WO2015111864A1 - Organic compound, and organic electroluminescent device containing same - Google Patents
Organic compound, and organic electroluminescent device containing same Download PDFInfo
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- WO2015111864A1 WO2015111864A1 PCT/KR2015/000353 KR2015000353W WO2015111864A1 WO 2015111864 A1 WO2015111864 A1 WO 2015111864A1 KR 2015000353 W KR2015000353 W KR 2015000353W WO 2015111864 A1 WO2015111864 A1 WO 2015111864A1
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- 150000002894 organic compounds Chemical class 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 317
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 230000005525 hole transport Effects 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims description 47
- 239000000126 substance Substances 0.000 claims description 42
- -1 alkyl boron Chemical compound 0.000 claims description 23
- 239000011368 organic material Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 125000005104 aryl silyl group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 10
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 8
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 125000005549 heteroarylene group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005264 aryl amine group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims 1
- 239000012044 organic layer Substances 0.000 abstract description 90
- 238000004020 luminiscence type Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 231
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 231
- 230000015572 biosynthetic process Effects 0.000 description 154
- 238000003786 synthesis reaction Methods 0.000 description 154
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 149
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 138
- 238000002360 preparation method Methods 0.000 description 82
- 238000004440 column chromatography Methods 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 77
- 238000003756 stirring Methods 0.000 description 76
- 229910052757 nitrogen Inorganic materials 0.000 description 75
- 239000010410 layer Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 0 CCC(C1)=CC(C2=CCC*=C2)=C(C)C1C1=CC=CCC1 Chemical compound CCC(C1)=CC(C2=CCC*=C2)=C(C)C1C1=CC=CCC1 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- WPWPOMNBTQPHDV-UHFFFAOYSA-N [3-(9-phenylcarbazol-3-yl)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=C3C4=CC=CC=C4N(C=4C=CC=CC=4)C3=CC=2)=C1 WPWPOMNBTQPHDV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- NLOHUARANQHPPJ-UHFFFAOYSA-N (3-dibenzothiophen-4-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=3SC4=CC=CC=C4C=3C=CC=2)=C1 NLOHUARANQHPPJ-UHFFFAOYSA-N 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 7
- NFFQEUGCDMASSS-UHFFFAOYSA-N (3-dibenzofuran-4-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=3OC4=CC=CC=C4C=3C=CC=2)=C1 NFFQEUGCDMASSS-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GOXNHPQCCUVWRO-UHFFFAOYSA-N dibenzothiophen-4-ylboronic acid Chemical compound C12=CC=CC=C2SC2=C1C=CC=C2B(O)O GOXNHPQCCUVWRO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 5
- MMKURQHAWQHNNS-UHFFFAOYSA-N 4-chloro-2,6-diphenylaniline Chemical compound NC1=C(C=2C=CC=CC=2)C=C(Cl)C=C1C1=CC=CC=C1 MMKURQHAWQHNNS-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IDQUIFLAFFZYEX-UHFFFAOYSA-N (3-carbazol-9-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 IDQUIFLAFFZYEX-UHFFFAOYSA-N 0.000 description 3
- YWHHCWDUCCYVFV-UHFFFAOYSA-N 1,3-dichloro-2-iodo-5-phenylbenzene Chemical group ClC=1C=C(C=C(C=1I)Cl)C1=CC=CC=C1 YWHHCWDUCCYVFV-UHFFFAOYSA-N 0.000 description 3
- NPPQHNGXMKRUDG-UHFFFAOYSA-N 2,6-dichloro-4-phenylaniline Chemical compound C1=C(Cl)C(N)=C(Cl)C=C1C1=CC=CC=C1 NPPQHNGXMKRUDG-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- FBSGGQRKQVPZEB-UHFFFAOYSA-N (3-dibenzothiophen-2-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=C3C4=CC=CC=C4SC3=CC=2)=C1 FBSGGQRKQVPZEB-UHFFFAOYSA-N 0.000 description 2
- XSAOVBUSKVZIBE-UHFFFAOYSA-N (9-phenylcarbazol-2-yl)boronic acid Chemical compound C=1C(B(O)O)=CC=C(C2=CC=CC=C22)C=1N2C1=CC=CC=C1 XSAOVBUSKVZIBE-UHFFFAOYSA-N 0.000 description 2
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 2
- 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
- UZKBSZSTDQSMDR-UHFFFAOYSA-N 1-[(4-chlorophenyl)-phenylmethyl]piperazine Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)N1CCNCC1 UZKBSZSTDQSMDR-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- HDWGHXANEMWCTJ-UHFFFAOYSA-N C1(=CC=CC=C1)N1C2=CC=CC=C2C=2C=CC(=CC1=2)C=1C=C(C=CC=1)B(O)O Chemical compound C1(=CC=CC=C1)N1C2=CC=CC=C2C=2C=CC(=CC1=2)C=1C=C(C=CC=1)B(O)O HDWGHXANEMWCTJ-UHFFFAOYSA-N 0.000 description 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N C[n]1c(cccc2)c2c2ccccc12 Chemical compound C[n]1c(cccc2)c2c2ccccc12 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- DSSBJZCMMKRJTF-UHFFFAOYSA-N dibenzofuran-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3OC2=C1 DSSBJZCMMKRJTF-UHFFFAOYSA-N 0.000 description 2
- CSLSCVHILGCSTE-UHFFFAOYSA-N dibenzothiophen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3SC2=C1 CSLSCVHILGCSTE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RUIIQTRTGLKGMK-UHFFFAOYSA-N (3-dibenzofuran-2-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=C3C4=CC=CC=C4OC3=CC=2)=C1 RUIIQTRTGLKGMK-UHFFFAOYSA-N 0.000 description 1
- KRVWTVYQGIOXQE-UHFFFAOYSA-N 1-(2,6-diphenoxyphenoxy)naphthalene Chemical group C=1C=CC(OC=2C=CC=CC=2)=C(OC=2C3=CC=CC=C3C=CC=2)C=1OC1=CC=CC=C1 KRVWTVYQGIOXQE-UHFFFAOYSA-N 0.000 description 1
- XEYLQXUJSOJWJV-UHFFFAOYSA-N 2,6-dibromo-4-chloroaniline Chemical compound NC1=C(Br)C=C(Cl)C=C1Br XEYLQXUJSOJWJV-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- NPQBZKNXJZARBJ-UHFFFAOYSA-N 4-bromo-2,6-dichloroaniline Chemical compound NC1=C(Cl)C=C(Br)C=C1Cl NPQBZKNXJZARBJ-UHFFFAOYSA-N 0.000 description 1
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- WZMTXEVUJIGKAB-CLTKARDFSA-N C/C=C\c1c(C=C)c2ccccc2[n]1N Chemical compound C/C=C\c1c(C=C)c2ccccc2[n]1N WZMTXEVUJIGKAB-CLTKARDFSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YQPYANHUFHCDHM-UHFFFAOYSA-N Clc1cc(-c2ccccc2)cc(-c2c3[s]c(cccc4)c4c3ccc2)c1-c1ccccc1 Chemical compound Clc1cc(-c2ccccc2)cc(-c2c3[s]c(cccc4)c4c3ccc2)c1-c1ccccc1 YQPYANHUFHCDHM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GAPTVVWZYYXYEW-GFOWMXPYSA-N OB(c1cccc(-c2cccc3c2[C@H]2SC2C2=C3CCCC2)c1)O Chemical compound OB(c1cccc(-c2cccc3c2[C@H]2SC2C2=C3CCCC2)c1)O GAPTVVWZYYXYEW-GFOWMXPYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002962 imidazol-1-yl group Chemical group [*]N1C([H])=NC([H])=C1[H] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
Definitions
- the present invention relates to a novel organic compound and an organic electroluminescent device comprising the same.
- the organic electroluminescent device when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine.
- the material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.
- the light emitting material may be classified into blue, green, and red light emitting materials according to the light emitting color, and yellow and orange light emitting materials required to realize a better natural color.
- a host / dopant system may be used as a light emitting material to increase luminous efficiency through an increase in color purity and energy transfer.
- the dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt.
- a metal complex compound containing heavy atoms such as Ir and Pt.
- anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer.
- a phosphorescent dopant material used in the light emitting layer metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and as a phosphorescent host material, 4,4-dicarbazolybiphenyl (CBP) is known.
- the existing materials have advantages in terms of light emission characteristics, but the thermal stability is low due to the low glass transition temperature, and thus the materials are not satisfactory in terms of lifespan of the organic EL device.
- An object of the present invention is to provide a novel organic compound which is excellent in thermal stability and excellent in light emitting performance and lifespan characteristics.
- an object of this invention is to provide the organic electroluminescent element containing the said organic compound.
- the present invention provides a compound represented by Formula 1 or 2 below:
- L 1 and L 2 are the same or different, each independently is a single bond, or C 6 ⁇ C 60 aryl group and a nuclear atoms is selected from the group consisting of 5 to 60 hetero arylene group;
- Ar 1 and Ar 2 are the same as or different from each other, and are each independently selected from the group consisting of a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;
- Ar 1 , Ar 2, and R 1 to R 10 is a substituent represented by Formula 3 or 4 below;
- X 1 is selected from the group consisting of NR 15 , O, and S;
- a, b and c are each an integer of 0 to 4.
- d is an integer from 0 to 3;
- a plurality of R 11 are the same or different from each other, a plurality of R 12 are the same or different from each other, a plurality of R 13 are the same or different from each other, and a plurality of R 14 are the same or different from each other;
- R 1 to R 15 are the same as or different from each other, and each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C Alkynyl group of 2 to C 40 , cycloalkyl group of C 3 to C 40 , heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ aryloxy C 60, C 1 ⁇ C 40 alkyl silyl group, C 6 ⁇ aryl silyl group of C 60, C 1 ⁇ C 40 group of an alkyl boron, C 6 ⁇ C group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a
- the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer is a compound represented by the formula (1) It provides an organic electroluminescent device comprising a.
- the organic material layer including the compound is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and is preferably a light emitting layer.
- the compound of Formula 1 when included in the emission layer, the compound is a phosphorescent host.
- the compound according to the present invention has excellent thermal stability, light emission characteristics, and lifetime characteristics, the compound may be used as a material of the organic material layer of the organic EL device.
- the compound according to the present invention when used as a phosphorescent host, an organic electroluminescent device having excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host can be manufactured, and furthermore, the performance and lifespan are improved.
- Color display panels can also be manufactured.
- novel compounds according to the invention are suitable for terphenylmoiety (preferably with carbon numbers 3 and 5 or 5 and 6 of the central benzene ring), with various functional groups, in particular carbazole groups, dibenzothiophene groups P-type functional groups such as a dibenzofuran group and a triphenylene group are directly introduced or introduced through an arylene group or a heteroarylene group to form a core, and a structure in which various substituents are bonded to the core. Characterized in that is represented.
- the compound represented by Chemical Formula 1 has a wide bandgap and high triplet energy as well as a thermally stable structure due to the p-type functional group introduced into the central benzene ring of the terphenyl moiety, and has a conventional host. Since the light emitting ability is superior to the material (for example, CBP) and has a long life, it can be used as an organic material layer material of the organic EL device, preferably a light emitting layer material (phosphorescent host). When the compound of Formula 1 is applied to an organic electroluminescent device, the luminous efficiency of the device is high, the driving life is excellent, and the power efficiency is high, thereby improving power consumption.
- At least one of Ar 1 , Ar 2 and R 1 to R 10 is each independently a substituent represented by Formula 3 or 4, and preferably Ar 1 and / or Ar 2 are each Independently represented by the formula (3) or (4).
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, or a C 6 to C 60 arylene group (eg, a phenylene group).
- the arylene group of L 1 and L 2 is deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms 5 to 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, substituted with one or more substituents selected from the group C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C
- R 1 to R 15 are the same as or different from each other, and each independently selected from the group consisting of hydrogen and C 6 ⁇ C 60 aryl group.
- the aryl group of R 1 to R 15 is deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ⁇ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ⁇ alkyloxy group of C 40, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 6 to C 60 arylphosphine group, C 6 ⁇ C 60 aryl phosphine oxide group and C 6 ⁇ C 60
- Examples of the compound represented by Chemical Formula 1 include a compound represented by the following Chemical Formulas 5 to 7, and the like.
- L 1 , L 2 , X 1 , R 1 to R 14 , a, b, c and d are the same as defined in Chemical Formula 1, respectively.
- examples of the compound represented by Chemical Formula 2 include a compound represented by the following Chemical Formulas 8 to 10, but are not limited thereto.
- L 1 , L 2 , X 1 , R 1 to R 14 , a, b, c and d are the same as defined in Chemical Formula 1, respectively.
- unsubstituted alkyl refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, non-limiting examples of which are methyl, ethyl, propyl, iso Butyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.
- unsubstituted alkenyl means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. do. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.
- unsubstituted alkynyl refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon of 2 to 40 carbon atoms having at least one carbon-carbon triple bond. do. Non-limiting examples thereof include ethynyl, 2-propynyl and the like.
- unsubstituted cycloalkyl means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms.
- saturated cyclic hydrocarbon saturated cyclic hydrocarbon
- Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
- unsubstituted heterocycloalkyl means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and at least one carbon in the ring , Preferably 1 to 3 carbons are substituted with a hetero atom such as N, O or S.
- a hetero atom such as N, O or S.
- Non-limiting examples thereof include morpholine, piperazine and the like.
- unsubstituted aryl means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, alone or in combination of two or more rings. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.
- unsubstituted heteroaryl is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably Preferably 1 to 3 carbons are substituted with heteroatoms such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se).
- the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group.
- heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.
- unsubstituted alkyloxy refers to a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and is linear, branched or cyclic. ) May include a structure.
- alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
- unsubstituted aryloxy refers to a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms.
- R'O- a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms.
- Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
- unsubstituted alkylsilyl refers to silyl substituted with alkyl having 1 to 40 carbon atoms
- arylsilyl means silyl substituted with aryl having 6 to 40 carbon atoms
- arylamine has 6 to 40 carbon atoms. Amine substituted with 60 aryl.
- unsubstituted alkyl boron group means a boron group substituted with alkyl having 1 to 40 carbon atoms
- unsubstituted aryl boron group means a boron group substituted with aryl having 6 to 60 carbon atoms
- Unsubstituted arylphosphine group means a phosphine group substituted with aryl having 1 to 60 carbon atoms
- unsubstituted arylphosphine oxide group means a phosphine oxide group substituted with aryl having 1 to 60 carbon atoms.
- condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
- the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1) according to the present invention described above.
- the organic electroluminescent device includes an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, at least one of the organic material layer is a compound represented by Formula 1 Contains more than one species.
- the compound represented by Formula 1 may be used alone or in combination of two or more.
- the at least one organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer includes a compound represented by the formula (1).
- the organic material layer including the compound of Formula 1 may be a light emitting layer.
- the compound represented by Formula 1 may be included in the organic EL device as a light emitting layer material, preferably a phosphorescent host, a fluorescent host or a dopant material, more preferably a phosphorescent host.
- the organic EL device may improve luminous efficiency, brightness, power efficiency, thermal stability, and device life.
- the structure of the organic EL device of the present invention is not particularly limited.
- the anode, one or more organic material layers and the cathode are sequentially stacked on the substrate, and an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.
- an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.
- the organic electroluminescent device may be one in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked on a substrate, and an electron injection layer may be selectively positioned on the electron hydrogen layer.
- at least one of the hole injection layer, the hole transport layer, and the light emitting layer may include at least one compound represented by Chemical Formula 1.
- the organic electroluminescent device of the present invention is an organic material layer and an electrode using materials and methods known in the art, except that at least one of the organic material layers (eg, the light emitting layer) is formed to include the compound represented by Chemical Formula 1 It can be prepared by forming a.
- the organic material layer may be formed by a vacuum deposition method or a solution coating method.
- the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
- the substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz or glass plates, metal plates, plastic films or sheets, and the like.
- examples of the anode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
- metals such as vanadium, chromium, copper, zinc and gold or alloys thereof.
- Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb
- Conductive polymers such as polythiophene, poly (3-methylthiophene
- examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
- the material used as the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited as long as it is a conventional material known in the art.
- 3,5-Dichlorobiphenyl-4-amine (15 g, 62.99 mmol) obtained in ⁇ Step 1> was mixed with HCl (75 ml) and methylene chloride (75 ml) and stirred at 0 ° C. Then aqueous sodium nitride solution (4.56 g, 66.13 mmol) was slowly added dropwise to the reactor, stirred at 0 ° C. for 1 hour, and then aqueous potassium iodide solution (11.50 g, 69.28 mmol) was slowly added dropwise and stirred for 4 hours.
- a glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 ⁇ was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried, and then transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes And the substrate was transferred to a vacuum evaporator.
- a solvent such as isopropyl alcohol, acetone, methanol
- a green organic EL device was manufactured in the same manner as in Example 1, except that each compound of Table 1 was used instead of the compound C1 used as a host material in forming the emission layer in Example 1.
- a green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound C1 used as a host material in forming the emission layer in Example 1.
- the structure of CBP used is as follows.
- the green organic EL device of Examples 1 to 65 using the compounds (C1 to C65) according to the present invention as a host material of the light emitting layer is the green organic EL device of Comparative Example 1 using CBP as a conventional host material. Compared with the device, it was found to show better performance in terms of current efficiency and driving voltage.
- a glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 ⁇ was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried, and then transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes And the substrate was transferred to a vacuum evaporator.
