WO2017086706A1 - Compound for organic electric element, organic electric element using same, and electronic device thereof - Google Patents
Compound for organic electric element, organic electric element using same, and electronic device thereof Download PDFInfo
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- WO2017086706A1 WO2017086706A1 PCT/KR2016/013255 KR2016013255W WO2017086706A1 WO 2017086706 A1 WO2017086706 A1 WO 2017086706A1 KR 2016013255 W KR2016013255 W KR 2016013255W WO 2017086706 A1 WO2017086706 A1 WO 2017086706A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 117
- 125000003118 aryl group Chemical group 0.000 claims description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 125000005842 heteroatom Chemical group 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 125000000623 heterocyclic group Chemical group 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 229910052717 sulfur Inorganic materials 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 28
- 239000007924 injection Substances 0.000 claims description 28
- 230000005525 hole transport Effects 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000011368 organic material Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 125000000304 alkynyl group Chemical group 0.000 claims description 21
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 15
- 229910052805 deuterium Inorganic materials 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- -1 fused ring group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 10
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 8
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 4
- 125000005567 fluorenylene group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000003413 spiro compounds Chemical class 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229910052722 tritium Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 172
- 238000003786 synthesis reaction Methods 0.000 description 172
- 239000010410 layer Substances 0.000 description 137
- 239000000047 product Substances 0.000 description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 69
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000001308 synthesis method Methods 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- 230000032258 transport Effects 0.000 description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 239000007858 starting material Substances 0.000 description 15
- 0 *(c(cccc1)c1-c1c2)c1c1N(c3cc(-c4nc(-c5c(cccc6)c6ccc5)cc(-c5c(cccc6)c6ccc5)n4)ccc3)c3ccccc3-c3cccc2c13 Chemical compound *(c(cccc1)c1-c1c2)c1c1N(c3cc(-c4nc(-c5c(cccc6)c6ccc5)cc(-c5c(cccc6)c6ccc5)n4)ccc3)c3ccccc3-c3cccc2c13 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- PHORKVSBWZGTEX-UHFFFAOYSA-N (2-methylsulfinylphenyl)boronic acid Chemical compound CS(=O)C1=CC=CC=C1B(O)O PHORKVSBWZGTEX-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- QLILRKBRWXALIE-UHFFFAOYSA-N 3-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CN=C1 QLILRKBRWXALIE-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000000732 arylene group Chemical group 0.000 description 5
- 238000000434 field desorption mass spectrometry Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- YDMRDHQUQIVWBE-UHFFFAOYSA-N (2-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1O YDMRDHQUQIVWBE-UHFFFAOYSA-N 0.000 description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 3
- BNGRQTHLQZQMHB-UHFFFAOYSA-N 1,5-dibromo-4-nitronaphthalene Chemical compound C1=CC(Br)=C2C([N+](=O)[O-])=CC=C(Br)C2=C1 BNGRQTHLQZQMHB-UHFFFAOYSA-N 0.000 description 3
- IQYOXJJFERHBAF-UHFFFAOYSA-N 3,8-dibromo-1-nitronaphthalene Chemical compound BrC=1C=C(C2=C(C=CC=C2C=1)Br)[N+](=O)[O-] IQYOXJJFERHBAF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 description 3
- 150000008045 alkali metal halides Chemical class 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
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ODAXNYMENLFYMY-UHFFFAOYSA-N (2-methoxycarbonylphenyl)boronic acid Chemical compound COC(=O)C1=CC=CC=C1B(O)O ODAXNYMENLFYMY-UHFFFAOYSA-N 0.000 description 2
- YYZXLDLOPKTNGX-UHFFFAOYSA-N 1,2-dibromo-8-nitronaphthalene Chemical compound BrC1=C(C=CC2=CC=CC(=C12)[N+](=O)[O-])Br YYZXLDLOPKTNGX-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- MINNPCPATJNJHN-UHFFFAOYSA-N Brc1c(-c2ccccc2Nc2ccc3)c2c3cc1 Chemical compound Brc1c(-c2ccccc2Nc2ccc3)c2c3cc1 MINNPCPATJNJHN-UHFFFAOYSA-N 0.000 description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- RDQAJZKDTXGIBL-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c(cc1)ccc1-c1ccccc1)c(cc1)ccc1-c1ccc(c2cc(-c3ccccc3N3)c4c3cccc4c2[s]2)c2c1 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c(cc1)ccc1-c1ccccc1)c(cc1)ccc1-c1ccc(c2cc(-c3ccccc3N3)c4c3cccc4c2[s]2)c2c1 RDQAJZKDTXGIBL-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000007243 oxidative cyclization reaction Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000006476 reductive cyclization reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 1
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- QPWVNIHGZBWIDN-UHFFFAOYSA-N 1,2-dibromo-10-nitrophenanthrene Chemical compound BrC1=C(C=CC=2C3=CC=CC=C3C=C(C1=2)[N+](=O)[O-])Br QPWVNIHGZBWIDN-UHFFFAOYSA-N 0.000 description 1
- FDZWOINJBBDQLI-UHFFFAOYSA-N 1,3-dibromo-8-nitronaphthalene Chemical compound BrC1=CC(=CC2=CC=CC(=C12)[N+](=O)[O-])Br FDZWOINJBBDQLI-UHFFFAOYSA-N 0.000 description 1
- VFFRLRQQWXGEBX-UHFFFAOYSA-N 1-aminonaphthalene-2-carboxylic acid Chemical compound C1=CC=C2C(N)=C(C(O)=O)C=CC2=C1 VFFRLRQQWXGEBX-UHFFFAOYSA-N 0.000 description 1
- AOEHEEBFRCAFGC-UHFFFAOYSA-N 2,4-dibromopyrimidine Chemical compound BrC1=CC=NC(Br)=N1 AOEHEEBFRCAFGC-UHFFFAOYSA-N 0.000 description 1
- BSWVSKQCYPFXJF-UHFFFAOYSA-N 2,4-dichloro-[1]benzothiolo[3,2-d]pyrimidine Chemical compound C1=CC=C2C3=NC(Cl)=NC(Cl)=C3SC2=C1 BSWVSKQCYPFXJF-UHFFFAOYSA-N 0.000 description 1
- WQGRAXGAXSNSDL-LQWWMWEPSA-N 2-(2,3,4,5,6,7,8-heptadeuterionaphthalen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound [2H]C=1C([2H])=C([2H])C2=C([2H])C([2H])=C([2H])C([2H])=C2C=1B1OC(C)(C)C(C)(C)O1 WQGRAXGAXSNSDL-LQWWMWEPSA-N 0.000 description 1
- XPRBSZLRNLZXNT-UHFFFAOYSA-N 2-dibenzothiophen-4-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC2=C1SC1=CC=CC=C12 XPRBSZLRNLZXNT-UHFFFAOYSA-N 0.000 description 1
- SPPZBAGKKBHZRW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-naphthalen-2-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=CC=C2)C2=C1 SPPZBAGKKBHZRW-UHFFFAOYSA-N 0.000 description 1
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- FRYRJNHMRVINIZ-UHFFFAOYSA-N B1CCOO1 Chemical compound B1CCOO1 FRYRJNHMRVINIZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MQLVSGXWFBUHQF-UHFFFAOYSA-N C=Cc(cc1)cc(C2(c3ccccc3)c3ccccc3)c1-c(cc1)c2cc1N(c1ccccc1)c(c(-c1ccc(c2cc(-c3ccccc3N3)c4c3cccc4c2[o]2)c2c1)c1)ccc1-c1ccccc1 Chemical compound C=Cc(cc1)cc(C2(c3ccccc3)c3ccccc3)c1-c(cc1)c2cc1N(c1ccccc1)c(c(-c1ccc(c2cc(-c3ccccc3N3)c4c3cccc4c2[o]2)c2c1)c1)ccc1-c1ccccc1 MQLVSGXWFBUHQF-UHFFFAOYSA-N 0.000 description 1
- KEHITGKVGAOPGJ-UHFFFAOYSA-N CC(C)(c1c-2cccc1)c1c-2c2cccc(-c(cccc3)c3N3c4nc5ccc(cccc6)c6c5c(-c5ccccc5)n4)c2c3c1 Chemical compound CC(C)(c1c-2cccc1)c1c-2c2cccc(-c(cccc3)c3N3c4nc5ccc(cccc6)c6c5c(-c5ccccc5)n4)c2c3c1 KEHITGKVGAOPGJ-UHFFFAOYSA-N 0.000 description 1
- XGTUZPUCSRMRMN-UHFFFAOYSA-N CC(C)(c1ccccc1-1)c2c-1c1cccc(-c(ccc(N(c(cc3)ccc3F)c(cc3)ccc3F)c3)c3N3)c1c3c2 Chemical compound CC(C)(c1ccccc1-1)c2c-1c1cccc(-c(ccc(N(c(cc3)ccc3F)c(cc3)ccc3F)c3)c3N3)c1c3c2 XGTUZPUCSRMRMN-UHFFFAOYSA-N 0.000 description 1
- VSUNTCZPPWWCOD-UHFFFAOYSA-N CC(C)(c1ccccc1-1)c2c-1c1cccc(-c(cccc3)c3N3)c1c3c2 Chemical compound CC(C)(c1ccccc1-1)c2c-1c1cccc(-c(cccc3)c3N3)c1c3c2 VSUNTCZPPWWCOD-UHFFFAOYSA-N 0.000 description 1
- OBMNUXLEYICVOE-UHFFFAOYSA-N CC(C)(c1ccccc1-c1c2)c1ccc2N(c1ccccc1)c(cc1)ccc1-c(cc1)cc(c2c3)c1[s]c2c1c2c3-c3ccccc3Nc2ccc1 Chemical compound CC(C)(c1ccccc1-c1c2)c1ccc2N(c1ccccc1)c(cc1)ccc1-c(cc1)cc(c2c3)c1[s]c2c1c2c3-c3ccccc3Nc2ccc1 OBMNUXLEYICVOE-UHFFFAOYSA-N 0.000 description 1
- VXLBBSLCTFTKOE-UHFFFAOYSA-N CC1(C)OB(c(cc2)cc3c2c2ccccc2c2c3cccc2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc3c2c2ccccc2c2c3cccc2)OC1(C)C VXLBBSLCTFTKOE-UHFFFAOYSA-N 0.000 description 1
- XJXJUWPXWMXLBI-UHFFFAOYSA-N CC1(C)c(c2cccc(Nc3ccccc3-3)c2c-3c2)c2-c2c1ccc(N(c(cc1)ccc1-c1cccc3c1[s]c1c3cccc1)c1cccc3c1[s]c1c3cccc1)c2 Chemical compound CC1(C)c(c2cccc(Nc3ccccc3-3)c2c-3c2)c2-c2c1ccc(N(c(cc1)ccc1-c1cccc3c1[s]c1c3cccc1)c1cccc3c1[s]c1c3cccc1)c2 XJXJUWPXWMXLBI-UHFFFAOYSA-N 0.000 description 1
- DHMBVMCMJORILF-UHFFFAOYSA-N COC(c(cccc1)c1-c1ccc2Nc3cc(N(c(cc4)ccc4F)c(cc4)ccc4F)ccc3-c3c2c1ccc3)=O Chemical compound COC(c(cccc1)c1-c1ccc2Nc3cc(N(c(cc4)ccc4F)c(cc4)ccc4F)ccc3-c3c2c1ccc3)=O DHMBVMCMJORILF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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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
- C07D401/02—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 two hetero rings
- C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- H—ELECTRICITY
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
- organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
- An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
- the organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
- the material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
- the difference in characteristics depending on the material structure is very large and applied to various layers as a material of an organic electric device.
- the band gap (HOMO, LUMO), electrical properties, chemical properties, and physical properties are different depending on the number of rings, the fused position, and the type and arrangement of heteroatoms. This has been going on.
- US Patent Application Publication No. US2008 / 0145708A1 discloses an embodiment in which a polycyclic cyclic compound is applied to a hole transport layer or a phosphorescent host of an organic electric device
- Korean Patent Application Publication No. 10-2007-0012218 discloses an embodiment in which a polycyclic cyclic compound is applied to an electron transport layer of an organic electric device.
- the development of materials for organic electric devices for the heteroatom type, number and position of polycyclic cyclic compounds is actively progressing.
- An object of the present invention is to provide a compound capable of improving the luminous efficiency and lifetime of the device while lowering the driving voltage of the device by using the properties of the polycyclic ring compound, an organic electric device using the same, and an electronic device thereof.
- the present invention provides a compound represented by the following formula. Any one of R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 in Formula 1 may form a condensed ring represented by Formula 1a.
- the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
- the compound of the present invention By using the compound of the present invention, not only the driving voltage of the device can be lowered, but also the light emitting efficiency and lifetime of the device can be greatly improved.
- FIG. 1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.
- halo or halogen as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
- alkyl or “alkyl group” has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
- heteroalkyl group means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
- alkenyl group or “alkynyl group”, unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.
- cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
- alkoxyl group means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
- alkenoxyl group means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
- aryloxyl group or “aryloxy group” means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
- aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
- an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
- the aryl group may be a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, fluorene group, spirofluorene group, spirobifluorene group.
- aryl or "ar” means a radical substituted with an aryl group.
- an arylalkyl group is an alkyl group substituted with an aryl group
- an arylalkenyl group is an alkenyl group substituted with an aryl group
- the radical substituted with an aryl group has the carbon number described herein.
- an arylalkoxy group means an alkoxy group substituted with an aryl group
- an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group
- an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group.
- the arylcarbonyl group is a carbonyl group substituted with an aryl group.
- heteroalkyl means an alkyl including one or more heteroatoms unless otherwise indicated.
- heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
- heterocyclic group includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
- heteroatom refers to N, O, S, P or Si unless otherwise stated.
- Heterocyclic groups may also include rings comprising SO 2 in place of the carbon forming the ring.
- a “heterocyclic group” includes the following compounds.
- aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
- aliphatic ring means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
- ring refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.
- heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
- carbonyl used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
- ether as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
- substituted in the term “substituted or unsubstituted” as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl group, C 1 ⁇ C 20 alkylamine group, C 1 ⁇ C 20 alkylthiophene group, C 6 ⁇ C 20 arylthiophene group, C 2 ⁇ C 20 alkenyl group, C 2 ⁇ C 20 alkynyl, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 20 aryl group, of a C 6 ⁇ C 20 substituted by deuterium aryl group, a C 8 ⁇ C 20 aryl alkenyl group, a silane group, a boron Group, germanium group, and C 2 ⁇ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of,
- the substituent R 1 when a is an integer of 0, the substituent R 1 is absent, when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 are each bonded as follows, where R 1 may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.
- FIG. 1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
- the organic electric device 100 includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110.
- the first electrode 120 may be an anode (anode)
- the second electrode 180 may be a cathode (cathode)
- the first electrode may be a cathode and the second electrode may be an anode.
- the organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed.
- the hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
- the organic electric device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.
- a protective layer or a light efficiency improving layer Capping layer
- the compound according to the present invention applied to the organic material layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improvement layer of the light emitting layer 150 It may be used as a material.
- the compound of the present invention may be used as the light emitting layer 150.
- the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layer, and thus the life of the organic electric device. And efficiency can be improved at the same time.
- the organic light emitting device may be manufactured using a physical vapor deposition (PVD) method.
- the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon.
- the organic material layer including the 160 and the electron injection layer 170 it can be prepared by depositing a material that can be used as the cathode 180 thereon.
- the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
- the organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
- WOLED White Organic Light Emitting Device
- Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
- CCM color conversion material
- the organic electroluminescent device according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.
- OLED organic light emitting diode
- OPC organic photoconductor
- organic TFT organic transistor
- Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device.
- the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
- R 1 to R 14 are each independently hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group or adjacent groups may combine with each other to form a ring, R 1 to R 14 which do not form a ring are the same as defined above,
- R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 forms a condensed ring represented by Formula 1a,
- R 5 and R 6 form a condensed ring represented by Formula 1a
- R 5 represents a bond connected to **
- R 6 represents a bond connected to *
- R 6 and R 7 form a condensed ring represented by Formula 1a
- R 6 represents a bond connected to **
- R 7 represents a bond connected to *
- R 8 and R 9 form a condensed ring represented by Formula 1a
- R 8 represents a bond connected to **
- R 9 represents a bond connected to *
- R 9 and R 10 form a condensed ring represented by Formula 1a
- R 9 represents a bond connected to **
- R 10 represents a bond connected to *
- X is one of S, O and C (Ar 2 ) (Ar 3 ),
- Ar 1 is independently of each other C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,
- Ar 2 and Ar 3 are each independently i) a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group, or ii) Ar 2 and Ar 3 may be bonded to each other to form a spiro compound with the C bonded thereto,
- R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; A C 2 -C 60 heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; And C 2 -C 20 Alkenyl group; It is selected from the group consisting of,
- L 1 and L a are each independently a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And divalent aliphatic hydrocarbon groups, each of L 1 and L a (excluding single bonds) is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with
- R c and R d are each independently a C 6 -C 60 aryl group; Fluorenyl group; It may be selected from the group consisting of; C 2 -C 60 heterocyclic group containing at least one hetero atom of O, N, S, Si and P.
- the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, each of the aryloxy group is deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected
- the carbon number may be 6 to 60, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, the carbon number is 2 to 60, preferably 2 carbon atoms. ⁇ 30, more preferably a hetero ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the carbon number is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably It may be an alkyl group of 1 to 10.
- the aryl group or arylene group is independently of each other a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group or phenylene group, biphenylene group, terphenylene group, naphthyl Or a phenanthrene group or the like.
- the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.
- Formula 1 may be represented by one of the following Formula 2 to Formula 5.
- R 1 to R 14 , X, Ar 1 and L 1 are the same as defined in Chemical Formula 1.
- Ar 1 of Chemical Formula 1 may be represented by one of Chemical Formulas A-1 to A-3.
- Q 1 to Q 4 are independently carbon (C) bonded to N, CR e , and L 1 , and one of Q 1 to Q 4 is carbon (C) bonded to L 1 . ego,
- Q 1 to Q 4 are each independently N and CR e ,
- Q 5 to Q 9 are independently of each other N, CR e ,
- Z is C 6 -C 60 monocyclic or polycyclic aromatic ring; Or a C 2 -C 60 heterocyclic group including at least one hetero atom of O, N, S, Si, and P,
- R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And arylalkenyl group of
- the Z ring of Chemical Formulas A-1 and A-2 may be independently one of the following Chemical Formulas.
- the mark * denotes a binding moiety that combines with a ring including Q 1 to Q 4 to form a fused ring.
- W 1 and W 2 are independently of each other a single bond, NL 2 -Ar 4 , S, O, C (Ar 5 ) (Ar 6 ),
- V is independently of each other N, CR e ,
- L 2 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And it is selected from the group consisting of divalent aliphatic hydrocarbon group,
- Ar 4 to Ar 6 is a C 6 -C 20 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,
- Ar 5 and Ar 6 may be bonded to each other to form a spiro compound together with the carbon (C) to which they are bonded,
- R e is the same as the definition of R e in Formulas A-1 to A-3.
