물 8-1(13g, 43%)을 얻었다. dibenzo [b, d] furan-4-ylboronic acid (20g, 94.34mmol), 1,3-dibromobenzene (22.3g, 94.34mmol), Pd (PPh 3 ) 4 (5.45g, 4.72mmol), K 2 CO 3 (39.1 g, 283.01 mmol) was added to 800 mL of Toluene, 200 mL of EtOH, and 200 mL of purified water, followed by stirring at 75 ° C. for 3 hours. After completion of the reaction, the mixture was left to stand and the oil layer was concentrated after removing the aqueous layer. Silica column purification gave compound 8-1 (13 g, 43%).
화합물 compound 8-28-2 의 제조Manufacturing
화합물 8-1 (13g, 40.23mmol)을 THF(300ml)에 녹이고 -78℃에서 2.5 M n-BuLi in Hexane (19 ml, 48.27 mmol)을 첨가한 후 한 시간 동안 교반하였다. B(Oi-propy)3(13.9ml,60.34mmol)을 천천히 첨가하여 12시간 동안 교반하였다. 반응 종결 후 정제수 20mL를 천천히 적가 하고 EA/NH4Cl aq. 로 추출 하였다. 유층은 농축 후 MC/Hexane으로 trituration 후 여과 하여 화합물 8-2 (6.8g, 58.7%)을 얻었다. Compound 8-1 (13 g, 40.23 mmol) was dissolved in THF (300 ml), 2.5 M n-BuLi in Hexane (19 ml, 48.27 mmol) was added at -78 ° C, and the mixture was stirred for an hour. B (Oi-propy) 3 (13.9 ml, 60.34 mmol) was added slowly and stirred for 12 hours. After completion of the reaction, 20 mL of purified water was slowly added dropwise and EA / NH 4 Cl aq. Extracted with. The oil layer was concentrated, triturated with MC / Hexane, and filtered to obtain compound 8-2 (6.8 g, 58.7%).
화합물 compound 8-38-3 의 제조Manufacturing
화합물 8-2 (6.8g, 23.6mmol), 2,4-dichloroquinazoline (5.38g, 23.6mmol), Na2CO3(9.8g,70.8mmol), Pd(PPh3)4(1.36g,1.18mmol)을 Toluene 240mL, 정제수 50mL 에 투입 후 95℃에서 12시간 동안 교반 하였다. 반응 종결 후 실온으로 냉각 한 뒤 정치하여 수층을 제거 하였다. 유층은 농축 후 THF/MeOH로 trituration 한 후 여과하여 건조 하였다. 건조 화합물에 Chloroform 3L에 녹인 뒤 실리카 필터를 실시 하고 여액은 농축 한 뒤 THF/MeOH 로 Trituration을 진행하여 화합물 8-3(3.8g, 40%)을 얻었다.Compound 8-2 (6.8g, 23.6mmol), 2,4-dichloroquinazoline (5.38g, 23.6mmol), Na 2 CO 3 (9.8g, 70.8mmol), Pd (PPh 3 ) 4 (1.36g, 1.18mmol) Toluene was added to 240mL of purified water and 50mL of purified water and stirred at 95 ° C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and left to stand to remove the aqueous layer. The oil layer was concentrated, triturated with THF / MeOH, filtered and dried. After dissolving in Chloroform 3L to a dry compound, the silica filter was filtered, the filtrate was concentrated and then triturated with THF / MeOH to give compound 8-3 (3.8g, 40%).
화합물 compound 3636 의 제조Manufacturing
화합물 1-1 (3.8g, 9.34mmol), 화합물 8-3 (3.8g, 9.34mmol)을 DMF 80mL에 현탁한 뒤 60% NaH (1.12g, 28.02mL)를 상온에서 투입 하였다. 12시간 동안 교반하였다. 정제수(1L) 투입 후 감압여과하였다. 얻어진 고체를 MeOH/EA로 trituration 하고 MC로 녹여 silica filter한 후 MC/n-Hexane 으로 trituration하여 목적화합물 36 (1.6g, 21 %) 얻었다.Compound 1-1 (3.8 g, 9.34 mmol) and compound 8-3 (3.8 g, 9.34 mmol) were suspended in 80 mL of DMF, and 60% NaH (1.12 g, 28.02 mL) was added at room temperature. Stir for 12 hours. Purified water (1L) and filtered under reduced pressure. The obtained solid was triturated with MeOH / EA, dissolved in MC, silica filtered, and triturated with MC / n-Hexane to obtain target compound 36 (1.6g, 21%).