- a solvent such as isopropyl alcohol, acetone, methanol
- a blue organic EL device was manufactured in the same manner as in Example 66, except that the compounds shown in Table 2 were used instead of the compound C1 used as the host material in forming the emission layer in Example 66.
- a blue organic electroluminescent device was manufactured in the same manner as in Example 66, except for using CBP instead of the compound C1 used as a host material in forming the emission layer in Example 66.
- Example 66 Compound c1 7.50 479 6.20
- Example 67 Compound c8 7.60 480 6.25
- Example 68 Compound c9 7.60 470 6.30
- Example 69 Compound c12 7.55 482 6.33
- Example 70 Compound c13 7.50 475 6.27
- Example 71 Compound c22 7.45 477 6.50
- Example 72 Compound c26 7.40 475 6.60
- Compound c28 7.50 480 6.30 Compound c36 7.40 477 6.34
- Example 75 Compound c39 7.45 479 6.43
- Example 76 Compound c45 7.50 475 6.40
- Example 77 Compound c47 7.70 477 6.40 Comparative Example 2 CBP 7.80 474 5.80
- the blue organic EL devices of Examples 66 to 121 using the compound according to the present invention as the host material of the light emitting layer compared with the blue organic EL devices of Comparative Example 2 using CBP, which is a conventional host material, It was found that excellent performance was achieved in terms of efficiency and driving voltage.
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Abstract
The present invention relates to: a novel compound having an excellent hole injection property, hole transport property, luminescent property and the like; and an organic electroluminescent device having improved characteristics such as luminescence efficiency, driving voltage and lifetime by containing the novel compound in an organic layer.
Description
본 발명은 신규 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device comprising the same.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 상기 유기물층에 포함되는 물질은 그 기능에 따라, 발광 물질, 정공 주입 물질, 정공 수송 물질, 전자 수송 물질, 전자 주입 물질 등으로 분류될 수 있다.In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.
상기 발광 물질은 발광색에 따라 청색, 녹색, 적색의 발광 물질과, 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색의 발광 물질로 구분될 수 있다. 또한 색순도의 증가와 에너지 전이를 통해 발광 효율을 증가시키기 위하여 발광 물질로서 호스트/도판트 계를 사용할 수 있다.The light emitting material may be classified into blue, green, and red light emitting materials according to the light emitting color, and yellow and orange light emitting materials required to realize a better natural color. In addition, a host / dopant system may be used as a light emitting material to increase luminous efficiency through an increase in color purity and energy transfer.
도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 이때 인광 도판트는 이론적으로 형광 도판트에 비해 최대 4배의 발광 효율을 향상시킬 수 있기 때문에 인광 도판트 뿐만 아니라 인광 호스트에 대한 연구가 많이 진행되고 있다.The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. In this case, since phosphorescent dopants can theoretically improve luminous efficiency up to 4 times compared to fluorescent dopants, studies on phosphorescent dopants as well as phosphorescent hosts are being conducted.
현재 발광층에 사용되는 형광 도판트/호스트 물질로는 안트라센 유도체들이 알려져 있다. 또한 발광층에 사용되는 인광 도판트 물질로는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등의 Ir을 포함하는 금속 착체 화합물이 알려져 있고, 인광 호스트 물질로는 4,4-dicarbazolybiphenyl(CBP)가 알려져 있다.At present, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. In addition, as a phosphorescent dopant material used in the light emitting layer, metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and as a phosphorescent host material, 4,4-dicarbazolybiphenyl (CBP) is known.
그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮아 열적 안정성이 떨어지기 때문에 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다.However, the existing materials have advantages in terms of light emission characteristics, but the thermal stability is low due to the low glass transition temperature, and thus the materials are not satisfactory in terms of lifespan of the organic EL device.
본 발명은 열적 안정성이 우수하고, 발광능 및 수명 특성이 우수한 신규 유기 화합물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a novel organic compound which is excellent in thermal stability and excellent in light emitting performance and lifespan characteristics.
또, 본 발명은 상기 유기 화합물을 포함하는 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the organic electroluminescent element containing the said organic compound.
본 발명은 하기 화학식 1 또는 2로 표시되는 화합물을 제공한다:The present invention provides a compound represented by Formula 1 or 2 below:
화학식 1 
Formula 1
화학식 2 
Formula 2
(상기 화학식에서,(In the above formula,
L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합이거나, 또는 C6~C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고;L 1 and L 2 are the same or different, each independently is a single bond, or C 6 ~ C 60 aryl group and a nuclear atoms is selected from the group consisting of 5 to 60 hetero arylene group;
Ar1 및 Ar2는 서로 동일하거나 상이하며, 각각 독립적으로 C6~C60의 아릴기, 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되고;Ar 1 and Ar 2 are the same as or different from each other, and are each independently selected from the group consisting of a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;
다만, Ar1, Ar2 및 R1 내지 R10 중에서 적어도 하나는 하기 화학식 3 또는 4로 표시되는 치환체이고;Provided that at least one of Ar 1 , Ar 2, and R 1 to R 10 is a substituent represented by Formula 3 or 4 below;
화학식 3 
Formula 3
화학식 4 
Formula 4
X1은 NR15, O, 및 S로 이루어진 군에서 선택되고;X 1 is selected from the group consisting of NR 15 , O, and S;
a, b 및 c는 각각 0 내지 4의 정수이고;a, b and c are each an integer of 0 to 4;
d는 0 내지 3의 정수이며;d is an integer from 0 to 3;
복수의 R11은 서로 동일하거나 상이하고, 복수의 R12는 서로 동일하거나 상이하며, 복수의 R13은 서로 동일하거나 상이하고, 복수의 R14는 서로 동일하거나 상이하며;A plurality of R 11 are the same or different from each other, a plurality of R 12 are the same or different from each other, a plurality of R 13 are the same or different from each other, and a plurality of R 14 are the same or different from each other;
R1 내지 R15는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소(D), 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합 방향족환 또는 축합 헤테로방향족환을 형성할 수 있고;R 1 to R 15 are the same as or different from each other, and each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C Alkynyl group of 2 to C 40 , cycloalkyl group of C 3 to C 40 , heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 1 ~ C 40 alkyl silyl group, C 6 ~ aryl silyl group of C 60, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or by an adjacent group condensed A condensed aromatic ring or a condensed heteroaromatic ring can be formed;
이때, 상기 L1 및 L2의 아릴렌기 및 헤테로아릴렌기, Ar1 및 Ar2의 아릴기, 헤테로아릴기, R1 내지 R15의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기, 아릴아민기는 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환되며, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이하다.In this case, the arylene group and heteroarylene group of L 1 and L 2, the aryl group of Ar 1 and Ar 2 , heteroaryl group, alkyl group of R 1 to R 15 , alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, Aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group, aryl amine group deuterium, halogen, cyano group , Nitro group, amino group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocyclo Alkyl group, C 6 -C 60 aryl group, nuclear atom 5 to 60 heteroaryl group, C 1 to C 40 alkyloxy group, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 ~ C aryl silyl group of 60, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine of C 60 Pinoksai If group and a C 6 ~ C 60 substituted with one or more selected from the group consisting of a substituent of the aryl amine species or is unsubstituted, but the plurality of the above substituents, which are the same or different from each other.
또, 본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자를 제공한다.In addition, the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer is a compound represented by the formula (1) It provides an organic electroluminescent device comprising a.
여기서, 상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 및 전자 주입층으로 이루어진 군에서 선택되고, 바람직하게는 발광층이다. Herein, the organic material layer including the compound is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and is preferably a light emitting layer.
특히, 상기 화학식 1의 화합물이 발광층에 포함될 경우, 상기 화합물은 인광 호스트이다.In particular, when the compound of Formula 1 is included in the emission layer, the compound is a phosphorescent host.
본 발명에 따른 화합물은 열적 안정성, 발광 특성 및 수명 특성이 우수하기 때문에, 유기 전계 발광 소자의 유기물층의 재료로 사용될 수 있다. 특히, 본 발명에 따른 화합물을 인광 호스트로 사용할 경우, 종래의 호스트에 비해 우수한 발광 성능, 낮은 구동전압, 높은 효율 및 장수명을 가지는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.Since the compound according to the present invention has excellent thermal stability, light emission characteristics, and lifetime characteristics, the compound may be used as a material of the organic material layer of the organic EL device. In particular, when the compound according to the present invention is used as a phosphorescent host, an organic electroluminescent device having excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host can be manufactured, and furthermore, the performance and lifespan are improved. Color display panels can also be manufactured.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명에 따른 신규 화합물은 터페닐 모이어티(terphenylmoiety)(바람직하게는 중심 벤젠 고리의 탄소번호 3번과 5번 또는 5번과 6번)에, 다양한 작용기, 특히 카바졸기, 디벤조싸이오펜기, 디벤조퓨란기, 트리페닐렌기 등의 P-type의 작용기가 직접 도입되거나, 또는 아릴렌기나 헤테로아릴렌기를 통해 도입되어 Core을 이루며, 이러한 Core에 다양한 치환체가 결합된 구조로서, 상기 화학식 1로 표시되는 것을 특징으로 한다. The novel compounds according to the invention are suitable for terphenylmoiety (preferably with carbon numbers 3 and 5 or 5 and 6 of the central benzene ring), with various functional groups, in particular carbazole groups, dibenzothiophene groups P-type functional groups such as a dibenzofuran group and a triphenylene group are directly introduced or introduced through an arylene group or a heteroarylene group to form a core, and a structure in which various substituents are bonded to the core. Characterized in that is represented.
상기 화학식 1로 표시되는 화합물은 상기 터페닐 모이어티의 중심 벤젠 고리에 도입된 p-type의 작용기로 인해서, 넓은 밴드갭과 높은 삼중항 에너지를 가질 뿐만 아니라, 열적으로 안정한 구조를 가지며, 종래 호스트 재료(예컨대, CBP)에 비해 발광능이 우수하고, 장수명을 갖기 때문에, 유기 전계 발광 소자의 유기물층 재료, 바람직하게 발광층 재료(인광 호스트)로 사용될 수 있다. 이와 같은 화학식 1의 화합물을 유기 전계 발광 소자에 적용할 경우, 소자의 발광 효율이 높고, 구동 수명이 우수할 뿐만 아니라, 전력 효율이 높아 소비전력을 개선시킬 수 있다.The compound represented by Chemical Formula 1 has a wide bandgap and high triplet energy as well as a thermally stable structure due to the p-type functional group introduced into the central benzene ring of the terphenyl moiety, and has a conventional host. Since the light emitting ability is superior to the material (for example, CBP) and has a long life, it can be used as an organic material layer material of the organic EL device, preferably a light emitting layer material (phosphorescent host). When the compound of Formula 1 is applied to an organic electroluminescent device, the luminous efficiency of the device is high, the driving life is excellent, and the power efficiency is high, thereby improving power consumption.
본 발명에 따른 화학식 1의 화합물에서, Ar1, Ar2 및 R1 내지 R10 중에서 적어도 하나는 각각 독립적으로 상기 화학식 3 또는 4로 표시되는 치환체이고, 바람직하게 Ar1 및/또는 Ar2는 각각 독립적으로 상기 화학식 3 또는 4로 표시되는 치환체이다.In the compound of Formula 1 according to the present invention, at least one of Ar 1 , Ar 2 and R 1 to R 10 is each independently a substituent represented by Formula 3 or 4, and preferably Ar 1 and / or Ar 2 are each Independently represented by the formula (3) or (4).
또, L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합이거나, 또는 C6~C60의 아릴렌기(예컨대, 페닐렌기)인 것이 바람직하다.L 1 and L 2 are the same as or different from each other, and are each independently a single bond, or a C 6 to C 60 arylene group (eg, a phenylene group).
이때, 상기 L1 및 L2의 아릴렌기는 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환된다. 다만, 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이하다.At this time, the arylene group of L 1 and L 2 is deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, substituted with one or more substituents selected from the group C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl amine, consisting of, or is unsubstituted. However, when the said substituent is two or more, they are the same or different from each other.
또, R1 내지 R15는 서로 동일하거나 상이하며, 각각 독립적으로 수소 및 C6~C60의 아릴기로 이루어진 군에서 선택되는 것이 바람직하다.In addition, R 1 to R 15 are the same as or different from each other, and each independently selected from the group consisting of hydrogen and C 6 ~ C 60 aryl group.
이때, 상기 R1 내지 R15의 아릴기는 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환되되, 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이하다.At this time, the aryl group of R 1 to R 15 is deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 6 to C 60 arylphosphine group, C 6 ~ C 60 aryl phosphine oxide group and C 6 ~ C 60 One or more substituents selected from the group consisting of arylamine group is unsubstituted or substituted, wherein the plurality of substituents , Are the same or different from one another.
상기 화학식 1로 표시되는 화합물의 예로는 하기 화학식 5 내지 7로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.Examples of the compound represented by Chemical Formula 1 include a compound represented by the following Chemical Formulas 5 to 7, and the like.
화학식 5 
Formula 5
화학식 6 
Formula 6
화학식 7 
Formula 7
상기 화학식 5 내지 7에서,In Chemical Formulas 5 to 7,
L1, L2, X1, R1 내지 R14, a, b, c 및 d는 각각 상기 화학식 1에서 정의한 바와 같다.L 1 , L 2 , X 1 , R 1 to R 14 , a, b, c and d are the same as defined in Chemical Formula 1, respectively.
또, 상기 화학식 2로 표시되는 화합물의 예로는 하기 화학식 8 내지 10으로 표시되는 화합물 등이 있는데, 이에 한정되지 않는다.In addition, examples of the compound represented by Chemical Formula 2 include a compound represented by the following Chemical Formulas 8 to 10, but are not limited thereto.
화학식 8 
Formula 8
화학식 9 
Formula 9
화학식 10 
Formula 10
상기 화학식 8 내지 10에서,In Chemical Formulas 8 to 10,
L1, L2, X1, R1 내지 R14, a, b, c 및 d는 각각 상기 화학식 1에서 정의한 바와 같다.L 1 , L 2 , X 1 , R 1 to R 14 , a, b, c and d are the same as defined in Chemical Formula 1, respectively.
본 발명에서 사용되는 "비치환된 알킬"은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 이의 비제한적인 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있다.As used herein, "unsubstituted alkyl" refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, non-limiting examples of which are methyl, ethyl, propyl, iso Butyl, sec-butyl, pentyl, iso-amyl, hexyl and the like.
본 발명에서 사용되는 "비치환된 알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진, 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있다.As used herein, "unsubstituted alkenyl" means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. do. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.
본 발명에서 사용되는 "비치환된 알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진, 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 에타인일(ethynyl), 2-프로파인일(2-propynyl) 등이 있다.As used herein, "unsubstituted alkynyl" refers to a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon of 2 to 40 carbon atoms having at least one carbon-carbon triple bond. do. Non-limiting examples thereof include ethynyl, 2-propynyl and the like.
본 발명에서 사용되는 "비치환된 시클로알킬"은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 시클로프로필, 시클로펜틸, 시클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine)등이 있다.As used herein, "unsubstituted cycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms. Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
본 발명에서 사용되는 "비치환된 헤테로시클로알킬"은 핵원자수 3 내지 40의 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로 원자로 치환된다. 이의 비제한적인 예로는 모르폴린, 피페라진 등이 있다.As used herein, "unsubstituted heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and at least one carbon in the ring , Preferably 1 to 3 carbons are substituted with a hetero atom such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.
본 발명에서 사용되는 "비치환된 아릴"은 단독 고리 또는 2 이상의 고리가 조합된, 탄소수 6 내지 60의 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이때, 2 이상의 고리는 서로 단순 부착되거나 축합된 형태로 부착될 수 있다. 이의 비제한적인 예로는 페닐, 비페닐, 터페닐(terphenyl), 나프틸, 페난트릴, 안트릴 등이 있다.As used herein, "unsubstituted aryl" means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, alone or in combination of two or more rings. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.
본 발명에서 사용되는 "비치환된 헤테로아릴"은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기로서, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 질소(N), 산소(O), 황(S) 또는 셀레늄(Se)과 같은 헤테로원자로 치환된다. 이때, 헤테로아릴은 2 이상의 고리가 서로 단순 부착되거나 축합된 형태로 부착될 수 있고, 나아가 아릴기와의 축합된 형태도 포함할 수 있다. 이러한 헤테로아릴의 비제한적인 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6원 모노사이클릭 고리; 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리; 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등이 있다.As used herein, "unsubstituted heteroaryl" is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably Preferably 1 to 3 carbons are substituted with heteroatoms such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se). In this case, the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.
본 발명에서 사용되는 "비치환된 알킬옥시"는 RO-로 표시되는 1가의 작용기를 의미하며, 상기 R은 탄소수 1 내지 40개의 알킬로서, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 이러한 알킬옥시의 비제한적인 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등이 있다.As used herein, "unsubstituted alkyloxy" refers to a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and is linear, branched or cyclic. ) May include a structure. Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서 사용되는 "비치환된 아릴옥시"는 R'O-로 표시되는 1가의 작용기를 의미하며, 상기 R'는 탄소수 6 내지 60의 아릴이다. 이러한 아릴옥시의 비제한적인 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있다.As used herein, "unsubstituted aryloxy" refers to a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
본 발명에서 사용되는 "비치환된 알킬실릴"은 탄소수 1 내지 40의 알킬로 치환된 실릴을 의미하며, 아릴실릴은 탄소수 6 내지 40의 아릴로 치환된 실릴을 의미하고, 아릴아민은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.As used herein, "unsubstituted alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 40 carbon atoms, and arylamine has 6 to 40 carbon atoms. Amine substituted with 60 aryl.