- At least one of Q 1 to Q 4 may be N.
- At least one of Q 1 to Q 4 includes a structure including N may be one of Formulas Z-16 to Z-50.
- W 1 and W 2 are independently of each other a single bond, NL 2 -Ar 4 , S, O, C (Ar 5 ) (Ar 6 ),
- R e is hydrogen; heavy hydrogen; halogen;
- R e in Chemical Formulas Z-16 to Z-50 are the same, but may be identical to or different from each other at each position in each Chemical Formula.
- five R e are each independently of the other hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O
- the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.
- the present invention provides a compound for an organic electric device represented by Chemical Formula 1.
- the present invention provides an organic electric device containing the compound represented by the formula (1).
- the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode.
- the organic material layer may include a compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 1 may be a hole injection layer or a hole transport layer of the organic material layer.
- the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may be contained in at least one layer.
- the compound represented by Formula 1 may be included in the hole transport layer or the light emitting auxiliary layer.
- the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer or an electron injection layer.
- the compound represented by Formula 1 may be used as a material of the light emitting layer.
- an organic electroluminescent device comprising one of the compounds represented by the formula (1) in the organic material layer, more specifically, It provides an organic electroluminescent device comprising a compound represented by the individual formulas (1-1 to 4-38) in the organic material layer.
- the compound is contained alone or in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer,
- an organic electroluminescent device characterized in that a compound is contained in a combination of two or more different from each other, or the compound is contained in a combination of two or more.
- each of the layers may include a compound corresponding to Formula 1 alone, and may include a mixture of two or more compounds of Formula 1, the compounds of claims 1 to 6, and compounds not corresponding to the present invention. And mixtures thereof.
- the compound not corresponding to the present invention may be a single compound or two or more compounds.
- the other compound when the compound is contained in a combination of two or more kinds of other compounds, the other compound may be a known compound of each organic material layer, or a compound to be developed in the future.
- the compound contained in the organic material layer may be made only of the same kind of compound, but may be a mixture of two or more kinds of the compound represented by the formula (1).
- the present invention provides a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric element further comprising.
- Sub 1A to Sub 1D of Schemes 1 to 4 may be synthesized by the reaction routes of Scheme 5 and Scheme 6, but are not limited thereto.
- R 5 , R 6 , R 8 , R 9 is Br.
- Sub 1A-II-1 (19.75 g, 66.69 mmol) obtained in the above synthesis was dissolved in THF (220 ml) in a round bottom flask, followed by (2- (methylsulfinyl) phenyl) boronic acid (12.27 g, 66.69 mmol), Pd ( PPh 3 ) 4 (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol), water (110 ml) were added and stirred at 80 ° C.
- Sub 1A-III'-2 (21.62 g, 69.89 mmol) obtained in the above synthesis was added to a round bottom flask together with Pd (OAc) 2 (1.57 g, 6.99 mmol) and 3-nitropyridine (0.87 g, 6.99 mmol).
- 6 F 6 (105 ml), dissolved in DMI (70 ml), and tert- butyl peroxybenzoate (27.15 g, 139.77 mmol) were added and stirred at 90 ° C.
- Sub 1C-II-1 (22.26 g, 75.16 mmol) obtained in the above synthesis was added to (4 '-(di ([1,1'-biphenyl] -4-yl) amino) -3- (methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (43.56 g, 75.16 mmol), Pd (PPh 3 ) 4 (3.47 g, 3.01 mmol), NaOH (9.02 g, 225.49 mmol), THF (250ml), water ( 125 ml) was added and 32.17 g (yield: 57%) of product was obtained using the Sub 1A-III-1 synthesis method.
- Sub 1D-II-1 (15.02 g, 50.72 mmol) obtained in the above synthesis was added to (3 '-([1,1'-biphenyl] -3-yl (phenyl) amino) -3- (methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (25.53 g, 50.72 mmol), Pd (PPh 3 ) 4 (2.34 g, 2.03 mmol), NaOH (6.09 g, 152.15 mmol), THF (170ml), water ( 85 ml) was added to give 18.48 g (yield: 54%) of product using the Sub 1A-III-1 synthesis.
- Compounds belonging to Sub 1A to Sub 1D may be the following compounds, but are not limited thereto.
- Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1A to Sub 1D.
- Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 22, but is not limited thereto. At this time, Hal 1 and Hal 2 are Br or Cl.
- Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.
- FD-MS Field Desorption-Mass Spectrometry
- Sub 1A to Sub 1D (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 2 (1 equiv), Pd 2 (dba) 3 (0.03 equiv), (t-Bu) 3 P (0.06 equiv), NaOt-Bu (3 equiv) was stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a final product.
- Sub 1A-1 (5.74 g, 17.75 mmol) obtained in the above synthesis was dissolved in toluene (180 ml) in a round bottom flask, and then Sub 2-50 (5.16 g, 17.75 mmol), Pd 2 (dba) 3 (0.49 g, 0.53 mmol), 50% P ( t -Bu) 3 (0.5ml, 1.06 mmol), NaO t -Bu (5.12 g, 53.25 mmol) were added and stirred at 100 ° C.
- Sub 1B-3 (6.73 g, 20.18 mmol) obtained in the above synthesis in Sub 2-50 (5.87 g, 20.18 mmol), Pd 2 (dba) 3 (0.55 g, 0.61 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.21 mmol), NaO t -Bu (5.82 g, 60.55 mmol), toluene (200 ml) were added and the product P. 1-10 was used to yield 7.12 g (yield: 60%) of the product.
- Sub 1D-7 (7.38 g, 20.65 mmol) obtained in the above synthesis in Sub 2-22 (7.91 g, 20.65 mmol), Pd 2 (dba) 3 (0.57 g, 0.62 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.24 mmol), NaO t -Bu (5.95 g, 61.95 mmol), toluene (205 ml) were added and the product P. 1-10 was used to yield 7.49 g (yield: 55%) of the product.
- the reaction of one of Sub 1A to Sub 1D and Sub 2-> Final Product in Schemes 1 to 4 is based on the Buchwald-Hartwig cross coupling reaction, and in Scheme 5, the Sub 1-II-> Sub 1-III reaction, Sub 1-II-> Sub 1-III 'reaction, Sub 1-II-> Sub 1-III ”reaction, starting materials in Scheme 6-> Sub 1-I reaction, starting materials in Scheme 22-> Sub 2 reaction It is based on the Suzuki cross-coupling reaction (in this case, in the case of a reactant containing an amine, Korean Patent No. 10-1251451 (published on Apr. 5, 2013) and 10-1298483 (Aug. 21, 2013) of the present applicant.
- An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer.
- a 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (abbreviated as 2-TNATA) film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a hole having a thickness of 60 nm.
- an NPD film was vacuum deposited to a thickness of 60 nm as a hole transport compound on the hole injection layer to form a hole transport layer.
- Compound P 1-1 of the present invention was used as a host on the hole transport layer, and tris (2-phenylpyridine) -iridium (hereinafter, abbreviated as “Ir (ppy) 3 ”) as a dopant material was 95: 5 by weight. Doped to deposit a light emitting layer to a thickness of 30nm.
- BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum
- An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound of the present invention shown in Table 4 instead of the compound P 1-1 according to Example 1 of the present invention as a green host material of the emission layer. .
- the device was manufactured.
- Electroluminescent (EL) characteristics of the photoresearch company PR-650 were applied by applying a forward bias DC voltage to the organic light emitting diodes prepared according to Examples 1 to 25 and Comparative Examples 1 to 3 of the present invention.
- the T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m 2 reference luminance. The measurement results are shown in Table 4 below.
- the hexagonal rings contain N and the core elements are included in the hexagonal rings than in the case of Comparative Compounds 2 to 4, wherein the hexagonal and pentagonal rings have the same key element as N. It can be seen that the compound of the present invention, which is a heteroatom type containing one of S, O, and CR'R ′′, exhibits higher efficiency and higher lifetime.
- Comparative Compounds 2 to 4 which are NN-type six-membered heterocyclic compounds, are NN-type heterocyclic cores when the molecules are stacked, so that the intermolecular sequence is edge-to-face. It is believed to cause charge carrier mobility and low oxidative stability.
- the heteroatoms in the cyclic compound since they have different heterocyclic cores, they have an antiparallelcofacial ⁇ -stacking structure in which the packing structure of the molecules faces in the reverse direction. This makes the arrangement order between molecules into face-to-face shape and due to the steric effect of Ar 1 of asymmetrically arranged heteroatoms N which is the cause of the stacked structure, it is considered to have a high efficiency due to the high carrier mobility. In addition, it has a high oxidative stability and is believed to significantly increase the lifespan.
- the compound of the present invention that contains N in the hexagonal ring has a more suitable form to accommodate both holes and electrons more stably than Comparative Compound 3, which is a case where N is included in the pentagonal ring. It is judged that the light emission efficiency and lifespan are increased.
- An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer.
- a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm.
- the NPD film is vacuum-deposited at a thickness of 60 nm as a hole transport compound on the hole injection layer.
- a transport layer was formed.
- Compound P 1-9 of the present invention was used as a host on the hole transport layer, and a light emitting layer was deposited to a thickness of 30 nm by doping a (piq) 2 Ir (acac) at a weight ratio of 95: 5 with a dopant material. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm using a hole blocking layer, and Alq 3 was formed to a thickness of 40 nm using an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic light emitting diode.
- LiF which is an alkali metal halide
- An organic light emitting diode was manufactured according to the same method as Example 26 except for using the compound of the present invention shown in Table 5 below instead of the compound P 1-9 according to Example 26 of the present invention as a red host material of the emission layer. .
- Comparative Compound 4 shown in Table 5 as a host material of the light emitting layer in the same manner as in Example 26 except that An organic light emitting device was manufactured by the method.
- the electroluminescence (EL) characteristics of the photoresearch company PR-650 were applied by applying a forward bias DC voltage to the organic light emitting diodes manufactured according to Examples 26 to 50 and Comparative Examples 4 to 6.
- the T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 2500 cd / m 2 reference luminance. The measurement results are shown in Table 5 below.
- the device using the compound according to an embodiment of the present invention as a phosphorescent red host material of the light emitting layer is significantly improved luminous efficiency and lifetime than Comparative Compound 1 and Comparative Compounds 5 to 9 It was confirmed.
- the heterocyclic atoms in the ring compound have heterocyclic heterocyclic cores and the structure in which the hexagonal ring contains N is used not only in the light emitting layer (used as a host) but also in the red organic light emitting element (used as a host). It can be seen that it acts as a major factor in improving device performance.
- the compound of the present invention used as a host material in the light emitting layer has high oxidative stability and high charge carrier mobility to achieve more effective charge balance.
- the introduction of specific substituents, such as benzofuropyrimidine, exhibits the appropriate conformation to accommodate both holes and electrons, and at the same time has an appropriate T1 value to facilitate charge transfer from the host to the dopant. It can be seen that it shows the best device results in luminous efficiency and lifetime.
- An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a hole transport material.
- a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then Compound P-40 of the present invention on the hole injection layer has a thickness of 60 nm.
- Vacuum deposition was performed to form a hole transport layer.
- 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as “CBP”) was used as a host on the hole transport layer, and dopant was doped with Ir (ppy) 3 in a 90:10 weight ratio.
- CBP 4,4'-N, N'-dicarbazole-biphenyl
- a light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm using a hole blocking layer, and Alq 3 was formed to a thickness of 40 nm using an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.
- LiF which is an alkali metal halide
- An organic light emitting diode was manufactured according to the same method as Example 51 except for using the compound of the present invention shown in Table 6 instead of the compound P 1-40 according to Example 51 of the present invention as a hole transport layer material.
- An organic light emitting diode was manufactured according to the same method as Example 51 except for using Comparative Compound 6 shown in Table 6 below instead of Compound P 1-00 according to Example 51 of the present invention as a hole transport layer material.
- Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic light emitting diodes prepared in Examples 51 to 71 and Comparative Example 7 of the present invention. Measurement Results The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m 2 reference luminance, and the measurement results are shown in Table 6 below.
- This result has a deep HOMO energy level and a high T1 value, which are inherent characteristics of the compound of the present invention, which improves the ability to block electrons and simultaneously transports holes to the light emitting layer. It is believed that the efficiency is improved while being more easily generated within. In addition, it has a high thermal stability it can be seen that the life is extended.
- the amine group (-L a -N (R a ) (R b )) in the same heterocyclic ring as the compound of the present invention It can be seen that the band gap, electrical characteristics, and interface characteristics can be greatly changed by the introduction, which can be seen as a major factor in improving device performance.
- the hole transport layer it is necessary to grasp the interrelationship with the light emitting layer (host), and even if a similar core is used, it will be very difficult even for a person skilled in the art to infer the characteristics shown in the hole transport layer in which the compound of the present invention is used.
- the evaluation results of the above-described device fabrication described the device characteristics of applying the compound of the present invention to the light emitting layer and the hole transporting material as a host material, but the compound of the present invention is applied to the hole injection layer, the light emitting auxiliary layer, the electron transporting layer, The electron injection layer, the light emitting auxiliary layer and the like can be applied to all other layers.
Abstract
The present invention provides: a compound capable of increasing high emission efficiency, a low driving voltage, and the life span of an element; an organic electric element using the same; and an electronic device therefor.
Description
본 발명은 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다.In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
헤테로원자를 포함하고 있는 다환 고리화합물의 경우 물질 구조에 따른 특성의 차이가 매우 커서 유기전기소자의 재료로 다양한 층에 적용되고 있다. 특히 환의 개수 및 fused 위치, 헤테로원자의 종류와 배열에 따라 밴드갭(HOMO, LUMO), 전기적 특성, 화학적 특성, 물성 등이 상이하다는 특징을 갖고 있어, 이를 이용한 다양한 유기전기소자의 층에 적용 개발이 진행되어져 왔다.In the case of polycyclic cyclic compounds containing heteroatoms, the difference in characteristics depending on the material structure is very large and applied to various layers as a material of an organic electric device. In particular, the band gap (HOMO, LUMO), electrical properties, chemical properties, and physical properties are different depending on the number of rings, the fused position, and the type and arrangement of heteroatoms. This has been going on.
예를 들어, 미국 특허출원공개공보 US2008/0145708A1 (2008.06.19)에는 다환 고리화합물을 유기전기소자의 정공수송층 또는 인광호스트에 적용한 실시예가 개시되어 있으며, 대한민국 공개특허공보 제10-2007-0012218호(2007.01.25)에는 다환 고리화합물을 유기전기소자의 전자수송층에 적용한 실시예가 개시되어 있다. 현재에도 다환 고리화합물의 헤테로원자 종류, 개수 및 위치에 대한 유기전기소자의 재료 개발이 활발히 진행되고 있다.For example, US Patent Application Publication No. US2008 / 0145708A1 (2008.06.19) discloses an embodiment in which a polycyclic cyclic compound is applied to a hole transport layer or a phosphorescent host of an organic electric device, and Korean Patent Application Publication No. 10-2007-0012218 (2007.01.25) discloses an embodiment in which a polycyclic cyclic compound is applied to an electron transport layer of an organic electric device. At present, the development of materials for organic electric devices for the heteroatom type, number and position of polycyclic cyclic compounds is actively progressing.
본 발명은 다환 고리 화합물의 특성을 이용하여 소자의 구동전압을 낮추면서, 소자의 발광효율 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound capable of improving the luminous efficiency and lifetime of the device while lowering the driving voltage of the device by using the properties of the polycyclic ring compound, an organic electric device using the same, and an electronic device thereof.
일 측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다. 하기 화학식 1의 R5와 R6, R6과 R7, R8와 R9 및 R9와 R10 중 어느 하나는 하기 화학식 1a로 표시되는 축합 고리를 형성할 수 있다.In one aspect, the present invention provides a compound represented by the following formula. Any one of R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 in Formula 1 may form a condensed ring represented by Formula 1a.
다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
본 발명 화합물을 이용함으로써 소자의 구동전압을 낮출 수 있을 뿐만 아니라, 소자의 발광 효율 및 수명을 크게 향상시킬 수 있다.By using the compound of the present invention, not only the driving voltage of the device can be lowered, but also the light emitting efficiency and lifetime of the device can be greatly improved.
도 1은 본 발명의 일실시예에 따른 유기발광소자의 단면도이다.1 is a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.
이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".
본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다.As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows.
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 시클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다.As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.
본 발명에 사용된 용어 "헤테로알킬기"는 알킬기를 구성하는 탄소 원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
본 발명에 사용된 용어 "알켄일기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다.The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
본 발명에 사용된 용어 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 터페닐기, 나프틸기, 안트라센일기, 플루오렌기, 스파이로플루오렌기, 스파이로바이플루오렌기일 수 있다.As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, fluorene group, spirofluorene group, spirobifluorene group.
접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다.The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described herein.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다.As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다.The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.
또한 "헤테로고리기"는, 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다."Heterocyclic groups" may also include rings comprising SO 2 in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다.Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다.Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "카르보닐"이란 -COR'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20 의 알킬기, 탄소수 6 내지 30 의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
다른 설명이 없는 한, 본 발명에 사용된 용어 "에테르"란 -R-O-R'로 표시되는 것이며, 여기서 R 또는 R'은 각각 서로 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕실기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알켄일기, C2~C20의 알킨일기, C3~C20의 시클로알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 arylthiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, a silane group, a boron Group, germanium group, and C 2 ~ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.
또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formula.
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하며, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.Herein, when a is an integer of 0, the substituent R 1 is absent, when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R 1 may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.
도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 본 발명에 따른 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다.The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층 또는 광효율 개선층(Capping layer)을 더 포함할 수 있다.In addition, although not shown, the organic electric device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer.
상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 광효율 개선층의 재료로 사용될 수 있을 것이다. 바람직하게는, 본 발명의 화합물은 발광층(150)으로 사용될 수 있을 것이다.The compound according to the present invention applied to the organic material layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improvement layer of the light emitting layer 150 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150.
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 장수명과 높은 효율을 동시에 달성할 수 있다.Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.
따라서, 본 발명에서는 화학식 1로 표시되는 화합물을 사용하여 발광층을 형성함으로써 각 유기물층 간의 에너지 레벨(level) 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다.Therefore, in the present invention, the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layer, and thus the life of the organic electric device. And efficiency can be improved at the same time.
본 발명의 일 실시예에 따른 유기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic light emitting device according to the embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정, 닥터 블레이딩 공정, 스크린 프린팅 공정, 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다.WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
또한, 본 발명에 따른 유기전기소자는 유기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.In addition, the organic electroluminescent device according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다. 본 발명의 일 측면에 따른 화합물은 하기 화학식 1로 표시된다. Hereinafter, the compound which concerns on one aspect of this invention is demonstrated. Compound according to an aspect of the present invention is represented by the following formula (1).
