KR20170136836A - Organic compounds and organic electro luminescence device comprising the same - Google Patents
Organic compounds and organic electro luminescence device comprising the same Download PDFInfo
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- KR20170136836A KR20170136836A KR1020160068871A KR20160068871A KR20170136836A KR 20170136836 A KR20170136836 A KR 20170136836A KR 1020160068871 A KR1020160068871 A KR 1020160068871A KR 20160068871 A KR20160068871 A KR 20160068871A KR 20170136836 A KR20170136836 A KR 20170136836A
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- South Korea
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- group
- compound
- aryl
- heteroaryl
- alkyl
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 9
- 238000005401 electroluminescence Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 123
- 239000010410 layer Substances 0.000 claims description 88
- 125000003118 aryl group Chemical group 0.000 claims description 54
- 125000001072 heteroaryl group Chemical group 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 38
- 125000004429 atom Chemical group 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 125000005264 aryl amine group Chemical group 0.000 claims description 11
- 229910052805 deuterium Inorganic materials 0.000 claims description 9
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000005549 heteroarylene group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000006413 ring segment Chemical group 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 4
- OVCXRBARSPBVMC-UHFFFAOYSA-N triazolopyridine Chemical compound C=1N2C(C(C)C)=NN=C2C=CC=1C=1OC=NC=1C1=CC=C(F)C=C1 OVCXRBARSPBVMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 24
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 6
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 239000002184 metal Substances 0.000 description 4
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- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 3
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- 125000005842 heteroatom Chemical group 0.000 description 3
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- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 2
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- DLGZLIXYVSQGOX-UHFFFAOYSA-N 4-[8-[4-(4-tert-butylpiperazin-1-yl)anilino]-[1,2,4]triazolo[1,5-a]pyrazin-5-yl]furan-2-carboxamide Chemical compound C1CN(C(C)(C)C)CCN1C(C=C1)=CC=C1NC(C1=NC=NN11)=NC=C1C1=COC(C(N)=O)=C1 DLGZLIXYVSQGOX-UHFFFAOYSA-N 0.000 description 2
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- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 2
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- HCCNBKFJYUWLEX-UHFFFAOYSA-N 7-(6-methoxypyridin-3-yl)-1-(2-propoxyethyl)-3-(pyrazin-2-ylmethylamino)pyrido[3,4-b]pyrazin-2-one Chemical compound O=C1N(CCOCCC)C2=CC(C=3C=NC(OC)=CC=3)=NC=C2N=C1NCC1=CN=CC=N1 HCCNBKFJYUWLEX-UHFFFAOYSA-N 0.000 description 2
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- UZFGRMDZHBRAPR-UHFFFAOYSA-N 2-(3-chlorophenyl)-4-phenylquinazoline Chemical compound ClC1=CC=CC(C=2N=C3C=CC=CC3=C(C=3C=CC=CC=3)N=2)=C1 UZFGRMDZHBRAPR-UHFFFAOYSA-N 0.000 description 1
- QLYUAISAKGDXCW-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-diphenylpyrimidine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=N1 QLYUAISAKGDXCW-UHFFFAOYSA-N 0.000 description 1
- PGIGQFHBEHJSQN-UHFFFAOYSA-N 2-[4-(3-chlorophenyl)phenyl]-4,6-diphenyl-1,3,5-triazine Chemical compound Clc1cccc(c1)-c1ccc(cc1)-c1nc(nc(n1)-c1ccccc1)-c1ccccc1 PGIGQFHBEHJSQN-UHFFFAOYSA-N 0.000 description 1
- FZMMYHLDBMXKGW-UHFFFAOYSA-N 2-bromo-2-methyl-1h-pyridine Chemical compound CC1(Br)NC=CC=C1 FZMMYHLDBMXKGW-UHFFFAOYSA-N 0.000 description 1
- YPIANBZIVBPMJS-UHFFFAOYSA-N 2-bromo-n,n-diphenylaniline Chemical compound BrC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 YPIANBZIVBPMJS-UHFFFAOYSA-N 0.000 description 1
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- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- DDGPPAMADXTGTN-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 DDGPPAMADXTGTN-UHFFFAOYSA-N 0.000 description 1
- MZVSTDHRRYQFGI-UHFFFAOYSA-N 2-chloro-4-methylpyridine Chemical compound CC1=CC=NC(Cl)=C1 MZVSTDHRRYQFGI-UHFFFAOYSA-N 0.000 description 1
- MVDYXUKNMGWCKS-UHFFFAOYSA-N 2-chloro-4-phenyl-1,3,5-triazine Chemical compound ClC1=NC=NC(C=2C=CC=CC=2)=N1 MVDYXUKNMGWCKS-UHFFFAOYSA-N 0.000 description 1
- SFKMVPQJJGJCMI-UHFFFAOYSA-N 2-chloro-4-phenylquinazoline Chemical compound C=12C=CC=CC2=NC(Cl)=NC=1C1=CC=CC=C1 SFKMVPQJJGJCMI-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- GHDBFGUOBVYEOV-UHFFFAOYSA-N 4-(4-bromophenyl)-2,6-diphenylpyrimidine Chemical compound C1=CC(Br)=CC=C1C1=CC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 GHDBFGUOBVYEOV-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- KFBZANLENFYLEH-UHFFFAOYSA-N 7'-bromo-10-phenylspiro[acridine-9,5'-indeno[1,2-b]pyridine] Chemical compound BrC=1C=C2C3(C=4C(=NC=CC=4)C2=CC=1)C1=CC=CC=C1N(C=1C=CC=CC=13)C1=CC=CC=C1 KFBZANLENFYLEH-UHFFFAOYSA-N 0.000 description 1
- ODUSLVCYHXDFJR-UHFFFAOYSA-N 7'-bromo-10-phenylspiro[acridine-9,9'-indeno[2,1-b]pyridine] Chemical compound BrC1=CC=2C3(C4=NC=CC=C4C=2C=C1)C1=CC=CC=C1N(C=1C=CC=CC=13)C1=CC=CC=C1 ODUSLVCYHXDFJR-UHFFFAOYSA-N 0.000 description 1
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- BTVSZRXAGULHGA-UHFFFAOYSA-N 7-bromospiro[indeno[2,1-b]pyridine-9,9'-xanthene] Chemical compound BrC1=CC2=C(C=C1)C=1C(=NC=CC=1)C21C2=CC=CC=C2OC=2C=CC=CC1=2 BTVSZRXAGULHGA-UHFFFAOYSA-N 0.000 description 1
- WTTDIDHEPMJNAB-UHFFFAOYSA-N BrC1=CC=2C(C3=NC=CC=C3C=2C=C1)(O)C1=C(C=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound BrC1=CC=2C(C3=NC=CC=C3C=2C=C1)(O)C1=C(C=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 WTTDIDHEPMJNAB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- JKHCVYDYGWHIFJ-UHFFFAOYSA-N Clc1nc(nc(n1)-c1ccc(cc1)-c1ccccc1)-c1ccccc1 Chemical compound Clc1nc(nc(n1)-c1ccc(cc1)-c1ccccc1)-c1ccccc1 JKHCVYDYGWHIFJ-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
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- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- LRFVTYWOQMYALW-UHFFFAOYSA-N Xanthine Natural products O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
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- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
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- 235000019270 ammonium chloride Nutrition 0.000 description 1
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- 125000005104 aryl silyl group Chemical group 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 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
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 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
- 230000004927 fusion Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000005283 ground state Effects 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
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- 125000002883 imidazolyl group Chemical group 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
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
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- 239000007924 injection Substances 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
- 239000002346 layers by function Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 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
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FTCFXBBBKDOQJA-UHFFFAOYSA-N n-(pyridin-2-ylmethyl)aniline Chemical compound C=1C=CC=NC=1CNC1=CC=CC=C1 FTCFXBBBKDOQJA-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- VMFMUJZRXZXYAH-UHFFFAOYSA-N n-[5-[[5-chloro-4-[2-[2-(dimethylamino)-2-oxoacetyl]anilino]pyrimidin-2-yl]amino]-4-methoxy-2-(4-methylpiperazin-1-yl)phenyl]prop-2-enamide Chemical compound C=CC(=O)NC=1C=C(NC=2N=C(NC=3C(=CC=CC=3)C(=O)C(=O)N(C)C)C(Cl)=CN=2)C(OC)=CC=1N1CCN(C)CC1 VMFMUJZRXZXYAH-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000002985 plastic film Substances 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
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- LENLQGBLVGGAMF-UHFFFAOYSA-N tributyl([1,2,4]triazolo[1,5-a]pyridin-6-yl)stannane Chemical compound C1=C([Sn](CCCC)(CCCC)CCCC)C=CC2=NC=NN21 LENLQGBLVGGAMF-UHFFFAOYSA-N 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
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940075420 xanthine Drugs 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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Abstract
Description
본 발명은 유기 전계 발광 소자용 재료로서 사용될 수 있는 신규 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescence device and an organic electroluminescence device including the same.