MS/FAB found 779, calculated 778.90MS / FAB found 779, calculated 778.90
[제조예 9] 화합물 37의 제조Preparation Example 9 Preparation of Compound 37
화합물 compound 9-19-1 의 제조Manufacturing
2000mL 둥근 바닥 플라스크에 1,3-dibromobenzene (16.5g, 0.2mol), dibenzo[b,d]thiophen-4-ylboronic acid (15g, 0.06mol), Pd(PPh3)4 (3.8g, 0.003mol), Na2CO3 (14g, 0.13mol), Toluene(330ml), H2O (70ml)을 넣은 후 80℃에서 12시간 교반하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후Column으로 흰색 고체, 화합물 9-1 (8.4g, 40 %) 을 얻었다.1,3-dibromobenzene (16.5g, 0.2mol), dibenzo [b, d] thiophen-4-ylboronic acid (15g, 0.06mol), Pd (PPh 3 ) 4 (3.8g, 0.003mol) in a 2000 mL round bottom flask , Na 2 CO 3 (14g, 0.13mol), Toluene (330ml), H 2 O (70ml) were added thereto, and the mixture was stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted using Ethyl Acetate, and the organic layer was dried with MgSO 4 , filtered, and then the solvent was removed under reduced pressure. Then, a white solid, Compound 9-1 (8.4 g, 40%) was obtained by column.
화합물 compound 9-29-2 의 제조Manufacturing
무수 조건의 500ml 둥근 바닥 플라스크에 dry 한 THF (200ml), 화합물 9-1 (8.4g, 0.025mol) 을 넣은 후 질소하에서 교반하면서 -78℃ 에서 n-BuLi (15ml, 2.25M solution in hexane) 을 천천히 넣어주었다. -78℃ 에서 1시간 교반하고, -78℃ 에서 B(O-iPr)3(11.4ml,0.05mol)을 천천히 넣은 후 상온으로 온도를 올려 12시간 반응하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후, Column하여 흰색 고체, 화합물 9-2 (6g, 80%)를 얻었다.Put dry THF (200ml), compound 9-1 (8.4g, 0.025mol) in anhydrous 500ml round bottom flask, and n-BuLi (15ml, 2.25M solution in hexane) at -78 ° C while stirring under nitrogen. I put it slowly. After stirring at -78 ° C for 1 hour, slowly adding B (O-iPr) 3 (11.4ml, 0.05mol) at -78 ° C, the temperature was raised to room temperature and reacted for 12 hours. After completion of the reaction, the mixture was extracted using Ethyl Acetate, and the organic layer was dried over MgSO 4 , filtered, and then the solvent was removed under reduced pressure, followed by column to obtain a white solid, Compound 9-2 (6g, 80%).
화합물 compound 9-39-3 의 제조Manufacturing
250ml 둥근 바닥 플라스크에 2,4-dichloroquinazoline (4.6g, 0.02mol), 화합물 9-2 (5.9g, 0.02mol), Pd(PPh3)4 (1.1g, 0.00097mol), Na2CO3 (6.2g, 0.058mol), Toluene (100ml), H2O (30ml), EtOH (14ml)을 넣은 후 70℃에서 3시간 교반하였다. 반응 종결 후 Ethyl Acetate를 사용하여 추출 한 뒤 유기 층을 MgSO4로 건조하고, 거른 후 감압 하에서 용매를 제거한 후 Column으로 화합물 9-3 (7.0g, 85 %) 을 얻었다.2,4-dichloroquinazoline (4.6 g, 0.02 mol), compound 9-2 (5.9 g, 0.02 mol), Pd (PPh 3 ) 4 (1.1 g, 0.00097 mol), Na 2 CO 3 (6.2 in a 250 ml round bottom flask. g, 0.058 mol), Toluene (100 ml), H 2 O (30 ml) and EtOH (14 ml) were added thereto, followed by stirring at 70 ° C. for 3 hours. After completion of the reaction, the mixture was extracted using Ethyl Acetate, and the organic layer was dried over MgSO 4 , filtered, and then the solvent was removed under reduced pressure, thereby obtaining Compound 9-3 (7.0 g, 85%) as a column.
화합물 compound 3737 의 제조Manufacturing
무수 조건의 250ml 둥근 바닥 플라스크에 NaH 60% (0.5g, 0.013mol)과 DMF (40ml)을 넣는다. 화합물 1-1 (3.7g, 0.009mol)을 DMF (30ml)에 녹여 NaH 둥근바닥 플라스크에 넣는다. 한시간 교반 후, 화합물 9-3 (4g, 0.0095mol)을 DMF (30ml)에 녹여 플라스크에 넣는다. 12시간 교반 후, 노란 고체를 filter하고, MeOH washing, THF Trituration, DMF Trituration하여 목적 화합물 37 (1.7g, 20%)을 얻는다.In a 250 ml round bottom flask with dry conditions add 60% NaH (0.5 g, 0.013 mol) and DMF (40 ml). Compound 1-1 (3.7 g, 0.009 mol) is dissolved in DMF (30 ml) and placed in a NaH round bottom flask. After stirring for one hour, Compound 9-3 (4 g, 0.0095 mol) is dissolved in DMF (30 ml) and placed in a flask. After stirring for 12 hours, the yellow solid was filtered, MeOH washing, THF trituration, and DMF trituration to obtain the target compound 37 (1.7 g, 20%).