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R14는 서로 독립적으로 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -La-N(Ra)(Rb); C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며, 고리를 형성하지 않는 R1 내지 R14는 상기에서 정의된 것과 동일하며,R 1 to R 14 are each independently hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group or adjacent groups may combine with each other to form a ring, R 1 to R 14 which do not form a ring are the same as defined above,
단, R5와 R6, R6과 R7, R8와 R9 및 R9와 R10 중 어느 하나는 상기 화학식 1a로 표시되는 축합 고리를 형성하며,Provided that any one of R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 forms a condensed ring represented by Formula 1a,
R5와 R6이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R5가 **에 연결된 결합을 나타내고 R6이 *에 연결된 결합을 나타내며,When R 5 and R 6 form a condensed ring represented by Formula 1a, R 5 represents a bond connected to ** and R 6 represents a bond connected to *,
R6과 R7이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R6이 **에 연결된 결합을 나타내고 R7이 *에 연결된 결합을 나타내며,When R 6 and R 7 form a condensed ring represented by Formula 1a, R 6 represents a bond connected to ** and R 7 represents a bond connected to *,
R8와 R9가 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R8이 **에 연결된 결합을 나타내고 R9가 *에 연결된 결합을 나타내며,When R 8 and R 9 form a condensed ring represented by Formula 1a, R 8 represents a bond connected to ** and R 9 represents a bond connected to *,
R9와 R10이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R9가 **에 연결된 결합을 나타내고 R10이 *에 연결된 결합을 나타내며,When R 9 and R 10 form a condensed ring represented by Formula 1a, R 9 represents a bond connected to ** and R 10 represents a bond connected to *,
X는 S, O 및 C(Ar2)(Ar3) 중 하나이며,X is one of S, O and C (Ar 2 ) (Ar 3 ),
Ar1은 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -La-N(Ra)(Rb); C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며, Ar 1 is independently of each other C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,
Ar2 및 Ar3은 i)서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되거나, 또는 ii) Ar2와 Ar3이 서로 결합하여 이들이 결합된 C 와 함께 스파이로(spiro) 화합물을 형성할 수 있으며,Ar 2 and Ar 3 are each independently i) a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group, or ii) Ar 2 and Ar 3 may be bonded to each other to form a spiro compound with the C bonded thereto,
Ra 및 Rb는 서로 독립적으로, C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; 및 C2-C20의 알켄일기;로 이루어진 군에서 선택되며,R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; A C 2 -C 60 heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; And C 2 -C 20 Alkenyl group; It is selected from the group consisting of,
L1 및 La는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 2가 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 2가 융합고리기; 및 2가의 지방족 탄화수소기로 이루어진 군에서 선택되며, L1 및 La(단일결합 제외) 각각은 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; -N(Rc)(Rd); 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있으며,L 1 and L a are each independently a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And divalent aliphatic hydrocarbon groups, each of L 1 and L a (excluding single bonds) is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; -N (R c ) (R d ); And an arylalkenyl group of C 8 -C 20 It can be substituted with one or more substituents selected from the group consisting of,
상기 Rc 및 Rd는 서로 독립적으로, C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기;로 이루어진 군에서 선택될 수 있다. R c and R d are each independently a C 6 -C 60 aryl group; Fluorenyl group; It may be selected from the group consisting of; C 2 -C 60 heterocyclic group containing at least one hetero atom of O, N, S, Si and P.
여기서, 상기 아릴기, 플루오렌일기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알킨일기, 알콕시기, 아릴옥시기 각각은 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있다.Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, each of the aryloxy group is deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of C 8 -C 20 arylalkenyl group.
여기서, 상기 아릴기인 경우 탄소수는 6~60, 바람직하게는 탄소수 6~40, 보다 바람직하게는 탄소수 6~30의 아릴기일 수 있으며, 상기 헤테로고리기인 경우 탄소수는 2~60, 바람직하게는 탄소수 2~30, 보다 바람직하게는 탄소수 2~20의 헤테로고리일 수 있으며, 상기 알킬기인 경우 탄소수는 1~50, 바람직하게는 탄소수 1~30, 보다 바람직하게는 탄소수 1~20, 특히 바람직하게는 탄소수 1~10의 알킬기일 수 있다. Here, in the case of the aryl group, the carbon number may be 6 to 60, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, the carbon number is 2 to 60, preferably 2 carbon atoms. ˜30, more preferably a hetero ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the carbon number is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably It may be an alkyl group of 1 to 10.
상기 전술한 아릴기 또는 아릴렌기일 경우, 구체적으로 아릴기 또는 아릴렌기는 서로 독립적으로 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난트릴기 또는 페닐렌기, 비페닐렌기, 터페닐렌기, 나프틸렌기 또는 페난트릴렌기 등일 수 있다.In the case of the aforementioned aryl group or arylene group, specifically, the aryl group or arylene group is independently of each other a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group or phenylene group, biphenylene group, terphenylene group, naphthyl Or a phenanthrene group or the like.
보다 구체적으로, 상기 화학식 1로 표시되는 화합물은 하기 화합물들 중 어느 하나일 수 있으며, 하기 화합물에만 한정하는 것은 아니다.More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.
상기 화학식 1은 하기 화학식 2 내지 화학식 5 중 하나로 표시될 수 있다.Formula 1 may be represented by one of the following Formula 2 to Formula 5.
상기 R1 내지 R14, X, Ar1 및 L1은 화학식 1에서 정의된 것과 동일하다. R 1 to R 14 , X, Ar 1 and L 1 are the same as defined in Chemical Formula 1.
상기 화학식 1의 Ar1은 하기 화학식 A-1 내지 화학식 A-3 중 하나로 표시될 수 있다.Ar 1 of Chemical Formula 1 may be represented by one of Chemical Formulas A-1 to A-3.
상기 화학식 A-1에서, Q1 내지 Q4는 서로 독립적으로 N, CRe, 및 L1과 결합하는 탄소(C)이며, Q1 내지 Q4 중 하나는 L1과 결합하는 탄소(C)이고, In Chemical Formula A-1, Q 1 to Q 4 are independently carbon (C) bonded to N, CR e , and L 1 , and one of Q 1 to Q 4 is carbon (C) bonded to L 1 . ego,
상기 화학식 A-2에서, Q1 내지 Q4는 서로 독립적으로 N, CRe이며,In Formula A-2, Q 1 to Q 4 are each independently N and CR e ,
상기 화학식 A-3에서, Q5 내지 Q9는 서로 독립적으로 N, CRe이며,In Formula A-3, Q 5 to Q 9 are independently of each other N, CR e ,
상기 화학식 A-1 및 A-2에서, Z는 C6-C60의 단일환 또는 다환의 방향족고리; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기로 이루어진 군에서 선택되며,In Chemical Formulas A-1 and A-2, Z is C 6 -C 60 monocyclic or polycyclic aromatic ring; Or a C 2 -C 60 heterocyclic group including at least one hetero atom of O, N, S, Si, and P,
상기 화학식 A-1 내지 A-3에서,In Chemical Formulas A-1 to A-3,
Re 는 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된다. R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And arylalkenyl group of C 8 -C 20 It is selected from the group consisting of.
상기 화학식 A-1 및 화학식 A-2의 Z환은 서로 독립적으로 하기 화학식 중 하나일 수 있다.The Z ring of Chemical Formulas A-1 and A-2 may be independently one of the following Chemical Formulas.
상기 화학식 Z-1 내지 화학식 Z-15에서, 표시 *은 Q1 내지 Q4를 포함하는 고리와 결합하여 융합고리를 형성하는 결합 부분을 표시하며, In Formulas Z-1 to Z-15, the mark * denotes a binding moiety that combines with a ring including Q 1 to Q 4 to form a fused ring.
W1 및 W2는 서로 독립적으로 단일결합, N-L2-Ar4, S, O, C(Ar5)(Ar6) 중 하나이며,W 1 and W 2 are independently of each other a single bond, NL 2 -Ar 4 , S, O, C (Ar 5 ) (Ar 6 ),
V는 서로 독립적으로 N, CRe이며, V is independently of each other N, CR e ,
L2는 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 2가 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 2가 융합고리기; 및 2가의 지방족 탄화수소기로 이루어진 군에서 선택되며,L 2 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And it is selected from the group consisting of divalent aliphatic hydrocarbon group,
Ar4 내지 Ar6은 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며,Ar 4 to Ar 6 is a C 6 -C 20 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,
Ar5과 Ar6이 서로 결합하여 이들이 결합된 탄소(C)와 함께 스파이로(spiro) 화합물을 형성할 수 있으며,Ar 5 and Ar 6 may be bonded to each other to form a spiro compound together with the carbon (C) to which they are bonded,
Re는 상기 화학식 A-1 내지 A-3에서의 Re의 정의와 동일하다.R e is the same as the definition of R e in Formulas A-1 to A-3.
상기 Q1 내지 Q4 중 적어도 하나는 N일 수 있다. At least one of Q 1 to Q 4 may be N.
상기 화학식 A-1 및 A-2에서, 상기 Q1 내지 Q4 중 적어도 하나는 N을 포함한 구조는 하기 화학식 Z-16 내지 화학식 Z-50 중 하나일 수 있다.In Formulas A-1 and A-2, at least one of Q 1 to Q 4 includes a structure including N may be one of Formulas Z-16 to Z-50.
W1 및 W2는 서로 독립적으로 단일결합, N-L2-Ar4, S, O, C(Ar5)(Ar6) 중 하나이며, Re는 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된다. W 1 and W 2 are independently of each other a single bond, NL 2 -Ar 4 , S, O, C (Ar 5 ) (Ar 6 ), R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And arylalkenyl group of C 8 -C 20 It is selected from the group consisting of.
이때 화학식 Z-16 내지 화학식 Z-50에서 Re가 동일하게 표시되었으나 각 화학식에서 각 위치에서 서로 독립적으로 동일할 수도 있고 상이할 수도 있다. 예를 들어 화학식 Z-16에서 5개의 Re들은 각각 서로 독립적으로 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택될 수 있다. In this case, R e in Chemical Formulas Z-16 to Z-50 are the same, but may be identical to or different from each other at each position in each Chemical Formula. For example, in Formula Z-16, five R e are each independently of the other hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And it may be selected from the group consisting of C 8 -C 20 arylalkenyl group.
보다 구체적으로, 상기 화학식 1로 표시되는 화합물은 하기 화합물들 중 어느 하나일 수 있으며, 하기 화합물에만 한정하는 것은 아니다.More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.
다른 실시예로서, 본 발명은 상기 화학식 1로 표시되는 유기전기소자용 화합물을 제공한다.In another embodiment, the present invention provides a compound for an organic electric device represented by Chemical Formula 1.
또 다른 실시예에서, 본 발명은 상기 화학식 1로 표시되는 화합물을 함유하는 유기전기소자를 제공한다.In another embodiment, the present invention provides an organic electric device containing the compound represented by the formula (1).
이때, 유기전기소자는 제 1전극; 제 2전극; 및 상기 제 1전극과 제2전극 사이에 위치하는 유기물층;을 포함할 수 있으며, 유기물층은 화학식 1로 표시되는 화합물을 포함할 수 있으며, 화학식 1로 표시되는 화합물은 유기물층의 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송층 및 전자주입층 중 적어도 하나의 층에 함유될 수 있을 것이다. 특히 화학식 1로 표시되는 화합물은 정공수송층 또는 발광보조층에 포함될 수 있다.In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 1 may be a hole injection layer or a hole transport layer of the organic material layer. The light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may be contained in at least one layer. In particular, the compound represented by Formula 1 may be included in the hole transport layer or the light emitting auxiliary layer.
즉, 화학식 1로 표시되는 화합물은 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송층 또는 전자주입층의 재료로 사용될 수 있다. 특히 화학식 1로 표시되는 화합물은 발광층의 재료로 사용될 수 있다. 구체적으로, 상기 유기물층에 상기 화학식 1로 표시되는 화합물 중 하나를 포함하는 유기전기소자를 제공하고, 보다 구체적으로, 상기 유기물층에 상기 개별 화학식(1-1 내지 4-38)로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer or an electron injection layer. In particular, the compound represented by Formula 1 may be used as a material of the light emitting layer. Specifically, to provide an organic electroluminescent device comprising one of the compounds represented by the formula (1) in the organic material layer, more specifically, It provides an organic electroluminescent device comprising a compound represented by the individual formulas (1-1 to 4-38) in the organic material layer.
또 다른 실시예에서, 상기 유기물층의 상기 정공주입층, 상기 정공수송층, 상기 발광보조층, 상기 발광층, 상기 전자수송층 및 상기 전자주입층 중 적어도 하나의 층에, 상기 화합물이 단독으로 함유되거나, 상기 화합물이 서로 다른 2종 이상의 조합으로 함유되거나, 상기 화합물이 다른 화합물과 2종 이상의 조합으로 함유된 것을 특징으로 하는 유기전기소자를 제공한다. 다시 말해서, 각각의 층들에는 화학식 1에 해당하는 화합물이 단독으로 포함될 수 있고, 2종 이상의 화학식 1의 화합물들의 혼합물이 포함될 수 있으며, 청구항 1항 내지 6항의 화합물과, 본 발명에 해당하지 않는 화합물과의 혼합물이 포함될 수 있다. 여기서 본 발명에 해당하지 않는 화합물은 단일의 화합물일 수 있고, 2종 이상의 화합물들일 수도 있다. 이때 상기 화합물이 다른 화합물과 2종 이상의 조합으로 함유될 경우 다른 화합물은 각 유기물층의 이미 알려진 화합물일 수도 있고, 앞으로 개발될 화합물 등일 수 있다. 이때 상기 유기물층에 함유된 화합물은 동종의 화합물로만 이루어질 수도 있지만, 화학식 1로 표시되는 이종의 화합물이 2이상 혼합된 혼합물일 수도 있다.In another embodiment, the compound is contained alone or in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, Provided is an organic electroluminescent device characterized in that a compound is contained in a combination of two or more different from each other, or the compound is contained in a combination of two or more. In other words, each of the layers may include a compound corresponding to Formula 1 alone, and may include a mixture of two or more compounds of Formula 1, the compounds of claims 1 to 6, and compounds not corresponding to the present invention. And mixtures thereof. Herein, the compound not corresponding to the present invention may be a single compound or two or more compounds. In this case, when the compound is contained in a combination of two or more kinds of other compounds, the other compound may be a known compound of each organic material layer, or a compound to be developed in the future. In this case, the compound contained in the organic material layer may be made only of the same kind of compound, but may be a mixture of two or more kinds of the compound represented by the formula (1).
본 발명의 또 다른 실시예에서, 본 발명은 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율 개선층을 더 포함하는 유기전기소자를 제공한다.In still another embodiment of the present invention, the present invention provides a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric element further comprising.
이하에서, 본 발명에 따른 화학식 1로 표시되는 화합물의 합성예 및 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.
[합성예]Synthesis Example
본 발명에 따른 화학식 1로 표시되는 화합물(final products)은 하기 반응식 1 내지 반응식 4와 같이 Sub 1A 내지 Sub 1D 중 하나와 Sub 2를 반응시켜 합성되며, 이에 한정되는 것은 아니다. 이때, R1 내지 R14, X, Ar1 및 L1은 화학식 1에서 정의된 것과 동일하며, Hal1은 Br 또는 Cl이다.Compounds represented by Formula 1 according to the present invention (final products) are synthesized by reacting one of Sub 1A to Sub 1D and Sub 2 as in Schemes 1 to 4 below, but is not limited thereto. At this time, R 1 to R 14 , X, Ar 1 and L 1 are the same as defined in Formula 1, Hal 1 is Br or Cl.
I. Sub 1A 내지 Sub 1D의 합성I. Synthesis of Sub 1A to Sub 1D
상기 반응식 1 내지 반응식 4의 Sub 1A 내지 Sub 1D는 하기 반응식 5 및 반응식 6의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 1A to Sub 1D of Schemes 1 to 4 may be synthesized by the reaction routes of Scheme 5 and Scheme 6, but are not limited thereto.
-BR은 R5, R6, R8, R9 중 하나가 Br인 것을 의미한다.-BR means that one of R 5 , R 6 , R 8 , R 9 is Br.
Sub 1에 속하는 구체적 화합물의 합성예는 다음과 같다.Synthesis examples of specific compounds belonging to Sub 1 are as follows.
1. Sub 1A-1 합성예1.Sub 1A-1 Synthesis Example
(1) Sub 1A-I-1 합성(1) Sub 1A-I-1 Synthesis
출발물질인 phenylboronic acid (41.33 g, 338.96 mmol)를 둥근바닥플라스크에 THF (1180ml)로 녹인 후에, 3,8-dibromo-1-nitronaphthalene (123.40 g, 372.86 mmol), Pd(PPh3)4 (15.67 g, 13.56 mmol), NaOH (40.68 g, 1016.89 mmol), 물 (590ml)을 첨가하고 80ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 71.19 g (수율: 64%)을 얻었다.After starting material phenylboronic acid (41.33 g, 338.96 mmol) was dissolved in THF (1180 ml) in a round bottom flask, 3,8-dibromo-1-nitronaphthalene (123.40 g, 372.86 mmol), Pd (PPh 3 ) 4 (15.67 g, 13.56 mmol), NaOH (40.68 g, 1016.89 mmol), water (590 ml) were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 71.19 g (yield: 64%) of the product.
(2) Sub 1A-II-1 합성(2) Sub 1A-II-1 Synthesis
상기 합성에서 얻어진 Sub 1A-I-1 (71.19 g, 216.94 mmol)를 둥근바닥플라스크에 o-dichlorobenzene (1900ml)으로 녹인 후에, triphenylphosphine (142.25 g, 542.34 mmol)을 첨가하고 200ㅀC에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 44.97 g (수율: 70%)를 얻었다.Sub 1A-I-1 (71.19 g, 216.94 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (1900 ml) in a round bottom flask, triphenylphosphine (142.25 g, 542.34 mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was purified by silicagel column and recrystallized to give 44.97 g (yield: 70%) of the product.
(3) Sub 1A-III-1 합성(3) Sub 1A-III-1 Synthesis
상기 합성에서 얻어진 Sub 1A-II-1 (19.75 g, 66.69 mmol)를 둥근바닥플라스크에 THF (220ml)로 녹인 후에, (2-(methylsulfinyl)phenyl)boronic acid (12.27 g, 66.69 mmol), Pd(PPh3)4 (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol), 물 (110ml)을 첨가하고 80ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 17.07 g (수율: 72%)을 얻었다.Sub 1A-II-1 (19.75 g, 66.69 mmol) obtained in the above synthesis was dissolved in THF (220 ml) in a round bottom flask, followed by (2- (methylsulfinyl) phenyl) boronic acid (12.27 g, 66.69 mmol), Pd ( PPh 3 ) 4 (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol), water (110 ml) were added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 17.07 g (yield: 72%) of the product.