1950년대 베르나소스(Bernanose)의 유기 박막 발광 관측을 시점으로 하여, 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광(electroluminescent, EL) 소자에 대한 연구가 이어져 오다가, 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 전계 발광 소자가 제시되었다. 이후, 고효율, 고수명의 유기 전계 발광 소자를 만들기 위하여, 소자 내 각각의 특징적인 유기물층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다.The electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals in 1965 were followed up with the observation of organic thin film emission from Bernanose in the 1950s. In 1987, Tang The organic light emitting device having a laminated structure in which the hole layer and the functional layer of the light emitting layer are divided. Thereafter, in order to form a high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form in which each organic material layer has been introduced into the device, leading to the development of specialized materials used therefor.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때, 유기물층으로 사용되는 물질은 그 기능에 따라, 발광물질, 정공주입 물질, 정공수송 물질, 전자수송 물질, 전자주입 물질 등으로 분류될 수 있다.In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material and the like depending on its function.
발광 물질은 발광색에 따라 청색, 녹색, 적색 발광 물질과, 보다 나은 천연색을 구현하기 위한 노란색 및 주황색 발광 물질로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도펀트 계를 사용할 수 있다.The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials to realize better natural colors. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material.
도펀트 물질은 유기 물질을 사용하는 형광 도펀트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도펀트로 나눌 수 있다. 이때, 인광 재료의 개발은 이론적으로 형광에 비해 4배까지 발광 효율을 향상시킬 수 있기 때문에, 인광 도펀트 뿐만 아니라 인광 호스트 재료들에 대한 연구도 많이 진행되고 있다.The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescence, the phosphorescent dopant as well as phosphorescent host materials are being studied extensively.
현재까지 정공 주입층, 정공 수송층. 정공 차단층, 전자 수송층 재료로는 NPB, BCP, Alq3 등이 널리 알려져 있으며, 발광층 재료로는 안트라센 유도체들이 보고되고 있다. 특히, 발광층 재료 중 효율 향상 측면에서 장점을 가지고 있는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색(blue), 녹색(green), 적색(red)의 인광 도판트 재료로 사용되고 있으며, 4,4-디카바졸리비페닐(4,4-dicarbazolybiphenyl, CBP)은 인광 호스트 재료로 사용되고 있다.Up to now, hole injecting layer, hole transporting layer. NPB, BCP and Alq 3 are widely known as electron transporting layer materials and anthracene derivatives as light emitting layer materials. Particularly, metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , (acac) Ir (btp) 2 and the like having advantages in terms of efficiency improvement of the light emitting layer material are blue, green, 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent dopant material for red phosphorescent dopants.
그러나 종래의 유기물층 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮아 열적 안정성이 매우 좋지 않기 때문에, 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다. 따라서, 성능이 뛰어난 유기물층 재료의 개발이 요구되고 있다.However, conventional organic material layers are advantageous from the viewpoint of light emitting properties, but their thermal stability is not very good due to their low glass transition temperature, and thus they are not satisfactory in terms of lifetime of the organic electroluminescent device. Therefore, development of an organic layer material having excellent performance is required.
본 발명은 상기한 문제점을 해결하기 위해, 유기 전계 발광 소자의 효율, 수명 및 안정성 등을 향상시킬 수 있는 신규 화합물 및 상기 화합물을 이용한 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems and it is an object of the present invention to provide a novel compound capable of improving the efficiency, lifetime and stability of the organic electroluminescent device and an organic electroluminescent device using the compound.
상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by the following formula (1): < EMI ID =
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
X는 O 또는 N(R1)이고;X is O or N (R < 1 >);
Z1 내지 Z12는 각각 독립적으로 N 또는 C(R2)이나, 상기 Z1 내지 Z12 중 적어도 하나는 N이며;Each of Z 1 to Z 12 is independently N or C (R 2 ), or at least one of Z 1 to Z 12 is N;
m은 0 내지 4의 정수이며;m is an integer from 0 to 4;
Ar1은 하기 화학식 2로 표시되는 치환기이고, 상기 Ar1이 복수 개인 경우 이들은 서로 동일하거나 상이하며;Ar 1 is a substituent represented by the following formula (2), and when a plurality of Ar 1 s are present, they are the same or different;
R1은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;R 1 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
R2는 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고, 상기 R2가 복수 개인 경우 이들은 서로 동일하거나 상이하며;R 2 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R 2 s are the same or different, ;
상기 R1 및 R2의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하며;The alkyl, aryl and heteroaryl groups of R 1 and R 2 are each independently selected from the group consisting of deuterium, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 6 to C 60 aryl, To 60 heteroaryl groups and C 6 to C 60 arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
[화학식 2](2)
상기 화학식 2에서,In Formula 2,
*은 결합이 이루어지는 부분을 의미하고;* Denotes the part where the bond is made;
L1 및 L2는 각각 독립적으로 단일결합, C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며;L 1 and L 2 are each independently selected from the group consisting of a single bond, a C 6 to C 18 arylene group and a heteroarylene group having 5 to 18 nucleus atoms;
R3은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;R 3 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
상기 L1 및 L2의 아릴렌기 및 헤테로아릴렌기와, 상기 R3의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.Wherein L 1, and arylene group of L 2 and a heteroarylene group, an alkyl group of said R 3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C substituted with 6 ~ C over a 60 aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ selected from the aryl group consisting of an amine group in the C 60 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other.
또한, 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 중에서 적어도 하나는 전술한 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.Also, the present invention is an organic electroluminescent device comprising a cathode, a cathode, and at least one organic compound layer interposed between the anode and the cathode, wherein at least one of the organic compound layers of the one or more layers is a compound And an organic electroluminescent device.
본 발명에서의 "알킬"은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있는데, 이에 한정되지 않는다."Alkyl" in the present invention is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl And the like, but are not limited thereto.
본 발명에서의 "알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진, 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있는데, 이에 한정되지 않는다.As used herein, the term "alkenyl" is a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include vinyl, But are not limited to, allyl, isopropenyl, 2-butenyl, and the like.
본 발명에서의 "알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진, 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등이 있는데, 이에 한정되지 않는다.The term "alkynyl" in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include ethynyl, , 2-propynyl, and the like, but are not limited thereto.
본 발명에서의 "아릴"은 단독 고리 또는 2 이상의 고리가 조합된, 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 축합되어 있고, 고리 형성 원자로서 탄소만을 포함(예를 들어, 탄소수는 8 내지 60일 수 있음)하고, 분자 전체가 비-방향족성(non-aromacity)를 갖는 1가 치환기도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴, 플루오레닐 등이 있는데, 이에 한정되지 않는다."Aryl" in the present invention means a monovalent substituent derived from a C6-C60 aromatic hydrocarbon having a single ring or a combination of two or more rings. In addition, it is also possible that two or more rings are condensed with each other and only carbon atoms are contained as ring-forming atoms (for example, the number of carbon atoms may be from 8 to 60), and the monovalent group having a non-aromacity throughout the molecule Substituents may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, and the like.
본 발명에서의 "헤테로아릴"은 핵원자수 5 내지 60개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, P, S 및 Se 중에서 선택된 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합되어 있고, 고리 형성 원자로서 탄소 외에 N, O, P, S 및 Se 중에서 선택된 헤테로 원자를 포함하고, 분자 전체가 비-방향족성(non-aromacity)를 갖는 1가 그룹도 포함하는 것으로 해석된다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리; 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리; 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등이 있는데, 이에 한정되지 않는다."Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein one or more carbons, preferably one to three carbons, of the ring are substituted with a heteroatom selected from N, O, P, S and Se. In addition, it is preferable that two or more rings are pendant or condensed with each other, and include hetero atoms selected from N, O, P, S and Se besides carbon as a ring-forming atom, < / RTI > aromacity). Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. ring; Imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
본 발명에서의 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 5 내지 60개의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있는데, 이에 한정되지 않는다.In the present invention, "aryloxy" means a monovalent substituent represented by RO-, and R represents aryl having 5 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
본 발명에서의 "알킬옥시"는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등이 있는데, 이에 한정되지 않는다.The term "alkyloxy" in the present invention means a monovalent substituent group represented by R'O-, wherein R 'represents 1 to 40 alkyl, and may be linear, branched or cyclic . ≪ / RTI > Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서의 "아릴아민"은 탄소수 6 내지 60개의 아릴로 치환된 아민을 의미한다."Arylamine" in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
본 발명에서의 "시클로알킬"은 탄소수 3 내지 40개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine) 등이 있는데, 이에 한정되지 않는다."Cycloalkyl" in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서의 "헤테로시클로알킬"은 핵원자수 3 내지 40개의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등이 있는데, 이에 한정되지 않는다."Heterocycloalkyl" in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one of the carbons, preferably one to three carbons, S or Se. ≪ / RTI > Examples of such heterocycloalkyls include, but are not limited to, morpholine, piperazine, and the like.