MS/FAB found 795, calculated 794.96 MS / FAB found 795, calculated 794.96
[제조예 10] 화합물 39의 제조Preparation Example 10 Preparation of Compound 39
화합물 compound 10-110-1 의 제조Manufacturing
화합물 1-1(14g, 34.3mmol)과 1-Bromo-4-iobenzene(48.5g, 171.4mmol), CuI(3.3 g, 17.1mmol), K3PO4(21.8 g, 102.9 mmol), EDA(2.3 ml, 34.3 mmol)을 Toluene 500ml 에 투입 후 하룻동안 환류교반하였다. EA로 추출 후 감압증류한 후 MC/Hex으로 column하여 화합물 10-1 (15.5 g, 80.1 %)를 얻었다. Compound 1-1 (14 g, 34.3 mmol) and 1-Bromo-4-iobenzene (48.5 g, 171.4 mmol), CuI (3.3 g, 17.1 mmol), K3PO4 (21.8 g, 102.9 mmol), EDA (2.3 ml, 34.3 mmol) was added to 500 ml of Toluene and stirred under reflux for one day. After extraction with EA and distillation under reduced pressure, Compound 10-1 (15.5 g, 80.1%) was obtained by column extraction with MC / Hex.
화합물 compound 10-210-2 의 제조Manufacturing
화합물 10-1(15.5g, 27.5mmol)을 THF(250ml)에 녹이고 -78℃에서 2.5 M n-BuLi in Hexane (17.6 ml, 44 mmol)을 첨가한 후 한 시간 동안 교반하였다. B(Oi-Pr)3(12.6ml, 55 mmol)을 천천히 첨가하여 2시간 동안 교반하였다. 2M HCl을 첨가하여 quenching 한 후 증류수와 EA로 추출하였다. MC와 Hex으로 재결정하여 화합물 10-2 (8.7g, 60 %)를 얻었다. Compound 10-1 (15.5g, 27.5mmol) was dissolved in THF (250ml) and 2.5M n-BuLi in Hexane (17.6ml, 44mmol) was added at -78 ° C and stirred for an hour. B (Oi-Pr) 3 (12.6 ml, 55 mmol) was added slowly and stirred for 2 hours. 2M HCl was added and quenched, followed by extraction with distilled water and EA. Recrystallization from MC and Hex gave compound 10-2 (8.7 g, 60%).
화합물 compound 3939 의 제조Manufacturing
화합물 3-1(3.2 g, 9.2 mmol), 화합물 10-2(4.9 g, 9.2 mmol), Pd(PPh3)4(532mg, 0.46 mmol), Na2CO3(2.9g,27.6mmol)을 Toluene(55ml), EtOH(14ml), 증류수(14 ml)에 녹인 후 90℃로 2시간 동안 교반하였다. 증류수와 EA로 추출한 후 MC와 헥산으로 column 하여 목적화합물 39 (5.5g, 75 %)을 얻었다. Toluene compound 3-1 (3.2 g, 9.2 mmol), compound 10-2 (4.9 g, 9.2 mmol), Pd (PPh 3 ) 4 (532 mg, 0.46 mmol), Na 2 CO 3 (2.9 g, 27.6 mmol) (55ml), EtOH (14ml), dissolved in distilled water (14ml) and stirred at 90 ℃ for 2 hours. Extracted with distilled water and EA and columned with MC and hexane to obtain the target compound 39 (5.5g, 75%).
MS/FAB found 795, calculated 794.96MS / FAB found 795, calculated 794.96
[제조예 11] 화합물 40의 제조Preparation Example 11 Preparation of Compound 40
화합물 compound 4040 의 제조Manufacturing
화합물 2-1(3.2 g, 9.2 mmol), 화합물 10-2(4.9 g, 9.2 mmol), Pd(PPh3)4(532mg, 0.46 mmol), Na2CO3(2.9g,27.6mmol)을 Toluene(55ml), EtOH(14ml), 증류수(14 ml)에 녹인 후 90℃로 2시간 동안 교반하였다. 증류수와 EA로 추출한 후 MC와 헥산으로 column 하여 목적화합물 40 (5.5g, 75 %)을 얻었다. Toluene compound 2-1 (3.2 g, 9.2 mmol), compound 10-2 (4.9 g, 9.2 mmol), Pd (PPh 3 ) 4 (532 mg, 0.46 mmol), Na 2 CO 3 (2.9 g, 27.6 mmol) (55ml), EtOH (14ml), dissolved in distilled water (14ml) and stirred at 90 ℃ for 2 hours. Extracted with distilled water and EA and columned with MC and hexane to obtain the target compound 40 (5.5g, 75%).