(4) Sub 1A-1 합성(4) Sub 1A-1 synthesis
상기 합성에서 얻어진 Sub 1A-III-1 (17.07 g, 48.02 mmol)를 둥근바닥플라스크에 triflic acid (63.7ml, 720.35 mmol)와 함께 넣고 상온에서 24시간 동안 교반한 뒤, pyridine 수용액 (840ml, pyridine : H2O = 1 : 5)을 천천히 적가하고 30 분 동안 환류 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 7.61 g (수율: 49%)를 얻었다.Sub 1A-III-1 (17.07 g, 48.02 mmol) obtained in the above synthesis was added to triflic acid (63.7ml, 720.35 mmol) in a round bottom flask and stirred at room temperature for 24 hours, followed by aqueous pyridine solution (840ml, pyridine: H 2 O = 1: 1) was slowly added dropwise and stirred at reflux for 30 minutes. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 7.61 g (yield: 49%).
2. Sub 1A-2 합성예2. Sub 1A-2 Synthesis Example
(1) Sub 1A-III'-2 합성(1) Sub 1A-III'-2 Synthesis
상기 합성에서 얻어진 Sub 1A-II-1 (24.94 g, 84.21 mmol)에 (2-hydroxyphenyl)boronic acid (11.62 g, 84.21 mmol), Pd(PPh3)4 (3.89 g, 3.37 mmol), NaOH (10.11 g, 252.63 mmol), THF (280ml), 물 (140ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 21.62 g (수율: 83%)을 얻었다.To Sub 1A-II-1 (24.94 g, 84.21 mmol) obtained in the above synthesis (2-hydroxyphenyl) boronic acid (11.62 g, 84.21 mmol), Pd (PPh 3 ) 4 (3.89 g, 3.37 mmol), NaOH (10.11 g, 252.63 mmol), THF (280ml), water (140ml) were added and 21.62 g (yield: 83%) of product was obtained using the Sub 1A-III-1 synthesis method.
(2) Sub 1A-2 합성(2) Sub 1A-2 synthesis
상기 합성에서 얻어진 Sub 1A-III'-2 (21.62 g, 69.89 mmol)를 둥근바닥플라스크에 Pd(OAc)2 (1.57 g, 6.99 mmol), 3-nitropyridine (0.87 g, 6.99 mmol)과 함께 넣고 C6F6 (105ml), DMI (70ml)로 녹인 후, tert-butyl peroxybenzoate (27.15 g, 139.77 mmol)를 첨가하고 90ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 8.81 g (수율: 41%)를 얻었다.Sub 1A-III'-2 (21.62 g, 69.89 mmol) obtained in the above synthesis was added to a round bottom flask together with Pd (OAc) 2 (1.57 g, 6.99 mmol) and 3-nitropyridine (0.87 g, 6.99 mmol). 6 F 6 (105 ml), dissolved in DMI (70 ml), and tert- butyl peroxybenzoate (27.15 g, 139.77 mmol) were added and stirred at 90 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 8.81 g (yield: 41%) of the product.
3. Sub 1A-6 합성예3. Synthesis Example of Sub 1A-6
(1) Sub 1A-I-6 합성(1) Sub 1A-I-6 Synthesis
출발물질인 (4-(9-phenyl-9H-carbazol-2-yl)phenyl)boronic acid (50.12 g, 137.99 mmol)에 3,8-dibromo-1-nitronaphthalene (50.24 g, 151.79 mmol), Pd(PPh3)4 (6.38 g, 5.52 mmol), NaOH (16.56 g, 413.96 mmol), THF (480ml), 물 (240ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 47.15 g (수율: 60%)을 얻었다.In the starting material (4- (9-phenyl-9H-carbazol-2-yl) phenyl) boronic acid (50.12 g, 137.99 mmol), 3,8-dibromo-1-nitronaphthalene (50.24 g, 151.79 mmol), Pd ( PPh 3 ) 4 (6.38 g, 5.52 mmol), NaOH (16.56 g, 413.96 mmol), THF (480 ml), water (240 ml) were added and the product 47.15 g (Yield: 60%).
(2) Sub 1A-II-6 합성(2) Sub 1A-II-6 Synthesis
상기 합성에서 얻어진 Sub 1A-I-6 (47.15 g, 82.80 mmol)에 triphenylphosphine (54.29 g, 207.00 mmol), o-dichlorobenzene (725ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 29.82 g (수율: 67%)를 얻었다.To the Sub 1A-I-6 (47.15 g, 82.80 mmol) obtained in the above synthesis, triphenylphosphine (54.29 g, 207.00 mmol) and o -dichlorobenzene (725 ml) were added and the product 29.82 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 67%) was obtained.
(3) Sub 1A-III-6 합성(3) Sub 1A-III-6 Synthesis
상기 합성에서 얻어진 Sub 1A-II-6 (29.82 g, 55.48 mmol)에 (2-(methylsulfinyl)phenyl)boronic acid (10.21 g, 55.48 mmol), Pd(PPh3)4 (2.56 g, 2.22 mmol), NaOH (6.66 g, 166.45 mmol), THF (180ml), 물 (90ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 24.83 g (수율: 75%)을 얻었다.To Sub 1A-II-6 (29.82 g, 55.48 mmol) obtained in the above synthesis (2- (methylsulfinyl) phenyl) boronic acid (10.21 g, 55.48 mmol), Pd (PPh 3 ) 4 (2.56 g, 2.22 mmol), NaOH (6.66 g, 166.45 mmol), THF (180 ml), water (90 ml) were added and 24.83 g (yield: 75%) of product was obtained using the Sub 1A-III-1 synthesis.
(4) Sub 1A-6 합성(4) Sub 1A-6 synthesis
상기 합성에서 얻어진 Sub 1A-III-6 (24.83 g, 41.61 mmol)에 triflic acid (55.2ml, 624.14 mmol), pyridine 수용액 (730ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 10.81 g (수율: 46%)을 얻었다.To Sub 1A-III-6 (24.83 g, 41.61 mmol) obtained in the above synthesis, triflic acid (55.2ml, 624.14 mmol) and pyridine aqueous solution (730ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 10.81 g (yield: 46%) of product was obtained using the 1 synthesis method.
4. Sub 1A-19 합성예4. Synthesis Example of Sub 1A-19
(1) Sub 1A-I-19 합성(1) Sub 1A-I-19 Synthesis
출발물질인 (3'-(dibenzo[b,d]thiophen-3-yl(9-phenyl-9H-carbazol-3-yl)amino)-[1,1'-biphenyl]-4-yl)boronic acid (91.41 g, 143.60 mmol)에 3,8-dibromo-1-nitronaphthalene (52.28 g, 157.96 mmol), Pd(PPh3)4 (6.64 g, 5.74 mmol), NaOH (17.23 g, 430.79 mmol), THF (500ml), 물 (250ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 70.19 g (수율: 58%)을 얻었다.Starting material (3 '-(dibenzo [b, d] thiophen-3-yl (9-phenyl-9H-carbazol-3-yl) amino)-[1,1'-biphenyl] -4-yl) boronic acid (91.41 g, 143.60 mmol) to 3,8-dibromo-1-nitronaphthalene (52.28 g, 157.96 mmol), Pd (PPh 3 ) 4 (6.64 g, 5.74 mmol), NaOH (17.23 g, 430.79 mmol), THF ( 500 ml), water (250 ml) were added and the product 70.19 g (yield: 58%) were obtained using the Sub 1A-I-1 synthesis method.
(2) Sub 1A-II-19 합성(2) Sub 1A-II-19 Synthesis
상기 합성에서 얻어진 Sub 1A-I-19 (70.19 g, 83.28 mmol)에 triphenylphosphine (54.61 g, 208.20 mmol), o-dichlorobenzene (730ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 42.54 g (수율: 63%)를 얻었다.To the Sub 1A-I-19 (70.19 g, 83.28 mmol) obtained in the above synthesis, triphenylphosphine (54.61 g, 208.20 mmol) and o -dichlorobenzene (730 ml) were added and the product 42.54 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 63%) was obtained.
(3) Sub 1A-III-19 합성(3) Sub 1A-III-19 Synthesis
상기 합성에서 얻어진 Sub 1A-II-19 (42.54 g, 52.47 mmol)에 (2-(methylsulfinyl)phenyl)boronic acid (9.65 g, 52.47 mmol), Pd(PPh3)4 (2.43 g, 2.10 mmol), NaOH (6.30 g, 157.40 mmol), THF (170ml), 물 (85ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 27.39 g (수율: 60%)을 얻었다.To Sub 1A-II-19 (42.54 g, 52.47 mmol) obtained in the above synthesis (2- (methylsulfinyl) phenyl) boronic acid (9.65 g, 52.47 mmol), Pd (PPh 3 ) 4 (2.43 g, 2.10 mmol), NaOH (6.30 g, 157.40 mmol), THF (170ml), water (85ml) were added and 27.39 g (yield: 60%) of product was obtained using the above Sub 1A-III-1 synthesis.
(4) Sub 1A-19 합성(4) Sub 1A-19 Synthesis
상기 합성에서 얻어진 Sub 1A-III-19 (27.39 g, 31.48 mmol)에 triflic acid (41.8ml, 472.19 mmol), pyridine 수용액 (550ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 11.34 g (수율: 43%)을 얻었다.To Sub 1A-III-19 (27.39 g, 31.48 mmol) obtained in the above synthesis, triflic acid (41.8ml, 472.19 mmol) and an aqueous solution of pyridine (550ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 1 synthesis was used to give 11.34 g (yield 43%) of product.
5. Sub 1B-1 합성예5. Sub 1B-1 Synthesis Example
(1) Sub 1B-I-1 합성(1) Synthesis of Sub 1B-I-1
출발물질인 phenylboronic acid (63.08 g, 517.35 mmol)에 1,5-dibromo-4-nitronaphthalene (188.34 g, 569.08 mmol), Pd(PPh3)4 (23.91 g, 20.69 mmol), NaOH (62.08 g, 1552.04 mmol), THF (1800ml), 물 (900ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 117.14 g (수율: 69%)을 얻었다.1,5-dibromo-4-nitronaphthalene (188.34 g, 569.08 mmol), Pd (PPh 3 ) 4 (23.91 g, 20.69 mmol), NaOH (62.08 g, 1552.04) in starting material phenylboronic acid (63.08 g, 517.35 mmol) mmol), THF (1800 ml), water (900 ml) were added and the above Sub 1A-I-1 synthesis gave 117.14 g (yield: 69%) of product.
(2) Sub 1B-II-1 합성(2) Sub 1B-II-1 Synthesis
상기 합성에서 얻어진 Sub 1B-I-1 (117.14 g, 356.96 mmol)에 triphenylphosphine (234.07 g, 892.40 mmol), o-dichlorobenzene (2500ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 78.23 g (수율: 74%)를 얻었다.To the Sub 1B-I-1 (117.14 g, 356.96 mmol) obtained in the above synthesis, triphenylphosphine (234.07 g, 892.40 mmol) and o -dichlorobenzene (2500 ml) were added, and the product 78.23 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 74%) was obtained.
(3) Sub 1B-III-1 합성(3) Sub 1B-III-1 Synthesis
상기 합성에서 얻어진 Sub 1B-II-1 (19.75 g, 66.69 mmol)에 (2-(methylsulfinyl)phenyl)boronic acid (12.27 g, 66.69 mmol), Pd(PPh3)4 (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol), THF (220ml), 물 (110ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 16.59 g (수율: 70%)을 얻었다.To Sub 1B-II-1 (19.75 g, 66.69 mmol) obtained in the above synthesis (2- (methylsulfinyl) phenyl) boronic acid (12.27 g, 66.69 mmol), Pd (PPh 3 ) 4 (3.08 g, 2.67 mmol), NaOH (8.00 g, 200.06 mmol), THF (220 ml), water (110 ml) were added and the product 16.59 g (yield: 70%) was obtained using the Sub 1A-III-1 synthesis method.
(4) Sub 1B-1 합성(4) Sub 1B-1 synthesis
상기 합성에서 얻어진 Sub 1B-III-1 (16.59 g, 46.67 mmol)에 triflic acid (62.0ml, 700.10 mmol), pyridine 수용액 (818ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 11.62 g (수율: 77%)을 얻었다.To Sub 1B-III-1 (16.59 g, 46.67 mmol) obtained in the above synthesis, triflic acid (62.0ml, 700.10 mmol) and an aqueous solution of pyridine (818ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 1 synthesis was used to obtain 11.62 g (yield 77%) of the product.
6. Sub 1B-2 합성예6. Sub 1B-2 Synthesis Example
(1) Sub 1B-III'-2 합성(1) Sub 1B-III'-2 Synthesis
상기 합성에서 얻어진 Sub 1B-II-1 (17.28 g, 58.35 mmol)에 (2-hydroxyphenyl)boronic acid (8.05 g, 58.35 mmol), Pd(PPh3)4 (2.70 g, 2.33 mmol), NaOH (7.00 g, 175.04 mmol), THF (190ml), 물 (95ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 15.52 g (수율: 86%)을 얻었다.To Sub 1B-II-1 (17.28 g, 58.35 mmol) obtained in the above synthesis (2-hydroxyphenyl) boronic acid (8.05 g, 58.35 mmol), Pd (PPh 3 ) 4 (2.70 g, 2.33 mmol), NaOH (7.00 g, 175.04 mmol), THF (190ml), water (95ml) were added and 15.52 g (yield: 86%) of the product was obtained using the Sub 1A-III-1 synthesis method.
(2) Sub 1B-2 합성(2) Sub 1B-2 synthesis
상기 합성에서 얻어진 Sub 1B-III'-2 (15.52 g, 50.17 mmol)에 Pd(OAc)2 (1.13 g, 5.02 mmol), 3-nitropyridine (0.62 g, 5.02 mmol), tert-butyl peroxybenzoate (19.49 g, 100.34 mmol), C6F6 (75ml), DMI (50ml)를 첨가하고 상기 Sub 1A-2 합성법을 사용하여 생성물 8.48 g (수율: 55%)을 얻었다.To Sub 1B-III'-2 (15.52 g, 50.17 mmol) obtained in the above synthesis, Pd (OAc) 2 (1.13 g, 5.02 mmol), 3-nitropyridine (0.62 g, 5.02 mmol), tert- butyl peroxybenzoate (19.49 g , 100.34 mmol), C 6 F 6 (75 ml), DMI (50 ml) were added and the product was obtained using the Sub 1A-2 synthesis method to yield 8.48 g (yield: 55%).
7. Sub 1B-3 합성예7. Sub 1B-3 Synthesis Example
(1) Sub 1B-III”-3 합성(1) Sub 1B-III ”-3 Synthesis
상기 합성에서 얻어진 Sub 1B-II-1 (25.01 g, 84.45 mmol)에 (2-(methoxycarbonyl)phenyl)boronic acid (15.20 g, 84.45 mmol), Pd(PPh3)4 (3.90 g, 3.38 mmol), NaOH (10.13 g, 253.34 mmol), THF (280ml), 물 (140ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 21.07 g (수율: 71%)을 얻었다.To Sub 1B-II-1 (25.01 g, 84.45 mmol) obtained in the above synthesis (2- (methoxycarbonyl) phenyl) boronic acid (15.20 g, 84.45 mmol), Pd (PPh 3 ) 4 (3.90 g, 3.38 mmol), NaOH (10.13 g, 253.34 mmol), THF (280 ml), water (140 ml) were added and the product 21.07 g (yield: 71%) was obtained using the Sub 1A-III-1 synthesis method.
(2) Sub 1B-3 합성(2) Sub 1B-3 synthesis
상기 합성에서 얻어진 Sub 1B-III”-3 (21.07 g, 59.96 mmol)를 둥근바닥플라스크에 THF(300ml)로 녹인 후에, methylmagnesium bromide 1.0M in THF (239.8ml, 239.84 mmol)을 천천히 적가시킨 후, 상온에서 교반하였다. 반응이 완료되면 diethyl ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 중간 생성물을 얻었다. 이 중간 생성물을 acetic acid 용액 (250ml)에 녹이고 HCl (5ml)를 첨가한 뒤 환류시켰다. 반응이 완료되면 물을 넣고 교반 후 생성된 고체를 감압여과 후 물과 메탄올로 세척하여 백색 분말로서 생성물 14.59 g (수율: 73% over two steps)를 얻었다.Sub 1B-III ”-3 (21.07 g, 59.96 mmol) obtained in the above synthesis was dissolved in THF (300 ml) in a round bottom flask, and methylmagnesium bromide 1.0M in THF (239.8 ml, 239.84 mmol) was slowly added dropwise thereto. Stir at room temperature. After the reaction was completed, the mixture was extracted with diethyl ether and water, the organic layer was dried over MgSO 4 and concentrated to give an intermediate product. This intermediate product was dissolved in acetic acid solution (250ml) and refluxed after addition of HCl (5ml). After the reaction was completed, water was added and the resulting solid was filtered under reduced pressure, washed with water and methanol to obtain 14.59 g (yield: 73% over two steps) as a white powder.
8. Sub 1B-11 합성예8. Sub 1B-11 Synthesis Example
(1) Sub 1B-III'-11 합성(1) Sub 1B-III'-11 Synthesis
상기 합성에서 얻어진 Sub 1B-II-1 (15.07 g, 50.88 mmol)에 (2-hydroxy-5-(phenanthren-2-yl(phenyl)amino)phenyl)boronic acid (20.62 g, 50.88 mmol), Pd(PPh3)4 (2.35 g, 2.04 mmol), NaOH (6.11 g, 152.65 mmol), THF (170ml), 물 (85ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 23.18 g (수율: 79%)을 얻었다.Sub 1B-II-1 obtained in the above synthesis (15.07 g, 50.88 mmol) to (2-hydroxy-5- (phenanthren-2-yl (phenyl) amino) phenyl) boronic acid (20.62 g, 50.88 mmol), Pd ( PPh 3 ) 4 (2.35 g, 2.04 mmol), NaOH (6.11 g, 152.65 mmol), THF (170ml), water (85ml) were added and the product 23.18 g (yield: using the Sub 1A-III-1 synthesis method above: 79%).
(2) Sub 1B-11 합성(2) Sub 1B-11 Synthesis
상기 합성에서 얻어진 Sub 1B-III'-2 (23.18 g, 40.20 mmol)에 Pd(OAc)2 (0.90 g, 4.02 mmol), 3-nitropyridine (0.50 g, 4.02 mmol), tert-butyl peroxybenzoate (15.61 g, 80.39 mmol), C6F6 (60ml), DMI (40ml)를 첨가하고 상기 Sub 1A-2 합성법을 사용하여 생성물 9.93 g (수율: 43%)을 얻었다.To Sub 1B-III'-2 (23.18 g, 40.20 mmol) obtained in the above synthesis, Pd (OAc) 2 (0.90 g, 4.02 mmol), 3-nitropyridine (0.50 g, 4.02 mmol), tert- butyl peroxybenzoate (15.61 g , 80.39 mmol), C 6 F 6 (60 ml), DMI (40 ml) were added and the Sub 1A-2 synthesis method gave 9.93 g (yield: 43%) of the product.