본 발명에서의 "알킬실릴"은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 5 내지 60개의 아릴로 치환된 실릴을 의미한다."Alkylsilyl" in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 60 carbon atoms.
본 발명에서의 "축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.In the present invention, the term "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.
본 발명의 화학식 1로 표시되는 화합물은 열적 안정성 및 발광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물층의 재료로 사용될 수 있다. 특히, 본 발명의 화학식 1로 표시되는 화합물을 인광 호스트 재료로 사용할 경우, 종래의 호스트 재료에 비해 우수한 발광 성능, 낮은 구동전압, 높은 효율 및 장수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.The compound represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, it is possible to produce an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency, and long life time, A full color display panel having improved performance and lifetime can be manufactured.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. 신규 유기 화합물1. New organic compounds
본 발명의 신규 화합물은 하기 화학식 1로 표시될 수 있다:The novel compounds of the present invention can be represented by the following formula
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
X는 O 또는 N(R1)이고;X is O or N (R < 1 >);
Z1 내지 Z12는 각각 독립적으로 N 또는 C(R2)이나, 상기 Z1 내지 Z12 중 적어도 하나는 N이며;Each of Z 1 to Z 12 is independently N or C (R 2 ), or at least one of Z 1 to Z 12 is N;
m은 0 내지 4의 정수이고, 바람직하게는 1 내지 3의 정수이며;m is an integer from 0 to 4, preferably from 1 to 3;
Ar1은 하기 화학식 2로 표시되는 치환기이고, 상기 Ar1이 복수 개인 경우 이들은 서로 동일하거나 상이하며;Ar 1 is a substituent represented by the following formula (2), and when a plurality of Ar 1 s are present, they are the same or different;
R1은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;R 1 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
R2는 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고, 상기 R2가 복수 개인 경우 이들은 서로 동일하거나 상이하며;R 2 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R 2 s are the same or different, ;
상기 R1 및 R2의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하며;The alkyl, aryl and heteroaryl groups of R 1 and R 2 are each independently selected from the group consisting of deuterium, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 6 to C 60 aryl, To 60 heteroaryl groups and C 6 to C 60 arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
[화학식 2] (2)
상기 화학식 2에서,In Formula 2,
*은 결합이 이루어지는 부분을 의미하고;* Denotes the part where the bond is made;
L1 및 L2는 각각 독립적으로 단일결합, C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며;L 1 and L 2 are each independently selected from the group consisting of a single bond, a C 6 to C 18 arylene group and a heteroarylene group having 5 to 18 nucleus atoms;
R3은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;R 3 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
상기 L1 및 L2의 아릴렌기 및 헤테로아릴렌기와, 상기 R3의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.Wherein L 1, and arylene group of L 2 and a heteroarylene group, an alkyl group of said R 3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C substituted with 6 ~ C over a 60 aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ selected from the aryl group consisting of an amine group in the C 60 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other.
본 발명의 상기 화학식 1로 표시되는 화합물은 헤테로원자인 N이 하나 이상 포함된 스파이로[아크리딘-플루오렌]계 모이어티 또는 스파이로[플루오렌-크산텐]계 핵심 코어에 EWG(electron-withdrawing group)과 결합되어, 전기화학적 안정성이 매우 우수하고, 기존의 스파이로[아크리딘-플루오렌]계 모이어티 또는 스파이로[플루오렌-크산텐]계 화합물보다 전자 이동성이 매우 증대되어 특히 우수할 뿐 높은 유리 전이온도 및 열적 안정이 우수하여 청색 발광 효율이 상승되는 특성들을 나타낸다.The compound represented by the formula (1) of the present invention is a compound represented by EWG (electron) in a core of spiro [acridine-fluorene] based moiety or spiro [fluorene-xanthene] based core containing at least one hetero atom, -withdrawing group), the electrochemical stability is excellent, and the electron mobility is greatly increased compared with the existing spiro [acridine-fluorene] based moiety or spiro [fluorene-xanthene] based compound Exhibits properties that are particularly excellent, and are excellent in high glass transition temperature and thermal stability, resulting in an increase in blue light emission efficiency.
이로 인해, 본 발명의 화학식 1로 표시되는 화합물은 전자 수송 능력 및 발광 특성이 우수하기 때문에, 유기 전계 발광 소자의 유기물층인 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나의 재료로 사용될 수 있다. 바람직하게는 발광층, 전자 수송층 및 전자 수송층에 추가로 적층되는 전자수송 보조층 중 어느 하나의 재료, 보다 바람직하게는 전자 수송층 또는 전자 수송 보조층의 재료로 사용될 수 있다. 또한, 전자 수송 보조층의 역할로는 높은 삼중항 에너지를 갖고 있기 때문에 TTF(triplet-triplet fusion) 효과로 인한 우수한 효율 상승을 나타낼 수 있다. 또한, 기본적으로 낮은 HOMO와 높은 LUMO 에너지 레벨로 인하여 넓은 밴드갭을 가지는 물리화학적 성질로 인하여 발광층에서 생성된 엑시톤이 발광층에 인접하는 전자 수송층 또는 정공 수송층으로 확산되는 것을 방지할 수 있다. 발광층 내에서 발광에 기여하는 엑시톤의 수가 증가되어 소자의 발광 효율이 개선될 수 있고, 소자의 내구성 및 안정성이 향상되어 소자의 수명이 효율적으로 증가될 수 있다. 개발된 재료들이 대부분 저전압 구동이 가능하고 분자간 결합이 원활하여 소자 제작 시 무정형의 형태(morphology) 특성이 우수하여 수명이 개선되는 물리적 특징들을 나타낸다.Accordingly, the compound represented by the general formula (1) of the present invention is excellent in electron transporting ability and light emitting property, and therefore, it is preferable that the compound represented by the general formula (1) It can be used as a material. Preferably an electron transporting auxiliary layer laminated on the light emitting layer, the electron transporting layer and the electron transporting layer, more preferably the material of the electron transporting layer or the electron transporting layer. In addition, since the electron transporting layer has high triplet energy, it can exhibit excellent efficiency due to the triplet-triplet fusion (TTF) effect. In addition, due to physico-chemical properties having a broad band gap due to a low HOMO and a high LUMO energy level, it is possible to prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. The number of the excitons contributing to light emission in the light emitting layer can be increased to improve the light emitting efficiency of the device and the durability and stability of the device can be improved and the lifetime of the device can be efficiently increased. Most of the developed materials exhibit physical characteristics that can be driven at low voltage and smooth intermolecular bonding, resulting in excellent amorphous morphology and improved lifetime.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화합물은 하기 화학식 3 내지 10 중 어느 하나로 표시되는 화합물인 것이 전자 수송 능력이 우수하다. 바람직하게는 하기 화학식 3 내지 6, 8 및 9 중 어느 하나로 표시되는 화합물일 수 있으며, 보다 바람직하게는 하기 화학식 3 내지 5, 8 및 9 중 어느 하나로 표시되는 화합물일 수 있다:According to one preferred embodiment of the present invention, the compound is a compound represented by any one of the following formulas (3) to (10). Preferably a compound represented by any one of the following Chemical Formulas 3 to 6, 8 and 9, more preferably a compound represented by any one of Chemical Formulas 3 to 5, 8 and 9:
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
[화학식 8] [Chemical Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Chemical formula 10]
상기 화학식 3 내지 10에서, In the above formulas 3 to 10,
R4 내지 R14는 각각 독립적으로 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고;R 4 to R 14 are each independently selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;
상기 R4 내지 R14의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하며;The alkyl, aryl and heteroaryl groups of R 4 to R 14 are each independently selected from the group consisting of deuterium, a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 6 to C 60 aryl group, To 60 heteroaryl groups and C 6 to C 60 arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
R1, Ar1 및 m 각각은 상기 화학식 1에서 정의된 바와 같다.Each of R 1 , Ar 1 and m is as defined in the above formula (1).
본 발명의 바람직한 한 구현 예에 따르면, 상기 화합물은 하기 화학식 11로 표시되는 화합물인 것이 전자 수송 능력이 우수하다:According to a preferred embodiment of the present invention, the compound is a compound represented by the following general formula (11):
[화학식 11](11)
상기 화학식 11에서,In Formula 11,
X, Z1 내지 Z12 및 Ar1 각각은 상기 화학식 1에서 정의된 바와 같다. X, Z 1 to Z 12 and Ar 1 are each as defined in the above formula (1).