MS/FAB found 779, calculated 778.90
MS / FAB found 779, calculated 778.90
[실시예1] 본 발명에 따른 유기 전자 재료용 화합물을 이용한 OLED 소자 제작Example 1 Fabrication of an OLED Device Using a Compound for Organic Electronic Materials According to the Present Invention
본 발명의 발광 재료를 이용한 구조의 OLED 소자를 제작하였다. 우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막(15Ω/□)을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로 진공 증착 장비의 기판 홀더에 ITO기판을 장착한 후, 진공 증착장비 내의 셀에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl) amino)phenyl)-N1-phenylbenzene-1,4-diamine을 넣고 챔버 내의 진공도가 10E-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 증발시켜 ITO 기판 위에 60nm 두께의 정공주입층을 증착하였다. 이어서, 진공 증착 장비 내의 다른 셀에 N,N'-di(4-biphenyl) -N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl을 넣고, 셀에 전류를 인가하여 증발시켜 정공주입층 위에 20nm 두께의 정공전달층을 증착하였다. 정공주입층, 정공전달층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 호스트로서 화합물 2를 넣고, 또 다른 셀에는 도판트로서 화합물 D-11을 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 4내지 20%중량으로 도핑 함으로서 상기 정공전달층위에 30nm 두께의 발광층을 증착하였다. 이어서 상기 발광층 위에 전자 전달층으로써 한쪽 셀에 이어서 상기 발광층 위에 전자 전달층으로써 한쪽 셀에 9,10-디(1-나프틸)-2-(4-페닐-1-페닐-1H-벤조[d] 이미다졸)안트라센[9,10-di(1-naphthyl)-2-(4-phenyl-1-phenyl-1H-benzo[d] imidazole)anthracene]을 넣고, 또다른 셀에는 리튬 퀴놀레이트(Lithium quinolate)를 각각 넣은 후, 두 물질을 다른속도로 증발시켜 30내지 70%중량으로 도핑 함으로서 30nm의 전자 전달층을 증착하였다. 이어서 전자 주입층으로 Lithium quinolate를 1내지 2nm 두께로 증착한 후, 다른 진공 증착장비를 이용하여 Al 음극을 150nm의 두께로 증착하여 OLED 소자를 제작하였다. 재료 별로 각 화합물은 10E-6 torr 하에서 진공 승화 정제하여 사용하였다.An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15? /?) Obtained from a glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially and stored in isopropanol Respectively. Next, the ITO substrate is mounted on the substrate holder of the vacuum deposition apparatus, and then N1- (naphthalen-2-yl) -N4, N4-bis (4- (naphthalen-2-yl (phenyl) amino) is placed on a cell in the vacuum deposition apparatus. ) phenyl) -N1-phenylbenzene-1,4-diamine was added and evacuated until the vacuum in the chamber reached 10E-6 torr. Then, a current was applied to the cell and evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Deposited. Subsequently, N, N'-di (4-biphenyl) -N, N'-di (4-biphenyl) -4,4'-diaminobiphenyl was added to another cell in the vacuum deposition apparatus, and the cell was applied with a current to evaporate. A 20 nm thick hole transport layer was deposited on the hole injection layer. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. Compound 2 as a host in one cell in a vacuum deposition apparatus, Compound D-11 as a dopant in each cell, and then the two materials are evaporated at different rates to be doped at 4 to 20% by weight to thereby transport the hole transport layer. A light emitting layer having a thickness of 30 nm was deposited on it. Then one cell as the electron transport layer on the light emitting layer, followed by 9,10-di (1-naphthyl) -2- (4-phenyl-1-phenyl-1H-benzo [d] in one cell as the electron transport layer on the light emitting layer. Imidazole) anthracene [9,10-di (1-naphthyl) -2- (4-phenyl-1-phenyl-1H-benzo [d] imidazole) anthracene] and another cell is lithium quinolate (Lithium) quinolate) was added, and then the two materials were evaporated at different rates to be doped at 30 to 70% by weight to deposit an electron transport layer of 30 nm. Subsequently, Lithium quinolate was deposited to a thickness of 1 to 2 nm as an electron injection layer, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED device. Each compound was used by vacuum sublimation purification under 10E-6 torr.
그 결과, 4.0V의 전압에서 14.0 mA/cm2의 전류가 흘렀으며, 1020 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 60시간 이상이었다. As a result, a current of 14.0 mA / cm 2 flowed at a voltage of 4.0 V, and red light emission of 1020 cd / m 2 was confirmed. It took more than 60 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예2] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 2 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 4, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 4 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 3.9 V의 전압에서 7.7 mA/cm2의 전류가 흘렀으며, 1030 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 200시간 이상이었다.As a result, a current of 7.7 mA / cm 2 flowed at a voltage of 3.9 V, and red light emission of 1030 cd / m 2 was confirmed. It took more than 200 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예3] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 3 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 13, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 13 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 3.9 V의 전압에서 7.1 mA/cm2의 전류가 흘렀으며, 1050 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 150시간 이상이었다.As a result, a current of 7.1 mA / cm 2 flowed at a voltage of 3.9 V, and red light emission of 1050 cd / m 2 was observed. It took more than 150 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예4] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 4 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 14, 도판트에는 화합물 D-7 을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 14 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 4.0 V의 전압에서 7.2 mA/cm2의 전류가 흘렀으며, 1090 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 150시간 이상이었다.As a result, a current of 7.2 mA / cm 2 flowed at a voltage of 4.0 V, and red light emission of 1090 cd / m 2 was confirmed. It took more than 150 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예5] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 5 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 21, 도판트에는 화합물 D-11을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 21 was used as a light emitting material and Compound D-11 was used as a dopant.