9. Sub 1B-23 합성예9. Sub 1B-23 Synthesis Example
(1) Sub 1B-I-23 합성(1) Synthesis of Sub 1B-I-23
출발물질인 (4-(bis(4-fluorophenyl)amino)phenyl)boronic acid (102.67 g, 315.79 mmol)에 1,5-dibromo-4-nitronaphthalene (114.97 g, 347.37 mmol), Pd(PPh3)4 (14.60 g, 12.63 mmol), NaOH (37.89 g, 947.37 mmol), THF (1100ml), 물 (550ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 88.93 g (수율: 53%)을 얻었다.Starting material (4- (bis (4-fluorophenyl) amino) phenyl) boronic acid (102.67 g, 315.79 mmol) in 1,5-dibromo-4-nitronaphthalene (114.97 g, 347.37 mmol), Pd (PPh 3 ) 4 (14.60 g, 12.63 mmol), NaOH (37.89 g, 947.37 mmol), THF (1100 ml), water (550 ml) were added and 88.93 g (yield: 53%) of the product was obtained using the Sub 1A-I-1 synthesis method. Got it.
(2) Sub 1B-II-23 합성(2) Sub 1B-II-23 Synthesis
상기 합성에서 얻어진 Sub 1B-I-23 (88.93 g, 167.37 mmol)에 triphenylphosphine (109.75 g, 418.42 mmol), o-dichlorobenzene (1465ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 50.14 g (수율: 60%)를 얻었다.To the Sub 1B-I-23 (88.93 g, 167.37 mmol) obtained in the above synthesis, triphenylphosphine (109.75 g, 418.42 mmol) and o -dichlorobenzene (1465 ml) were added and the product 50.14 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 60%) was obtained.
(3) Sub 1B-III”-23 합성(3) Sub 1B-III ”-23 Synthesis
상기 합성에서 얻어진 Sub 1B-II-23 (50.14 g, 100.41 mmol)에 (2-(methoxycarbonyl)phenyl)boronic acid (18.07 g, 100.41 mmol), Pd(PPh3)4 (4.64 g, 4.02 mmol), NaOH (12.05 g, 301.23 mmol), THF (330ml), 물 (165ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 32.85 g (수율: 59%)을 얻었다.To Sub 1B-II-23 (50.14 g, 100.41 mmol) obtained in the above synthesis (2- (methoxycarbonyl) phenyl) boronic acid (18.07 g, 100.41 mmol), Pd (PPh 3 ) 4 (4.64 g, 4.02 mmol), NaOH (12.05 g, 301.23 mmol), THF (330 ml), water (165 ml) were added and the product 32.85 g (yield: 59%) was obtained using the above Sub 1A-III-1 synthesis.
(4) Sub 1B-23 합성(4) Sub 1B-23 Synthesis
상기 합성에서 얻어진 Sub 1B-III”-23 (32.85 g, 59.23 mmol)에 methylmagnesium bromide 1.0M in THF (236.9ml, 236.94 mmol), THF(295ml)을 사용하여 중간 생성물을 얻은 후, acetic acid 용액(250ml), HCl (5ml)를 첨가하여 상기 Sub 1B-3 합성법을 사용하여 생성물 19.71 g (수율: 62% over two steps)를 얻었다.Sub 1B-III ”-23 (32.85 g, 59.23 mmol) obtained in the above synthesis was obtained with methylmagnesium bromide 1.0M in THF (236.9ml, 236.94 mmol) and THF (295ml), followed by acetic acid solution ( 250 ml), HCl (5 ml) were added to give 19.71 g (yield: 62% over two steps) of product using the Sub 1B-3 synthesis.
10. Sub 1C-1 합성예10.Sub 1C-1 Synthesis Example
(1) Sub 1C-I-1 합성(1) Synthesis of Sub 1C-I-1
출발물질인 phenylboronic acid (38.41 g, 315.02 mmol)에 1,3-dibromo-8-nitronaphthalene (114.68 g, 346.52 mmol), Pd(PPh3)4 (14.56 g, 12.60 mmol), NaOH (37.80 g, 945.05 mmol), THF (1100ml), 물 (550ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 77.53 g (수율: 75%)을 얻었다.1,3-dibromo-8-nitronaphthalene (114.68 g, 346.52 mmol), Pd (PPh 3 ) 4 (14.56 g, 12.60 mmol), NaOH (37.80 g, 945.05) in the starting material phenylboronic acid (38.41 g, 315.02 mmol) mmol), THF (1100 ml), water (550 ml) were added and 77.53 g (yield: 75%) of product was obtained using the Sub 1A-I-1 synthesis method.
(2) Sub 1C-II-1 합성(2) Sub 1C-II-1 Synthesis
상기 합성에서 얻어진 Sub 1C-I-1 (77.53 g, 236.26 mmol)에 triphenylphosphine (154.92 g, 590.64 mmol), o-dichlorobenzene (1655ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 47.58 g (수율: 68%)를 얻었다.To the Sub 1C-I-1 (77.53 g, 236.26 mmol) obtained in the above synthesis, triphenylphosphine (154.92 g, 590.64 mmol) and o -dichlorobenzene (1655 ml) were added and the product 47.58 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 68%) was obtained.
(3) Sub 1C-III-1 합성(3) Sub 1C-III-1 Synthesis
상기 합성에서 얻어진 Sub 1C-II-1 (26.89 g, 90.80 mmol)에 (2-(methylsulfinyl)phenyl)boronic acid (16.71 g, 90.80 mmol), Pd(PPh3)4 (4.20 g, 3.63 mmol), NaOH (10.90 g, 272.39 mmol), THF (300ml), 물 (150ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 23.56 g (수율: 73%)을 얻었다.To Sub 1C-II-1 (26.89 g, 90.80 mmol) obtained in the above synthesis (2- (methylsulfinyl) phenyl) boronic acid (16.71 g, 90.80 mmol), Pd (PPh 3 ) 4 (4.20 g, 3.63 mmol), NaOH (10.90 g, 272.39 mmol), THF (300 ml), water (150 ml) were added and the product 23.56 g (yield: 73%) was obtained using the above Sub 1A-III-1 synthesis.
(4) Sub 1C-1 합성(4) Sub 1C-1 synthesis
상기 합성에서 얻어진 Sub 1C-III-1 (23.56 g, 66.28 mmol)에 triflic acid (88.0ml, 994.23 mmol), pyridine 수용액 (1160ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 10.08 g (수율: 47%)을 얻었다.To Sub 1C-III-1 (23.56 g, 66.28 mmol) obtained in the above synthesis, triflic acid (88.0ml, 994.23 mmol) and an aqueous solution of pyridine (1160ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 10.08 g (yield 47%) of product was obtained using 1 synthesis method.
11. Sub 1C-2 합성예11.Sub 1C-2 Synthesis Example
(1) Sub 1C-III'-2 합성(1) Sub 1C-III'-2 Synthesis
상기 합성에서 얻어진 Sub 1C-II-1 (20.28 g, 68.48 mmol)에 (2-hydroxyphenyl)boronic acid (9.44 g, 68.48 mmol), Pd(PPh3)4 (3.17 g, 2.74 mmol), NaOH (8.22 g, 205.43 mmol), THF (230ml), 물 (115ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 18.64 g (수율: 88%)을 얻었다.To Sub 1C-II-1 (20.28 g, 68.48 mmol) obtained in the above synthesis (2-hydroxyphenyl) boronic acid (9.44 g, 68.48 mmol), Pd (PPh 3 ) 4 (3.17 g, 2.74 mmol), NaOH (8.22 g, 205.43 mmol), THF (230 ml), water (115 ml) were added and 18.64 g (yield: 88%) of product was obtained using the Sub 1A-III-1 synthesis method above.
(2) Sub 1C-2 합성(2) Sub 1C-2 synthesis
상기 합성에서 얻어진 Sub 1C-III'-2 (18.64 g, 60.25 mmol)에 Pd(OAc)2 (1.35 g, 6.03 mmol), 3-nitropyridine (0.75 g, 6.03 mmol), tert-butyl peroxybenzoate (23.41 g, 120.51 mmol), C6F6 (90ml), DMI (60ml)를 첨가하고 상기 Sub 1A-2 합성법을 사용하여 생성물 7.78 g (수율: 42%)을 얻었다.To Sub 1C-III'-2 (18.64 g, 60.25 mmol) obtained in the above synthesis, Pd (OAc) 2 (1.35 g, 6.03 mmol), 3-nitropyridine (0.75 g, 6.03 mmol), tert- butyl peroxybenzoate (23.41 g , 120.51 mmol), C 6 F 6 (90 ml), DMI (60 ml) were added and the product was obtained using the Sub 1A-2 synthesis method to yield 7.78 g (yield: 42%).
12. Sub 1C-29 합성예12.Synthesis example of Sub 1C-29
(1) Sub 1C-III-30 합성(1) Sub 1C-III-30 Synthesis
상기 합성에서 얻어진 Sub 1C-II-1 (22.26 g, 75.16 mmol)에 (4'-(di([1,1'-biphenyl]-4-yl)amino)-3-(methylsulfinyl)-[1,1'-biphenyl]-4-yl)boronic acid (43.56 g, 75.16 mmol), Pd(PPh3)4 (3.47 g, 3.01 mmol), NaOH (9.02 g, 225.49 mmol), THF (250ml), 물 (125ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 32.17 g (수율: 57%)을 얻었다.Sub 1C-II-1 (22.26 g, 75.16 mmol) obtained in the above synthesis was added to (4 '-(di ([1,1'-biphenyl] -4-yl) amino) -3- (methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (43.56 g, 75.16 mmol), Pd (PPh 3 ) 4 (3.47 g, 3.01 mmol), NaOH (9.02 g, 225.49 mmol), THF (250ml), water ( 125 ml) was added and 32.17 g (yield: 57%) of product was obtained using the Sub 1A-III-1 synthesis method.
(2) Sub 1C-30 합성(2) Sub 1C-30 Synthesis
상기 합성에서 얻어진 Sub 1C-III-30 (32.17 g, 42.84 mmol)에 triflic acid (56.9ml, 642.59 mmol), pyridine 수용액 (750ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 12.32 g (수율: 40%)을 얻었다.To Sub 1C-III-30 (32.17 g, 42.84 mmol) obtained in the above synthesis, triflic acid (56.9ml, 642.59 mmol) and an aqueous solution of pyridine (750ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 12.32 g (yield: 40%) of product were obtained using the 1 synthesis method.
13. Sub 1D-1 합성예13. Sub 1D-1 Synthesis Example
(1) Sub 1D-I-1 합성(1) Synthesis of Sub 1D-I-1
출발물질인 phenylboronic acid (37.04 g, 303.78 mmol)에 1,2-dibromo-8-nitronaphthalene (110.59 g, 334.16 mmol), Pd(PPh3)4 (14.04 g, 12.15 mmol), NaOH (36.45 g, 911.34 mmol), THF (1000ml), 물 (500ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 52.84 g (수율: 53%)을 얻었다.Starting material, phenylboronic acid (37.04 g, 303.78 mmol), 1,2-dibromo-8-nitronaphthalene (110.59 g, 334.16 mmol), Pd (PPh 3 ) 4 (14.04 g, 12.15 mmol), NaOH (36.45 g, 911.34 mmol), THF (1000 ml), water (500 ml) were added and 52.84 g (yield: 53%) of the product was obtained using the Sub 1A-I-1 synthesis method.
(2) Sub 1D-II-1 합성(2) Sub 1D-II-1 Synthesis
상기 합성에서 얻어진 Sub 1D-I-1 (52.84 g, 161.02 mmol)에 triphenylphosphine (105.58 g, 402.55 mmol), o-dichlorobenzene (1100ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 32.43 g (수율: 68%)를 얻었다.To the Sub 1D-I-1 (52.84 g, 161.02 mmol) obtained in the above synthesis, triphenylphosphine (105.58 g, 402.55 mmol) and o- dichlorobenzene (1100 ml) were added and the product 32.43 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 68%) was obtained.
(3) Sub 1D-III-1 합성(3) Sub 1D-III-1 Synthesis
상기 합성에서 얻어진 Sub 1D-II-1 (16.71 g, 56.42 mmol)에 (2-(methylsulfinyl)phenyl)boronic acid (10.38 g, 56.42 mmol), Pd(PPh3)4 (2.61 g, 2.26 mmol), NaOH (6.77 g, 169.27 mmol), THF (180ml), 물 (90ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 15.04 g (수율: 75%)을 얻었다.To Sub 1D-II-1 (16.71 g, 56.42 mmol) obtained in the above synthesis (2- (methylsulfinyl) phenyl) boronic acid (10.38 g, 56.42 mmol), Pd (PPh 3 ) 4 (2.61 g, 2.26 mmol), NaOH (6.77 g, 169.27 mmol), THF (180 ml), water (90 ml) were added and 15.04 g (yield: 75%) of product was obtained using the Sub 1A-III-1 synthesis method.
(4) Sub 1D-1 합성(4) Sub 1D-1 synthesis
상기 합성에서 얻어진 Sub 1D-III-1 (15.04 g, 42.31 mmol)에 triflic acid (56.2ml, 634.69 mmol), pyridine 수용액 (740ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 8.76 g (수율: 64%)을 얻었다.To Sub 1D-III-1 (15.04 g, 42.31 mmol) obtained in the above synthesis, triflic acid (56.2ml, 634.69 mmol) and pyridine aqueous solution (740ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- The synthesis was carried out to give 8.76 g (yield: 64%) of the product.
14. Sub 1D-7 합성예14.Synthesis Example of Sub 1D-7
(1) Sub 1D-I-7 합성(1) Synthesis of Sub 1D-I-7
출발물질인 phenylboronic acid (28.66 g, 235.05 mmol)에 1,2-dibromo-10-nitrophenanthrene (98.52 g, 258.56 mmol), Pd(PPh3)4 (10.86 g, 9.40 mmol), NaOH (28.21 g, 705.16 mmol), THF (820ml), 물 (410ml)을 첨가하고 상기 Sub 1A-I-1 합성법을 사용하여 생성물 41.78 g (수율: 47%)을 얻었다.Starting material, phenylboronic acid (28.66 g, 235.05 mmol), 1,2-dibromo-10-nitrophenanthrene (98.52 g, 258.56 mmol), Pd (PPh 3 ) 4 (10.86 g, 9.40 mmol), NaOH (28.21 g, 705.16 mmol), THF (820 ml), water (410 ml) were added and the product 41.78 g (yield: 47%) was obtained using the Sub 1A-I-1 synthesis method.
(2) Sub 1D-II-7 합성(2) Sub 1D-II-7 Synthesis
상기 합성에서 얻어진 Sub 1D-I-7 (41.78 g, 110.46 mmol)에 triphenylphosphine (72.43 g, 276.16 mmol), o-dichlorobenzene (770ml)을 첨가하고 상기 Sub 1A-II-1 합성법을 사용하여 생성물 22.95 g (수율: 60%)를 얻었다.To the Sub 1D-I-7 (41.78 g, 110.46 mmol) obtained in the above synthesis, triphenylphosphine (72.43 g, 276.16 mmol) and o -dichlorobenzene (770 ml) were added and the product 22.95 g was obtained using the Sub 1A-II-1 synthesis method. (Yield 60%) was obtained.
(3) Sub 1D-III'-7 합성(3) Sub 1D-III'-7 Synthesis
상기 합성에서 얻어진 Sub 1D-II-7 (22.95 g, 66.29 mmol)에 (2-hydroxyphenyl)boronic acid (9.14 g, 66.29 mmol), Pd(PPh3)4 (3.06 g, 2.65 mmol), NaOH (7.95 g, 198.86 mmol), THF (220ml), 물 (110ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 19.54 g (수율: 82%)을 얻었다.Sub 1D-II-7 (22.95 g, 66.29 mmol) obtained in the above synthesis of (2-hydroxyphenyl) boronic acid (9.14 g, 66.29 mmol), Pd (PPh 3 ) 4 (3.06 g, 2.65 mmol), NaOH (7.95 g, 198.86 mmol), THF (220 ml), water (110 ml) were added and 19.54 g (yield: 82%) of product was obtained using the Sub 1A-III-1 synthesis method.
(4) Sub 1D-7 합성(4) Sub 1D-7 Synthesis
상기 합성에서 얻어진 Sub 1D-III'-7 (19.54 g, 54.37 mmol)에 Pd(OAc)2 (1.22 g, 5.44 mmol), 3-nitropyridine (0.67 g, 5.44 mmol), tert-butyl peroxybenzoate (21.12 g, 108.73 mmol), C6F6 (82ml), DMI (54ml)를 첨가하고 상기 Sub 1A-2 합성법을 사용하여 생성물 10.49 g (수율: 54%)을 얻었다.To Sub 1D-III'-7 (19.54 g, 54.37 mmol) obtained in the above synthesis, Pd (OAc) 2 (1.22 g, 5.44 mmol), 3-nitropyridine (0.67 g, 5.44 mmol), tert- butyl peroxybenzoate (21.12 g , 108.73 mmol), C 6 F 6 (82 ml), DMI (54 ml) were added and the product 10.49 g (yield: 54%) was obtained using the Sub 1A-2 synthesis method.
15. Sub 1D-12 합성예15.Sub 1D-12 Synthesis Example
(1) Sub 1D-III-12 합성(1) Sub 1D-III-12 Synthesis
상기 합성에서 얻어진 Sub 1D-II-1 (15.02 g, 50.72 mmol)에 (3'-([1,1'-biphenyl]-3-yl(phenyl)amino)-3-(methylsulfinyl)-[1,1'-biphenyl]-4-yl)boronic acid (25.53 g, 50.72 mmol), Pd(PPh3)4 (2.34 g, 2.03 mmol), NaOH (6.09 g, 152.15 mmol), THF (170ml), 물 (85ml)을 첨가하고 상기 Sub 1A-III-1 합성법을 사용하여 생성물 18.48 g (수율: 54%)을 얻었다.Sub 1D-II-1 (15.02 g, 50.72 mmol) obtained in the above synthesis was added to (3 '-([1,1'-biphenyl] -3-yl (phenyl) amino) -3- (methylsulfinyl)-[1, 1'-biphenyl] -4-yl) boronic acid (25.53 g, 50.72 mmol), Pd (PPh 3 ) 4 (2.34 g, 2.03 mmol), NaOH (6.09 g, 152.15 mmol), THF (170ml), water ( 85 ml) was added to give 18.48 g (yield: 54%) of product using the Sub 1A-III-1 synthesis.
(2) Sub 1D-12 합성(2) Sub 1D-12 Synthesis
상기 합성에서 얻어진 Sub 1D-III-12 (18.48 g, 27.38 mmol)에 triflic acid (36.3ml, 410.76 mmol), pyridine 수용액 (480ml, pyridine : H2O = 1 : 5)을 첨가하고 상기 Sub 1A-1 합성법을 사용하여 생성물 11.09 g (수율: 63%)을 얻었다.To Sub 1D-III-12 (18.48 g, 27.38 mmol) obtained in the above synthesis, triflic acid (36.3 ml, 410.76 mmol) and an aqueous pyridine solution (480 ml, pyridine: H 2 O = 1: 5) were added and the Sub 1A- 1 synthesis was used to obtain 11.09 g (yield 63%) of the product.