본 발명의 바람직한 한 구현 예에 따르며, 상기 L1 및 L2는 각각 독립적으로 페닐렌기, 비페닐렌기, 나프탈레닐기, 플루오레닐기 및 카바졸릴기로 이루어진 군에서 선택되며,According to a preferred embodiment of the present invention, each of L 1 and L 2 is independently selected from the group consisting of a phenylene group, a biphenylene group, a naphthalenyl group, a fluorenyl group and a carbazolyl group,
상기 L1 및 L2의 페닐렌기, 비페닐렌기, 나프탈레닐기, 플루오레닐기 및 카바졸릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.Wherein L 1 and the phenyl group, a biphenyl of the L 2 group, a naphthyl Frontale group, a fluorenyl group and carbazolyl groups are each independently a heavy hydrogen, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C 6 ~ If C 60 aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ substituted by one substituent at least one selected from the group consisting of an aryl amine of the C 60 or is unsubstituted, substituted by a plurality of substituents, these are They are the same or different.
본 발명의 바람직한 한 구현 예에 따르면, 상기 Ar1은 하기 화학식 12 내지 14 중 어느 하나로 표시되는 치환기일 수 있다:According to a preferred embodiment of the present invention, Ar 1 may be a substituent represented by any of the following formulas 12 to 14:
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
[화학식 14][Chemical Formula 14]
상기 화학식 12 내지 14에서,In the above Formulas 12 to 14,
*은 결합이 이루어지는 부분을 의미하고;* Denotes the part where the bond is made;
R3은 상기 화학식 2에서 정의된 바와 같다.R 3 is as defined in the above formula (2).
본 발명의 바람직한 한 구현 예에 따르면, 상기 R3은 핵원자수 5 내지 60개의 헤테로아릴기인 것이 바람직하고, 보다 바람직하게는 적어도 2개 이상의 N을 포함하는 핵원자수 5 내지 60개의 헤테로아릴기일 수 있다.According to a preferred embodiment of the present invention, R 3 is preferably a heteroaryl group having 5 to 60 nuclear atoms, more preferably 5 to 60 heteroaryl groups containing at least 2 N atoms .
본 발명의 보다 바람직한 한 구현 예에 따르면, 상기 R3은 피리미딘, 피라진, 트리아진, 이미다졸, 벤즈이미다졸, 페난트로이미다졸, 이미다조피리딘, 퀴나졸린 및 트리아졸로피리딘로 이루어진 군에서 선택되며,According to one more preferred embodiment of the present invention, R 3 is selected from the group consisting of pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine And,
상기 R3의 피리미딘, 피라진, 트리아진, 이미다졸, 벤즈이미다졸, 페난트로이미다졸, 이미다조피리딘, 퀴나졸린 및 트리아졸로피리딘은 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다. The pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine of R 3 are each independently selected from deuterium, a C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 6 ~ C 60 aryl group, nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ C is substituted by at least at 60 the group consisting of an aryl amine of the selected one more substituents or being unsubstituted , When they are substituted with a plurality of substituents, they may be the same or different.
본 발명의 보다 바람직한 한 구현 예에 따르면, 상기 R3은 하기 A1 내지 A13 중 어느 하나로 표시되는 치환기일 수 있다:According to one more preferred embodiment of the present invention, R 3 may be a substituent represented by any one of the following Al to A13:
상기 A1 내지 A13에서,In the above-mentioned A1 to A13,
*은 결합이 이루어지는 부분을 의미하고;* Denotes the part where the bond is made;
p는 0 내지 3의 정수이며;p is an integer from 0 to 3;
q는 0 내지 2의 정수이며;q is an integer from 0 to 2;
R15는 C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 상기 R15가 복수 개인 경우 이들은 서로 동일하거나 상이하며;R 15 is selected from the group consisting of C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ with an aryl amine of the C 60 of the R 15 is When plural are the same or different from each other;
R16은 수소, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며;R 16 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having a C 6 to C 60 ;
상기 R15 및 R16의 알킬기, 아릴기, 헤테로아릴기 및 아릴아민기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.The alkyl, aryl, heteroaryl and arylamine groups of R 15 and R 16 are each independently selected from the group consisting of deuterium, a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 6 to C 60 aryl group, A heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having 6 to 60 carbon atoms, and when they are substituted with a plurality of substituents, they are the same as or different from each other.
본 발명의 바람직한 한 구현 예에 따르면, 상기 R15는 C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택될 수 있고, 보다 바람직하게는 C6~C60의 아릴기일 수 있다.According to a preferred embodiment of the present invention, R 15 may be selected from the group consisting of a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms, Preferably a C 6 to C 60 aryl group.
본 발명의 바람직한 한 구현 예에 따르면, 상기 R16은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택될 수 있고, 보다 바람직하게는 C6~C60의 아릴기일 수 있다. According to a preferred embodiment of the present invention, R 16 may be selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms , More preferably a C 6 to C 60 aryl group.
본 발명의 화학식 1로 표시되는 화합물은 하기 화합물로 나타낼 수 있으나 이에 한정되는 것은 아니다:The compounds represented by formula (1) of the present invention can be represented by the following compounds, but are not limited thereto:
본 발명에서 상기 화학식 1로 표시되는 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.In the present invention, the compound represented by Formula 1 may be synthesized according to a general synthetic method (Chem. Rev., 60: 313 (1960), J. Chem. SOC. 4482 (1955) 2457 (1995)). Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.
2. 유기 2. Organic 전계Field 발광 소자 Light emitting element
한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(유기 EL 소자)에 관한 것이다.Another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the general formula (1) according to the present invention described above.
구체적으로, 본 발명은 양극(anode), 음극(cathode), 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 포함한다. 이때, 상기 화합물은 단독 또는 2 이상 혼합되어 사용될 수 있다.Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes Include compounds represented by the above formula (1). At this time, the compounds may be used singly or in combination of two or more.
상기 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광층, 발광 보조층, 수명 개선층, 전자 수송층, 전자수송 보조층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. The at least one organic material layer may be at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, a light emitting auxiliary layer, a life improving layer, an electron transporting layer, an electron transporting auxiliary layer and an electron injecting layer, 1 < / RTI >
본 발명에서 상기 화학식 1로 표시되는 화합물의 스파이로플루오렌크산텐 또는 스파이로아크리딘플루오렌의 모이어티는 기본적으로 전기화학적 안정성이 매우 우수하고, 높은 유리전이온도와 캐리어 수송 능력이 우수하며, 전자 이동성 또한 매우 우수하여 청색 발광 효율이 상승되는 특성들을 나타낸다. 상기 화학식 1로 대표되는 재료들은 핵심 코어와 EWG(electron-withdrawing group)과 결합하는 것이 구조적인 특징적이며, 전자 이동성이 특히 우수할 뿐 높은 유리 전이온도 및 열적 안정이 우수하다. 따라서 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 발광층, 전자 수송층 또는 전자 수송 보조층인 것이 바람직하다.In the present invention, the spiropyroxenic acid or the spiroacridine fluorene moiety of the compound represented by the above formula (1) is basically excellent in electrochemical stability, has a high glass transition temperature and carrier transporting ability, The mobility is also excellent and the blue luminescence efficiency is enhanced. The materials represented by Formula 1 are structurally characteristic to be bonded with core core and EWG (electron withdrawing group), and have excellent electron mobility and excellent high glass transition temperature and thermal stability. Therefore, it is preferable that the organic material layer containing the compound represented by Formula 1 is a light emitting layer, an electron transporting layer, or an electron transporting supporting layer.
본 발명의 일례에 따르면, 유기 전계 발광 소자의 발광층은 호스트 재료를 포함할 수 있는데, 이때 호스트 재료로서 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 이와 같이, 상기 화학식 1로 표시되는 화합물을 유기 전계 발광 소자의 발광층 재료, 바람직하게는 녹색의 인광 호스트로 포함할 경우, 발광층에서 정공과 전자의 결합력이 높아지기 때문에, 유기 전계 발광 소자의 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등이 향상될 수 있다.According to an embodiment of the present invention, the light emitting layer of the organic electroluminescent device may include a host material, which may include a compound represented by the above formula (1) as a host material. Thus, when the compound represented by Formula 1 is incorporated as a light emitting layer material of an organic electroluminescent device, preferably a green phosphorescent host, the bonding strength between holes and electrons in the light emitting layer increases, Efficiency and power efficiency), lifetime, luminance and driving voltage, etc., can be improved.
전술한 본 발명에 따른 유기 전계 발광 소자의 구조는 특별히 한정되지 않으며, 예컨대 기판, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 상기 발광층과 전자 수송층 사이에는 전자 수송 보조층이 추가로 적층될 수 있고, 상기 전자수송층 위에는 전자 주입층이 추가로 적층될 수 있다. 본 발명에서 상기 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 수송 보조층 및 전자 주입층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 포함할 수 있고, 바람직하게는 발광층, 전자 수송층 또는 전자 수송 보조층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. The structure of the organic electroluminescent device according to the present invention is not particularly limited and may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode are sequentially stacked. At this time, an electron transporting auxiliary layer may be further laminated between the light emitting layer and the electron transporting layer, and an electron injection layer may further be laminated on the electron transporting layer. In the present invention, at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, the electron transporting auxiliary layer, and the electron injecting layer may include the compound represented by the above Formula 1, And the transporting auxiliary layer may include the compound represented by the above formula (1).