본 발명에서"비치환된 알킬보론기"는 탄소수 1 내지 40의 알킬로 치환된 보론기를 의미하며, "비치환된 아릴보론기"는 탄소수 6 내지 60의 아릴로 치환된 보론기를 의미하고, "비치환된 아릴포스핀기"는 탄소수 1 내지 60의 아릴로 치환된 포스핀기를 의미하고, "비치환된 아릴포스핀옥사이드기" 탄소수 1 내지 60의 아릴로 치환된 포스핀옥사이드기를 의미한다.In the present invention, "unsubstituted alkyl boron group" means a boron group substituted with alkyl having 1 to 40 carbon atoms, "unsubstituted aryl boron group" means a boron group substituted with aryl having 6 to 60 carbon atoms, " Unsubstituted arylphosphine group "means a phosphine group substituted with aryl having 1 to 60 carbon atoms," unsubstituted arylphosphine oxide group "means a phosphine oxide group substituted with aryl having 1 to 60 carbon atoms.
본 발명에서 사용되는 "축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.As used herein, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
본 발명의 화학식 1의 화합물은 일반적인 합성방법에 따라 합성될 수 있다(Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95: 2457 (1995) 등 참조). 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다. Compounds of formula 1 of the present invention can be synthesized according to general synthetic methods ( Chem. Rev. , 60 : 313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995) ) And so on). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
한편, 본 발명은 전술한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.On the other hand, the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1) according to the present invention described above.
구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 1종 이상 포함한다. 이때, 상기 화학식 1로 표시되는 화합물은 단독 또는 2 이상 혼합되어 사용될 수 있다.Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, at least one of the organic material layer is a compound represented by Formula 1 Contains more than one species. In this case, the compound represented by Formula 1 may be used alone or in combination of two or more.
상기 1층 이상의 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는데, 이 중에서 적어도 하나의 유기물층은 상기 화학식 1로 표시되는 화합물을 포함한다. 바람직하게 상기 화학식 1의 화합물을 포함하는 유기물층은 발광층일 수 있다. 이때, 상기 화학식 1로 표시되는 화합물은 발광층 물질, 바람직하게는 인광 호스트, 형광 호스트 또는 도펀트 재료, 더 바람직하는 인광 호스트로서 유기 전계 발광 소자에 포함될 수 있다. 이 경우, 유기 전계 발광 소자는 발광효율, 휘도, 전력효율, 열적 안정성 및 소자 수명이 향상될 수 있다.The at least one organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer includes a compound represented by the formula (1). Preferably, the organic material layer including the compound of Formula 1 may be a light emitting layer. In this case, the compound represented by Formula 1 may be included in the organic EL device as a light emitting layer material, preferably a phosphorescent host, a fluorescent host or a dopant material, more preferably a phosphorescent host. In this case, the organic EL device may improve luminous efficiency, brightness, power efficiency, thermal stability, and device life.
이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 예컨대 기판 위에, 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층될 뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.The structure of the organic EL device of the present invention is not particularly limited. For example, the anode, one or more organic material layers and the cathode are sequentially stacked on the substrate, and an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer. Can be.
구체적으로, 상기 유기 전계 발광 소자는 기판 위에, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 것일 수 있고, 선택적으로 상기 전자 수소층 위에 전자 주입층이 위치할 수 있다. 이때, 정공 주입층, 정공 수송층 및 발광층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 1종 이상 포함할 수 있다. 본 발명의 유기 전계 발광 소자는 유기물층 중 적어도 하나(예컨대, 발광층)가 상기 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 유기물층 및 전극을 형성함으로써 제조될 수 있다. In detail, the organic electroluminescent device may be one in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked on a substrate, and an electron injection layer may be selectively positioned on the electron hydrogen layer. have. In this case, at least one of the hole injection layer, the hole transport layer, and the light emitting layer may include at least one compound represented by Chemical Formula 1. The organic electroluminescent device of the present invention is an organic material layer and an electrode using materials and methods known in the art, except that at least one of the organic material layers (eg, the light emitting layer) is formed to include the compound represented by Chemical Formula 1 It can be prepared by forming a.
상기 유기물층은 진공증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에 한정되지는 않는다.The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
본 발명에서 사용 가능한 기판으로는 특별히 한정되지 않으며, 비제한적인 예로는 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 있다.The substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz or glass plates, metal plates, plastic films or sheets, and the like.
또, 양극 물질의 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자; 또는 카본블랙 등이 있으나, 이들에 한정되는 것은 아니다.In addition, examples of the anode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
또, 음극 물질의 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에 한정되는 것은 아니다.Further, examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층으로 사용되는 물질은 당업계에 알려진 통상의 물질이라면 특별히 한정되지 않는다.In addition, the material used as the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited as long as it is a conventional material known in the art.
이하, 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[준비예 1] 화합물 a-1의 합성Preparation Example 1 Synthesis of Compound a-1
<단계 1> 3,5-dichlorobiphenyl-4-amine의 합성<Step 1> Synthesis of 3,5-dichlorobiphenyl-4-amine
질소 기류 하에서 4-bromo-2,6-dichloroaniline (20.0 g, 83.01 mmol), phenylboronic acid (10.12 g, 83.01 mmol), K2CO3 (34.41 g, 249.03 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/ 40 ml)를 넣고 교반한 후, Pd(PPh3)4 (4.79 g, 4.15 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고, 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 3,5-dichlorobiphenyl-4-amine (16.2g)을 얻었다.4-bromo-2,6-dichloroaniline (20.0 g, 83.01 mmol), phenylboronic acid (10.12 g, 83.01 mmol), K 2 CO 3 (34.41 g, 249.03 mmol) and Toluene / H 2 O / EtOH ( 200 ml / 40 ml / 40 ml) was added and stirred, followed by Pd (PPh 3 ) 4 (4.79 g, 4.15 mmol), followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure, and then purified by column chromatography to obtain the title compound 3,5-dichlorobiphenyl-4-amine (16.2g).
GC-Mass (이론치: 238.11 g/mol, 측정치: 238 g/mol)GC-Mass (Theoretical value: 238.11 g / mol, Measured value: 238 g / mol)
1H-NMR: δ 6.27 (s, 2H), 7.50 (m, 5H), 7.71 (s, 2H) 1 H-NMR: δ 6.27 (s, 2H), 7.50 (m, 5H), 7.71 (s, 2H)
<단계 2> 3,5-dichloro-4-iodobiphenyl의 합성<Step 2> Synthesis of 3,5-dichloro-4-iodobiphenyl
상기 <단계 1>에서 얻은 3,5-Dichlorobiphenyl-4-amine (15 g, 62.99 mmol)을 HCl (75 ml)와 methylene chloride (75 ml)에 혼합하여 0℃에서 교반하였다. 이어서, Sodium nitride 수용액 (4.56 g, 66.13 mmol)을 반응기에 천천히 적가하고, 0℃에서 1 시간 동안 교반한 다음, potassium iodide 수용액(11.50 g, 69.28 mmol)을 천천히 적가하고, 4시간 동안 교반하였다. 이후, Sodium bicarbonate 수용액과 methylene chloride을 넣고, 10분동안 교반한 다음, 유기층을 분리한 후 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 3,5-dichloro-4-iodobiphenyl (18.6g) 얻었다.3,5-Dichlorobiphenyl-4-amine (15 g, 62.99 mmol) obtained in <Step 1> was mixed with HCl (75 ml) and methylene chloride (75 ml) and stirred at 0 ° C. Then aqueous sodium nitride solution (4.56 g, 66.13 mmol) was slowly added dropwise to the reactor, stirred at 0 ° C. for 1 hour, and then aqueous potassium iodide solution (11.50 g, 69.28 mmol) was slowly added dropwise and stirred for 4 hours. Then, an aqueous sodium bicarbonate solution and methylene chloride were added thereto, stirred for 10 minutes, and the organic layer was separated, concentrated under reduced pressure, and subjected to column chromatography to obtain the target compound 3,5-dichloro-4-iodobiphenyl (18.6 g). .
GC-Mass (이론치: 348.99 g/mol, 측정치: 348 g/mol)GC-Mass (Theoretical value: 348.99 g / mol, Measured value: 348 g / mol)
1H-NMR: δ 7.40 (t, 1H), 7.55 (t, 2H), 7.58 (d, 2H), 7.70 (s, 2H) 1 H-NMR: δ 7.40 (t, 1H), 7.55 (t, 2H), 7.58 (d, 2H), 7.70 (s, 2H)
<단계 3> 화합물 a-1의 합성Step 3 Synthesis of Compound a-1
질소 기류 하에서 상기 <단계 2>에서 얻은 3,5-dichloro-4-iodobiphenyl (15.0 g, 42.98 mmol), phenylboronic acid (5.24 g, 42.98 mmol), K2CO3 (17.82 g, 128.94 mmol) 및 Toluene/H2O/EtOH(150 ml/37 ml/ 37 ml)를 넣고 교반한 후, Pd(PPh3)4 (2.48 g, 2.14 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-1 (9.2g)을 얻었다.3,5-dichloro-4-iodobiphenyl (15.0 g, 42.98 mmol), phenylboronic acid (5.24 g, 42.98 mmol), K 2 CO 3 (17.82 g, 128.94 mmol) and Toluene obtained in <Step 2> under a nitrogen stream / H 2 O / EtOH (150 ml / 37 ml / 37 ml) was added thereto and stirred, followed by Pd (PPh 3 ) 4 (2.48 g, 2.14 mmol), followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, and then concentrated under reduced pressure and the target compound a-1 (9.2g) by column chromatography.
GC-Mass (이론치: 299.19 g/mol, 측정치: 299 g/mol)GC-Mass (Theoretical value: 299.19 g / mol, Measured value: 299 g / mol)
1H-NMR: δ 7.40 (t, 2H), 7.52 (m, 8H), 8.0 (s, 2H) 1 H-NMR: δ 7.40 (t, 2H), 7.52 (m, 8H), 8.0 (s, 2H)
[[
준비예Preparation
2] 화합물 a-2의 합성 2] Synthesis of Compound a-2
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(9H-carbazol-9-yl)phenylboronic acid (9.59 g, 33.42 mmol), K2CO3
(13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고, 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 후, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-2 (10.9 g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (9H-carbazol-9-yl) phenylboronic acid (9.59 g, 33.42 mmol), K 2 CO 3 synthesized in Preparation Example 1 under nitrogen stream (13.85 g, 100.26 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol) and 100 ° C. Stirred for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and the target compound a-2 (10.9 g) was obtained by column chromatography.
GC-Mass (이론치: 506.04 g/mol, 측정치: 506 g/mol)GC-Mass (Theoretical value: 506.04 g / mol, Measured value: 506 g / mol)
1H-NMR: δ 7.51 (m, 17H), 7.65 (m, 2H), 7.96 (d, 1H), 8.3 (s, 1H), 8.15 (m, 2H), 8.60 (d, 1H) 1 H-NMR: δ 7.51 (m, 17H), 7.65 (m, 2H), 7.96 (d, 1H), 8.3 (s, 1H), 8.15 (m, 2H), 8.60 (d, 1H)
[준비예 3] 화합물 a-3의 합성Preparation Example 3 Synthesis of Compound a-3
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (9.59 g, 33.42 mmol), K2CO3 (13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-3 (12.4 g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (9.59 g, 33.42 mmol), K 2 CO 3 (13.85 g, synthesized in Preparation Example 1) under nitrogen stream 100.26 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol), followed by stirring at 100 ° C. for 5 hours. It was. After completion of the reaction, the organic layer was extracted with methylene chloride, then concentrated under reduced pressure and the target compound a-3 (12.4 g) was obtained by column chromatography.
GC-Mass (이론치: 506.04 g/mol, 측정치: 506 g/mol)GC-Mass (Theoretical value: 506.04 g / mol, Measured value: 506 g / mol)
1H-NMR: δ 7.55 (m, 17H), 7.70 (m, 2H), 7.86 (d, 1H), 8.5 (s, 1H), 8.15 (m, 2H), 8.60 (d, 1H) 1 H-NMR: δ 7.55 (m, 17H), 7.70 (m, 2H), 7.86 (d, 1H), 8.5 (s, 1H), 8.15 (m, 2H), 8.60 (d, 1H)
[준비예 4] 화합물 a-4의 합성Preparation Example 4 Synthesis of Compound a-4
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (7.62 g, 33.42 mmol), K2CO3 (13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-4 (9.3 g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (7.62 g, 33.42 mmol), K 2 CO 3 (13.85 g, 100.26) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the mixture was extracted with methylene chloride, concentrated under reduced pressure and the target compound a-4 (9.3 g) was obtained using column chromatography.
GC-Mass (이론치: 446.99 g/mol, 측정치: 446 g/mol)GC-Mass (Theoretical value: 446.99 g / mol, Measured value: 446 g / mol)
1H-NMR: δ 7.51 (m, 14H), 7.03 (m, 2H), 7.58 (d, 1H), 8.40 (m, 2H) 1 H-NMR: δ 7.51 (m, 14H), 7.03 (m, 2H), 7.58 (d, 1H), 8.40 (m, 2H)
[준비예 5] 화합물 a-5의 합성Preparation Example 5 Synthesis of Compound a-5
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (10.16 g, 33.42 mmol), K2CO3 (13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-5 (10.5 g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (10.16 g, 33.42 mmol), K 2 CO 3 synthesized in Preparation Example 1 under a nitrogen stream. (13.85 g, 100.26 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol). Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, and then concentrated under reduced pressure and the target compound a-5 (10.5 g) was obtained by column chromatography.
GC-Mass (이론치: 523.09 g/mol, 측정치: 523 g/mol)GC-Mass (Theoretical value: 523.09 g / mol, Measured value: 523 g / mol)
1H-NMR: δ 7.50 (m, 17H), 7.70 (s, 1H), 7.95 (d, 1H), 8.05 (s, 1H), 8.25 (d, 1H), 8.45 (m, 2H) 1 H-NMR: δ 7.50 (m, 17H), 7.70 (s, 1H), 7.95 (d, 1H), 8.05 (s, 1H), 8.25 (d, 1H), 8.45 (m, 2H)
[준비예 6] 화합물 a-6의 합성Preparation Example 6 Synthesis of Compound a-6
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]furan-4-ylboronic acid (7.08 g, 33.42 mmol), K2CO3 (13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고, 컬럼크로마토그래피를 이용하여 목적 화합물 a-6 (10.8 g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] furan-4-ylboronic acid (7.08 g, 33.42 mmol), K 2 CO 3 (13.85 g, 100.26) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, and then concentrated under reduced pressure, to give the target compound a-6 (10.8 g) by column chromatography.
GC-Mass (이론치: 430.92 g/mol, 측정치: 430 g/mol)GC-Mass (Theoretical value: 430.92 g / mol, Measured value: 430 g / mol)
1H-NMR: δ 7.55 (m, 14H), 7.10 (m, 2H), 7.62 (d, 1H), 8.45 (m, 2H) 1 H-NMR: δ 7.55 (m, 14H), 7.10 (m, 2H), 7.62 (d, 1H), 8.45 (m, 2H)
[준비예 7] 화합물 a-7의 합성Preparation Example 7 Synthesis of Compound a-7
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]furan-4-ylboronic acid (9.62 g, 33.42 mmol), K2CO3 (13.85 g, 100.26 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.93 g, 1.67 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 a-7 (11.4 g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] furan-4-ylboronic acid (9.62 g, 33.42 mmol), K 2 CO 3 (13.85 g, 100.26) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.93 g, 1.67 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, and then concentrated under reduced pressure and the target compound a-7 (11.4 g) was obtained by column chromatography.
GC-Mass (이론치: 507.02 g/mol, 측정치: 507 g/mol)GC-Mass (Theoretical value: 507.02 g / mol, Measured value: 507 g / mol)
1H-NMR: δ 7.52 (m, 17H), 7.75 (s, 1H), 7.95 (d, 1H), 8.05 (s, 1H), 8.30 (d, 1H), 8.45 (m, 2H) 1 H-NMR: δ 7.52 (m, 17H), 7.75 (s, 1H), 7.95 (d, 1H), 8.05 (s, 1H), 8.30 (d, 1H), 8.45 (m, 2H)
[준비예 8] 화합물 b-1의 합성Preparation Example 8 Synthesis of Compound b-1
<단계 1> 4-chloro-2,6-diphenylaniline의 합성Step 1 Synthesis of 4-chloro-2,6-diphenylaniline
질소 기류 하에서 2,6-dibromo-4-chloroaniline (20.0 g, 70.08 mmol), phenylboronic acid (8.54 g, 83.01 mmol), K2CO3 (29.05 g, 210.24 mmol) 및 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (4.04 g, 3.50 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 4-chloro-2,6-diphenylaniline (15.8g)을 얻었다.2,6-dibromo-4-chloroaniline (20.0 g, 70.08 mmol), phenylboronic acid (8.54 g, 83.01 mmol), K 2 CO 3 (29.05 g, 210.24 mmol) and Toluene / H 2 O / EtOH ( 200 ml / 40 ml / 40 ml) was added and stirred, followed by Pd (PPh 3 ) 4 (4.04 g, 3.50 mmol), followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the mixture was extracted with methylene chloride, concentrated under reduced pressure, and subjected to column chromatography to obtain the title compound 4-chloro-2,6-diphenylaniline (15.8g).