Sub 1A 내지 Sub 1D에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 1은 Sub 1A 내지 Sub 1D에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.Compounds belonging to Sub 1A to Sub 1D may be the following compounds, but are not limited thereto. Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1A to Sub 1D.
표 1 
Table 1
II. Sub 2의 합성II. Synthesis of Sub 2
상기 반응식 1의 Sub 2는 반응식 22의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다. 이때, Hal1 및 Hal2는 Br 또는 Cl이다.Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 22, but is not limited thereto. At this time, Hal 1 and Hal 2 are Br or Cl.
Sub 2에 속하는 구체적 화합물의 합성예는 다음과 같다.Synthesis examples of specific compounds belonging to Sub 2 are as follows.
1. Sub 2-22 합성예1.Sub 2-22 Synthesis Example
출발물질인 1,3-dibromobenzene (20.17 g, 85.50 mmol)을 둥근바닥플라스크에 THF (300ml)로 녹인 후에, 4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane (33.32 g, 94.05 mmol), Pd(PPh3)4 (3.95 g, 3.42 mmol), K2CO3 (35.45 g, 256.51 mmol), 물 (150ml)을 첨가하고 90ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 20.65 g (수율: 63%)를 얻었다.The starting material 1,3-dibromobenzene (20.17 g, 85.50 mmol) was dissolved in THF (300 ml) in a round bottom flask, and then 4,4,5,5-tetramethyl-2- (triphenylen-2-yl) -1, Add 3,2-dioxaborolane (33.32 g, 94.05 mmol), Pd (PPh 3 ) 4 (3.95 g, 3.42 mmol), K 2 CO 3 (35.45 g, 256.51 mmol), water (150ml) and at 90 ° C Stirred. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 20.65 g (yield: 63%) of the product.
2. Sub 2-28 합성예2.Sub 2-28 Synthesis Example
출발물질인 1,3-dibromobenzene (18.92 g, 80.20 mmol)에 2-(dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (27.37 g, 88.22 mmol), Pd(PPh3)4 (3.71 g, 3.21 mmol), K2CO3 (33.25 g, 240.61 mmol), THF (280ml), 물 (140ml)을 첨가하고 상기 Sub 2-22 합성법을 사용하여 생성물 19.32 g (수율: 71%)를 얻었다.The starting material 1,3-dibromobenzene (18.92 g, 80.20 mmol) was added 2- (dibenzo [b, d] thiophen-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 27.37 g, 88.22 mmol), Pd (PPh 3 ) 4 (3.71 g, 3.21 mmol), K 2 CO 3 (33.25 g, 240.61 mmol), THF (280ml), water (140ml) were added and the Sub 2-22 Synthesis gave 19.32 g (yield 71%) of product.
3. Sub 2-31 합성예3. Synthesis Example of Sub 2-31
출발물질인 2,4-dibromopyrimidine (24.46 g, 102.82 mmol)에 4,4,5,5-tetramethyl-2-(naphthalen-1-yl-d7)-1,3,2-dioxaborolane (29.54 g, 113.11 mmol), Pd(PPh3)4 (4.75 g, 4.11 mmol), K2CO3 (42.63 g, 308.47 mmol), THF (360ml), 물 (180ml)을 첨가하고 상기 Sub 2-22 합성법을 사용하여 생성물 18.03 g (수율: 60%)를 얻었다.4,4,5,5-tetramethyl-2- (naphthalen-1-yl-d7) -1,3,2-dioxaborolane (29.54 g, 113.11) in starting material 2,4-dibromopyrimidine (24.46 g, 102.82 mmol) mmol), Pd (PPh 3 ) 4 (4.75 g, 4.11 mmol), K 2 CO 3 (42.63 g, 308.47 mmol), THF (360ml), water (180ml) were added and the above Sub 2-22 synthesis was performed. 18.03 g (yield: 60%) of product were obtained.
4. Sub 2-50 합성예4. Sub 2-50 Synthesis Example
(1) Sub 2-I-50 합성(1) Sub 2-I-50 Synthesis
출발물질인 1-amino-2-naphthoic acid (75.11 g, 401.25 mmol)를 둥근바닥플라스크에 urea (168.69 g, 2808.75 mmol)와 함께 넣고 160ㅀC에서 교반하였다. TLC로 반응을 확인한 후, 100ㅀC까지 냉각시키고 물 (200ml)을 첨가하여 1시간 동안 교반하였다. 반응이 완료되면 생성된 고체를 감압여과하고 물로 세척 후 건조하여 생성물 63.86 g (수율: 75%)를 얻었다.Starting material 1-amino-2-naphthoic acid (75.11 g, 401.25 mmol) was added together with urea (168.69 g, 2808.75 mmol) in a round bottom flask and stirred at 160 ° C. After confirming the reaction by TLC, it was cooled to 100 ° C and water (200ml) was added and stirred for 1 hour. When the reaction was completed, the resulting solid was filtered under reduced pressure, washed with water and dried to give 63.86 g (yield: 75%) of the product.
(2) Sub 2-II-50 합성(2) Sub 2-II-50 Synthesis
상기 합성에서 얻어진 Sub 2-I-50 (63.86 g, 300.94 mmol)을 둥근바닥플라스크에 POCl3 (200ml)를 상온에서 녹인 후에, N,N-Diisopropylethylamine (97.23 g, 752.36 mmol)을 천천히 적가시킨 후, 90ㅀC에서 교반하였다. 반응이 완료되면 농축 한 후 얼음물 (500ml)을 넣고 상온에서 1시간동안 교반하였다. 생성된 고체를 감압여과하고 건조하여 생성물 67.47 g (수율: 90%)를 얻었다.Sub-I-50 (63.86 g, 300.94 mmol) obtained in the above synthesis was dissolved in a round bottom flask with POCl 3 (200 ml) at room temperature, and then slowly added dropwise with N , N- Diisopropylethylamine (97.23 g, 752.36 mmol). And stirred at 90 ° C. When the reaction was completed, concentrated and then added ice water (500ml) and stirred for 1 hour at room temperature. The resulting solid was filtered under reduced pressure and dried to give 67.47 g (yield: 90%) of product.
(3) Sub 2-50 합성(3) Sub 2-50 synthesis
상기 합성에서 얻어진 Sub 2-II-50 (67.47 g, 270.86 mmol)에 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (60.80 g, 297.94 mmol), Pd(PPh3)4 (12.52 g, 10.83 mmol), K2CO3 (112.30 g, 812.57 mmol), THF (950ml), 물 (475ml)을 첨가하고 상기 Sub 2-22 합성법을 사용하여 생성물 44.89 g (수율: 57%)를 얻었다.To Sub 2-II-50 (67.47 g, 270.86 mmol) obtained in the above synthesis, 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (60.80 g, 297.94 mmol), Pd (PPh 3 ) 4 (12.52 g, 10.83 mmol), K 2 CO 3 (112.30 g, 812.57 mmol), THF (950 ml), water (475 ml) were added and 44.89 g of product using the Sub 2-22 synthesis (yield: 57%).
5. Sub 2-70 합성예5. Sub 2-70 Synthesis Example
출발물질인 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (32.01 g, 125.47 mmol)에 4,4,5,5-tetramethyl-2-(naphthalen-2-yl)-1,3,2-dioxaborolane (35.07 g, 138.02 mmol), Pd(PPh3)4 (5.80 g, 5.02 mmol), K2CO3 (52.02 g, 376.41 mmol), THF (440ml), 물 (220ml)을 첨가하고 상기 Sub 2-22 합성법을 사용하여 생성물 19.58 g (수율: 45%)를 얻었다.The starting material 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (32.01 g, 125.47 mmol) was added to 4,4,5,5-tetramethyl-2- (naphthalen-2-yl)- 1,3,2-dioxaborolane (35.07 g, 138.02 mmol), Pd (PPh 3 ) 4 (5.80 g, 5.02 mmol), K 2 CO 3 (52.02 g, 376.41 mmol), THF (440ml), water (220ml) Was added and 19.58 g (yield: 45%) of product was obtained using the above Sub 2-22 synthesis.
Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 2는 Sub 2에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.Compounds belonging to Sub 2 may be the following compounds, but are not limited thereto, and Table 2 shows Field Desorption-Mass Spectrometry (FD-MS) values of some compounds belonging to Sub 2.
표 2 
TABLE 2
III. Product 합성III. Product Synthesis
Sub 1A 내지 Sub 1D 중 하나 (1 당량)를 둥근바닥플라스크에 Toluene으로 녹인 후에, Sub 2 (1 당량), Pd2(dba)3 (0.03 당량), (t-Bu)3P (0.06 당량), NaOt-Bu (3 당량)을 100ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 최종 생성물(final product)를 얻었다.One of Sub 1A to Sub 1D (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 2 (1 equiv), Pd 2 (dba) 3 (0.03 equiv), (t-Bu) 3 P (0.06 equiv), NaOt-Bu (3 equiv) was stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a final product.
1. P 1-10 합성예1.P 1-10 Synthesis Example
상기 합성에서 얻어진 Sub 1A-1 (5.74 g, 17.75 mmol)을 둥근바닥플라스크에 toluene (180ml)으로 녹인 후에, Sub 2-50 (5.16 g, 17.75 mmol), Pd2(dba)3 (0.49 g, 0.53 mmol), 50% P(t-Bu)3 (0.5ml, 1.06 mmol), NaOt-Bu (5.12 g, 53.25 mmol)을 첨가하고 100ㅀC에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 7.18 g (수율: 70%)를 얻었다.Sub 1A-1 (5.74 g, 17.75 mmol) obtained in the above synthesis was dissolved in toluene (180 ml) in a round bottom flask, and then Sub 2-50 (5.16 g, 17.75 mmol), Pd 2 (dba) 3 (0.49 g, 0.53 mmol), 50% P ( t -Bu) 3 (0.5ml, 1.06 mmol), NaO t -Bu (5.12 g, 53.25 mmol) were added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain the product 7.18 g (yield: 70%).
2. P 1-19 합성예2. Synthesis Example P 1-19
상기 합성에서 얻어진 Sub 1A-6 (7.89 g, 13.97 mmol)에 Sub 2-1 (2.19 g, 13.97 mmol), Pd2(dba)3 (0.38 g, 0.42 mmol) 50% P(t-Bu)3 (0.4ml, 0.84 mmol), NaOt-Bu (4.03 g, 41.92 mmol), toluene (140ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.52 g (수율: 84%)를 얻었다.Sub 1A-6 (7.89 g, 13.97 mmol) obtained in the above synthesis in Sub 2-1 (2.19 g, 13.97 mmol), Pd 2 (dba) 3 (0.38 g, 0.42 mmol) 50% P ( t -Bu) 3 (0.4 ml, 0.84 mmol), NaO t -Bu (4.03 g, 41.92 mmol), toluene (140 ml) were added and 7.52 g (yield: 84%) of the product was obtained using the P 1-10 synthesis.
3. P 1-22 합성예3. P 1-22 Synthesis Example
상기 합성에서 얻어진 Sub 1A-2 (6.26 g, 20.37 mmol)에 Sub 2-19 (5.73 g, 20.37 mmol), Pd2(dba)3 (0.56 g, 0.61 mmol) 50% P(t-Bu)3 (0.6ml, 1.22 mmol), NaOt-Bu (5.87 g, 61.10 mmol), toluene (205ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.34 g (수율: 71%)를 얻었다.Sub 1A-2 (6.26 g, 20.37 mmol) obtained in the above synthesis to Sub 2-19 (5.73 g, 20.37 mmol), Pd 2 (dba) 3 (0.56 g, 0.61 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.22 mmol), NaO t -Bu (5.87 g, 61.10 mmol), toluene (205 ml) were added to give 7.34 g (yield: 71%) of the product using the P 1-10 synthesis.
4. P 1-47 합성예4. Synthesis Example P 1-47
상기 합성에서 얻어진 Sub 1A-19 (9.31 g, 11.11 mmol)에 Sub 2-8 (2.59 g, 11.11 mmol), Pd2(dba)3 (0.31 g, 0.33 mmol) 50% P(t-Bu)3 (0.3ml, 0.67 mmol), NaOt-Bu (3.20 g, 33.33 mmol), toluene (110ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.04 g (수율: 64%)를 얻었다.To Sub 1A-19 (9.31 g, 11.11 mmol) obtained in the above synthesis, Sub 2-8 (2.59 g, 11.11 mmol), Pd 2 (dba) 3 (0.31 g, 0.33 mmol) 50% P ( t -Bu) 3 (0.3 ml, 0.67 mmol), NaO t -Bu (3.20 g, 33.33 mmol), toluene (110 ml) were added to give 7.04 g (yield: 64%) of the product using the P 1-10 synthesis.
5. P 2-4 합성예5. P 2-4 Synthesis Example
상기 합성에서 얻어진 Sub 1B-1 (6.14 g, 18.99 mmol)에 Sub 2-31 (5.55 g, 18.99 mmol), Pd2(dba)3 (0.52 g, 0.57 mmol) 50% P(t-Bu)3 (0.6ml, 1.14 mmol), NaOt-Bu (5.47 g, 56.96 mmol), toluene (190ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.82 g (수율: 77%)를 얻었다.Sub 1B-1 (6.14 g, 18.99 mmol) obtained in the above synthesis to Sub 2-31 (5.55 g, 18.99 mmol), Pd 2 (dba) 3 (0.52 g, 0.57 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.14 mmol), NaO t -Bu (5.47 g, 56.96 mmol), toluene (190 ml) were added and the product P. 7-10 was used to yield 7.82 g (yield: 77%) of the product.
6. P 2-30 합성예6. Synthesis of P 2-30
상기 합성에서 얻어진 Sub 1B-2 (6.15 g, 20.01 mmol)에 Sub 2-70 (6.94 g, 20.01 mmol), Pd2(dba)3 (0.55 g, 0.60 mmol) 50% P(t-Bu)3 (0.6ml, 1.20 mmol), NaOt-Bu (5.77 g, 60.03 mmol), toluene (200ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.66 g (수율: 62%)를 얻었다.To Sub 1B-2 (6.15 g, 20.01 mmol) obtained in the above synthesis, Sub 2-70 (6.94 g, 20.01 mmol), Pd 2 (dba) 3 (0.55 g, 0.60 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.20 mmol), NaO t -Bu (5.77 g, 60.03 mmol), toluene (200 ml) were added and the product 1,66 g (yield: 62%) was obtained using the P 1-10 synthesis.
7. P 2-34 합성예7.P 2-34 Synthesis Example
상기 합성에서 얻어진 Sub 1B-3 (6.73 g, 20.18 mmol)에 Sub 2-50 (5.87 g, 20.18 mmol), Pd2(dba)3 (0.55 g, 0.61 mmol) 50% P(t-Bu)3 (0.6ml, 1.21 mmol), NaOt-Bu (5.82 g, 60.55 mmol), toluene (200ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.12 g (수율: 60%)를 얻었다.Sub 1B-3 (6.73 g, 20.18 mmol) obtained in the above synthesis in Sub 2-50 (5.87 g, 20.18 mmol), Pd 2 (dba) 3 (0.55 g, 0.61 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.21 mmol), NaO t -Bu (5.82 g, 60.55 mmol), toluene (200 ml) were added and the product P. 1-10 was used to yield 7.12 g (yield: 60%) of the product.
8. P 2-39 합성예8. Synthesis Example P 2-39
상기 합성에서 얻어진 Sub 1B-11 (6.92 g, 12.04 mmol)에 Sub 2-25 (3.88 g, 12.04 mmol), Pd2(dba)3 (0.33 g, 0.36 mmol) 50% P(t-Bu)3 (0.4ml, 0.72 mmol), NaOt-Bu (3.47 g, 36.13 mmol), toluene (120ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.17 g (수율: 73%)를 얻었다.Sub 1B-11 (6.92 g, 12.04 mmol) obtained in the above synthesis in Sub 2-25 (3.88 g, 12.04 mmol), Pd 2 (dba) 3 (0.33 g, 0.36 mmol) 50% P ( t -Bu) 3 (0.4 ml, 0.72 mmol), NaO t -Bu (3.47 g, 36.13 mmol), toluene (120 ml) were added and 7.17 g (yield: 73%) of the product was obtained using the P 1-10 synthesis method.
9. P 2-50 합성예9.P 2-50 Synthesis Example
상기 합성에서 얻어진 Sub 1B-23 (8.75 g, 16.31 mmol)에 Sub 2-21 (5.01 g, 16.31 mmol), Pd2(dba)3 (0.45 g, 0.49 mmol) 50% P(t-Bu)3 (0.5ml, 0.98 mmol), NaOt-Bu (4.70 g, 48.92 mmol), toluene (160ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.09 g (수율: 57%)를 얻었다.Sub 1B-23 (8.75 g, 16.31 mmol) obtained in the above synthesis in Sub 2-21 (5.01 g, 16.31 mmol), Pd 2 (dba) 3 (0.45 g, 0.49 mmol) 50% P ( t -Bu) 3 (0.5 ml, 0.98 mmol), NaO t -Bu (4.70 g, 48.92 mmol), toluene (160 ml) were added to give 7.09 g (yield: 57%) of the product using the P 1-10 synthesis.
10. P 3-1 합성예10.P 3-1 Synthesis Example
상기 합성에서 얻어진 Sub 1C-1 (7.73 g, 23.90 mmol)에 Sub 2-1 (3.75 g, 23.90 mmol), Pd2(dba)3 (0.66 g, 0.72 mmol) 50% P(t-Bu)3 (0.7ml, 1.43 mmol), NaOt-Bu (6.89 g, 71.70 mmol), toluene (240ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.54 g (수율: 79%)를 얻었다.Sub 1C-1 (7.73 g, 23.90 mmol) obtained in the above synthesis in Sub 2-1 (3.75 g, 23.90 mmol), Pd 2 (dba) 3 (0.66 g, 0.72 mmol) 50% P ( t -Bu) 3 (0.7 ml, 1.43 mmol), NaO t -Bu (6.89 g, 71.70 mmol), toluene (240 ml) were added and 7.54 g (yield: 79%) of the product was obtained using the P 1-10 synthesis.
11. P 3-14 합성예11.P 3-14 Synthesis Example
상기 합성에서 얻어진 Sub 1C-2 (6.09 g, 19.82 mmol)에 Sub 2-50 (5.76 g, 19.82 mmol), Pd2(dba)3 (0.54 g, 0.59 mmol) 50% P(t-Bu)3 (0.6ml, 1.19 mmol), NaOt-Bu (5.71 g, 59.45 mmol), toluene (200ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.79 g (수율: 70%)를 얻었다.Sub 1C-2 (6.09 g, 19.82 mmol) obtained in the above synthesis in Sub 2-50 (5.76 g, 19.82 mmol), Pd 2 (dba) 3 (0.54 g, 0.59 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.19 mmol), NaO t -Bu (5.71 g, 59.45 mmol), toluene (200 ml) were added and the product P. 7-10 synthesized to yield 7.79 g (yield: 70%).