또, 본 발명의 유기 전계 발광 소자의 구조는 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층될 뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.In addition, the structure of the organic electroluminescent device of the present invention may be a structure in which not only an anode, one or more organic compound layers and a cathode are sequentially laminated but also an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic compound layer.
본 발명의 유기 전계 발광 소자는 상기 유기물층 중 적어도 하나 이상(예컨대, 전자 수송층 또는 전자 수송 보조층)이 상기 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 다른 유기물층 및 전극을 형성하여 제조될 수 있다.The organic electroluminescent device of the present invention can be formed by using a material known in the art (for example, an electron transport layer or an electron transporting auxiliary layer) such that at least one or more of the organic material layers And forming other organic layers and electrodes using the method.
상기 유기물층은 진공 증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이에 한정되지 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, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등이 사용될 수 있다.The substrate usable in the present invention is not particularly limited, and a silicon wafer, quartz, a glass plate, a metal plate, a plastic film and a sheet can be used.
또, 양극 물질로는 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 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등이 있으나, 이에 한정되지는 않는다.Examples of the positive electrode 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), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.
또, 음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이에 한정되지는 않는다.The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or an alloy thereof; And multi-layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.
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 examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[[ 준비예Preparation Example 1] Core 1의 합성 1] Synthesis of Core 1
7-7- 브로모스파이로[인데노[2,1-b]Bromo spiro [indeno [2,1-b] 피리딘-9,9'-크산텐]의 합성Synthesis of pyridine-9,9'-xanthene]
7-브로모-9H-인데노[2,1-b]피리딘-9-온 30 g (0.12 mol)과 페놀 108.6 g (1.15 mol)에 메탄설폰산 30 mL (0.46 mol)를 가하였다. 혼합액을 120℃에서 12시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 정제수 300 mL로 반응을 종결하였다. 혼합액을 CH2Cl2 1.0 L로 추출한 후, 분리한 유기층을 포화탄산칼슘 500 mL로 중화하고, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 31.4 g (수율 66%)을 얻었다.30 mL (0.46 mol) of methanesulfonic acid was added to 30 g (0.12 mol) of 7-bromo-9H-indeno [2,1- b] pyridin-9-one and 108.6 g (1.15 mol) of phenol. The mixture was heated to 120 DEG C for 12 hours under reflux. The reaction mixture was cooled to room temperature and the reaction was terminated with 300 mL of purified water. The mixture was extracted with 1.0 L of CH 2 Cl 2 , and the separated organic layer was neutralized with 500 mL of saturated calcium carbonate and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 31.4 g (yield 66%) of the desired compound.
1H-NMR (in CDCl3) : δ 8.35 (d, 1H), 7.83 (d, 1H), 7.60 (d, 1H), 7.40 (t, 1H), 7.29 (d, 1H), 7.25 (m, 4H), 7.15 (d, 1H), 6.77 (t, 2H), 6.40 (d, 2H) 1 H-NMR (in CDCl 3 ): δ 8.35 (d, 1H), 7.83 (d, 1H), 7.60 (d, 1H), 7.40 (t, 1H), 7.29 (d, 1H), 7.25 (m, 4H), 7.15 (d, IH), 6.77 (t, 2H), 6.40 (d, 2H)
[LCMS] : 412[LCMS]: 412
[[ 준비예Preparation Example 2] 7-(4,4,5,5- 2] 7- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)스파이로[Yl) spiro [ 인데It is 노[2,1-b]피리딘-9,9'-크산텐]의 합성Ylo [2,1-b] pyridine-9,9'-xanthene]
상기 <준비예 1>에서 합성된 7-브로모스파이로[인데노[2,1-b]피리딘-9,9'-크산텐] 31.0 g (75.2 mmol)과 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-비(1,3,2-디옥사보로란) 22.9 g (90.2 mmol)에 디옥산 600 mL를 가하였다. 다음, Pd(dppf)Cl2 3.1 g (3.8 mmol)와 KOAc 22.1 g (226 mmol)을 첨가한 후 130 에서 3시간 동안 가열환류하였다. 그 다음, 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시키고, E.A 1.0 L로 추출하고, 증류수로 세척하였다. 이후, 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 26.9 g (수율 78%)을 얻었다.31.0 g (75.2 mmol) of 7-bromospiro [indeno [2,1-b] pyridine-9,9'-xanthene] synthesized in Preparation Example 1 and 4,4,4 ' Dioxane was added to 22.9 g (90.2 mmol) of 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane). Then 3.1 g (3.8 mmol) of Pd (dppf) Cl 2 and 22.1 g (226 mmol) of KOAc were added and the mixture was heated to reflux at 130 for 3 hours. Then, the reaction solution was cooled to room temperature and 500 mL of ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The reaction solution was extracted with 1.0 L of EA and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 26.9 g (yield 78%) of the desired compound.
[LCMS] : 459[LCMS]: 459
[[ 준비예Preparation Example 3] Core 2의 합성 3] Synthesis of Core 2
7-7- 브로모스파이로[인데노[1,2-b]Bromo-spiro [indeno [1,2-b] 피리딘-5,9'-크산텐]의 합성Pyridine-5,9'-xanthene]
상기 [준비예 1]과 동일한 과정을 수행하여 Core 2의 구조이성질체에 해당하는 목적 화합물 32.3 g (68%)을 얻었다.The same procedure as in [Preparation Example 1] was conducted to obtain 32.3 g (68%) of the target compound corresponding to the structural isomer of Core 2.
[LCMS] : 412[LCMS]: 412
[[ 준비예Preparation Example 4] 7-(4,4,5,5- 4] 7- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)스파이로[Yl) spiro [ 인데노[1,2-b]피리딘Indeno [l, 2-b] pyridine -5,9'-크산텐]의 합성-5,9'-xanthene]
상기 [준비예 2]와 동일한 과정을 수행하여 준비예 2의 구조이성질체에 해당하는 목적 화합물 18,7 g (76%)을 얻었다.The procedure of Preparation Example 2 was repeated to obtain 18.7 g (76%) of the target compound corresponding to the structural isomer of Preparation Example 2.
[LCMS] : 459[LCMS]: 459
[[ 준비예Preparation Example 5] Core 3의 합성 5] Synthesis of Core 3
<단계 1> 7-<Step 1> 7- 브로모Bromo -9-(2-(-9- (2- ( 디페닐아미노Diphenylamino )페닐)-9H-) Phenyl) -9H- 인데노[2,1-b]피리딘Indeno [2,1-b] pyridine -9-올의 합성-9-ol
2-브로모-N,N-디페닐아닐린 30 g (92.5 mmol)에 THF 500 mL를 가하였다. 반응액의 온도를 -78 ℃로 낮추고 n-BuLi 2.5M 용액 42.1 mL (105 mmol)를 1시간에 걸쳐 천천히 적가하였다. 다음, 7-브로모-9H-인데노[2,1-b]피리딘-9-온 25.1 g (102 mmol)을 THF 500 mL에 용해시켜 반응액에 천천히 첨가한 후 동일 온도에서 1시간 동안 교반하고, 상온에서 24시간 동안 추가로 교반하였다. 그 다음, 반응액에 정제수 500 mL를 투입하여 반응을 종결시킨 후 E.A 1.5 L로 추출하고, 증류수로 세척하였다. 이후, 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 33.2 g (수율 75%)을 얻었다.To 30 g (92.5 mmol) of 2-bromo-N, N-diphenyl aniline was added 500 mL of THF. The temperature of the reaction solution was lowered to -78 ° C, and 42.1 mL (105 mmol) of a 2.5M solution of n-BuLi was slowly added dropwise over 1 hour. Then 25.1 g (102 mmol) of 7-bromo-9H-indeno [2,1-b] pyridin-9-one was dissolved in 500 mL of THF and slowly added to the reaction solution. And further stirred at room temperature for 24 hours. Then, 500 mL of purified water was added to the reaction solution to terminate the reaction, and the mixture was extracted with 1.5 L of EA and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 33.2 g (yield 75%) of the target compound.