GC-Mass (이론치: 285.36 g/mol, 측정치: 285 g/mol)GC-Mass (Theoretical value: 285.36 g / mol, Measured value: 285 g / mol)
1H-NMR: δ 6.30 (s, 1H), 7.10 (d, 4H), 7.58 (t, 4H), 7.70 (t, 2H), 8.05 (s, 2H) 1 H-NMR: δ 6.30 (s, 1H), 7.10 (d, 4H), 7.58 (t, 4H), 7.70 (t, 2H), 8.05 (s, 2H)
<단계 2> 4'-(9H-carbazol-9-yl)-3,5-diphenyllbiphenyl-4-amine의 합성<Step 2> Synthesis of 4 '-(9H-carbazol-9-yl) -3,5-diphenyllbiphenyl-4-amine
질소 기류 하에서 상기 <단계 1>에서 얻은 4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (20.52 g, 71.48 mmol), K2CO3 (29.63 g, 214.44 mmol) 및 Toluene/H2O/EtOH(400 ml/100 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (4.12 g, 3.57 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고컬럼크로마토그래피를 이용하여 목적 화합물 4'-(9H-carbazol-9-yl)-3,5-diphenyllbiphenyl-4-amine (22.7g)을 얻었다.4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (20.52 g, 71.48 mmol) obtained in the above <Step 1> under a nitrogen stream, K 2 CO 3 (29.63 g, 214.44 mmol) and Toluene / H 2 O / EtOH (400 ml / 100 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (4.12 g, 3.57 mmol) and 100 Stir at 5 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, and then concentrated under reduced pressure, and then subjected to column chromatography to give the title compound 4 '-(9H-carbazol-9-yl) -3,5-diphenyllbiphenyl-4-amine (22.7 g )
GC-Mass (이론치: 486.61 g/mol, 측정치: 486 g/mol)GC-Mass (Theoretical value: 486.61 g / mol, Measured value: 486 g / mol)
1H-NMR: δ 6.25 (s, 1H), 7.10 (d, 4H), 7.58 (m, 12H), 7.70 (d, 2H), 7.90 (d, 2H), 8.18 (d, 2H), 8.25 (d, 2H) 1 H-NMR: δ 6.25 (s, 1H), 7.10 (d, 4H), 7.58 (m, 12H), 7.70 (d, 2H), 7.90 (d, 2H), 8.18 (d, 2H), 8.25 ( d, 2H)
<단계 3> 화합물 b-1의 합성<Step 3> Synthesis of Compound b-1
상기 <단계 2>에서 얻은 4'-(9H-carbazol-9-yl)-3,5-diphenyllbiphenyl-4-amine (15 g, 30.82 mmol)을 HCl (154 ml)와 methylene chloride (154 ml)에 혼합하여 0℃에서 교반하였다. 이어서, Sodium nitride 수용액(2.23g, 32.36 mmol)을 반응기에 천천히 적가하고, 0℃ 에서 1 시간 동안 교반한 다음, potassium iodide 수용액(5.62g, 33.90 mmol)을 천천히 적가하고 4시간 동안 교반하였다. 이후, Sodium bicarbonate 수용액과 methylene chloride을 넣고 10분동안 교반한 다음, 유기층을 분리한 후 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 b-1 (12.0g)을 얻었다.4 '-(9H-carbazol-9-yl) -3,5-diphenyllbiphenyl-4-amine (15 g, 30.82 mmol) obtained in <Step 2> was dissolved in HCl (154 ml) and methylene chloride (154 ml). Mix and stir at 0 ° C. Subsequently, aqueous sodium nitride solution (2.23 g, 32.36 mmol) was slowly added dropwise to the reactor, stirred at 0 ° C. for 1 hour, and then aqueous potassium iodide solution (5.62 g, 33.90 mmol) was slowly added dropwise and stirred for 4 hours. Thereafter, an aqueous solution of sodium bicarbonate and methylene chloride were added thereto, the mixture was stirred for 10 minutes. The organic layer was separated, concentrated under reduced pressure, and subjected to column chromatography to obtain the target compound b-1 (12.0 g).
GC-Mass (이론치: 597.49 g/mol, 측정치: 597 g/mol)GC-Mass (Theoretical value: 597.49 g / mol, Measured value: 597 g / mol)
1H-NMR: δ 7.12 (d, 4H), 7.60 (m, 12H), 7.75 (d, 2H), 7.95 (d, 2H), 8.20 (d, 2H), 8.43 (d, 2H) 1 H-NMR: δ 7.12 (d, 4H), 7.60 (m, 12H), 7.75 (d, 2H), 7.95 (d, 2H), 8.20 (d, 2H), 8.43 (d, 2H)
[준비예 9] 화합물 b-2의 합성Preparation Example 9 Synthesis of Compound b-2
<단계 1> 3'-(dibenzo[b,d]thiophen-4-yl)-3,5-diphethylbiphenyl-4-amine 의 합성<Step 1> Synthesis of 3 '-(dibenzo [b, d] thiophen-4-yl) -3,5-diphethylbiphenyl-4-amine
질소 기류 하에서 준비예 8의 <단계 1>에서 합성된 4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (21.74 g, 71.48 mmol), K2CO3 (29.63 g, 214.44 mmol) 및 Toluene/H2O/EtOH (400 ml/100 ml/100 ml)를 넣고 교반한 후, Pd(PPh3)4 (4.12 g, 3.57 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출한 다음, 감압조건에서 농축하고 컬럼크로마토그래피를 이용하여 목적 화합물 3'-(dibenzo[b,d]thiophen-4-yl)-3,5-diphethylbiphenyl-4-amine (22.7g)을 얻었다.4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (21.74) synthesized in <Step 1> of Preparation Example 8 under nitrogen stream g, 71.48 mmol), K 2 CO 3 (29.63 g, 214.44 mmol) and Toluene / H 2 O / EtOH (400 ml / 100 ml / 100 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (4.12 g , 3.57 mmol) was added and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and subjected to column chromatography using target chromatography 3 '-(dibenzo [b, d] thiophen-4-yl) -3,5-diphethylbiphenyl-4- amine (22.7 g) was obtained.
GC-Mass (이론치: 503.66 g/mol, 측정치: 503 g/mol)GC-Mass (Theoretical value: 503.66 g / mol, Measured value: 503 g / mol)
1H-NMR: δ 6.30 (s, 1H), 7.10 (d, 4H), 7.50 (m, 14H), 7.70 (s, 1H), 7.90 (s, 1H), 8.25 (d, 1H), 8.45 (d, 2H) 1 H-NMR: δ 6.30 (s, 1H), 7.10 (d, 4H), 7.50 (m, 14H), 7.70 (s, 1H), 7.90 (s, 1H), 8.25 (d, 1H), 8.45 ( d, 2H)
<단계 2> 화합물 b-2의 합성<Step 2> Synthesis of Compound b-2
상기 <단계 1>에서 얻은 3'-(dibenzo[b,d]thiophen-4-yl)-3,5-diphethylbiphenyl-4-amine (20 g, 39.76 mmol)을 HCl (100 ml)와 methylene chloride (100 ml)에 혼합하여 0℃에서 교반하였다. 이어서, Sodium nitride 수용액(2.88g, 41.74 mmol)을 반응기에 천천히 적가하고, 0℃에서 1 시간 동안 교반한 다음, potassium iodide 수용액(7.26g, 43.73 mmol)을 천천히 적가하고, 4시간 동안 교반하였다. 이후, Sodium bicarbonate 수용액과 methylene chloride을 넣고 10분 동안 교반하고 유기층을 분리한 후, 감압조건에서 농축한 다음 컬럼크로마토그래피를 이용하여 목적 화합물 b-2 (16.1g)를 얻었다.3 '-(dibenzo [b, d] thiophen-4-yl) -3,5-diphethylbiphenyl-4-amine (20 g, 39.76 mmol) obtained in <Step 1> was purified by HCl (100 ml) and methylene chloride ( 100 ml) and stirred at 0 ° C. Subsequently, aqueous sodium nitride solution (2.88 g, 41.74 mmol) was slowly added dropwise to the reactor, stirred at 0 ° C. for 1 hour, and then aqueous potassium iodide solution (7.26 g, 43.73 mmol) was slowly added dropwise and stirred for 4 hours. Thereafter, an aqueous sodium bicarbonate solution and methylene chloride were added thereto, stirred for 10 minutes, an organic layer was separated, concentrated under reduced pressure, and then subjected to column chromatography to obtain target compound b-2 (16.1g).
GC-Mass (이론치: 614.54 g/mol, 측정치: 613 g/mol)GC-Mass (Theoretical value: 614.54 g / mol, Measured value: 613 g / mol)
1H-NMR: δ 7.12 (d, 4H), 7.55 (m, 14H), 7.72 (s, 1H), 7.95 (s, 1H), 8.25 (d, 1H), 8.60 (d, 2H) 1 H-NMR: δ 7.12 (d, 4H), 7.55 (m, 14H), 7.72 (s, 1H), 7.95 (s, 1H), 8.25 (d, 1H), 8.60 (d, 2H)
[준비예 10] 화합물 b-3의 합성Preparation Example 10 Synthesis of Compound b-3
<단계 1> 3'-(dibenzo[b,d]furan-4-yl)-3,5-diphethylbiphenyl-4-amine 의 합성<Step 1> Synthesis of 3 '-(dibenzo [b, d] furan-4-yl) -3,5-diphethylbiphenyl-4-amine
질소 기류 하에서 준비예 8의 <단계 1>에서 합성된 4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (20.59 g, 71.48 mmol), K2CO3 (29.63 g, 214.44 mmol) 및 Toluene/H2O/EtOH (400 ml/100 ml/100 ml)를 넣고 교반한 후, Pd(PPh3)4 (4.12 g, 3.57 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 3'-(dibenzo[b,d]furan-4-yl)-3,5-diphethylbiphenyl-4-amine (26.1g)을 얻었다.4-chloro-2,6-diphenylaniline (20.0 g, 71.48 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (20.59) synthesized in <Step 1> of Preparation Example 8 under nitrogen stream g, 71.48 mmol), K 2 CO 3 (29.63 g, 214.44 mmol) and Toluene / H 2 O / EtOH (400 ml / 100 ml / 100 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (4.12 g , 3.57 mmol) was added and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure, and then purified by column chromatography to give the title compound 3 '-(dibenzo [b, d] furan-4-yl) -3,5-diphethylbiphenyl-4- amine (26.1 g) was obtained.
GC-Mass (이론치: 487.59 g/mol, 측정치: 487 g/mol)GC-Mass (Theoretical value: 487.59 g / mol, Measured value: 487 g / mol)
1H-NMR: δ 6.30 (s, 1H), 7.12 (d, 4H), 7.54 (m, 14H), 7.78 (s, 1H), 8.20 (s, 1H), 8.35 (d, 1H), 8.48 (d, 2H) 1 H-NMR: δ 6.30 (s, 1H), 7.12 (d, 4H), 7.54 (m, 14H), 7.78 (s, 1H), 8.20 (s, 1H), 8.35 (d, 1H), 8.48 ( d, 2H)
<단계 2> 화합물 b-3의 합성<Step 2> Synthesis of Compound b-3
상기 <단계 1>에서 얻은 3'-(dibenzo[b,d]furan-4-yl)-3,5-dimethylbiphenyl-4-amine (20 g, 41.01 mmol)을 HCl (100 ml)와 methylene chloride (100 ml)에 혼합하여 0℃에서 교반하였다. 이어서, Sodium nitride 수용액(2.97g, 43.06 mmol)을 반응기에 천천히 적가하고, 0℃에서 1 시간 동안 교반한 다음, potassium iodide 수용액(7.86g, 47.37 mmol)을 천천히 적가하고, 4시간 동안 교반하였다. 이후, Sodium bicarbonate 수용액과 methylene chloride을 넣은 후, 10분동안 교반하고 유기층을 분리한 후, 감압조건에서 농축한 다음 컬럼크로마토그래피를 이용하여 목적 화합물 b-3 (14.2g)을 얻었다. 3 '-(dibenzo [b, d] furan-4-yl) -3,5-dimethylbiphenyl-4-amine (20 g, 41.01 mmol) obtained in <Step 1> was purified by HCl (100 ml) and methylene chloride ( 100 ml) and stirred at 0 ° C. Subsequently, aqueous sodium nitride solution (2.97 g, 43.06 mmol) was slowly added dropwise to the reactor, stirred at 0 ° C. for 1 hour, and then aqueous potassium iodide solution (7.86 g, 47.37 mmol) was slowly added dropwise and stirred for 4 hours. Thereafter, an aqueous sodium bicarbonate solution and methylene chloride were added thereto, stirred for 10 minutes, an organic layer was separated, concentrated under reduced pressure, and then subjected to column chromatography to obtain target compound b-3 (14.2g).
GC-Mass (이론치: 598.47 g/mol, 측정치: 598 g/mol)GC-Mass (Theoretical value: 598.47 g / mol, Measured value: 598 g / mol)
1H-NMR: δ 7.20 (d, 4H), 7.58 (m, 14H), 7.80 (s, 1H), 7.95 (s, 1H), 8.30 (d, 1H), 8.60 (d, 2H) 1 H-NMR: δ 7.20 (d, 4H), 7.58 (m, 14H), 7.80 (s, 1H), 7.95 (s, 1H), 8.30 (d, 1H), 8.60 (d, 2H)
[합성예 1] 화합물 C1의 합성Synthesis Example 1 Synthesis of Compound C1
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 9H-carbazole (13.97 g, 83.55 mmol), Pd2(dba)3 (1.83 g, 2.00 mmol), P(t-bu)3 (1.35 g, 6.68 mmol), NaO(t-bu) (16.06 g, 167.12 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음 MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C1 (10.5 g) 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 9H-carbazole (13.97 g, 83.55 mmol), Pd 2 (dba) 3 (1.83 g, 2.00 mmol), P (t-) synthesized in Preparation Example 1 under nitrogen stream bu) 3 (1.35 g, 6.68 mmol), NaO (t-bu) (16.06 g, 167.12 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer to obtain the target compound C1 (10.5 g) using column chromatography.
GC-Mass (이론치: 560.69 g/mol, 측정치: 560 g/mol)GC-Mass (Theoretical value: 560.69 g / mol, Measured value: 560 g / mol)
[합성예 2] 화합물 C2의 합성Synthesis Example 2 Synthesis of Compound C2
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(9H-carbazol-9-yl)phenylboronic acid (23.99 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol) 및 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C2 (18.2g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (9H-carbazol-9-yl) phenylboronic acid (23.99 g, 83.56 mmol) synthesized in Preparation Example 1 under nitrogen stream, K 2 CO 3 (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto and stirred at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure, and then purified by column chromatography to obtain the target compound C2 (18.2g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 3] 화합물 C3의 합성Synthesis Example 3 Synthesis of Compound C3
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (23.99 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C3 (16.2g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (23.99 g, 83.56 mmol), K 2 CO 3 (27.72 g, synthesized in Preparation Example 1 under nitrogen stream) 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. It was. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C3 (16.2g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 4] 화합물 C4의 합성Synthesis Example 4 Synthesis of Compound C4
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (23.99 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C4 (15.4g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (23.99 g, 83.56 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under nitrogen stream mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C4 (15.4g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 5] 화합물 C5의 합성Synthesis Example 5 Synthesis of Compound C5
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 9-phenyl-9H-carbazol-2-ylboronic acid (23.99 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C5 (15.0g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 9-phenyl-9H-carbazol-2-ylboronic acid (23.99 g, 83.56 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under nitrogen stream mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol), followed by stirring at 100 ° C. for 5 hours. . After the completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure and then subjected to column chromatography to give the target compound C5 (15.0g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 6] 화합물 C6의 합성Synthesis Example 6 Synthesis of Compound C6
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (30.35 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C6 (17.8g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (30.35 g, 83.56 mmol), K 2 CO 3 synthesized in Preparation Example 1 under nitrogen stream (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C6 (17.8g).
GC-Mass (이론치: 885.07 g/mol, 측정치: 885 g/mol)GC-Mass (Theoretical value: 885.07 g / mol, Measured value: 885 g / mol)
[합성예 7] 화합물 C7의 합성Synthesis Example 7 Synthesis of Compound C7
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(9-phenyl-9H-carbazol-2-yl)phenylboronic acid (30.35 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C7 (16.4g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (9-phenyl-9H-carbazol-2-yl) phenylboronic acid (30.35 g, 83.56 mmol), K 2 CO 3 synthesized in Preparation Example 1 under nitrogen stream (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure, and then purified by column chromatography to obtain the target compound C7 (16.4g).
GC-Mass (이론치: 885.07 g/mol, 측정치: 885 g/mol)GC-Mass (Theoretical value: 885.07 g / mol, Measured value: 885 g / mol)
[합성예 8] 화합물 C8의 합성Synthesis Example 8 Synthesis of Compound C8
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (20.0 g, 83.01 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (19.06 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C8 (13.4g)를 얻었다.Compound a-1 (20.0 g, 83.01 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (19.06 g, 83.56 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C8 (13.4g).
GC-Mass (이론치: 594.79 g/mol, 측정치: 594 g/mol)GC-Mass (Theoretical value: 594.79 g / mol, Measured value: 594 g / mol)
[합성예 9] 화합물 C9의 합성Synthesis Example 9 Synthesis of Compound C9
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]thiophen-2-ylboronic acid (19.06 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C9 (12.2g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] thiophen-2-ylboronic acid (19.06 g, 83.56 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C9 (12.2g) by column chromatography.