12. P 3-36 합성예12.P 3-36 Synthesis Example
상기 합성에서 얻어진 Sub 1C-30 (10.01 g, 13.92 mmol)에 Sub 2-1 (2.19 g, 13.92 mmol), Pd2(dba)3 (0.38 g, 0.42 mmol) 50% P(t-Bu)3 (0.4ml, 0.84 mmol), NaOt-Bu (4.01 g, 41.77 mmol), toluene (140ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.53 g (수율: 68%)를 얻었다.Sub 1C-30 (10.01 g, 13.92 mmol) obtained in the above synthesis in Sub 2-1 (2.19 g, 13.92 mmol), Pd 2 (dba) 3 (0.38 g, 0.42 mmol) 50% P ( t -Bu) 3 (0.4 ml, 0.84 mmol), NaO t -Bu (4.01 g, 41.77 mmol), toluene (140 ml) were added and the product P. 7-10 was used to yield 7.53 g (yield: 68%) of the product.
13. P 4-3 합성예13.P 4-3 Synthesis Example
상기 합성에서 얻어진 Sub 1D-1 (5.29 g, 16.36 mmol)에 Sub 2-28 (5.55 g, 16.36 mmol), Pd2(dba)3 (0.45 g, 0.49 mmol) 50% P(t-Bu)3 (0.5ml, 0.98 mmol), NaOt-Bu (4.72 g, 49.07 mmol), toluene (165ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.14 g (수율: 75%)를 얻었다.Sub 1D-1 (5.29 g, 16.36 mmol) obtained in the above synthesis in Sub 2-28 (5.55 g, 16.36 mmol), Pd 2 (dba) 3 (0.45 g, 0.49 mmol) 50% P ( t -Bu) 3 (0.5 ml, 0.98 mmol), NaO t -Bu (4.72 g, 49.07 mmol) and toluene (165 ml) were added and the product P. 7-10 was used to yield 7.14 g (yield: 75%) of the product.
14. P 4-8 합성예14. Synthesis of P 4-8
상기 합성에서 얻어진 Sub 1D-1 (6.04 g, 18.68 mmol)에 Sub 2-50 (5.43 g, 18.68 mmol), Pd2(dba)3 (0.51 g, 0.56 mmol) 50% P(t-Bu)3 (0.5ml, 1.12 mmol), NaOt-Bu (5.38 g, 56.03 mmol), toluene (190ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.23 g (수율: 67%)를 얻었다.Sub 1D-1 (6.04 g, 18.68 mmol) obtained in the above synthesis in Sub 2-50 (5.43 g, 18.68 mmol), Pd 2 (dba) 3 (0.51 g, 0.56 mmol) 50% P ( t -Bu) 3 (0.5 ml, 1.12 mmol), NaO t -Bu (5.38 g, 56.03 mmol), toluene (190 ml) were added and the product P. 7-10 was used to yield 7.23 g (yield: 67%) of the product.
15. P 4-19 합성예15.P 4-19 Synthesis Example
상기 합성에서 얻어진 Sub 1D-7 (7.38 g, 20.65 mmol)에 Sub 2-22 (7.91 g, 20.65 mmol), Pd2(dba)3 (0.57 g, 0.62 mmol) 50% P(t-Bu)3 (0.6ml, 1.24 mmol), NaOt-Bu (5.95 g, 61.95 mmol), toluene (205ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.49 g (수율: 55%)를 얻었다.Sub 1D-7 (7.38 g, 20.65 mmol) obtained in the above synthesis in Sub 2-22 (7.91 g, 20.65 mmol), Pd 2 (dba) 3 (0.57 g, 0.62 mmol) 50% P ( t -Bu) 3 (0.6 ml, 1.24 mmol), NaO t -Bu (5.95 g, 61.95 mmol), toluene (205 ml) were added and the product P. 1-10 was used to yield 7.49 g (yield: 55%) of the product.
16. P 4-35 합성예16.P 4-35 Synthesis Example
상기 합성에서 얻어진 Sub 1D-12 (8.84 g, 13.75 mmol)에 Sub 2-14 (4.25 g, 13.75 mmol), Pd2(dba)3 (0.38 g, 0.41 mmol) 50% P(t-Bu)3 (0.4ml, 0.83 mmol), NaOt-Bu (3.97 g, 41.26 mmol), toluene (140ml)을 첨가하고 상기 P 1-10 합성법을 사용하여 생성물 7.07 g (수율: 59%)를 얻었다.Sub 1D-12 (8.84 g, 13.75 mmol) obtained in the above synthesis in Sub 2-14 (4.25 g, 13.75 mmol), Pd 2 (dba) 3 (0.38 g, 0.41 mmol) 50% P ( t -Bu) 3 (0.4 ml, 0.83 mmol), NaO t -Bu (3.97 g, 41.26 mmol), toluene (140 ml) were added and the product P. 7-10 was used to yield 7.07 g (yield: 59%).
상기와 같은 합성예에 따라 제조된 본 발명의 일부 화합물의 FD-MS 값은 하기 표 3과 같다.The FD-MS values of some compounds of the present invention prepared according to the synthesis examples described above are shown in Table 3 below.
표 3 
TABLE 3
한편, 상기에서는 화학식 1로 표시되는 본 발명의 예시적 합성예를 설명하였지만, 이들은 모두 Buchwald-Hartwig cross coupling 반응, Suzuki cross-coupling 반응, PPh3-mediated reductive cyclization 반응 (J. Org. Chem. 2005, 70, 5014.), Intramolecular acid-induced cyclization 반응 (J. mater. Chem. 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization 반응 (Org. Lett. 2011, 13, 5504), Grignard 반응 및 Cyclic Dehydration 반응 등에 기초한 것으로 구체적 합성예에 명시된 치환기 이외에 화학식 1에 정의된 다른 치환기 (R1 내지 R14, X, Ar1 및 L1등의 치환기)가 결합되더라도 상기 반응이 진행된다는 것을 당업자라면 쉽게 이해할 수 있을 것이다.On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), all of them are Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, PPh 3 -mediated reductive cyclization reaction ( J. Org. Chem . 2005 , 70 , 5014.), Intramolecular acid-induced cyclization reaction ( J. mater. Chem. 1999, 9 , 2095.), Pd (II) -catalyzed oxidative cyclization reaction ( Org. Lett. 2011, 13 , 5504), Grignard Those skilled in the art know that the reaction proceeds even if other substituents (substituents such as R 1 to R 14 , X, Ar 1, and L 1 ) defined in Formula 1 are combined, in addition to the substituents specified in the specific synthesis examples, based on the reaction, the Cyclic Dehydration reaction, and the like. If you can easily understand.
예컨데, 반응식 1내지 반응식 4에서 Sub 1A 내지 Sub 1D 중 하나와 Sub 2 -> Final Product 반응은 Buchwald-Hartwig cross coupling 반응에 기초한 것이고, 반응식 5에서 Sub 1-II -> Sub 1-III 반응, Sub 1-II -> Sub 1-III' 반응, Sub 1-II -> Sub 1-III” 반응, 반응식 6에서 출발물질 -> Sub 1-I 반응, 반응식 22에서 출발물질 -> Sub 2 반응은 모두 Suzuki cross-coupling 반응에 기초한 것이며, (이때, 아민을 포함하는 반응물의 경우는 본 출원인의 한국등록특허 제10-1251451호 (2013.04.05일자 등록공고)와 제 10-1298483호 (2013.08.21일자 등록공고)에 개시된 합성방법을 사용하였다.) 반응식 5에서 Sub 1-III -> Sub 1 반응은 Intramolecular acid-induced cyclization 반응 (J. mater. Chem. 1999, 9, 2095.)에 기초한 것이다. 이어서, 반응식 5에서 Sub 1-III' -> Sub 1 반응은 Pd(II)-catalyzed oxidative cyclization 반응 (Org. Lett. 2011, 13, 5504)에 기초한 것이고, 반응식 5에서 Sub 1-III” -> Sub 1 반응은 Grignard 반응 및 Cyclic Dehydration 반응 등에 기초한 것이며, 반응식 6에서 Sub 1-I -> Sub 1-II 반응은 PPh3-mediated reductive cyclization 반응 (J. Org. Chem. 2005, 70, 5014.)에 기초한 것이다. 구체적으로 명시되지 않은 치환기가 결합되더라도 상기 반응들은 진행할 것이다.For example, the reaction of one of Sub 1A to Sub 1D and Sub 2-> Final Product in Schemes 1 to 4 is based on the Buchwald-Hartwig cross coupling reaction, and in Scheme 5, the Sub 1-II-> Sub 1-III reaction, Sub 1-II-> Sub 1-III 'reaction, Sub 1-II-> Sub 1-III ”reaction, starting materials in Scheme 6-> Sub 1-I reaction, starting materials in Scheme 22-> Sub 2 reaction It is based on the Suzuki cross-coupling reaction (in this case, in the case of a reactant containing an amine, Korean Patent No. 10-1251451 (published on Apr. 5, 2013) and 10-1298483 (Aug. 21, 2013) of the present applicant. The Synthesis method disclosed in the above) was used.) The reaction of Sub 1-III-> Sub 1 in Scheme 5 is based on the Intramolecular acid-induced cyclization reaction ( J. mater. Chem. 1999, 9 , 2095.). Sub 1-III '-> Sub 1 reaction in Scheme 5 is then based on the Pd (II) -catalyzed oxidative cyclization reaction ( Org. Lett. 2011, 13 , 5504), and in Sub Scheme 5 Sub 1-III ”-> The Sub 1 reaction is based on the Grignard reaction and the Cyclic Dehydration reaction, and the reaction of Sub 1-I to Sub 1-II in Scheme 6 is PPh 3 -mediated reductive cyclization reaction ( J. Org. Chem . 2005, 70 , 5014.) Is based on. The reactions will proceed even if a substituent not specifically specified is attached.
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
[실시예 1] 녹색 유기발광소자 (인광호스트)Example 1 Green Organic Light Emitting Diode (Phosphorescent Host)
본 발명의 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA로 약기함)막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 정공주입층 위에 정공수송 화합물로서 NPD 막을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공수송층 상부에 호스트로서는 상기 본 발명 화합물 P 1-1을 사용하였으며, 도판트 물질로 tris(2-phenylpyridine)-iridium (이하, “Ir(ppy)3”으로 약기함)을 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 정공저지층으로 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약기함)을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (abbreviated as 2-TNATA) film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a hole having a thickness of 60 nm. After the injection layer was formed, an NPD film was vacuum deposited to a thickness of 60 nm as a hole transport compound on the hole injection layer to form a hole transport layer. Compound P 1-1 of the present invention was used as a host on the hole transport layer, and tris (2-phenylpyridine) -iridium (hereinafter, abbreviated as “Ir (ppy) 3 ”) as a dopant material was 95: 5 by weight. Doped to deposit a light emitting layer to a thickness of 30nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm with a hole blocking layer, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited to a thickness of 40 nm as a transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.
[실시예 2] 내지 [실시예 25] 그린 유기발광소자[Example 2] to [Example 25] green organic light emitting device
발광층의 그린호스트 물질로 본 발명의 실시예 1에 따른 화합물 P 1-1 대신 하기 표 4에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound of the present invention shown in Table 4 instead of the compound P 1-1 according to Example 1 of the present invention as a green host material of the emission layer. .
[비교예 1] 내지 [비교예 3][Comparative Example 1] to [Comparative Example 3]
발광층의 호스트 물질로 본 발명의 실시예 1에 따른 화합물 P 1-1 대신 하기 표 4에 기재된 비교화합물 1 내지 비교화합물 3 중 하나를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기발광소자를 제조하였다.An organic light-emitting device in the same manner as in Example 1, except for using one of Comparative Compounds 1 to 3 shown in Table 4 instead of Compound P 1-1 according to Example 1 of the present invention as a host material of the emission layer. The device was manufactured.
본 발명의 실시예 1 내지 실시예 25 및 비교예 1 내지 비교예 3에 의해 제조된 유기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 5000cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 4와 같다.Electroluminescent (EL) characteristics of the photoresearch company PR-650 were applied by applying a forward bias DC voltage to the organic light emitting diodes prepared according to Examples 1 to 25 and Comparative Examples 1 to 3 of the present invention. The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m 2 reference luminance. The measurement results are shown in Table 4 below.
표 4 
Table 4
상기 표 4의 측정 결과에서 알 수 있듯이, 본 발명의 일 실시예에 따른 화합물을 발광층의 인광 녹색 호스트 재료로 사용한 소자가 비교화합물 1 내지 비교화합물 4보다 발광 효율과 수명이 현저히 개선된 것을 확인하였다.As can be seen from the measurement results of Table 4, it was confirmed that the device using the compound according to an embodiment of the present invention as a phosphorescent green host material of the light emitting layer significantly improved luminous efficiency and lifetime than Comparative Compound 1 to Comparative Compound 4. .
6환의 헤테로고리화합물들을 비교해 보면, 육각고리 및 오각고리에 핵심 원소가 동일하게 N이 포함된 타입인 비교화합물 2 내지 비교화합물 4의 경우보다 육각고리에 핵심 원소가 N이 포함되고 오각고리에 핵심 원소가 S, O, CR'R” 중 하나가 포함되는 이형원자 타입인 본 발명 화합물이 더 높은 효율 및 높은 수명을 나타내는 것을 확인할 수 있다.Comparing the heterocyclic compounds of six rings, the hexagonal rings contain N and the core elements are included in the hexagonal rings than in the case of Comparative Compounds 2 to 4, wherein the hexagonal and pentagonal rings have the same key element as N. It can be seen that the compound of the present invention, which is a heteroatom type containing one of S, O, and CR'R ″, exhibits higher efficiency and higher lifetime.
일반적으로 분자가 적층될 때, 인접한 π-전자가 많아짐에 따라 강한 전기적 상호작용을 갖게 되는데, 이는 전하 캐리어 이동도와 밀접한 연관이 있다.In general, when molecules are stacked, there is a strong electrical interaction with more adjacent π-electrons, which is closely related to charge carrier mobility.
N-N type의 6환의 헤테로고리화합물인 비교화합물 2 내지 비교화합물 4는 분자가 적층될 때, N-N type으로 동형의 헤테로고리코어이기 때문에 분자간의 배열순서가 edge-to-face 형태를 갖게 되고, 이는 낮은 전하 캐리어 이동도 및 낮은 산화 안정성을 야기하는 것으로 판단된다.Comparative Compounds 2 to 4, which are NN-type six-membered heterocyclic compounds, are NN-type heterocyclic cores when the molecules are stacked, so that the intermolecular sequence is edge-to-face. It is believed to cause charge carrier mobility and low oxidative stability.
본 발명 화합물의 경우는 고리화합물 내 헤테로원자가 서로 다른 이형 헤테로고리 코어를 갖기 때문에 분자의 패킹구조가 역방향으로 마주보는 파이-적층구조(antiparallelcofacial π-stacking structure)를 갖는다. 이는 분자간의 배열 순서를 face-to-face 형태로 만들며, 이 적층구조의 원인인 비대칭으로 배치된 헤테로원자 N의 Ar1의 입체효과로 인하여 현저히 높은 캐리어 이동도를 야기하여 높은 효율을 갖는 것으로 판단되며, 높은 산화안정성을 가지기 때문에 수명이 현저히 증가 되는 것으로 판단된다.In the case of the compound of the present invention, since the heteroatoms in the cyclic compound have different heterocyclic cores, they have an antiparallelcofacial π-stacking structure in which the packing structure of the molecules faces in the reverse direction. This makes the arrangement order between molecules into face-to-face shape and due to the steric effect of Ar 1 of asymmetrically arranged heteroatoms N which is the cause of the stacked structure, it is considered to have a high efficiency due to the high carrier mobility. In addition, it has a high oxidative stability and is believed to significantly increase the lifespan.
또한, 육각고리에 N이 포함되는 본 발명 화합물은 오각고리에 N이 포함되는 경우인 비교화합물 3보다 정공과 전자를 모두 안정적으로 수용하기에 더 적합한 형태를 가짐으로써 결과적으로 발광층 내 전하 균형을 보다 좋게 하여 발광 효율 및 수명이 증가되는 것으로 판단된다.In addition, the compound of the present invention that contains N in the hexagonal ring has a more suitable form to accommodate both holes and electrons more stably than Comparative Compound 3, which is a case where N is included in the pentagonal ring. It is judged that the light emission efficiency and lifespan are increased.
[실시예 26] 적색 유기발광소자 (인광호스트)Example 26 Red Organic Light Emitting Diode (Phosphorescent Host)
본 발명의 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 2-TNATA 막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 정공주입층 위에 정공수송 화합물로서 NPD 막을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공수송층 상부에 호스트로서는 상기 본 발명 화합물P 1-9를 사용하였으며, 도판트 물질로 (piq)2Ir(acac)를 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 정공저지층으로 BAlq를 10 nm 두께로 진공증착하고, 전자수송층으로 Alq3을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전계발광소자를 제조하였다An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm.Then, the NPD film is vacuum-deposited at a thickness of 60 nm as a hole transport compound on the hole injection layer. A transport layer was formed. Compound P 1-9 of the present invention was used as a host on the hole transport layer, and a light emitting layer was deposited to a thickness of 30 nm by doping a (piq) 2 Ir (acac) at a weight ratio of 95: 5 with a dopant material. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm using a hole blocking layer, and Alq 3 was formed to a thickness of 40 nm using an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic light emitting diode.
[실시예 27] 내지 [실시예 50] 레드 유기발광소자Example 27 to Example 50 Red Organic Light Emitting Diode
발광층의 레드호스트 물질로 본 발명의 실시예 26에 따른 화합물 P 1-9 대신 하기 표 5에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예26과 동일한 방법으로 유기발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 26 except for using the compound of the present invention shown in Table 5 below instead of the compound P 1-9 according to Example 26 of the present invention as a red host material of the emission layer. .
[비교예 4] 내지 [비교예 6][Comparative Example 4] to [Comparative Example 6]
발광층의 호스트 물질로 본 발명의 실시예 26에 따른 화합물 P 1-9 대신 하기 표 5에 기재된 비교화합물 1, 비교화합물 4, 비교화합물 5 중 하나를 사용한 점을 제외하고는 상기 실시예 26과 동일한 방법으로 유기발광소자를 제조하였다.Except for using the compound P 1-9 of Comparative Example 1, Comparative Compound 4, Comparative Compound 5 shown in Table 5 as a host material of the light emitting layer in the same manner as in Example 26 except that An organic light emitting device was manufactured by the method.
본 발명의 실시예 26 내지 실시예 50, 비교예 4 내지 비교예 6에 의해 제조된 유기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 2500cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 5와 같다.The electroluminescence (EL) characteristics of the photoresearch company PR-650 were applied by applying a forward bias DC voltage to the organic light emitting diodes manufactured according to Examples 26 to 50 and Comparative Examples 4 to 6. The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 2500 cd / m 2 reference luminance. The measurement results are shown in Table 5 below.