[LCMS] : 505[LCMS]: 505
<단계 2> 7'-≪ Step 2 > 브로모Bromo -10-페닐-10H-스파이로[아크리딘-9,9'--10-phenyl-10H-spiro [acridine-9,9'- 인데노[2,1-b]피리딘Indeno [2,1-b] pyridine ]의 합성] Synthesis of
7-브로모-9-(2-(디페닐아미노)페닐)-9H-인데노[2,1-b]피리딘-9-올 33.0 g (65.3 mmol)에 AcOH 330 mL와 conc.HCl 3 방울을 가하였다. 반응액을 100℃에서 2시간 동안 가열 환류하였다. 상온으로 온도를 냉각하고, 반응액에 정제수 500 mL를 투입하여 반응을 종결시킨 후 생성된 고체를 감압여과하고 훈풍 건조하여 목적 화합물 28.6 g (수율 90%)을 얻었다.To 33.0 g (65.3 mmol) of 7-bromo-9- (2- (diphenylamino) phenyl) -9H-indeno [2,1- b] pyridin-9- ol were added 330 mL of AcOH and 3 drops Were added. The reaction solution was heated to reflux at 100 ° C for 2 hours. After the reaction mixture was cooled to room temperature, 500 mL of purified water was added to the reaction mixture to terminate the reaction. The resultant solid was filtered under reduced pressure and dried under a humid atmosphere to obtain the desired compound (28.6 g, yield 90%).
[LCMS] : 487[LCMS]: 487
[[ 준비예Preparation Example 6] 10-페닐-7'-(4,4,5,5- 6] 10-phenyl-7 '- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]의 합성Yl) -10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine]
7-브로모스파이로[인데노[2,1-b]피리딘-9,9'-크산텐] 대신 7'-브로모-10-페닐-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]을 사용한 것을 제외하고는 [준비예 2]와 동일한 과정을 수행하여 목적 화합물 22.1 g (수율 72%)을 얻었다.Bromo-10-phenyl-10H-spiro [acridine-9,9 ' -methanol instead of 7-bromospiro [indeno [2,1- - indeno [2,1-b] pyridine] was used in place of [N, N-dimethylformamide] in the same manner as in [Preparation Example 2] to obtain 22.1 g (yield 72%) of the desired compound.
[LCMS] : 534[LCMS]: 534
[[ 준비예Preparation Example 7] Core 4의 합성 7] Synthesis of Core 4
<단계 1> 7-<Step 1> 7- 브로모Bromo -5-(2-(-5- (2- ( 디페닐아미노Diphenylamino )페닐)-5H-) Phenyl) -5H- 인데노[1,2-b]피리딘Indeno [l, 2-b] pyridine -5-올의 합성Synthesis of 5-ol
상기 [준비예 5]의 단계 1과 동일한 과정을 수행하여 준비예 5의 구조이성질체에 해당하는 목적 화합물 20.5 g (72%)을 얻었다.The procedure of Step 1 of [Preparation Example 5] was repeated to obtain 20.5 g (72%) of the target compound corresponding to the structural isomer of Preparation Example 5. [
[LCMS] : 505[LCMS]: 505
<단계 2> 7'-≪ Step 2 > 브로모Bromo -10-페닐-10H-스파이로[아크리딘-9,5'--10-phenyl-10H-spiro [acridine-9,5'- 인데노[1,2-b]피리딘Indeno [l, 2-b] pyridine ]의 합성] Synthesis of
상기 [준비예 5]의 단계 2와 동일한 과정을 수행하여 준비예 5의 구조이성질체에 해당하는 목적 화합물 20.5 g (72%)을 얻었다.The procedure of Step 2 of [Preparation Example 5] was repeated to obtain 20.5 g (72%) of the target compound corresponding to the structural isomer of Preparation Example 5. [
[LCMS] : 487[LCMS]: 487
[[ 준비예Preparation Example 8] 10-페닐-7'-(4,4,5,5- 8] 10-phenyl-7 '- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]의 합성Yl) -10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine]
7-브로모스파이로[인데노[2,1-b]피리딘-9,9'-크산텐] 대신 7'-브로모-10-페닐-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]을 사용한 것을 제외하고는 [준비예 2]와 동일한 과정을 수행하여 목적 화합물 14.5 g (수율 65%)을 얻었다.Bromo-10-phenyl-10H-spiro [acridine-9,5 '] pyridine-9,9'-xanthene was used instead of 7-bromospiro [indeno [ - indeno [1, 2-b] pyridine] was used in place of 2-bromoaniline to give the title compound (14.5 g, yield 65%).
[LCMS] : 534[LCMS]: 534
[[ 준비예Preparation Example 9] Core 9] Core 5 의5 of 합성 synthesis
2-2- 브로모스파이로[플루오렌-9,10'-피라노Bromospyro [fluorene-9,10'-pyrano [3,2-[3,2- c:5c: 5 ,6-c'], 6-c '] 디피리딘Dipyridine ]의 합성] Synthesis of
페놀 대신 4-하이드록시피리딘을 사용한 것을 제외하고는 [준비예 1]과 동일한 과정을 수행하여 목적 화합물 13.5 g (수율 48%)을 얻었다.The procedure of Preparation Example 1 was repeated except that 4-hydroxypyridine was used instead of phenol to obtain 13.5 g (yield: 48%) of the desired compound.
[LCMS] : 413[LCMS]: 413
[[ 준비예Preparation Example 10] 2-(4,4,5,5- 10] 2- (4,4,5,5- 테트라메틸Tetramethyl -1,3,2--1,3,2- 디옥사보로란Dioxaborolane -2-일)스파이로[Yl) spiro [ 플루오렌Fluorene -9,10'-피라노[3,2-c:5,6-c']디피리딘]의 합성-9,10'-pyrano [3,2-c: 5,6-c '] dipyridine]
7-브로모스파이로[인데노[2,1-b]피리딘-9,9'-크산텐] 대신 2-브로모스파이로[플루오렌-9,10'-피라노[3,2-c:5,6-c']디피리딘]을 사용한 것을 제외하고는 [준비예 2]와 동일한 과정을 수행하여 목적 화합물 9.8 g (수율 52%)을 얻었다.Bromopyrrolo [9,10'-pyrano [3,2-c] pyridine-9,9'-xanthene was used instead of 7-bromospiro [indeno [2,1- : 5,6-c '] dipyridine] was used in place of [N, N-dimethylformamide], to obtain 9.8 g (yield 52%) of the desired compound.
[LCMS] : 460[LCMS]: 460
[[ 합성예Synthetic example 1] 화합물 1의 합성 1] Synthesis of Compound 1
준비예 1의 Core 1 5.0 g (12.1 mmol)과 2-클로로-4,6-디페닐-1,3,5-트리아진 4.9 g (18.2 mmol)에 DMF 100 mL를 가하였다. 60% NaH 0.97g (24.3 mmol)을 반응액에 첨가하였다. 상온에서 12시간 동안 교반 후 정제수 100 mL를 가하여 반응을 종결하였다. 혼합액을 E.A 300 mL로 추출한 후, 증류수로 2회 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 4.2 g (수율 62%)을 얻었다.To 5.0 g (12.1 mmol) of Core 1 of Preparation Example 1 and 4.9 g (18.2 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine were added 100 mL of DMF. 0.97 g (24.3 mmol) of 60% NaH was added to the reaction solution. After stirring at room temperature for 12 hours, 100 mL of purified water was added to terminate the reaction. The mixture was extracted with 300 mL of EA and washed twice with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure and purified by silica gel column chromatography to obtain 4.2 g (yield 62%) of the target compound.
[LCMS] : 564[LCMS]: 564
[[ 합성예Synthetic example 2] 화합물 6의 합성 2] Synthesis of Compound 6
준비예 2의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐] 7.0 g (15.2 mmol)과 2-클로로-4-페닐퀴나졸린 4.8 g (19.8 mmol)에 디옥산 200 mL, H2O 50 mL를 가하였다. Pd(PPh3)4 0.88 g (0.8 mmol), K2CO3 6.3 g (45.7 mmol)을 첨가 후 120℃에서 6시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 정제수 500 mL로 반응을 종결하였다. 혼합액을 E.A 1.0 L로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 4.3 g (수율 52%)을 얻었다.Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- 9'- xanthene] was added 7.0 g (15.2 mmol) and 2-chloro-4-phenyl-quinazoline 4.8 g of dioxane, 200 mL, H 2 O 50 mL in (19.8 mmol). Pd (PPh 3) 4 0.88 g (0.8 mmol), K 2 CO 3 6.3 g After the addition of (45.7 mmol) was heated to reflux at 120 ℃ 6 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of purified water. The mixture was extracted with 1.0 L of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and purified by silica gel column chromatography to obtain the desired compound (4.3 g, yield 52%).
[LCMS] : 537[LCMS]: 537
[[ 합성예Synthetic example 3] 화합물 7의 합성 3] Synthesis of Compound 7
준비예 2의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-브로모-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.8 g (수율 45%)을 얻었다.Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- The same procedure as in [Synthesis Example 2] was repeated except for using 2-bromo-6-methyl-9'-xanthene and 2-bromo-6,8-diphenyl- [1,2,4] triazolo [ To obtain 3.8 g of the desired compound (yield: 45%).