그 결과, 4.3 V의 전압에서 13.2 mA/cm2의 전류가 흘렀으며, 1010 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 150시간 이상이었다.As a result, a current of 13.2 mA / cm 2 flowed at a voltage of 4.3 V, and red emission of 1010 cd / m 2 was confirmed. It took more than 150 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예6] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 6 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 33, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 33 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 4.2 V의 전압에서 7.2 mA/cm2의 전류가 흘렀으며, 1040 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 130시간 이상이었다.As a result, a current of 7.2 mA / cm 2 flowed at a voltage of 4.2 V, and red light emission of 1040 cd / m 2 was confirmed. It took more than 130 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예7] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 7 OLED device fabrication using organic light emitting compound according to the present invention
발광재료로서 호스트에는 화합물 34, 도판트에는 화합물 D-11을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 34 was used as a light emitting material and Compound D-11 was used as a dopant.
그 결과, 4.3 V의 전압에서 12.8 mA/cm2의 전류가 흘렀으며, 1010 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 130시간 이상이었다.As a result, a current of 12.8 mA / cm 2 flowed at a voltage of 4.3 V, and red emission of 1010 cd / m 2 was confirmed. It took more than 130 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예8] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 8 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 36, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 36 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 4.1 V의 전압에서 7.3 mA/cm2의 전류가 흘렀으며, 1080 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 150시간 이상이었다.As a result, a current of 7.3 mA / cm 2 flowed at a voltage of 4.1 V, and red light emission of 1080 cd / m 2 was confirmed. It took more than 150 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예9] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 9 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 37, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 37 was used as a light emitting material and Compound D-7 was used as a dopant.
그 결과, 4.1 V의 전압에서 7.5 mA/cm2의 전류가 흘렀으며, 1080 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 150시간 이상이었다.As a result, a current of 7.5 mA / cm 2 flowed at a voltage of 4.1 V, and red light emission of 1080 cd / m 2 was confirmed. It took more than 150 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예10] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 10 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 39, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 39 was used as a light emitting material and 占 ™ Compound D-7 was used as a dopant.
그 결과, 4.0 V의 전압에서 6.7 mA/cm2의 전류가 흘렀으며, 1050 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 120시간 이상이었다.As a result, a current of 6.7 mA / cm 2 flowed at a voltage of 4.0 V, and red light emission of 1050 cd / m 2 was confirmed. It took more than 120 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[실시예11] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 11 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention
발광재료로서 호스트에는 화합물 40, 도판트에는 화합물 D-7을 사용한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.As a light-emitting material has a host compound 40, the dopant is to manufacture an OLED device in the same manner as in Example 1 except that the compound D-7.
그 결과, 4.0 V의 전압에서 6.8 mA/cm2의 전류가 흘렀으며, 1070 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는데 걸린 시간이 120시간 이상이었다.
As a result, a current of 6.8 mA / cm 2 flowed at a voltage of 4.0 V, and red light emission of 1070 cd / m 2 was confirmed. It took more than 120 hours for the light emission to drop to 90% at a brightness of 5000 nits.
[비교예1] 종래에 발광재료를 이용한 OLED 소자 제작[Comparative Example 1] Conventional OLED element fabrication using a light emitting material
발광재료로서 호스트에는 4,4'-N,N'-dicarbazole-biphenyl, 도판트로는 화합물 D-11을 사용하고, 정공전달층위에 30nm 두께의 발광층을 증착하고, 정공 저지층으로 aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate을 10nm 두께로 증착한 것 외에는 실시예1과 동일한 방법으로 OLED소자를 제작하였다.4,4'-N, N'-dicarbazole-biphenyl is used as a light emitting material and compound D-11 is used as a dopant. A light emitting layer having a thickness of 30 nm is deposited on the hole transport layer, and aluminum (III) is used as the hole blocking layer. An OLED device was manufactured in the same manner as in Example 1, except that bis (2-methyl-8-quinolinato) 4-phenylphenolate was deposited to a thickness of 10 nm.