GC-Mass (이론치: 594.79 g/mol, 측정치: 594 g/mol)GC-Mass (Theoretical value: 594.79 g / mol, Measured value: 594 g / mol)
[합성예 10] 화합물 C10의 합성Synthesis Example 10 Synthesis of Compound C10
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (25.42 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C10 (17.0g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (25.42 g, 83.56 mmol), K 2 CO 3 synthesized in Preparation Example 1 under a nitrogen stream. (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) and 5 at 100 ° C. Stir for hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure and then subjected to column chromatography to give the target compound C10 (17.0g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 11] 화합물 C11의 합성Synthesis Example 11 Synthesis of Compound C11
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(dibenzo[b,d]thiophen-2-yl)phenylboronic acid (25.42 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C11 (18.0g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (dibenzo [b, d] thiophen-2-yl) phenylboronic acid (25.42 g, 83.56 mmol), K 2 CO 3 synthesized in Preparation Example 1 under a nitrogen stream. (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) and 5 at 100 ° C. Stir for hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C11 (18.0g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 12] 화합물 C12의 합성Synthesis Example 12 Synthesis of Compound C12
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]furan-4-ylboronic acid (10.12 g, 83.01 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C12 (15.0g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] furan-4-ylboronic acid (10.12 g, 83.01 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol), followed by stirring at 100 ° C. for 5 hours. . After the completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C12 (15.0g) using column chromatography.
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 13] 화합물 C13의 합성Synthesis Example 13 Synthesis of Compound C13
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), dibenzo[b,d]furan-2-ylboronic acid (10.12 g, 83.01 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C13 (15.0g)을 얻었다.Compound a-1 (10.0 g, 33.42 mmol), dibenzo [b, d] furan-2-ylboronic acid (10.12 g, 83.01 mmol), K 2 CO 3 (27.72 g, 200.54) synthesized in Preparation Example 1 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure and then subjected to column chromatography to give the target compound C13 (15.0g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712.88 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712.88 g / mol)
[합성예 14] 화합물 C14의 합성Synthesis Example 14 Synthesis of Compound C14
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (24.07 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C14 (15.0g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (24.07 g, 83.56 mmol), K 2 CO 3 synthesized in Preparation Example 1 under a nitrogen stream. (27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C14 (15.0g).
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 15] 화합물 C15의 합성Synthesis Example 15 Synthesis of Compound C15
질소 기류 하에서 준비예 1에서 합성된 화합물 a-1 (10.0 g, 33.42 mmol), 3-(dibenzo[b,d]furan-2-yl)phenylboronic (24.07 g, 83.56 mmol), K2CO3 (27.72 g, 200.54 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (3.86 g, 3.34 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C15 (15.0g)를 얻었다.Compound a-1 (10.0 g, 33.42 mmol), 3- (dibenzo [b, d] furan-2-yl) phenylboronic (24.07 g, 83.56 mmol) synthesized in Preparation Example 1 under nitrogen stream, K 2 CO 3 ( 27.72 g, 200.54 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (3.86 g, 3.34 mmol) and 5 at 100 ° C. Stir for hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C15 (15.0g).
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 16] 화합물 C16의 합성Synthesis Example 16 Synthesis of Compound C16
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.76 mmol), triphenylen-2-ylboronic acid (5.91 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C16 (8.5g)을 얻었다.Compound a-2 (10.0 g, 19.76 mmol), triphenylen-2-ylboronic acid (5.91 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28 mmol) synthesized in Preparation Example 2 under nitrogen stream and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C16 (8.5g).
GC-Mass (이론치: 697.86 g/mol, 측정치: 697 g/mol)GC-Mass (Theoretical value: 697.86 g / mol, Measured value: 697 g / mol)
[합성예 17] 화합물 C17의 합성Synthesis Example 17 Synthesis of Compound C17
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.76 mmol), triphenylen-2-ylboronic acid (5.91 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C17 (7.4g)를 얻었다.Compound a-3 (10.0 g, 19.76 mmol), triphenylen-2-ylboronic acid (5.91 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28 mmol) synthesized in Preparation Example 3 under nitrogen stream and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C17 (7.4g) using column chromatography.
GC-Mass (이론치: 697.86 g/mol, 측정치: 697 g/mol) GC-Mass (Theoretical value: 697.86 g / mol, Measured value: 697 g / mol)
[합성예 18] 화합물 C18의 합성Synthesis Example 18 Synthesis of Compound C18
질소 기류 하에서 준비예 4에서 합성된 화합물 a-4 (10.0 g, 22.37 mmol), triphenylen-2-ylboronic acid (6.70 g, 24.61 mmol), K2CO3 (9.28 g, 67.12 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.29 g, 1.12 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C18 (7.4g)를 얻었다.Compound a-4 (10.0 g, 22.37 mmol), triphenylen-2-ylboronic acid (6.70 g, 24.61 mmol), K 2 CO 3 (9.28 g, 67.12 mmol) synthesized in Preparation Example 4 under nitrogen stream and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.29 g, 1.12 mmol), followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to obtain the target compound C18 (7.4g).
GC-Mass (이론치: 638.82 g/mol, 측정치: 638 g/mol)GC-Mass (Theoretical value: 638.82 g / mol, Measured value: 638 g / mol)
[합성예 19] 화합물 C19의 합성Synthesis Example 19 Synthesis of Compound C19
질소 기류 하에서 준비예 5에서 합성된 화합물 a-5 (10.0 g, 19.09 mmol), triphenylen-2-ylboronic acid (5.71 g, 21.00 mmol), K2CO3 (7.91 g, 57.26 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.10 g, 0.95 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C19 (8.5g)를 얻었다.Compound a-5 (10.0 g, 19.09 mmol), triphenylen-2-ylboronic acid (5.71 g, 21.00 mmol), K 2 CO 3 (7.91 g, 57.26 mmol) and Toluene / H synthesized in Preparation Example 5 under a nitrogen stream. 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (1.10 g, 0.95 mmol) was added thereto and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C19 (8.5g) by column chromatography.
GC-Mass (이론치: 714.91 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.91 g / mol, Measured value: 714 g / mol)
[합성예 20] 화합물 C20의 합성Synthesis Example 20 Synthesis of Compound C20
질소 기류 하에서 준비예 6에서 합성된 화합물 a-6 (10.0 g, 23.21 mmol), triphenylen-2-ylboronic acid (6.95 g, 25.53 mmol), K2CO3 (9.62 g, 69.62 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.34 g, 1.16 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C20 (6.4g)을 얻었다.Compound a-6 (10.0 g, 23.21 mmol), triphenylen-2-ylboronic acid (6.95 g, 25.53 mmol), K 2 CO 3 (9.62 g, 69.62 mmol) and Toluene / H synthesized in Preparation Example 6 under a nitrogen stream. 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (1.34 g, 1.16 mmol) was added thereto and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to obtain the target compound C20 (6.4g).
GC-Mass (이론치: 622.75 g/mol, 측정치: 622 g/mol)GC-Mass (Theoretical value: 622.75 g / mol, Measured value: 622 g / mol)
[합성예 21] 화합물 C21의 합성Synthesis Example 21 Synthesis of Compound C21
질소 기류 하에서 준비예 7에서 합성된 화합물인 a-7 (10.0 g, 19.72 mmol), triphenylen-2-ylboronic acid (5.90 g, 21.70 mmol), K2CO3 (8.18 g, 59.17 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C21 (7.2g)을 얻었다.A-7 (10.0 g, 19.72 mmol), triphenylen-2-ylboronic acid (5.90 g, 21.70 mmol), K 2 CO 3 (8.18 g, 59.17 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C21 (7.2g).
GC-Mass (이론치: 698.85 g/mol, 측정치: 698 g/mol)GC-Mass (Theoretical value: 698.85 g / mol, Measured value: 698 g / mol)
[합성예 22] 화합물 C22의 합성Synthesis Example 22 Synthesis of Compound C22
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.76 mmol), 9H-carbazole (3.63 g, 21.74 mmol), Pd2(dba)3 (0.54 g, 0.59 mmol), P(t-bu)3 (0.40 g, 1.98 mmol), NaO(t-bu) (4.75 g, 49.40 mmol) 및 toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C22 (8.2 g)를 획득하였다. Compound a-2 (10.0 g, 19.76 mmol), 9H-carbazole (3.63 g, 21.74 mmol), Pd 2 (dba) 3 (0.54 g, 0.59 mmol), P (t-), synthesized in Preparation Example 2 under nitrogen stream bu) 3 (0.40 g, 1.98 mmol), NaO (t-bu) (4.75 g, 49.40 mmol) and toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer to obtain the target compound C22 (8.2 g) using column chromatography.
GC-Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)GC-Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 23] 화합물 C23의 합성Synthesis Example 23 Synthesis of Compound C23
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.72 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (6.24 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C23 (6.8g)을 얻었다.Compound a-2 (10.0 g, 19.72 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (6.24 g, 21.74 mmol), K 2 CO 3 (8.19 g,) synthesized in Preparation Example 2 under nitrogen stream 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto and stirred at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C23 (6.8g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 24] 화합물 C24의 합성Synthesis Example 24 Synthesis of Compound C24
질소 기류 하에서 준비예 2에서 합성된 화합물인 a-2 (10.0 g, 19.72 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (7.90 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C24 (5.4g)를 얻었다.A-2 (10.0 g, 19.72 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (7.90 g, 21.74 mmol), K 2 CO, a compound synthesized in Preparation Example 2 under nitrogen stream 3 (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol), and 100 ° C. Stirred for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C24 (5.4g).
GC-Mass (이론치: 788.97 g/mol, 측정치: 788 g/mol)GC-Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)
[합성예 25] 화합물 C25의 합성Synthesis Example 25 Synthesis of Compound C25
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.72 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (4.96 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C25 (6.1g)를 얻었다.Compound a-2 (10.0 g, 19.72 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (4.96 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28) synthesized in Preparation Example 2 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C25 (6.1g).
GC-Mass (이론치: 653.83 g/mol, 측정치: 653 g/mol)GC-Mass (Theoretical value: 653.83 g / mol, Measured value: 653 g / mol)
[합성예 26] 화합물 C26의 합성Synthesis Example 26 Synthesis of Compound C26
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (6.61 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C26 (7.2g)을 얻었다.Compound a-2 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (6.61 g, 21.74 mmol), K 2 CO 3 synthesized in Preparation Example 2 under a nitrogen stream. (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) and 5 at 100 ° C. Stir for hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C26 (7.2g) by column chromatography.
GC-Mass (이론치: 729.93 g/mol, 측정치: 729 g/mol)GC-Mass (Theoretical value: 729.93 g / mol, Measured value: 729 g / mol)
[합성예 27] 화합물 C27의 합성Synthesis Example 27 Synthesis of Compound C27
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.72 mmol), dibenzo[b,d]furan-4-ylboronic acid (4.61 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C27 (6.5g)을 얻었다.Compound a-2 (10.0 g, 19.72 mmol), dibenzo [b, d] furan-4-ylboronic acid (4.61 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28) synthesized in Preparation Example 2 under nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto and stirred at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C27 (6.5g).
GC-Mass (이론치: 637.77 g/mol, 측정치: 637 g/mol)GC-Mass (Theoretical value: 637.77 g / mol, Measured value: 637 g / mol)
[합성예 28] 화합물 C28의 합성Synthesis Example 28 Synthesis of Compound C28
질소 기류 하에서 준비예 2에서 합성된 화합물 a-2 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (6.26 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C28 (6.0g)을 얻었다.Compound a-2 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (6.26 g, 21.74 mmol), K 2 CO 3 synthesized in Preparation Example 2 under a nitrogen stream. (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol). Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C28 (6.0 g) by column chromatography.
GC-Mass (이론치: 713.86 g/mol, 측정치: 713 g/mol)GC-Mass (Theoretical value: 713.86 g / mol, Measured value: 713 g / mol)
[합성예 29] 화합물 C29의 합성Synthesis Example 29 Synthesis of Compound C29
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.76 mmol), 9H-carbazole (3.63 g, 21.74 mmol), Pd2(dba)3 (0.54 g, 0.59 mmol), P(t-bu)3 (0.40 g, 1.98 mmol), NaO(t-bu) (4.75 g, 49.40 mmol) 및 toluene (100 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C29 (7.5 g)를 획득하였다. Compound a-3 (10.0 g, 19.76 mmol), 9H-carbazole (3.63 g, 21.74 mmol), Pd 2 (dba) 3 (0.54 g, 0.59 mmol), P (t-), synthesized in Preparation Example 3 under nitrogen stream bu) 3 (0.40 g, 1.98 mmol), NaO (t-bu) (4.75 g, 49.40 mmol) and toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer to obtain the target compound C29 (7.5 g) using column chromatography.
GC-Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)GC-Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 30] 화합물 C30의 합성Synthesis Example 30 Synthesis of Compound C30
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.72 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (7.90 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C30 (7.5g)을 얻었다.Compound a-3 (10.0 g, 19.72 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (7.90 g, 21.74 mmol), K 2 CO 3 synthesized in Preparation Example 3 under nitrogen stream (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH was (200 ml / 40 ml / 40 ml) was stirred into a, Pd (PPh 3) 4 into the (1.14 g, 0.99 mmol) in 100 ℃ 5 Stir for hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure and then subjected to column chromatography to give the target compound C30 (7.5g).
GC-Mass (이론치: 788.97 g/mol, 측정치: 788 g/mol)GC-Mass (Theoretical value: 788.97 g / mol, Measured value: 788 g / mol)
[합성예 31] 화합물 C31의 합성Synthesis Example 31 Synthesis of Compound C31
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.72 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (4.96 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C31 (5.3g)을 얻었다.Compound a-3 (10.0 g, 19.72 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (4.96 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28) synthesized in Preparation Example 3 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure and then subjected to column chromatography to give the title compound C31 (5.3g).
GC-Mass (이론치: 653.83 g/mol, 측정치: 653 g/mol)GC-Mass (Theoretical value: 653.83 g / mol, Measured value: 653 g / mol)
[합성예 32] 화합물 C32의 합성Synthesis Example 32 Synthesis of Compound C32
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (6.61 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C32 (6.5g)를 얻었다.Compound a-3 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (6.61 g, 21.74 mmol), K 2 CO 3 synthesized in Preparation Example 3 under a nitrogen stream. (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol). Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C32 (6.5g) by column chromatography.
GC-Mass (이론치: 729.93 g/mol, 측정치: 729 g/mol)GC-Mass (Theoretical value: 729.93 g / mol, Measured value: 729 g / mol)
[합성예 33] 화합물 C33의 합성Synthesis Example 33 Synthesis of Compound C33
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.72 mmol), dibenzo[b,d]furan-4-ylboronic acid (4.61 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C33 (4.8g)을 얻었다.Compound a-3 (10.0 g, 19.72 mmol), dibenzo [b, d] furan-4-ylboronic acid (4.61 g, 21.74 mmol), K 2 CO 3 (8.19 g, 59.28) synthesized in Preparation Example 3 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the title compound C33 (4.8g).
GC-Mass (이론치: 637.77 g/mol, 측정치: 637 g/mol)GC-Mass (Theoretical value: 637.77 g / mol, Measured value: 637 g / mol)
[합성예 34] 화합물 C34의 합성Synthesis Example 34 Synthesis of Compound C34
질소 기류 하에서 준비예 3에서 합성된 화합물 a-3 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (6.26 g, 21.74 mmol), K2CO3 (8.19 g, 59.28 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C34 (6.4g)를 얻었다.Compound a-3 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (6.26 g, 21.74 mmol), K 2 CO 3 synthesized in Preparation Example 3 under a nitrogen stream. (8.19 g, 59.28 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring, followed by Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol). Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C34 (6.4g) by column chromatography.
GC-Mass (이론치: 713.86 g/mol, 측정치: 713 g/mol)GC-Mass (Theoretical value: 713.86 g / mol, Measured value: 713 g / mol)
[합성예 35] 화합물 C35의 합성Synthesis Example 35 Synthesis of Compound C35
질소 기류 하에서 준비예 4에서 합성된 화합물 a-4 (10.0 g, 23.37 mmol), 9H-carbazole (4.11 g, 24.61 mmol), Pd2(dba)3 (0.61 g, 0.67 mmol), P(t-bu)3 (0.45 g, 2.24 mmol), NaO(t-bu) (5.37 g, 55.93 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C35 (7.5 g)를 획득하였다. Compound a-4 (10.0 g, 23.37 mmol), 9H-carbazole (4.11 g, 24.61 mmol), Pd 2 (dba) 3 (0.61 g, 0.67 mmol), P (t-), synthesized in Preparation Example 4 under nitrogen stream bu) 3 (0.45 g, 2.24 mmol), NaO (t-bu) (5.37 g, 55.93 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C35 (7.5 g) was obtained using column chromatography.
GC-Mass (이론치: 577.74 g/mol, 측정치: 577 g/mol)GC-Mass (Theoretical value: 577.74 g / mol, Measured value: 577 g / mol)
[합성예 36] 화학식 C36의 합성Synthesis Example 36 Synthesis of Chemical Formula C36
질소 기류 하에서 준비예 4에서 합성된 화합물 a-4 (10.0 g, 19.72 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (8.94 g, 24.61 mmol), K2CO3 (9.28 g, 67.12 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.29 g, 1.12 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C36 (6.4g)을 얻었다.Compound a-4 (10.0 g, 19.72 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (8.94 g, 24.61 mmol), K 2 CO 3 synthesized in Preparation Example 4 under a nitrogen stream. (9.28 g, 67.12 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.29 g, 1.12 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C36 (6.4g).