[LCMS] : 602[LCMS]: 602
[[ 합성예Synthetic example 4] 화합물 15의 합성 4] Synthesis of Compound 15
준비예 2의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 4-([1,1'-비페닐]-4-일)-6-(3-브로모페닐)-2-페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 2.9 g (수율 53%)을 얻었다.Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (3-bromophenyl) -2-phenylpyrimidine was used instead of 4 - ([1,1'-biphenyl] ] To obtain the objective compound (2.9 g, yield 53%).
[LCMS] : 715[LCMS]: 715
[[ 합성예Synthetic example 5] 화합물 17의 합성 5] Synthesis of Compound 17
준비예 2의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 4-([1,1'-비페닐]-4-일)-6-(4-브로모페닐)-2-페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.5 g (수율 40%)을 얻었다.Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (4-bromophenyl) -2-phenylpyrimidine was used instead of 4 - ([1,1'-biphenyl] ], 3.5 g (yield 40%) of the desired compound was obtained.
[LCMS] : 715[LCMS]: 715
[[ 합성예Synthetic example 6] 화합물 21의 합성 6] Synthesis of Compound 21
준비예 2 의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-(4-클로로페닐)-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.5 g (수율 34%)을 얻었다.Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthine] and 2- (4-chlorophenyl) -6,8-diphenyl- [1,2,4] triazolo [1,5- a] pyridine were used in place of [ (Yield: 34%) of the target compound.
[LCMS] : 678[LCMS]: 678
[[ 합성예Synthetic example 7] 화합물 22의 합성 7] Synthesis of Compound 22
준비예 2 의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-(3'-클로로-[1,1'-비페닐]-3-일)-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.4 g (수율 54%)을 얻었다.Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthene] and 2- (3'-chloro- [1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5- Example 2] to obtain 4.4 g of the desired compound (yield: 54%).
[LCMS] : 716[LCMS]: 716
[[ 합성예Synthetic example 8] 화합물 24의 합성 8] Synthesis of Compound 24
준비예 2 의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-(3'-클로로-[1,1'-비페닐]-4-일)-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.2 g (수율 48%)을 얻었다. Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthene] and 2- (3'-chloro- [1,1'-biphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine was used Example 2] to obtain the object compound (4.2 g, yield: 48%).
[LCMS] : 716[LCMS]: 716
[[ 합성예Synthetic example 9] 화합물 28의 합성 9] Synthesis of Compound 28
준비예 2 의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 4-(3'-클로로-[1,1'-비페닐]-3-일)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 6.0 g (수율 45%)을 얻었다. Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthan] and 4- (3'-chloro- [1,1'-biphenyl] -3-yl) -2,6-diphenylpyrimidine were used in place of [ To obtain 6.0 g of the desired compound (yield: 45%).
[LCMS] : 715[LCMS]: 715
[[ 합성예Synthetic example 10] 화합물 32의 합성 10] Synthesis of Compound 32
준비예 2의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-([1,1'-비페닐]-4-일)-4-(4'-클로로-[1,1'-비페닐]-3-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.1 g (수율 54%)을 얻었다. Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (4'-chloro-1,1'-biphenyl-3-yl) -6- Phenyl-1,3,5-triazine was used, 3.1 g (yield 54%) of the title compound was obtained by carrying out the same procedure as in [Synthesis Example 2].
[LCMS] : 792[LCMS]: 792
[[ 합성예Synthetic example 11] 화합물 39의 합성 11] Synthesis of Compound 39
준비예 2 의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[2,1-b]피리딘-9,9'-크산텐]과 2-(3'-클로로-[1,1'-비페닐]-3-일)-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.0 g (수율 52%)을 얻었다. Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- [1,1'-biphenyl] -3-yl) -6,8-diphenyl- [1,2,4] triazolo [1,5- a] Pyridine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (4.0 g, yield 52%).
[LCMS] : 754[LCMS]: 754
[[ 합성예Synthetic example 12] 화합물 44의 합성 12] Synthesis of Compound 44
준비예 3의 7-브로모스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 2-([1,1'-비페닐]-4-일)-4-클로로-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 5.8 g (수율 43%)을 얻었다. Biphenyl-5,9'-xanthene] and 2 - ([1,1'-biphenyl] -4-yl) -4 -Chloro-6-phenyl-1,3,5-triazine was used in place of 2-chloro-6-phenyl-1,3,5-triazine in the same manner as in [Synthesis Example 1] to obtain the desired compound (5.8 g, yield 43%).
[LCMS] : 640[LCMS]: 640
[[ 합성예Synthetic example 13] 화합물 53의 합성 13] Synthesis of Compound 53
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 4-(4-브로모페닐)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.3 g (수율 49%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- 3.3 g (yield: 49%) of the desired compound was obtained by carrying out the same processes as in [Synthesis Example 2] except that 4- (4-bromophenyl) ).
[LCMS] : 639[LCMS]: 639
[[ 합성예Synthetic example 14] 화합물 58의 합성 14] Synthesis of Compound 58
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 2-(3-클로로페닐)-4-페닐퀴나졸린을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.4 g (수율 40%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- (40%) was obtained by carrying out the same processes as in [Synthesis Example 2] except that 2- (3-chlorophenyl) -4'-xanthene and 2- (3-chlorophenyl) -4-phenylquinazoline were used.
[LCMS] : 613[LCMS]: 613
[[ 합성예Synthetic example 15] 화합물 67의 합성 15] Synthesis of Compound 67
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 2-(3'-클로로-[1,1'-비페닐]-4-일)-4,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 7.2 g (수율 60%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- Synthesis Example 2] was repeated except that 9'-xanthene and 2- (3'-chloro- [1,1'-biphenyl] -4-yl) -4,6-diphenylpyrimidine were used. The same procedure was followed to obtain 7.2 g of the title compound (yield: 60%).
[LCMS] : 715[LCMS]: 715
[[ 합성예Synthetic example 16] 화합물 71의 합성 16] Synthesis of Compound 71
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 2-([1,1'-비페닐]-4-일)-4-(3'-클로로-[1,1'-비페닐]-3-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.6 g (수율 42%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- Biphenyl-3-yl) -6- (4-methylpiperidin-1-yl) Phenyl-1,3,5-triazine was used in place of the compound obtained in Synthesis Example 1 to obtain 5.6 g (yield: 42%) of the desired compound.
[LCMS] : 792[LCMS]: 792
[[ 합성예Synthetic example 17] 화합물 74의 합성 17] Synthesis of Compound 74
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 4-([1,1'-비페닐]-4-일)-6-(3'-클로로-[1,1'-비페닐]-3-일)-2-페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.9 g (수율 50%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- 4'-yl) -6- (3'-chloro- [1,1'-biphenyl] -3-yl) -2- Phenylpyrimidine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (4.9 g, yield 50%).
[LCMS] : 791[LCMS]: 791
[[ 합성예Synthetic example 18] 화합물 78의 합성 18] Synthesis of Compound 78
준비예 4의 7-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[인데노[1,2-b]피리딘-5,9'-크산텐]과 2-(4'-클로로-[1,1'-비페닐]-3-일)-4-페닐퀴나졸린을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.0 g (수율 59%)을 얻었다. Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- The same procedure as in [Synthesis Example 2] was carried out except that 9'-xanthene was used and 2- (4'-chloro - [1,1'-biphenyl] -3-yl) -4-phenylquinazoline was used To obtain 3.0 g of the objective compound (yield: 59%).
[LCMS] : 689[LCMS]: 689
[[ 합성예Synthetic example 19] 화합물 81의 합성 19] Synthesis of Compound 81
준비예 5의 7'-브로모-10-페닐-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-클로로-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 2.6 g (수율 41%)을 얻었다. Synthesis of 7'-bromo-10-phenyl-10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine] of Preparation Example 5 and 2-chloro-4,6- -1,3,5-triazine was used in place of 2-chloro-4-methylpyridine, the target compound (2.6 g, yield: 41%) was obtained in the same manner as in [Synthesis Example 1].
[LCMS] : 639[LCMS]: 639
[[ 합성예Synthetic example 20] 화합물 91의 합성 20] Synthesis of Compound 91
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-(4-브로모페닐)-4,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.5 g (수율 44%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 2- (4-bromophenyl) -4,6-diphenylpyrimidine were used in place of [ To obtain 5.5 g of the desired compound (yield: 44%).
[LCMS] : 714[LCMS]: 714
[[ 합성예Synthetic example 21] 화합물 94의 합성 21] Synthesis of Compound 94
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-([1,1'-비페닐]-4-일)-4-(3-브로모페닐)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.0 g (수율 52%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- (3-bromophenyl) -6-phenyl-1, 9'-indeno [2,1-b] pyridine] and 2- The same procedure as in [Synthesis Example 2] was conducted except that 3,5-triazine was used to obtain the desired compound (4.0 g, yield 52%).