표 5 
Table 5
상기 표 5의 측정 결과에서 알 수 있듯이, 본 발명의 일 실시예에 따른 화합물을 발광층의 인광적색 호스트 재료로 사용한 소자가 비교화합물 1 및 비교화합물 5 내지 비교화합물 9보다 발광 효율과 수명이 현저히 개선된 것을 확인하였다. 이는 고리화합물 내 헤테로원자가 서로 다른 이형 헤테로고리 코어를 가지는 형태 및 육각고리에 N이 포함되는 구조가 녹색 유기발광소자의 발광층(호스트로 사용) 뿐만 아니라 적색 유기발광소자의 발광층(호스트로 사용)에서도 소자의 성능향상에 주요인자로 작용하는 것을 확인 할 수 있다.As can be seen from the measurement results of Table 5, the device using the compound according to an embodiment of the present invention as a phosphorescent red host material of the light emitting layer is significantly improved luminous efficiency and lifetime than Comparative Compound 1 and Comparative Compounds 5 to 9 It was confirmed. This is because the heterocyclic atoms in the ring compound have heterocyclic heterocyclic cores and the structure in which the hexagonal ring contains N is used not only in the light emitting layer (used as a host) but also in the red organic light emitting element (used as a host). It can be seen that it acts as a major factor in improving device performance.
발광층 내에 호스트 재료로 사용한 본 발명 화합물은 높은 산화 안정성 및 높은 전하 캐리어 이동도를 가져 보다 효과적인 전하 균형을 이루며, 특히 본 발명의 화합물 중 벤조퀴나졸린(benzoquinazoline), 벤조티에노피리미딘(benzothienopyrimidine), 벤조퓨로피리미딘(benzofuropyrimidine)과 같은 특정 치환기를 도입한 경우는 정공과 전자를 모두 수용하기에 적절한 구조형태를 보임과 동시에 호스트에서 도판트로의 전하 이동이 용이하도록 적절한 T1 값을 가져, 결과적으로 발광 효율 및 수명에서 가장 우수한 소자 결과를 나타내는 것을 확인할 수 있다. The compound of the present invention used as a host material in the light emitting layer has high oxidative stability and high charge carrier mobility to achieve more effective charge balance. The introduction of specific substituents, such as benzofuropyrimidine, exhibits the appropriate conformation to accommodate both holes and electrons, and at the same time has an appropriate T1 value to facilitate charge transfer from the host to the dopant. It can be seen that it shows the best device results in luminous efficiency and lifetime.
또한, 인광호스트의 경우 정공수송층 및 도펀트와의 상호관계를 파악해야 하는 바, 유사한 코어를 사용하더라도 본 발명의 화합물이 인광호스트에서 나타내는 우수한 전기적 특성을 유추하기는 매우 어려울 것이다.In addition, in the case of the phosphorescent host, it is very difficult to infer the excellent electrical properties exhibited by the compound of the present invention, even if a similar core is used, since the correlation between the hole transport layer and the dopant is required.
[실시예 51] 녹색 유기발광소자 (정공수송층)Example 51 Green Organic Light-Emitting Device (Hole Transport Layer)
본 발명의 화합물을 정공수송층 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 2-TNATA 막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 상기 정공주입층 상에 본 발명의 화합물 P-40을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공수송층 상부에 호스트로서는 4,4'-N,N'-dicarbazole-biphenyl (이하, “CBP”로 약기함)을 사용하였으며, 도판트 물질로 Ir(ppy)3를 90:10 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 정공저지층으로 BAlq를 10 nm 두께로 진공증착하고, 전자수송층으로 Alq3을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전계발광소자를 제조하였다.An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a hole transport material. First, a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then Compound P-40 of the present invention on the hole injection layer has a thickness of 60 nm. Vacuum deposition was performed to form a hole transport layer. 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as “CBP”) was used as a host on the hole transport layer, and dopant was doped with Ir (ppy) 3 in a 90:10 weight ratio. A light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm using a hole blocking layer, and Alq 3 was formed to a thickness of 40 nm using an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.
[실시예 52] 내지 [실시예 71] 녹색 유기발광소자[Example 52] to [Example 71] green organic light emitting device
정공수송층 물질로 본 발명의 실시예 51에 따른 화합물 P 1-40 대신 하기 표 6에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예 51과 동일한 방법으로 유기발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 51 except for using the compound of the present invention shown in Table 6 instead of the compound P 1-40 according to Example 51 of the present invention as a hole transport layer material.
[비교예 7]Comparative Example 7
정공수송층 물질로 본 발명의 실시예 51에 따른 화합물 P 1-00 대신 하기 표 6에 기재된 비교화합물 6을 사용한 점을 제외하고는 상기 실시예 51과 동일한 방법으로 유기발광소자를 제조하였다.An organic light emitting diode was manufactured according to the same method as Example 51 except for using Comparative Compound 6 shown in Table 6 below instead of Compound P 1-00 according to Example 51 of the present invention as a hole transport layer material.
본 발명의 실시예 51 내지 실시예 71 및 비교예 7에 의해 제조된 유기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 5000cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 6과 같다.Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic light emitting diodes prepared in Examples 51 to 71 and Comparative Example 7 of the present invention. Measurement Results The T95 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at 5000 cd / m 2 reference luminance, and the measurement results are shown in Table 6 below.
표 6 
Table 6
상기 표 6의 측정 결과에서 알 수 있듯이, 본 발명의 일 실시예에 따른 화합물을 정공수송층 재료로 사용한 소자가 비교화합물 6 보다 발광 효율과 수명이 현저히 개선된 것을 확인하였다.As can be seen from the measurement results of Table 6, it was confirmed that the device using the compound according to an embodiment of the present invention as a hole transport layer material significantly improved luminous efficiency and lifespan than Comparative Compound 6.
이와 같은 결과는, 본 발명 화합물의 고유 특성인 깊은 HOMO 에너지 레벨과 높은 T1 값을 갖기 때문에, 전자를 저지(blocking)하는 능력을 향상시킴과 동시에 정공이 발광층으로 원활하게 수송되어 결과적으로 엑시톤이 발광층 내에 더욱 쉽게 생성되면서 효율이 향상되는 것으로 판단된다. 또한 높은 열적 안정성을 가져 수명이 늘어나는 것을 확인할 수 있다. This result has a deep HOMO energy level and a high T1 value, which are inherent characteristics of the compound of the present invention, which improves the ability to block electrons and simultaneously transports holes to the light emitting layer. It is believed that the efficiency is improved while being more easily generated within. In addition, it has a high thermal stability it can be seen that the life is extended.
앞에서 설명한 특성인 깊은 HOMO 에너지 레벨, 높은 T1 값, 높은 열적 안정성 등을 종합해 보면, 본 발명 화합물과 같은 6환 헤테로고리에 아민기(-La-N(Ra)(Rb))를 도입함에 따라 밴드 갭, 전기적 특성, 계면 특성 등이 크게 변화될 수 있다는 것을 보여주며 이는 소자의 성능향상에 주요 인자로 작용한다는 것을 확인할 수 있다. 또한 정공수송층의 경우에는 발광층(호스트)과의 상호관계를 파악해야 하는바, 유사한 코어를 사용하더라도 본 발명 화합물이 사용된 정공수송층에서 나타내는 특징을 유추하는 것은 통상의 기술자라 하더라도 매우 어려울 것이다.Taking into account the characteristics of the above-described deep HOMO energy level, high T1 value, high thermal stability, and the like, the amine group (-L a -N (R a ) (R b )) in the same heterocyclic ring as the compound of the present invention It can be seen that the band gap, electrical characteristics, and interface characteristics can be greatly changed by the introduction, which can be seen as a major factor in improving device performance. In addition, in the case of the hole transport layer, it is necessary to grasp the interrelationship with the light emitting layer (host), and even if a similar core is used, it will be very difficult even for a person skilled in the art to infer the characteristics shown in the hole transport layer in which the compound of the present invention is used.
아울러, 전술한 소자 제작의 평가 결과에서는 본 발명의 화합물을 호스트물질로 발광층 및 정공수송 물질로 정공수송층에 적용한 소자 특성을 설명하였으나, 본 발명의 화합물을 정공주입층과 발광보조층, 전자수송층, 전자주입층, 발광보조층 등 다른 모두 층에 적용하여 사용될 수 있다.In addition, the evaluation results of the above-described device fabrication described the device characteristics of applying the compound of the present invention to the light emitting layer and the hole transporting material as a host material, but the compound of the present invention is applied to the hole injection layer, the light emitting auxiliary layer, the electron transporting layer, The electron injection layer, the light emitting auxiliary layer and the like can be applied to all other layers.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명에 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아나라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 한다.The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications can be made without departing from the essential features of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention, and the spirit and scope of the present invention are not limited to these embodiments. The scope of protection of the present invention should be interpreted by the claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2015년 11월 17일 한국에 출원한 특허출원번호 제 10-2015-0160797호에 대해 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application claims priority to Korean Patent Application No. 10-2015-0160797 filed on November 17, 2015 in Korea, the contents of which are hereby incorporated by reference in their entirety. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.
Claims (12)
- 하기 화학식 1로 표시되는 화합물.A compound represented by the following formula (1).
상기 화학식 1에서,In Chemical Formula 1,상기 R1 내지 R14는 서로 독립적으로 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -La-N(Ra)(Rb); C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며, 고리를 형성하지 않는 R1 내지 R14는 상기에서 정의된 것과 동일하며,R 1 to R 14 are each independently hydrogen; heavy hydrogen; Tritium; halogen; Cyano group; Nitro group; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group or adjacent groups may combine with each other to form a ring, R 1 to R 14 which do not form a ring are the same as defined above,상기 R5와 R6, R6과 R7, R8와 R9 및 R9와 R10 중 어느 하나는 상기 화학식 1a로표시되는 축합 고리를 형성하며,Any one of R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 form a condensed ring represented by Formula 1a,상기 R5와 R6이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R5가 **에 연결된 결합을 나타내고 R6이 *에 연결된 결합을 나타내며,When R 5 and R 6 form a condensed ring represented by Formula 1a, R 5 represents a bond connected to ** and R 6 represents a bond connected to *,상기 R6과 R7이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R6이 **에 연결된 결합을 나타내고 R7이 *에 연결된 결합을 나타내며,When R 6 and R 7 form a condensed ring represented by Formula 1a, R 6 represents a bond connected to ** and R 7 represents a bond connected to *,상기 R8와 R9가 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R8이 **에 연결된 결합을 나타내고 R9가 *에 연결된 결합을 나타내며,When R 8 and R 9 form a condensed ring represented by Formula 1a, R 8 represents a bond connected to ** and R 9 represents a bond connected to *,상기 R9와 R10이 상기 화학식 1a로 표시되는 축합 고리를 형성하는 경우는 R9가 **에 연결된 결합을 나타내고 R10이 *에 연결된 결합을 나타내며,When R 9 and R 10 form a condensed ring represented by Formula 1a, R 9 represents a bond connected to ** and R 10 represents a bond connected to *,상기 X는 S, O 및 C(Ar2)(Ar3) 중 하나이며,X is one of S, O and C (Ar 2 ) (Ar 3 ),상기 Ar1은 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -La-N(Ra)(Rb); C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며, Ar 1 is independently of each other C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L a -N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,상기 Ar2 및 Ar3은 i)서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되거나, 또는 ii) Ar2와 Ar3이 서로 결합하여 이들이 결합된 C 와 함께 스파이로(spiro) 화합물을 형성할 수 있으며,Ar 2 and Ar 3 are i) each independently of the C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 It is selected from the group consisting of an aryloxy group, or ii) Ar 2 and Ar 3 may be bonded to each other to form a spiro compound with the C bonded thereto,상기 Ra 및 Rb는 서로 독립적으로, C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; 및 C2-C20의 알켄일기;로 이루어진 군에서 선택되며,R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; A C 2 -C 60 heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; And C 2 -C 20 Alkenyl group; It is selected from the group consisting of,상기 L1 및 La는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 2가 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 2가 융합고리기; 및 2가의 지방족 탄화수소기로 이루어진 군에서 선택되며, 상기 L1 및 La(단일결합 제외) 각각은 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; -N(Rc)(Rd); 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있으며,L 1 and L a are each independently a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And divalent aliphatic hydrocarbon groups, wherein L 1 and L a (except for single bonds) are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; -N (R c ) (R d ); And an arylalkenyl group of C 8 -C 20 It can be substituted with one or more substituents selected from the group consisting of,상기 Rc 및 Rd는 서로 독립적으로, C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기;로 이루어진 군에서 선택되며, R c and R d are each independently a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group containing at least one hetero atom of O, N, S, Si and P;상기 아릴기, 플루오렌일기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알킨일기, 알콕시기, 아릴옥시기 각각은 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있다.Each of the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group is deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of C 8 -C 20 arylalkenyl group. - 제 1항에 있어서,The method of claim 1,상기 화학식 1은 하기 화학식 2 내지 화학식 5 중 하나로 표시되는 것을 특징으로 하는 화합물.Formula 1 is a compound, characterized in that represented by one of the following formula (2).
상기 R1 내지 R14, X, Ar1 및 L1은 상기 화학식 1에서 정의된 것과 동일하다. R 1 to R 14 , X, Ar 1 and L 1 are the same as defined in Chemical Formula 1. - 제 1항에 있어서,The method of claim 1,상기 화학식 1의 Ar1은 하기 화학식 A-1 내지 화학식 A-3 중 하나로 표시되는 것을 특징으로 하는 화합물.Ar 1 of Formula 1 is a compound, characterized in that represented by one of the formula A-1 to A-3.
상기 화학식 A-1에서, Q1 내지 Q4는 서로 독립적으로 N, CRe, 및 L1과 결합하는 탄소(C)이며, Q1 내지 Q4 중 하나는 L1과 결합하는 탄소(C)이고, In Chemical Formula A-1, Q 1 to Q 4 are independently carbon (C) bonded to N, CR e , and L 1 , and one of Q 1 to Q 4 is carbon (C) bonded to L 1 . ego,상기 화학식 A-2에서, Q1 내지 Q4는 서로 독립적으로 N, CRe이며,In Formula A-2, Q 1 to Q 4 are each independently N and CR e ,상기 화학식 A-3에서, Q5 내지 Q9는 서로 독립적으로 N, CRe이며,In Formula A-3, Q 5 to Q 9 are independently of each other N, CR e ,상기 화학식 A-1 및 A-2에서, Z는 C6-C60의 단일환 또는 다환의 방향족고리; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기로 이루어진 군에서 선택되며,In Chemical Formulas A-1 and A-2, Z is C 6 -C 60 monocyclic or polycyclic aromatic ring; Or a C 2 -C 60 heterocyclic group including at least one hetero atom of O, N, S, Si, and P,상기 화학식 A-1 내지 A-3에서,In Chemical Formulas A-1 to A-3,Re 는 수소; 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된다. R e is hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom of O, N, S, Si, and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; And arylalkenyl group of C 8 -C 20 It is selected from the group consisting of. - 제 3항에 있어서,The method of claim 3, wherein상기 화학식 A-1 및 화학식 A-2의 Z환은 서로 독립적으로 하기 화학식 중 하나인 것을 특징으로 하는 화합물.The Z ring of Chemical Formula A-1 and A-2 is independently one of the following Chemical Formulas.
상기 화학식 Z-1 내지 화학식 Z-15에서, 표시 *은 Q1 내지 Q4를 포함하는 고리와 결합하여 융합고리를 형성하는 결합 부분을 표시하며, In Formulas Z-1 to Z-15, the mark * denotes a binding moiety that combines with a ring including Q 1 to Q 4 to form a fused ring.W1 및 W2는 서로 독립적으로 단일결합, N-L2-Ar4, S, O, C(Ar5)(Ar6) 중 하나이며,W 1 and W 2 are independently of each other a single bond, NL 2 -Ar 4 , S, O, C (Ar 5 ) (Ar 6 ),V는 서로 독립적으로 N, CRe이며, V is independently of each other N, CR e ,L2는 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 2가 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 2가 융합고리기; 및 2가의 지방족 탄화수소기로 이루어진 군에서 선택되며,L 2 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A C 2 -C 60 divalent heterocyclic group comprising at least one hetero atom of O, N, S, Si, and P; Divalent fused ring group of C 3 -C 60 aliphatic ring and C 6 -C 60 aromatic ring; And it is selected from the group consisting of divalent aliphatic hydrocarbon group,Ar4 내지 Ar6은 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되며,Ar 4 to Ar 6 is an aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And it is selected from the group consisting of C 6 -C 30 aryloxy group,Ar5과 Ar6이 서로 결합하여 이들이 결합된 탄소(C)와 함께 스파이로(spiro) 화합물을 형성할 수 있으며,Ar 5 and Ar 6 may be bonded to each other to form a spiro compound together with the carbon (C) to which they are bonded,Re는 제3항에서 정의된 상기 Re와 동일하다.R e is the same as R e defined in claim 3. - 제 3항에 있어서, The method of claim 3, wherein상기 Q1 내지 Q4 중 적어도 하나는 N인 것을 특징으로 하는 화합물.At least one of Q 1 to Q 4 is N;
- 제 1항에 있어서, The method of claim 1,하기 화합물 중 하나인 것을 특징으로 하는 화합물.Compound which is one of the following compounds.
- 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함하는 유기전기소자에 있어서, 상기 유기물층은 제 1항 내지 제 6항 중 어느 한 항의 화합물을 함유하는 것을 특징으로 하는 유기전기소자.A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 1 to 6.
- 제 7항에 있어서,The method of claim 7, wherein상기 유기물층의 정공주입층, 정공수송층, 발광보조층 및 발광층 중 적어도 하나의 층에 상기 화합물이 함유되며, 상기 화합물은 1종 단독 화합물 또는 2종 이상의 화합물을 혼합물의 성분으로서 포함하는 것을 특징으로 하는 유기전기소자.The compound is contained in at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer and a light emitting layer of the organic material layer, the compound is characterized in that it comprises a single compound or two or more compounds as a component of the mixture Organic electrical devices.
- 제 7항에 있어서,The method of claim 7, wherein상기 화합물은 상기 발광층의 인광 호스트 물질로 사용되는 것을 특징으로 하는 유기전기소자.And the compound is used as a phosphorescent host material of the light emitting layer.
- 제 7항에 있어서,The method of claim 7, wherein상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 또는 롤투롤 공정에 의해 형성되는 것을 특징으로 하는 유기전기소자.The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
- 제 7항의 유기전기소자를 포함하는 디스플레이장치; 및 A display device comprising the organic electronic device of claim 7; And상기 디스플레이장치를 구동하는 제어부를 포함하는 전자장치.And a controller for driving the display device.
- 제 11항에 있어서,The method of claim 11,상기 유기전기소자는 유기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 하나인 것을 특징으로 하는 전자장치.The organic electronic device is an electronic device, characterized in that one of an organic light emitting device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.
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| CN110526896A (en) * | 2018-05-25 | 2019-12-03 | 北京鼎材科技有限公司 | A kind of luminescent material and application |
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| CN109824522A (en) * | 2019-03-29 | 2019-05-31 | 吉林奥来德光电材料股份有限公司 | A kind of organic luminescent compounds and its preparation method and application |
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