GC-Mass (이론치: 729.93 g/mol, 측정치: 729 g/mol)GC-Mass (Theoretical value: 729.93 g / mol, Measured value: 729 g / mol)
[합성예 37] 화학식 C37의 합성Synthesis Example 37 Synthesis of Chemical Formula C37
질소 기류 하에서 준비예 4에서 합성된 화합물인 a-4 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (7.49 g, 24.61 mmol), K2CO3 (9.28 g, 67.12 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.29 g, 1.12 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C37 (6.0g)를 얻었다.A-4 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (7.49 g, 24.61 mmol), K 2 CO, a compound synthesized in Preparation Example 4 under a nitrogen stream. 3 (9.28 g, 67.12 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.29 g, 1.12 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the title compound C37 (6.0g).
GC-Mass (이론치: 670.88 g/mol, 측정치: 670 g/mol)GC-Mass (Theoretical value: 670.88 g / mol, Measured value: 670 g / mol)
[합성예 38] 화학식 C38의 합성Synthesis Example 38 Synthesis of Chemical Formula C38
질소 기류 하에서 준비예 4에서 합성된 화합물 a-4 (10.0 g, 19.72 mmol), dibenzo[b,d]furan-4-ylboronic acid (5.22 g, 24.61 mmol), K2CO3 (9.28 g, 67.12 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.29 g, 1.12 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C38 (5.5g)를 얻었다.Compound a-4 (10.0 g, 19.72 mmol), dibenzo [b, d] furan-4-ylboronic acid (5.22 g, 24.61 mmol), K 2 CO 3 (9.28 g, 67.12) synthesized in Preparation Example 4 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.29 g, 1.12 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the title compound C38 (5.5g).
GC-Mass (이론치: 578.72 g/mol, 측정치: 578 g/mol)GC-Mass (Theoretical value: 578.72 g / mol, Measured value: 578 g / mol)
[합성예 39] 화학식 C39의 합성Synthesis Example 39 Synthesis of Chemical Formula C39
질소 기류 하에서 준비예 4에서 합성된 화합물 a-4 (10.0 g, 19.72 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (7.09 g, 24.61 mmol), K2CO3 (9.28 g, 67.12 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.29 g, 1.12 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C39 (6.8g)를 얻었다.Compound a-4 (10.0 g, 19.72 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (7.09 g, 24.61 mmol), K 2 CO 3 synthesized in Preparation Example 4 under a nitrogen stream. (9.28 g, 67.12 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.29 g, 1.12 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C39 (6.8g).
GC-Mass (이론치: 654.82 g/mol, 측정치: 654 g/mol)GC-Mass (Theoretical value: 654.82 g / mol, Measured value: 654 g / mol)
[합성예 40] 화학식 C40의 합성Synthesis Example 40 Synthesis of Chemical Formula C40
질소 기류 하에서 준비예 5에서 합성된 화합물 a-5 (10.0 g, 19.12 mmol), 9H-carbazole (3.52 g, 21.03 mmol), Pd2(dba)3 (0.53 g, 0.57 mmol), P(t-bu)3 (0.39 g, 1.91 mmol), NaO(t-bu) (4.59 g, 47.79 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C40 (6.4 g)을 획득하였다. Compound a-5 (10.0 g, 19.12 mmol), 9H-carbazole (3.52 g, 21.03 mmol), Pd 2 (dba) 3 (0.53 g, 0.57 mmol), P (t-), synthesized in Preparation Example 5 under nitrogen stream bu) 3 (0.39 g, 1.91 mmol), NaO (t-bu) (4.59 g, 47.79 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C40 (6.4 g) was obtained using column chromatography.
GC-Mass (이론치: 653.83 g/mol, 측정치: 653 g/mol)GC-Mass (Theoretical value: 653.83 g / mol, Measured value: 653 g / mol)
[합성예 41] 화학식 C41의 합성Synthesis Example 41 Synthesis of Chemical Formula C41
질소 기류 하에서 준비예 5에서 합성된 화합물 a-5 (10.0 g, 19.72 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (7.64 g, 21.03 mmol), K2CO3 (7.93 g, 57.35 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.10 g, 0.96 mmol)를 넣고 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C41 (6.8g)을 얻었다.Compound a-5 (10.0 g, 19.72 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (7.64 g, 21.03 mmol), K 2 CO 3 synthesized in Preparation Example 5 under a nitrogen stream. (7.93 g, 57.35 mmol) and Toluene / H 2 O / EtOH was (200 ml / 40 ml / 40 ml) was stirred into a, Pd (PPh 3) 4 into the (1.10 g, 0.96 mmol) in 100 ℃ 5 Stir for hours. After the completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C41 (6.8g) by column chromatography.
GC-Mass (이론치: 806.02 g/mol, 측정치: 806 g/mol)GC-Mass (Theoretical value: 806.02 g / mol, Measured value: 806 g / mol)
[합성예 42] 화학식 C42의 합성Synthesis Example 42 Synthesis of Chemical Formula C42
질소 기류 하에서 준비예 5에서 합성된 화합물 a-5 (10.0 g, 19.72 mmol), dibenzo[b,d]furan-4-ylboronic acid (4.46 g, 21.03 mmol), K2CO3 (7.93 g, 57.35 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.10 g, 0.96 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C42 (4.8g)를 얻었다.Compound a-5 (10.0 g, 19.72 mmol), dibenzo [b, d] furan-4-ylboronic acid (4.46 g, 21.03 mmol), K 2 CO 3 (7.93 g, 57.35) synthesized in Preparation Example 5 under nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.10 g, 0.96 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C42 (4.8g).
GC-Mass (이론치: 654.82 g/mol, 측정치: 654 g/mol)GC-Mass (Theoretical value: 654.82 g / mol, Measured value: 654 g / mol)
[합성예 43] 화학식 C43의 합성Synthesis Example 43 Synthesis of Chemical Formula C43
질소 기류 하에서 준비예 5에서 합성된 화합물 a-5 (10.0 g, 19.72 mmol), dibenzo[b,d]furan-4-ylboronic acid (6.02 g, 21.03 mmol), K2CO3 (7.93 g, 57.35 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.10 g, 0.96 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C43 (5.2g)을 얻었다.Compound a-5 (10.0 g, 19.72 mmol), dibenzo [b, d] furan-4-ylboronic acid (6.02 g, 21.03 mmol), K 2 CO 3 (7.93 g, 57.35) synthesized in Preparation Example 5 under nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (1.10 g, 0.96 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure and then subjected to column chromatography to give the target compound C43 (5.2g).
GC-Mass (이론치: 730.91 g/mol, 측정치: 730 g/mol)GC-Mass (Theoretical value: 730.91 g / mol, Measured value: 730 g / mol)
[합성예 44] 화학식 C44의 합성Synthesis Example 44 Synthesis of Chemical Formula C44
질소 기류 하에서 준비예 6에서 합성된 화합물 a-6 (10.0 g, 23.21 mmol), 9H-carbazole (4.27 g, 25.53 mmol), Pd2(dba)3 (0.64 g, 0.70 mmol), P(t-bu)3 (0.47 g, 2.32 mmol), NaO(t-bu) (5.58 g, 58.02 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C44 (5.5 g)를 획득하였다. Compound a-6 (10.0 g, 23.21 mmol), 9H-carbazole (4.27 g, 25.53 mmol), Pd 2 (dba) 3 (0.64 g, 0.70 mmol), P (t-) synthesized in Preparation Example 6 under nitrogen stream bu) 3 (0.47 g, 2.32 mmol), NaO (t-bu) (5.58 g, 58.02 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C44 (5.5 g) was obtained using column chromatography.
GC-Mass (이론치: 561.67 g/mol, 측정치: 561 g/mol)GC-Mass (Theoretical value: 561.67 g / mol, Measured value: 561 g / mol)
[합성예 45] 화학식 C45의 합성Synthesis Example 45 Synthesis of Chemical Formula C45
질소 기류 하에서 준비예 6에서 합성된 화합물 a-6 (10.0 g, 23.21 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (9.27 g, 25.53 mmol), K2CO3 (9.62 g, 69.62 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.34 g, 1.16 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C45 (6.5g)를 얻었다.Compound a-6 (10.0 g, 23.21 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (9.27 g, 25.53 mmol), K 2 CO 3 synthesized in Preparation Example 6 under a nitrogen stream. (9.62 g, 69.62 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.34 g, 1.16 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C45 (6.5g).
GC-Mass (이론치: 713.86 g/mol, 측정치: 713 g/mol)GC-Mass (Theoretical value: 713.86 g / mol, Measured value: 713 g / mol)
[합성예 46] 화학식 C46의 합성Synthesis Example 46 Synthesis of Chemical Formula C46
질소 기류 하에서 준비예 7에서 합성된 화합물 a-7 (10.0 g, 19.72 mmol), 9H-carbazole (3.63 g, 21.70 mmol), Pd2(dba)3 (0.54 g, 0.59 mmol), P(t-bu)3 (0.40 g, 1.97 mmol), NaO(t-bu) (4.74 g, 49.31 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C46 (6.1 g)을 획득하였다. Compound a-7 synthesized in Preparation Example 7 under nitrogen stream (10.0 g, 19.72 mmol), 9H-carbazole (3.63 g, 21.70 mmol), Pd 2 (dba) 3 (0.54 g, 0.59 mmol), P (t- bu) 3 (0.40 g, 1.97 mmol), NaO (t-bu) (4.74 g, 49.31 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C46 (6.1 g) was obtained using column chromatography.
GC-Mass (이론치: 637.77 g/mol, 측정치: 637 g/mol)GC-Mass (Theoretical value: 637.77 g / mol, Measured value: 637 g / mol)
[합성예 47] 화학식 C47의 합성Synthesis Example 47 Synthesis of Chemical Formula C47
질소 기류 하에서 준비예 7에서 합성된 화합물 a-7 (10.0 g, 19.72 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (7.88 g, 21.70 mmol), K2CO3 (8.18 g, 59.17 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (1.14 g, 0.99 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C47 (6.7g)를 얻었다.Compound a-7 (10.0 g, 19.72 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (7.88 g, 21.70 mmol), K 2 CO 3 synthesized in Preparation Example 7 under nitrogen stream (8.18 g, 59.17 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (1.14 g, 0.99 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C47 (6.7g).
GC-Mass (이론치: 789.96 g/mol, 측정치: 789 g/mol)GC-Mass (Theoretical value: 789.96 g / mol, Measured value: 789 g / mol)
[합성예 48] 화학식 C48의 합성Synthesis Example 48 Synthesis of Chemical Formula C48
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 9H-carbazole (3.08 g, 18.41 mmol), Pd2(dba)3 (0.56 g, 0.50 mmol), P(t-bu)3 (0.34 g, 1.67 mmol), NaO(t-bu) (4.02 g, 41.84 mmol) 및 toluene (200 ml)를 혼합하고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 에틸아세테이트로 유기층을 추출한 다음, MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C48 (7.2 g)을 획득하였다. Compound b-1 (10.0 g, 16.74 mmol), 9H-carbazole (3.08 g, 18.41 mmol), Pd 2 (dba) 3 (0.56 g, 0.50 mmol), P (t-) synthesized in Preparation Example 8 under nitrogen stream bu) 3 (0.34 g, 1.67 mmol), NaO (t-bu) (4.02 g, 41.84 mmol) and toluene (200 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the organic layer was extracted with ethyl acetate, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C48 (7.2 g) was obtained using column chromatography.
GC-Mass (이론치: 636.78 g/mol, 측정치: 636 g/mol)GC-Mass (Theoretical value: 636.78 g / mol, Measured value: 636 g / mol)
[합성예 49] 화학식 C49의 합성Synthesis Example 49 Synthesis of Chemical Formula C49
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 3-(9H-carbazol-9-yl)phenylboronic acid (5.29 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C49 (6.7g)를 얻었다.Compound b-1 (10.0 g, 16.74 mmol), 3- (9H-carbazol-9-yl) phenylboronic acid (5.29 g, 18.41 mmol), K 2 CO 3 (6.94 g, synthesized in Preparation Example 8) under nitrogen stream 50.21 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto and stirred at 100 ° C. for 5 hours. It was. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C49 (6.7g) using column chromatography.
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 50] 화학식 C50의 합성Synthesis Example 50 Synthesis of Chemical Formula C50
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (5.29 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C50 (5.4g)을 얻었다.Compound b-1 (10.0 g, 16.74 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (5.29 g, 18.41 mmol) synthesized in Preparation Example 8 under nitrogen stream, K 2 CO 3 (6.94 g, 50.21 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto and stirred at 100 ° C. for 5 hours. It was. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C50 (5.4g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 51] 화학식 C51의 합성Synthesis Example 51 Synthesis of Chemical Formula C51
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (5.29 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH (200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C51 (5.8g)을 얻었다.Compound b-1 (10.0 g, 16.74 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid (5.29 g, 18.41 mmol), K 2 CO 3 (6.94 g, 50.21) synthesized in Preparation Example 8 under nitrogen stream mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C51 (5.8g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 52] 화학식 C52의 합성Synthesis Example 52 Synthesis of Chemical Formula C52
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 9-phenyl-9H-carbazol-2-ylboronic acid (5.29 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C52 (5.8g)를 얻었다.Compound b-1 (10.0 g, 16.74 mmol) synthesized in Preparation Example 8 under nitrogen stream, 9-phenyl-9H-carbazol-2-ylboronic acid (5.29 g, 18.41 mmol), K 2 CO 3 (6.94 g, 50.21 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C52 (5.8g).
GC-Mass (이론치: 712.88 g/mol, 측정치: 712 g/mol)GC-Mass (Theoretical value: 712.88 g / mol, Measured value: 712 g / mol)
[합성예 53] 화학식 C53의 합성Synthesis Example 53 Synthesis of Chemical Formula C53
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 3-(9-phenyl-9H-carbazol-3-yl)phenylboronic acid (6.69 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C53 (5.8g)을 얻었다.Compound b-1 (10.0 g, 16.74 mmol), 3- (9-phenyl-9H-carbazol-3-yl) phenylboronic acid (6.69 g, 18.41 mmol), K 2 CO 3 synthesized in Preparation Example 8 under nitrogen stream (6.94 g, 50.21 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C53 (5.8g) using column chromatography.
GC-Mass (이론치: 766.97 g/mol, 측정치: 766 g/mol)GC-Mass (Theoretical value: 766.97 g / mol, Measured value: 766 g / mol)
[합성예 54] 화학식 C54의 합성Synthesis Example 54 Synthesis of Chemical Formula C54
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), 3-(9-phenyl-9H-carbazol-2-yl)phenylboronic acid (6.69 g, 18.41 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C54 (6.2g)를 얻었다.Compound b-1 (10.0 g, 16.74 mmol), 3- (9-phenyl-9H-carbazol-2-yl) phenylboronic acid (6.69 g, 18.41 mmol), K 2 CO 3 synthesized in Preparation Example 8 under nitrogen stream (6.94 g, 50.21 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the target compound C54 (6.2g).
GC-Mass (이론치: 766.97 g/mol, 측정치: 766 g/mol)GC-Mass (Theoretical value: 766.97 g / mol, Measured value: 766 g / mol)
[합성예 55] 화학식 C55의 합성Synthesis Example 55 Synthesis of Chemical Formula C55
질소 기류 하에서 준비예 9에서 합성된 화합물 b-2 (10.0 g, 16.27 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (4.08 g, 17.90 mmol), K2CO3 (6.75 g, 48.82 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.94 g, 0.81 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C55 (6.2g)를 얻었다.Compound b-2 (10.0 g, 16.27 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (4.08 g, 17.90 mmol), K 2 CO 3 (6.75 g, 48.82) synthesized in Preparation Example 9 under nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (0.94 g, 0.81 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C55 (6.2g) using column chromatography.
GC-Mass (이론치: 670.88 g/mol, 측정치: 670 g/mol)GC-Mass (Theoretical value: 670.88 g / mol, Measured value: 670 g / mol)
[합성예 56] 화학식 C56의 합성Synthesis Example 56 Synthesis of Chemical Formula C56
질소 기류 하에서 준비예 9에서 합성된 화합물 b-2 (10.0 g, 16.27 mmol), dibenzo[b,d]thiophen-2-ylboronic acid (4.08 g, 17.90 mmol), K2CO3 (6.75 g, 48.82 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.94 g, 0.81 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C56 (6.1g)을 얻었다.Compound b-2 (10.0 g, 16.27 mmol), dibenzo [b, d] thiophen-2-ylboronic acid (4.08 g, 17.90 mmol), K 2 CO 3 (6.75 g, 48.82) synthesized in Preparation Example 9 under nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added and stirred, followed by Pd (PPh 3 ) 4 (0.94 g, 0.81 mmol), followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C56 (6.1g).
GC-Mass (이론치: 670.88 g/mol, 측정치: 670 g/mol)GC-Mass (Theoretical value: 670.88 g / mol, Measured value: 670 g / mol)
[합성예 57] 화학식 C57의 합성Synthesis Example 57 Synthesis of Chemical Formula C57
질소 기류 하에서 준비예 9에서 합성된 화합물 b-2 (10.0 g, 16.74 mmol), 3-(dibenzo[b,d]thiophen-4-yl)phenylboronic acid (5.44 g, 17.90 mmol), K2CO3 (6.75 g, 48.82 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.94 g, 0.81 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C57 (7.2g)을 얻었다.Compound b-2 (10.0 g, 16.74 mmol), 3- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid (5.44 g, 17.90 mmol), K 2 CO 3 , synthesized in Preparation Example 9 under a nitrogen stream. (6.75 g, 48.82 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.94 g, 0.81 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C57 (7.2g) by column chromatography.