그 결과, 8.2 V의 전압에서 20.0 mA/cm2의 전류가 흘렀으며, 1000 cd/m2의 적색발광이 확인되었다. 5000nit의 휘도에서 발광이 90%로 떨어지는 시간이 10시간 이상이었다. As a result, a current of 20.0 mA / cm 2 flowed at a voltage of 8.2 V, and red light emission of 1000 cd / m 2 was confirmed. At the luminance of 5000 nits, the time when the light emission dropped to 90% was 10 hours or more.
본 발명에서 개발한 유기 전자 재료용 화합물들의 발광 특성이 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있었다. 또한 본 발명에 따른 유기 전자 재료용 화합물을 발광용 호스트 재료로 사용한 소자는 발광특성이 뛰어날 뿐만 아니라 구동전압을 강하시켜줌으로써 전력효율의 상승을 유도하여 소비전력을 개선시킬 수 있었다.It was confirmed that the luminescent properties of the compounds for organic electronic materials developed in the present invention showed superior characteristics compared to the conventional materials. In addition, the device using the organic electronic material compound according to the present invention as a light emitting host material was excellent in the light emitting characteristics, it was possible to improve the power consumption by inducing the increase in power efficiency by lowering the driving voltage.
Claims (10)
[화학식 1]
상기 화학식 1에서,
L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환된 (C5-C30)헤테로아릴렌, 치환 또는 비치환된 (C6-C30)아릴렌, 치환 또는 비치환된 (C6-C30)시클로알킬렌이고;
X1은 CH 또는 N이며;
Y1 및 Y2는 각각 독립적으로 -O-, -S-, -CR8R9- 또는 -NR10-이고;
R1 내지 R10은 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아르(C1-C30)알킬, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 5원 내지 7원의 헤테로시클로알킬이거나 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 (C3-C30)시클로알킬, -NR21R22, -SiR23R24R25, -SR26, -OR27, (C2-C30)알케닐, (C2-C30)알키닐, 시아노, 니트로 또는 히드록시이거나 인접한 치환체와 융합고리를 포함하거나 포함하지 않는 치환 또는 비치환된 (C3-C30)알킬렌 또는 치환 또는 비치환된 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있고, 상기 형성된 지환족 고리 및 단일환 또는 다환의 방향족 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있으며;
상기 R21 내지 R27은 상기 R1 내지 R10의 정의와 동일하며,
a, b, e, g는 각각 독립적으로 1 내지 4의 정수이며, a, b, g, e가 2이상의 정수인 경우 동일하거나 상이할수 있고;
c, d, f는 각각 독립적으로 1 내지 3의 정수이며, c, d, f가 2이상의 정수인 경우 동일하거나 상이할수 있고;
상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.
A compound for an organic electronic material represented by Formula 1 below:
[Formula 1]
In Chemical Formula 1,
L 1 and L 2 are each independently a single bond, substituted or unsubstituted (C5-C30) heteroarylene, substituted or unsubstituted (C6-C30) arylene, substituted or unsubstituted (C6-C30) cyclo Alkylene;
X 1 is CH or N;
Y 1 and Y 2 are each independently —O—, —S—, —CR 8 R 9 —, or —NR 10 —;
R 1 to R 10 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, cycloalkyl At least one fused substituted or unsubstituted (C6-C30) aryl, a 5 to 7 membered heterocycloalkyl fused at least one substituted or unsubstituted aromatic ring, or at least one fused substituted or unsubstituted aromatic ring (C3-C30) cycloalkyl, -NR 21 R 22 , -SiR 23 R 24 R 25 , -SR 26 , -OR 27, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, Substituted or unsubstituted (C3-C30) alkylene or substituted or unsubstituted (C3-C30) with or without nitro or hydroxy or with a fused ring with adjacent substituents May be linked to alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, wherein the carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring are one or more selected from nitrogen, oxygen, and sulfur May be substituted with a heteroatom;
R 21 to R 27 are the same as the definitions of R 1 to R 10 ,
a, b, e and g are each independently integers of 1 to 4, and may be the same or different when a, b, g and e are integers of 2 or more;
c, d and f are each independently integers of 1 to 3, and may be the same or different when c, d and f are integers of 2 or more;
The heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.
상기 L1 및 L2, R1 내지 R10 및 R21 내지 R27에 더 치환되는 치환기는 서로 독립적으로 중수소, 할로겐, (C1-C30)알킬, 할로겐이 치환된 (C1-C30)알킬, (C6-C30)아릴, (C5-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C5-C30)헤테로아릴, (C3-C30)시클로알킬, 헤테로시클로알킬, (C1-C30)알킬실릴, (C6-C30)아릴실릴, (C1-C30)알킬(C6-C30)아릴실릴, (C2-C30)알케닐, (C6-C30)알키닐, 시아노, 카바졸릴, (C1-C30)알킬아미노, (C6-C30)아릴아미노, (C1-C30)알킬(C6-C30)아릴아미노, (C6-C30)아릴보로닐, (C1-C30)알킬보로닐, (C1-C30)알킬(C6-C30)아릴보로닐, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, 카르보닐, 카르복실, 니트로 또는 히드록시로 이루어진 군으로부터 선택되는 것인 유기 전자재료용 화합물.