GC-Mass (이론치: 746.98 g/mol, 측정치: 746 g/mol)GC-Mass (Theoretical value: 746.98 g / mol, Measured value: 746 g / mol)
[합성예 58] 화학식 C58의 합성Synthesis Example 58 Synthesis of Chemical Formula C58
질소 기류 하에서 준비예 9에서 합성된 화합물 b-2 (10.0 g, 16.74 mmol), 3-(dibenzo[b,d]thiophen-2-yl)phenylboronic acid (5.44 g, 17.90 mmol), K2CO3 (6.75 g, 48.82 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.94 g, 0.81 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C58 (7.2g)을 얻었다.Compound b-2 (10.0 g, 16.74 mmol), 3- (dibenzo [b, d] thiophen-2-yl) phenylboronic acid (5.44 g, 17.90 mmol), K 2 CO 3 synthesized in Preparation Example 9 under a nitrogen stream. (6.75 g, 48.82 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.94 g, 0.81 mmol) was added thereto at 100 ° C. Stir for 5 hours. After the completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to give the target compound C58 (7.2g) by column chromatography.
GC-Mass (이론치: 746.98 g/mol, 측정치: 746 g/mol)GC-Mass (Theoretical value: 746.98 g / mol, Measured value: 746 g / mol)
[합성예 59] 화학식 C59의 합성Synthesis Example 59 Synthesis of Chemical Formula C59
질소 기류 하에서 준비예 10에서 합성된 화합물 b-3 (10.0 g, 16.71 mmol), dibenzo[b,d]furan-4-ylboronic acid (6.68 g, 18.38 mmol), K2CO3 (6.93 g, 50.13 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C59 (7.2g)를 얻었다.Compound b-3 (10.0 g, 16.71 mmol), dibenzo [b, d] furan-4-ylboronic acid (6.68 g, 18.38 mmol), K 2 CO 3 (6.93 g, 50.13) synthesized in Preparation Example 10 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to give the target compound C59 (7.2g) by column chromatography.
GC-Mass (이론치: 638.75 g/mol, 측정치: 638 g/mol)GC-Mass (Theoretical value: 638.75 g / mol, Measured value: 638 g / mol)
[합성예 60] 화학식 C60의 합성Synthesis Example 60 Synthesis of Chemical Formula C60
질소 기류 하에서 준비예 10에서 합성된 화합물 b-3 (10.0 g, 16.71 mmol), dibenzo[b,d]furan-2-ylboronic acid (6.68 g, 18.38 mmol), K2CO3 (6.93 g, 50.13 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C60 (7.5g)을 얻었다.Compound b-3 (10.0 g, 16.71 mmol), dibenzo [b, d] furan-2-ylboronic acid (6.68 g, 18.38 mmol), K 2 CO 3 (6.93 g, 50.13) synthesized in Preparation Example 10 under a nitrogen stream. mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C60 (7.5g) by column chromatography.
GC-Mass (이론치: 638.75 g/mol, 측정치: 638 g/mol)GC-Mass (Theoretical value: 638.75 g / mol, Measured value: 638 g / mol)
[합성예 61] 화학식 C61의 합성Synthesis Example 61 Synthesis of Chemical Formula C61
질소 기류 하에서 준비예 10에서 합성된 화합물 b-3 (10.0 g, 16.71 mmol), 3-(dibenzo[b,d]furan-4-yl)phenylboronic acid (5.30 g, 18.38 mmol), K2CO3 (6.93 g, 50.13 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C61 (7.5g)를 얻었다.Compound b-3 (10.0 g, 16.71 mmol), 3- (dibenzo [b, d] furan-4-yl) phenylboronic acid (5.30 g, 18.38 mmol), K 2 CO 3 , synthesized in Preparation Example 10 under a nitrogen stream. (6.93 g, 50.13 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto at 100 ° C. Stir for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C61 (7.5g) by column chromatography.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 62] 화학식 C62의 합성Synthesis Example 62 Synthesis of Chemical Formula C62
질소 기류 하에서 준비예 10에서 합성된 화합물 b-3 (10.0 g, 16.71 mmol), 3-(dibenzo[b,d]furan-2-yl)phenylboronic acid (5.30 g, 18.38 mmol), K2CO3 (6.93 g, 50.13 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C62 (8.5g)를 얻었다.Compound b-3 (10.0 g, 16.71 mmol), 3- (dibenzo [b, d] furan-2-yl) phenylboronic acid (5.30 g, 18.38 mmol), K 2 CO 3 , synthesized in Preparation Example 10 under a nitrogen stream. (6.93 g, 50.13 mmol) and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) were added thereto, followed by stirring. Then, Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto at 100 ° C. Stir for 5 hours. After the completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, to obtain the target compound C62 (8.5g) using column chromatography.
GC-Mass (이론치: 714.85 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)
[합성예 63] 화학식 C63의 합성Synthesis Example 63 Synthesis of Chemical Formula C63
질소 기류 하에서 준비예 8에서 합성된 화합물 b-1 (10.0 g, 16.74 mmol), triphenylen-2-ylboronic acid (5.00 g, 18.38 mmol), K2CO3 (6.94 g, 50.21 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C63 (6.2g)을 얻었다.Compound b-1 (10.0 g, 16.74 mmol), triphenylen-2-ylboronic acid (5.00 g, 18.38 mmol), K 2 CO 3 (6.94 g, 50.21 mmol) synthesized in Preparation Example 8 under nitrogen stream and Toluene / H 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C63 (6.2g).
GC-Mass (이론치: 697.86 g/mol, 측정치: 697 g/mol)GC-Mass (Theoretical value: 697.86 g / mol, Measured value: 697 g / mol)
[합성예 64] 화학식 C64의 합성Synthesis Example 64 Synthesis of Chemical Formula C64
질소 기류 하에서 준비예 9에서 합성된 화합물 b-2 (10.0 g, 16.27 mmol), triphenylen-2-ylboronic acid (4.87 g, 17.90 mmol), K2CO3 (6.75 g, 48.82 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.94 g, 0.81 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C64 (8.0g)를 얻었다.Compound b-2 (10.0 g, 16.27 mmol), triphenylen-2-ylboronic acid (4.87 g, 17.90 mmol), K 2 CO 3 (6.75 g, 48.82 mmol) and Toluene / H synthesized in Preparation Example 9 under a nitrogen stream. 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.94 g, 0.81 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, concentrated under reduced pressure, and then purified by column chromatography to give the target compound C64 (8.0 g).
GC-Mass (이론치: 714.91 g/mol, 측정치: 714 g/mol)GC-Mass (Theoretical value: 714.91 g / mol, Measured value: 714 g / mol)
[합성예 65] 화학식 C65의 합성Synthesis Example 65 Synthesis of Chemical Formula C65
질소 기류 하에서 준비예 10에서 합성된 화합물 b-3 (10.0 g, 16.71 mmol), triphenylen-2-ylboronic acid (4.87 g, 17.90 mmol), K2CO3 (6.93 g, 50.13 mmol)와 Toluene/H2O/EtOH(200 ml/40 ml/40 ml)를 넣고 교반한 후, Pd(PPh3)4 (0.97 g, 0.84 mmol)를 넣고, 100℃에서 5시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고 감압조건에서 농축한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 C65 (8.5g)를 얻었다.Compound b-3 (10.0 g, 16.71 mmol), triphenylen-2-ylboronic acid (4.87 g, 17.90 mmol), K 2 CO 3 (6.93 g, 50.13 mmol) and Toluene / H synthesized in Preparation Example 10 under a nitrogen stream. 2 O / EtOH (200 ml / 40 ml / 40 ml) was added thereto, followed by stirring. Pd (PPh 3 ) 4 (0.97 g, 0.84 mmol) was added thereto, followed by stirring at 100 ° C. for 5 hours. After completion of the reaction, the organic layer was extracted with methylene chloride and concentrated under reduced pressure, and then purified by column chromatography to give the title compound C65 (8.5g).
GC-Mass (이론치: 698.85 g/mol, 측정치: 698 g/mol)GC-Mass (Theoretical value: 698.85 g / mol, Measured value: 698 g / mol)
[실시예 1] 녹색 유기 EL 소자의 제조Example 1 Manufacture of Green Organic EL Device
합성예 1에서 합성된 화합물 C1을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기 과정에 따라 녹색 유기 EL 소자를 제조하였다.Compound C1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a conventionally known method, and then a green organic EL device was manufactured according to the following procedure.
ITO (Indium tin oxide)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.A glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried, and then transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes And the substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 화합물 C1 + 10 % Ir(ppy)3 (30nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 EL 소자를 제조하였다.M-MTDATA (60 nm) / TCTA (80 nm) / Compound C1 + 10% Ir (ppy) 3 (30nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF on the prepared ITO transparent electrode (1 nm) / Al (200 nm) was laminated in order to prepare an organic EL device.
사용된 m-MTDATA, TCTA, Ir(ppy)3 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 and BCP used are as follows.
[실시예 2] ~ [실시예 65] 녹색 유기 EL 소자의 제조[Example 2] to [Example 65] Fabrication of Green Organic EL Device
실시예 1에서 발광층 형성시 호스트 물질로 사용된 화합물 C1 대신 표 1에 기재된 화합물을 각각 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 녹색 유기 EL 소자를 제조하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that each compound of Table 1 was used instead of the compound C1 used as a host material in forming the emission layer in Example 1.
[비교예 1] 녹색 유기 EL 소자의 제조Comparative Example 1 Fabrication of Green Organic EL Device
실시예 1에서 발광층 형성시 호스트 물질로 사용된 화합물 C1 대신 CBP를 사용하는 것을 제외하고는, 실시예 1과 동일한 과정으로 녹색 유기 EL 소자를 제작하였다. A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound C1 used as a host material in forming the emission layer in Example 1.
사용된 CBP의 구조는 하기와 같다.The structure of CBP used is as follows.
[평가예 1][Evaluation Example 1]
실시예 1 내지 65, 비교예 1에서 각각 제조된 녹색 유기 EL 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하였고, 그 결과를 하기 표 1에 나타내었다.For green organic EL devices prepared in Examples 1 to 65 and Comparative Example 1, driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.
표 1
Table 1
| 샘플 | 호스트 | 구동 전압 (V) | EL 피크 (nm) | 전류효율 (cd/A) |
| 실시예 1 | 화합물 C1 | 6.30 | 519 | 41.1 |
| 실시예 2 | 화합물 C2 | 6.35 | 518 | 40.8 |
| 실시예 3 | 화합물 C3 | 6.35 | 519 | 40.7 |
| 실시예 4 | 화합물 C4 | 6.30 | 519 | 41.0 |
| 실시예 5 | 화합물 C5 | 6.40 | 520 | 42.4 |
| 실시예 6 | 화합물 C6 | 6.35 | 518 | 41.6 |
| 실시예 7 | 화합물 C7 | 6.40 | 518 | 41.4 |
| 실시예 8 | 화합물 C8 | 6.54 | 517 | 42.1 |
| 실시예 9 | 화합물 C9 | 6.55 | 517 | 41.8 |
| 실시예 10 | 화합물 C10 | 6.60 | 519 | 41.0 |
| 실시예 11 | 화합물 C11 | 6.55 | 518 | 40.8 |
| 실시예 12 | 화합물 C12 | 6.60 | 518 | 38.6 |
| 실시예 13 | 화합물 C13 | 6.65 | 518 | 38.4 |
| 실시예 14 | 화합물 C14 | 6.65 | 520 | 37.2 |
| 실시예 15 | 화합물 C15 | 6.70 | 519 | 35.5 |
| 실시예 16 | 화합물 C16 | 6.80 | 518 | 38.5 |
| 실시예 17 | 화합물 C17 | 6.88 | 518 | 39.5 |
| 실시예 18 | 화합물 C18 | 6.70 | 517 | 39.0 |
| 실시예 19 | 화합물 C19 | 6.90 | 517 | 39.2 |
| 실시예 20 | 화합물 C20 | 6.80 | 520 | 39.5 |
| 실시예 21 | 화합물 C21 | 6.80 | 517 | 39.5 |
| 실시예 22 | 화합물 C22 | 6.30 | 518 | 41.1 |
| 실시예 23 | 화합물 C23 | 6.35 | 517 | 40.8 |
| 실시예 24 | 화합물 C24 | 6.35 | 518 | 40.7 |
| 실시예 25 | 화합물 C25 | 6.35 | 520 | 41.0 |
| 실시예 26 | 화합물 C26 | 6.40 | 519 | 42.4 |
| 실시예 27 | 화합물 C27 | 6.40 | 518 | 41.6 |
| 실시예 28 | 화합물 C28 | 6.50 | 519 | 41.4 |
| 실시예 29 | 화합물 C29 | 6.50 | 519 | 42.1 |
| 실시예 30 | 화합물 C30 | 6.55 | 520 | 41.8 |
| 실시예 31 | 화합물 C31 | 6.35 | 518 | 41.0 |
| 실시예 32 | 화합물 C32 | 6.25 | 518 | 40.8 |
| 실시예 33 | 화합물 C33 | 6.35 | 517 | 41.6 |
| 실시예 34 | 화합물 C34 | 6.40 | 517 | 41.4 |
| 실시예 35 | 화합물 C35 | 6.45 | 519 | 41.2 |
| 실시예 36 | 화합물 C36 | 6.40 | 518 | 42.5 |
| 실시예 37 | 화합물 C37 | 6.40 | 518 | 41.3 |
| 실시예 38 | 화합물 C38 | 6.45 | 518 | 41.5 |
| 실시예 39 | 화합물 C39 | 6.35 | 520 | 41.6 |
| 실시예 40 | 화합물 C40 | 6.35 | 519 | 41.0 |
| 실시예 41 | 화합물 C41 | 6.35 | 518 | 41.5 |
| 실시예 42 | 화합물 C42 | 6.30 | 518 | 41.9 |
| 실시예 43 | 화합물 C43 | 6.35 | 517 | 42.1 |
| 실시예 44 | 화합물 C44 | 6.35 | 517 | 42.3 |
| 실시예 45 | 화합물 C45 | 6.35 | 520 | 43.1 |
| 실시예 46 | 화합물 C46 | 6.30 | 517 | 42.9 |
| 실시예 47 | 화합물 C47 | 6.35 | 518 | 41.1 |
| 실시예 48 | 화합물 C48 | 6.40 | 517 | 41.4 |
| 실시예 49 | 화합물 C49 | 6.54 | 518 | 41.8 |
| 실시예 50 | 화합물 C50 | 6.55 | 520 | 41.5 |
| 실시예 51 | 화합물 C51 | 6.40 | 517 | 40.2 |
| 실시예 52 | 화합물 C52 | 6.54 | 517 | 40.7 |
| 실시예 53 | 화합물 C53 | 6.55 | 520 | 40.5 |
| 실시예 54 | 화합물 C54 | 6.60 | 517 | 40.0 |
| 실시예 55 | 화합물 C55 | 6.55 | 518 | 40.2 |
| 실시예 56 | 화합물 C56 | 6.60 | 517 | 38.5 |
| 실시예 57 | 화합물 C57 | 6.55 | 518 | 39.5 |
| 실시예 58 | 화합물 C58 | 6.60 | 520 | 39.2 |
| 실시예 59 | 화합물 C59 | 6.55 | 517 | 38.5 |
| 실시예 60 | 화합물 C60 | 6.60 | 517 | 39.5 |
| 실시예 61 | 화합물 C61 | 6.60 | 520 | 39.0 |
| 실시예 62 | 화합물 C62 | 6.55 | 517 | 39.2 |
| 실시예 63 | 화합물 C63 | 6.85 | 518 | 39.5 |
| 실시예 64 | 화합물 C64 | 6.91 | 517 | 38.5 |
| 실시예 65 | 화합물 C65 | 6.92 | 518 | 38.5 |
| 비교예 1 | CBP | 6.93 | 516 | 38.2 |
| Sample | Host | Driving voltage (V) | EL peak (nm) | Current efficiency (cd / A) |
| Example 1 | Compound c1 | 6.30 | 519 | 41.1 |
| Example 2 | Compound c2 | 6.35 | 518 | 40.8 |
| Example 3 | Compound c3 | 6.35 | 519 | 40.7 |
| Example 4 | Compound c4 | 6.30 | 519 | 41.0 |
| Example 5 | Compound c5 | 6.40 | 520 | 42.4 |
| Example 6 | Compound c6 | 6.35 | 518 | 41.6 |
| Example 7 | Compound c7 | 6.40 | 518 | 41.4 |
| Example 8 | Compound c8 | 6.54 | 517 | 42.1 |
| Example 9 | Compound c9 | 6.55 | 517 | 41.8 |
| Example 10 | Compound c10 | 6.60 | 519 | 41.0 |
| Example 11 | Compound c11 | 6.55 | 518 | 40.8 |
| Example 12 | Compound c12 | 6.60 | 518 | 38.6 |
| Example 13 | Compound c13 | 6.65 | 518 | 38.4 |
| Example 14 | Compound c14 | 6.65 | 520 | 37.2 |
| Example 15 | Compound c15 | 6.70 | 519 | 35.5 |
| Example 16 | Compound c16 | 6.80 | 518 | 38.5 |
| Example 17 | Compound c17 | 6.88 | 518 | 39.5 |
| Example 18 | Compound c18 | 6.70 | 517 | 39.0 |
| Example 19 | Compound c19 | 6.90 | 517 | 39.2 |
| Example 20 | Compound c20 | 6.80 | 520 | 39.5 |
| Example 21 | Compound c21 | 6.80 | 517 | 39.5 |
| Example 22 | Compound c22 | 6.30 | 518 | 41.1 |
| Example 23 | Compound c23 | 6.35 | 517 | 40.8 |
| Example 24 | Compound c24 | 6.35 | 518 | 40.7 |
| Example 25 | Compound c25 | 6.35 | 520 | 41.0 |
| Example 26 | Compound c26 | 6.40 | 519 | 42.4 |
| Example 27 | Compound c27 | 6.40 | 518 | 41.6 |
| Example 28 | Compound c28 | 6.50 | 519 | 41.4 |
| Example 29 | Compound c29 | 6.50 | 519 | 42.1 |
| Example 30 | Compound c30 | 6.55 | 520 | 41.8 |
| Example 31 | Compound c31 | 6.35 | 518 | 41.0 |
| Example 32 | Compound c32 | 6.25 | 518 | 40.8 |
| Example 33 | Compound c33 | 6.35 | 517 | 41.6 |
| Example 34 | Compound c34 | 6.40 | 517 | 41.4 |
| Example 35 | Compound c35 | 6.45 | 519 | 41.2 |
| Example 36 | Compound c36 | 6.40 | 518 | 42.5 |
| Example 37 | Compound c37 | 6.40 | 518 | 41.3 |
| Example 38 | Compound c38 | 6.45 | 518 | 41.5 |
| Example 39 | Compound c39 | 6.35 | 520 | 41.6 |
| Example 40 | Compound c40 | 6.35 | 519 | 41.0 |
| Example 41 | Compound c41 | 6.35 | 518 | 41.5 |
| Example 42 | Compound c42 | 6.30 | 518 | 41.9 |
| Example 43 | Compound c43 | 6.35 | 517 | 42.1 |
| Example 44 | Compound c44 | 6.35 | 517 | 42.3 |
| Example 45 | Compound c45 | 6.35 | 520 | 43.1 |
| Example 46 | Compound c46 | 6.30 | 517 | 42.9 |
| Example 47 | Compound c47 | 6.35 | 518 | 41.1 |
| Example 48 | Compound c48 | 6.40 | 517 | 41.4 |
| Example 49 | Compound c49 | 6.54 | 518 | 41.8 |
| Example 50 | Compound c50 | 6.55 | 520 | 41.5 |
| Example 51 | Compound c51 | 6.40 | 517 | 40.2 |
| Example 52 | Compound c52 | 6.54 | 517 | 40.7 |
| Example 53 | Compound c53 | 6.55 | 520 | 40.5 |
| Example 54 | Compound c54 | 6.60 | 517 | 40.0 |
| Example 55 | Compound c55 | 6.55 | 518 | 40.2 |
| Example 56 | Compound c56 | 6.60 | 517 | 38.5 |
| Example 57 | Compound c57 | 6.55 | 518 | 39.5 |
| Example 58 | Compound c58 | 6.60 | 520 | 39.2 |
| Example 59 | Compound c59 | 6.55 | 517 | 38.5 |
| Example 60 | Compound c60 | 6.60 | 517 | 39.5 |
| Example 61 | Compound c61 | 6.60 | 520 | 39.0 |
| Example 62 | Compound c62 | 6.55 | 517 | 39.2 |
| Example 63 | Compound c63 | 6.85 | 518 | 39.5 |
| Example 64 | Compound c64 | 6.91 | 517 | 38.5 |
| Example 65 | Compound c65 | 6.92 | 518 | 38.5 |
| Comparative Example 1 | CBP | 6.93 | 516 | 38.2 |
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물(C1~C65)을 발광층의 호스트 물질로 사용한 실시예 1 내지 65의 녹색 유기 EL 소자는, 종래 호스트 물질인 CBP 사용한 비교예 1의 녹색 유기 EL 소자에 비해, 전류 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 1, the green organic EL device of Examples 1 to 65 using the compounds (C1 to C65) according to the present invention as a host material of the light emitting layer is the green organic EL device of Comparative Example 1 using CBP as a conventional host material. Compared with the device, it was found to show better performance in terms of current efficiency and driving voltage.