The method of claim 1,
Substituents further substituted with L 1 and L 2, R 1 to R 10 and R 21 to R 27 are each independently deuterium, halogen, (C 1 -C 30) alkyl, halogen substituted (C 1 -C 30) alkyl, ( C6-C30) aryl, (C5-C30) heteroaryl, (C6-C30) aryl substituted (C5-C30) heteroaryl, (C3-C30) cycloalkyl, heterocycloalkyl, (C1-C30) alkylsilyl , (C6-C30) arylsilyl, (C1-C30) alkyl (C6-C30) arylsilyl, (C2-C30) alkenyl, (C6-C30) alkynyl, cyano, carbazolyl, (C1-C30) Alkylamino, (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C6-C30) arylboronyl, (C1-C30) alkylboronyl, (C1-C30) Group consisting of alkyl (C6-C30) arylboronyl, (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carbonyl, carboxyl, nitro or hydroxy The compound for an organic electronic material is selected from.
상기 X1은 CH 또는 N이며;
L1 및 L2은 각각 독립적으로 단일결합, 페닐렌, 나프틸렌, 비페닐렌, 터페닐렌, 안트릴렌, 안데닐렌, 플루오레닐렌, 페난트릴렌, 트리페닐레닐렌, 피렌일렌, 페릴렌일렌, 크라이세닐렌, 나프타세닐렌, 플루오란텐일, 퓨릴렌, 티오페닐렌, 피롤릴렌, 이미다졸릴렌, 피라졸릴렌, 티아졸릴렌, 티아디아졸릴렌, 이소티아졸릴렌, 이속사졸릴렌, 옥사졸릴렌, 옥사디아졸릴렌, 트리아진일렌, 테트라진일렌, 트리아졸릴렌, 테트라졸릴렌, 퓨라잔일렌, 피리딜렌, 피라진일렌, 피리미딘일렌, 피리다진일렌, 벤조퓨란일렌, 벤조티오펜일렌, 이소벤조퓨란일렌, 벤조이미다졸릴렌, 벤조티아졸릴렌, 벤조이소티아졸릴렌, 벤조이속사졸릴렌, 벤조옥사졸릴렌, 이소인돌릴렌, 인돌릴렌, 인다졸릴렌, 벤조티아디아졸릴렌, 퀴놀릴렌, 이소퀴놀릴렌, 신놀리닐렌, 퀴나졸리닐렌, 퀴녹살리닐렌, 카바졸릴렌, 페난트리딘일렌, 벤조디옥솔릴렌, 다이벤조퓨란닐렌, 다이벤조싸이오페닐렌로 구성된 군으로부터 선택되는 것인 유기 전자재료용 화합물.
The method of claim 1,
X 1 is CH or N;
L 1 and L 2 are each independently a single bond, phenylene, naphthylene, biphenylene, terphenylene, anthylene, andenylene, fluorenylene, phenanthryl, triphenylenylene, pyrenylene, pehen Reyleneylene, Chrysenylene, Naphthacelene, Fluoranthenyl, Purylene, Thiophenylene, Pyrrylene, Imidazolene, Pyrazolylene, Thiazolylene, Tiadiazolylene, Isothiazolylene, Isoxa Zoleylene, oxazolylene, oxadiazolylene, triazineylene, tetrazinylene, triazolylene, tetrazoylene, furazanthylene, pyridylene, pyrazinylene, pyrimidinylene, pyridazineylene, benzofuranylene, Benzothiophenylene, isobenzofuranylene, benzoimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzooxazolylene, isoindoleylene, indolylene, indazolylene, benzo Thiadiazolylene, quinolylene, isoquinolylene, cinnolinylene, quinazolinylene And quinoxalinylene, carbazolylene, phenanthridinylene, benzodioxoleylene, dibenzofuranylene, and dibenzothiophenylene.
상기
The method of claim 1,
remind
하기 화합물로부터 선택되는 유기 전자재료용 화합물.
The method of claim 1,
A compound for organic electronic materials selected from the following compounds.
An organic electroluminescent device comprising the compound for organic electronic material of any one of claims 1 to 5.
상기 유기 전계 발광 소자가 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층을 가지며, 이 유기물층이 상기 유기 전자 재료용 화합물 중 하나 이상과 하기 화학식 2로 표시되는 인광 도판트 중 하나 이상을 포함하는 것인 유기 전계 발광 소자:
[화학식 2]
M 1 L 101 L 102 L 103
상기 화학식 2에서,
M1은 Ir, Pt, Pd, Os으로 이루어진 군으로부터 선택되고;
리간드 L101, L102 및 L103 는 서로 독립적으로 하기 구조로부터 선택되며;
R201 내지 R203은 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬, (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴 또는 할로겐이고;
R204 내지 R219는 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C1-C30)알콕시, 치환 또는 비치환된(C3-C30)시클로알킬, 치환 또는 비치환된(C2-C30)알케닐, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된 모노 또는 치환 또는 비치환된 디-(C1-C30)알킬아미노, 치환 또는 비치환된 모노 또는 디-(C6-C30)아릴아미노, SF5, 치환 또는 비치환된 트리(C1-C30)알킬실릴, 치환 또는 비치환된 디(C1-C30)알킬(C6-C30)아릴실릴, 치환 또는 비치환된 트리(C6-C30)아릴실릴, 시아노 또는 할로겐이고;
R220 내지 R223는 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬 또는 (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴이고;
R224 및 R225는 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이거나, R224와 R225는 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성하며;
R226은 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된(C5-C30)헤테로아릴 또는 할로겐이고;
R227 내지 R229은 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이고;
Q는
The method according to claim 6,
The organic electroluminescent device comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one of the compounds for organic electronic materials and at least one phosphorescent dopant represented by Formula 2 below. Organic electroluminescent element:
(2)
M 1 L 101 L 102 L 103
In Formula 2,
M 1 is selected from the group consisting of Ir, Pt, Pd, Os;
The ligands L 101 , L 102 and L 103 are independently selected from the following structures;
R 201 to R 203 independently represent hydrogen, deuterium, (C 1 -C 30) alkyl in which the halogen is optionally substituted (C 1 -C 30) alkyl, (C 6 -C 30) aryl or halogen in which the (C 1 -C 30) alkyl is optionally substituted;
R 204 to R 219 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, Substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted mono or substituted or unsubstituted di- (C1-C30) alkylamino, substituted or unsubstituted Substituted mono or di- (C6-C30) arylamino, SF 5 , substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl , Substituted or unsubstituted tri (C6-C30) arylsilyl, cyano or halogen;
R 220 to R 223 are each independently hydrogen, deuterium, (C1-C30) alkyl with or without halogen, or (C6-C30) aryl with or without (C1-C30) alkyl;
R 224 and R 225 are independently of each other hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R 224 and R 225 contain fused rings Linked with (C3-C12) alkylene or (C3-C12) alkenylene with or without formation to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
R 226 is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C5-C30) heteroaryl or halogen;
R 227 to R 229 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen;
Q is
상기 인광 도판트는 하기 화합물로부터 선택되는 것인 유기 전계 발광 소자.
The method of claim 7, wherein
The phosphorescent dopant is selected from the following compounds.
상기 유기물층이 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 아민계 화합물(A); 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 금속을 포함하는 착체화합물(B); 또는 이들의 혼합물을 포함하는 것인 유기 전계 발광 소자.
The method of claim 7, wherein
At least one amine compound (A) wherein the organic material layer is selected from the group consisting of an arylamine compound or a styrylarylamine compound; Complex compounds (B) comprising at least one metal or metal selected from the group consisting of Group 1, Group 2, 4 and 5 cycle transition metals, lanthanide series metals and organic metals of d-transition elements; Or an organic electroluminescent device comprising a mixture thereof.
상기 유기물층이 청색, 적색 또는 녹색 발광을 하는 유기발광층 하나 이상을 더 포함하여 백색 발광을 하는 것인 유기 전계 발광 소자.The method of claim 7, wherein
The organic light emitting device of claim 1, wherein the organic material layer further comprises at least one organic light emitting layer emitting blue, red, or green light.
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| KR1020110033910A KR20120116269A (en) | 2011-04-12 | 2011-04-12 | Novel compounds for organic electronic material and organic electroluminescence device using the same |
| CN201280028741.XA CN103619833A (en) | 2011-04-12 | 2012-04-12 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| PCT/KR2012/002762 WO2012141499A1 (en) | 2011-04-12 | 2012-04-12 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| EP12771699.1A EP2697216A4 (en) | 2011-04-12 | 2012-04-12 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| JP2014505079A JP2014513083A (en) | 2011-04-12 | 2012-04-12 | Novel compounds for organic electronic materials and organic electroluminescent devices using them |
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| KR20210046613A (en) * | 2014-11-10 | 2021-04-28 | 엘지디스플레이 주식회사 | Hetero compounds and organic light emitting devices comprising the same |
| WO2020071860A1 (en) * | 2018-10-04 | 2020-04-09 | 주식회사 엘지화학 | Compound and organic light emitting diode comprising same |
| US11997927B2 (en) | 2018-10-04 | 2024-05-28 | Lg Chem, Ltd. | Compound and organic light emitting diode comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014513083A (en) | 2014-05-29 |
| EP2697216A4 (en) | 2014-10-15 |
| WO2012141499A1 (en) | 2012-10-18 |
| CN103619833A (en) | 2014-03-05 |
| EP2697216A1 (en) | 2014-02-19 |
| TW201249960A (en) | 2012-12-16 |
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