[실시예 66] 청색 유기 EL 소자의 제조Example 66 Fabrication of Blue Organic EL Devices
합성예 1에서 합성된 화합물 C1을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기 과정에 따라 청색 유기 전계 발광 소자를 제조하였다.Compound C1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a conventionally known method, and then a blue organic EL device was manufactured according to the following procedure.
ITO (Indium tin oxide)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.A glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried, and then transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes And the substrate was transferred to a vacuum evaporator.
상기와 같이 ITO 투명 전극 위에 CuPc (10 nm)/ TPAC (30 nm)/ 화합물 C1 + 7 % Flrpic (30nm)/ Alq3 (30 nm)/ LiF (0.2 nm)/Al (150 nm) 순으로 적층하여 유기 EL 소자를 제작하였다. CuPc (10 nm) / TPAC (30 nm) / Compound C1 + 7% Flrpic (30 nm) / Alq 3 (30 nm) / LiF (0.2 nm) / Al (150 nm) on the ITO transparent electrode as described above To an organic EL device.
사용된 CuPc, TPAC, Flrpic의 구조는 하기와 같다.The structures of CuPc, TPAC, and Flrpic used are as follows.
[실시예 67 ~ 77] 청색 유기 EL 소자의 제조Examples 67 to 77 Manufacture of Blue Organic EL Devices
실시예 66에서 발광층 형성시 호스트 물질로 사용된 화합물 C1 대신 표 2에 기재된 화합물을 각각 사용하는 것을 제외하고는, 실시예 66과 동일하게 수행하여 청색 유기 EL 소자를 제조하였다.A blue organic EL device was manufactured in the same manner as in Example 66, except that the compounds shown in Table 2 were used instead of the compound C1 used as the host material in forming the emission layer in Example 66.
[비교예 2] 청색 유기 EL 소자의 제작Comparative Example 2 Fabrication of Blue Organic EL Device
실시예 66 에서 발광층 형성시 호스트 물질로 사용된 화합물 C1 대신 CBP를 사용하는 것을 제외하고는, 상기 실시예 66과 동일한 과정으로 청색 유기 전계 발광 소자를 제조하였다.A blue organic electroluminescent device was manufactured in the same manner as in Example 66, except for using CBP instead of the compound C1 used as a host material in forming the emission layer in Example 66.
[평가예 2][Evaluation Example 2]
실시예 66 내지 121, 및 비교예 2에서 각각 제조된 청색 유기 EL 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압 및 전류효율을 측정하였고, 그 결과를 하기 표 2에 나타내었다.For the blue organic EL devices manufactured in Examples 66 to 121 and Comparative Example 2, the driving voltage and the current efficiency at the current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below.
표 2
TABLE 2
| 샘플 | 호스트 | 구동 전압(V) | EL 피크(nm) | 전류효율(cd/A) |
| 실시예 66 | 화합물 C1 | 7.50 | 479 | 6.20 |
| 실시예 67 | 화합물 C8 | 7.60 | 480 | 6.25 |
| 실시예 68 | 화합물 C9 | 7.60 | 470 | 6.30 |
| 실시예 69 | 화합물 C12 | 7.55 | 482 | 6.33 |
| 실시예 70 | 화합물 C13 | 7.50 | 475 | 6.27 |
| 실시예 71 | 화합물 C22 | 7.45 | 477 | 6.50 |
| 실시예 72 | 화합물 C26 | 7.40 | 475 | 6.60 |
| 실시예 73 | 화합물 C28 | 7.50 | 480 | 6.30 |
| 실시예 74 | 화합물 C36 | 7.40 | 477 | 6.34 |
| 실시예 75 | 화합물 C39 | 7.45 | 479 | 6.43 |
| 실시예 76 | 화합물 C45 | 7.50 | 475 | 6.40 |
| 실시예 77 | 화합물 C47 | 7.70 | 477 | 6.40 |
| 비교예 2 | CBP | 7.80 | 474 | 5.80 |
| Sample | Host | Drive voltage (V) | EL peak (nm) | Current efficiency (cd / A) |
| Example 66 | Compound c1 | 7.50 | 479 | 6.20 |
| Example 67 | Compound c8 | 7.60 | 480 | 6.25 |
| Example 68 | Compound c9 | 7.60 | 470 | 6.30 |
| Example 69 | Compound c12 | 7.55 | 482 | 6.33 |
| Example 70 | Compound c13 | 7.50 | 475 | 6.27 |
| Example 71 | Compound c22 | 7.45 | 477 | 6.50 |
| Example 72 | Compound c26 | 7.40 | 475 | 6.60 |
| Example 73 | Compound c28 | 7.50 | 480 | 6.30 |
| Example 74 | Compound c36 | 7.40 | 477 | 6.34 |
| Example 75 | Compound c39 | 7.45 | 479 | 6.43 |
| Example 76 | Compound c45 | 7.50 | 475 | 6.40 |
| Example 77 | Compound c47 | 7.70 | 477 | 6.40 |
| Comparative Example 2 | CBP | 7.80 | 474 | 5.80 |
상기 표2 에 나타낸 바와 같이, 본 발명에 따른 화합물을 발광층의 호스트 재료로 사용한 실시예 66 내지 121의 청색 유기 EL 소자는, 종래 호스트 물질인 CBP를 사용한 비교예 2의 청색 유기 EL 소자 비해, 전류 효율 및 구동전압 면에서 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 2, the blue organic EL devices of Examples 66 to 121 using the compound according to the present invention as the host material of the light emitting layer, compared with the blue organic EL devices of Comparative Example 2 using CBP, which is a conventional host material, It was found that excellent performance was achieved in terms of efficiency and driving voltage.
Claims (7)
- 하기 화학식 1 또는 2로 표시되는 화합물:Compound represented by the following formula (1) or (2):[화학식 1][Formula 1]
[화학식 2][Formula 2]
(상기 화학식에서,(In the above formula,L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합이거나, 또는 C6~C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고;L 1 and L 2 are the same or different, each independently is a single bond, or C 6 ~ C 60 aryl group and a nuclear atoms is selected from the group consisting of 5 to 60 hetero arylene group;Ar1 및 Ar2는 서로 동일하거나 상이하며, 각각 독립적으로 C6~C60의 아릴기, 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되고;Ar 1 and Ar 2 are the same as or different from each other, and are each independently selected from the group consisting of a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;다만, Ar1, Ar2 및 R1 내지 R10 중에서 적어도 하나는 하기 화학식 3 또는 4로 표시되는 치환체이고;Provided that at least one of Ar 1 , Ar 2, and R 1 to R 10 is a substituent represented by Formula 3 or 4 below;[화학식 3][Formula 3]
[화학식 4][Formula 4]X1은 NR15, O, 및 S로 이루어진 군에서 선택되고;X 1 is selected from the group consisting of NR 15 , O, and S;a, b 및 c는 각각 0 내지 4의 정수이고;a, b and c are each an integer of 0 to 4;d는 0 내지 3의 정수이며;d is an integer from 0 to 3;복수의 R11은 서로 동일하거나 상이하고, 복수의 R12는 서로 동일하거나 상이하며, 복수의 R13은 서로 동일하거나 상이하고, 복수의 R14는 서로 동일하거나 상이하며;A plurality of R 11 are the same or different from each other, a plurality of R 12 are the same or different from each other, a plurality of R 13 are the same or different from each other, and a plurality of R 14 are the same or different from each other;R1 내지 R15는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소(D), 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합 방향족환 또는 축합 헤테로방향족환을 형성할 수 있고;R 1 to R 15 are the same as or different from each other, and each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C Alkynyl group of 2 to C 40 , cycloalkyl group of C 3 to C 40 , heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 1 ~ C 40 alkyl silyl group, C 6 ~ aryl silyl group of C 60, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or by an adjacent group condensed A condensed aromatic ring or a condensed heteroaromatic ring can be formed;이때, 상기 L1 및 L2의 아릴렌기 및 헤테로아릴렌기, Ar1 및 Ar2의 아릴기, 헤테로아릴기, R1 내지 R15의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기, 아릴아민기는 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환되며, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이함).In this case, the arylene group and heteroarylene group of L 1 and L 2, the aryl group of Ar 1 and Ar 2 , heteroaryl group, alkyl group of R 1 to R 15 , alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, Aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group, aryl amine group deuterium, halogen, cyano group , Nitro group, amino group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocyclo Alkyl group, C 6 -C 60 aryl group, nuclear atom 5 to 60 heteroaryl group, C 1 to C 40 alkyloxy group, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 ~ C aryl silyl group of 60, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine of C 60 Pinoksai Group and a C 6 ~ C when being substituted with at least 60 selected from the group consisting arylamine one kind of substituent or is unsubstituted, but the plurality of the said substituents, all of which are the same or different from each other). - 제1항에 있어서,The method of claim 1,상기 화합물은 하기 화학식 5 내지 10 중 어느 하나로 표시되는 화합물인 것이 특징인 화합물:The compound is a compound characterized in that the compound represented by any one of the following formulas 5 to 10:[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
(상기 화학식 5 내지 10에서,(In Chemical Formulas 5 to 10,L1, L2, X1, R1 내지 R14, a, b, c 및 d는 각각 제1항에서 정의한 바와 같음).L 1 , L 2 , X 1 , R 1 to R 14 , a, b, c and d are each as defined in claim 1). - 제1항에 있어서,The method of claim 1,L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합이거나, 또는 페닐렌기인 것이 특징인 화합물.L 1 and L 2 are the same as or different from each other, and each independently a single bond or a phenylene group, characterized in that the group.
- 제1항에 있어서,The method of claim 1,R1 내지 R15는 서로 동일하거나 상이하며, 각각 독립적으로 수소 및 C6~C60의 아릴기로 이루어진 군에서 선택되고,R 1 to R 15 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen and C 6 ~ C 60 aryl group,상기 R1 내지 R15의 아릴기는 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환되며, 다만 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이한 것이 특징인 화합물.The aryl group of R 1 to R 15 is deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C 6 -C 60 aryl group, C 5-60 heteroaryl group, C 1 -C 40 alkyloxy group, C 6- C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ substituted with C 60 aryl phosphine group, at least one substituent selected from the group consisting of C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ with an aryl amine of the C 60 in or unsubstituted and ring, the just plurality which the substituent In which case they are characterized by the same or different from each other.
- 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서,An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode.상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제4항 중 어느 한 항에 기재된 화합물을 포함하는 것이 특징인 유기 전계 발광 소자.At least one of the one or more organic material layers comprises the compound according to any one of claims 1 to 4.
- 제5항에 있어서,The method of claim 5,상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층으로 이루어진 군에서 선택되는 것이 특징인 유기 전계 발광 소자.The organic material layer containing the compound is an organic electroluminescent device, characterized in that selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
- 제5항에 있어서,The method of claim 5,상기 화합물을 포함하는 유기물층은 발광층이며,The organic material layer containing the compound is a light emitting layer,상기 화합물은 인광 호스트인 것이 특징인 유기 전계 발광 소자.The compound is an organic electroluminescent device, characterized in that the phosphorescent host.
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| KR20110021073A (en) * | 2009-08-25 | 2011-03-04 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
| KR20130024915A (en) * | 2010-04-22 | 2013-03-08 | 캐논 가부시끼가이샤 | Novel m-terphenyl compound and organic light emitting device including the same |
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- 2014-01-21 KR KR1020140007431A patent/KR101618426B1/en active IP Right Grant
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2015
- 2015-01-13 WO PCT/KR2015/000353 patent/WO2015111864A1/en active Application Filing
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| KR20060021143A (en) * | 2004-09-02 | 2006-03-07 | 삼성에스디아이 주식회사 | Terphenyl-based compound and organic electroluminescence display device employing the same |
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| KR20110021073A (en) * | 2009-08-25 | 2011-03-04 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017153731A1 (en) * | 2016-03-08 | 2017-09-14 | Cambridge Display Technology Limited | Dibenzofuran and dibenzothiophene derivatives and organic light-emitting devices containing them |
| US11136303B2 (en) | 2016-03-08 | 2021-10-05 | Cambridge Display Technology Limited | Dibenzofuran and dibenzothiophene derivatives and organic light-emitting devices containing them |
| DE102016108332B3 (en) * | 2016-05-04 | 2017-02-23 | Cynora Gmbh | Organic molecules, in particular for use in organic optoelectronic devices |
| WO2017190885A1 (en) * | 2016-05-04 | 2017-11-09 | Cynora Gmbh | Organic molecules, especially for use in optoelectronic devices |
| WO2019114610A1 (en) * | 2017-12-14 | 2019-06-20 | 广州华睿光电材料有限公司 | Carbazole tribenzene organic compound, superpolymer, mixture and composition, and use thereof |
| CN111247133A (en) * | 2017-12-14 | 2020-06-05 | 广州华睿光电材料有限公司 | Carbazole triphenyl organic compound, high polymer, mixture, composition and application thereof |
| US11053228B2 (en) | 2018-07-20 | 2021-07-06 | Samsung Electronics Co., Ltd. | Condensed cyclic compound, composition including the condensed cyclic compound, and organic light-emitting device including the condensed cyclic compound |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101618426B1 (en) | 2016-05-04 |
| KR20150087045A (en) | 2015-07-29 |
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