[LCMS] : 791[LCMS]: 791
[[ 합성예Synthetic example 22] 화합물 99의 합성 22] Synthesis of compound 99
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-(4-클로로페닐)-4-페닐퀴나졸린을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 2.2 g (수율 65%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- The procedure was the same as in [Synthesis Example 2], except that 2-bromo-2-methylpyridine, 9'-indeno [2,1- g (yield: 65%).
[LCMS] : 688[LCMS]: 688
[[ 합성예Synthetic example 23] 화합물 102의 합성 23] Synthesis of Compound 102
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-(3'-클로로-[1,1'-비페닐]-3-일)-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.3 g (수율 40%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 2- (3'-chloro- [1,1'- biphenyl] The procedure of Synthesis Example 2 was repeated except that 5-triazine was used to obtain 5.3 g of the desired compound (yield: 40%).
[LCMS] : 791[LCMS]: 791
[[ 합성예Synthetic example 24] 화합물 110의 합성 24] Synthesis of compound 110
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 4-(3'-클로로-[1,1'-비페닐]-4-일)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.2 g (수율 35%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 4- (3'-chloro- [1,1'- biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was carried out to obtain 4.2 g of the desired compound (yield: 35%).
[LCMS] : 790[LCMS]: 790
[[ 합성예Synthetic example 25] 화합물 116의 합성 25] Synthesis of Compound 116
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 4-([1,1'-비페닐]-4-일)-6-(3'-클로로-[1,1'-비페닐]-4-일)-2-페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.2 g (수율 46%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1- b] pyridine] and 4 - ([1,1'-biphenyl] -4-yl) -6- (3'-chloro- [ ] -4-yl) -2-phenylpyrimidine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (5.2 g, yield: 46%).
[LCMS] : 867[LCMS]: 867
[[ 합성예Synthetic example 26] 화합물 120의 합성 26] Synthesis of Compound 120
준비예 6의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,9'-인데노[2,1-b]피리딘]과 2-(3'-클로로-[1,1'-비페닐]-4-일)-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.2 g (수율 46%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1- b] pyridine] and 2- (3'-chloro- [1,1'- biphenyl] -4- yl) -6,8- , 4] triazolo [l, 5-a] pyridine was used in place of 2-pyridylmethylaniline to obtain 5.2 g (yield 46%) of the desired compound.
[LCMS] : 830[LCMS]: 830
[[ 합성예Synthetic example 27] 화합물 121의 합성 27] Synthesis of Compound 121
준비예 7의 7'-브로모-10-페닐-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]과 2-클로로-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 3.7 g (수율 45%)을 얻었다. Synthesis of 7'-bromo-10-phenyl-10H-spiro [acridine-9,5'-indeno [1,2- b] pyridine] of Preparation Example 7 and 2-chloro-4,6- -1,3,5-triazine was used in place of 1,3,5-triazine, the procedure of Synthesis Example 1 was repeated to obtain 3.7 g of the desired compound (yield: 45%).
[LCMS] : 639[LCMS]: 639
[[ 합성예Synthetic example 28] 화합물 130의 합성 28] Synthesis of Compound 130
준비예 8의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]과 2-(3-브로모페닐)-4,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.2 g (수율 46%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (3-bromophenyl) -4,6-diphenylpyrimidine were used in place of [ To obtain 5.2 g of the desired compound (yield: 46%).
[LCMS] : 714[LCMS]: 714
[[ 합성예Synthetic example 29] 화합물 151의 합성 29] Synthesis of Compound 151
준비예 8의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]과 2-(4-클로로페닐)-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 4.7 g (수율 54%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (4-chlorophenyl) -6,8-diphenyl- [1,2,4] triazolo [ The same procedure as in [Synthesis Example 2] was repeated to obtain the desired compound (4.7 g, yield: 54%).
[LCMS] : 753[LCMS]: 753
[[ 합성예Synthetic example 30] 화합물 152의 합성 30] Synthesis of compound 152
준비예 8의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]과 2-(3'-클로로-[1,1'-비페닐]-3-일)-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.3 g (수율 49%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (3'-chloro- [1,1'-biphenyl] The procedure of Synthesis Example 2 was repeated except that 5-triazine was used to obtain 3.3 g of the desired compound (yield 49%).
[LCMS] : 791[LCMS]: 791
[[ 합성예Synthetic example 31] 화합물 160의 합성 31] Synthesis of Compound 160
준비예 8의 10-페닐-7'-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-10H-스파이로[아크리딘-9,5'-인데노[1,2-b]피리딘]과 4-(3'-클로로-[1,1'-비페닐]-4-일)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.2 g (수율 41%)을 얻었다. Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 4- (3'-chloro- [1,1'-biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was conducted to obtain 5.2 g of the desired compound (yield: 41%).
[LCMS] : 790[LCMS]: 790
[[ 합성예Synthetic example 32] 화합물 166의 합성 32] Synthesis of Compound 166
준비예 10의 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[플루오렌-9,10'-피라노[3,2-c:5,6-c']디피리딘]과 4-(4-브로모페닐)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 7.7 g (수율 67%)을 얻었다. Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 4- (4-bromophenyl) -2,6-diphenylpyrimidine were used in place of [ 7.7 g (yield 67%) of the desired compound was obtained.
[LCMS] : 640[LCMS]: 640
[[ 합성예Synthetic example 33] 화합물 173의 합성 33] Synthesis of Compound 173
준비예 10의 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[플루오렌-9,10'-피라노[3,2-c:5,6-c']디피리딘]과 2-(3-클로로페닐)-6,8-디페닐-[1,2,4]트리아졸로[1,5-a]피리딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.4 g (수율 49%)을 얻었다. Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c] 5,6-c '] dipyridine and 2- (3-chlorophenyl) -6,8-diphenyl- [l, 2,4] triazolo [ The procedure of Synthesis Example 2 was followed except that 5.4 g (yield 49%) of the desired compound was obtained.
[LCMS] : 679[LCMS]: 679
[[ 합성예Synthetic example 34] 화합물 175의 합성 34] Synthesis of Compound 175
준비예 10의 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[플루오렌-9,10'-피라노[3,2-c:5,6-c']디피리딘]과 2-(3'-클로로-[1,1'-비페닐]-3-일)-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 3.1 g (수율 59%)을 얻었다. Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 2- (3'-chloro- [1,1'-biphenyl] -Triazine was used, 3.1 g (yield: 59%) of the desired compound was obtained by carrying out the same procedure as in [Synthesis Example 2].
[LCMS] : 717[LCMS]: 717
[[ 합성예Synthetic example 35] 화합물 183의 합성 35] Synthesis of compound 183
준비예 10의 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)스파이로[플루오렌-9,10'-피라노[3,2-c:5,6-c']디피리딘]과 4-(3'-클로로-[1,1'-비페닐]-4-일)-2,6-디페닐피리미딘을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 2.7 g (수율 55%)을 얻었다. Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 4- (3'-chloro- [1,1'-biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was repeated to obtain 2.7 g of the desired compound (yield: 55%).
[LCMS] : 716[LCMS]: 716
[[ 실시예Example 1 내지 15] 청색 유기 1 to 15] blue organic 전계Field 발광 소자의 제작 Fabrication of light emitting device
합성예에서 합성된 화합물 1, 7, 17, 21, 24, 44, 53, 78, 81, 91, 99, 121, 151, 166, 183을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기와 같이 청색 유기 전계 발광 소자를 제작하였다.Compounds 1, 7, 17, 21, 24, 44, 53, 78, 81, 91, 99, 121, 151, 166 and 183 synthesized in Synthesis Example were subjected to high purity sublimation purification by a conventionally known method, A blue organic electroluminescent device was prepared.
먼저. 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.first. Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, and methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech), and the substrate was cleaned using UV for 5 minutes The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (㈜두산전자, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (㈜두산전자, 30nm)/화합물 1, 7, 17, 21, 24, 44, 53, 78, 81, 91, 99, 121, 151, 166, 183 각각의 화합물 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.NPN (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30 nm) / Compound 1, 7, 17 and 21 (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to form an organic electroluminescent device, Respectively.
[[ 비교예Comparative Example 1] 청색 유기 1] Blue organic 전계Field 발광 소자의 제작 Fabrication of light emitting device
전자 수송층 물질로서 화합물 1 대신 Alq3을 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Alq 3 was used instead of Compound 1 as the electron transport layer material.
[[ 비교예Comparative Example 2] 청색 유기 2] Blue organic 전계Field 발광 소자의 제작 Fabrication of light emitting device
전자 수송층 물질로서 화합물 1를 사용하지 않은 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Compound 1 was not used as the electron transport layer material.
상기 실시예 1 내지 15 및 비교예 1, 2에서 사용된 NPB, AND 및 Alq3의 구조는 하기와 같다.The structures of NPB, AND and Alq3 used in Examples 1 to 15 and Comparative Examples 1 and 2 are as follows.
[[ 평가예Evaluation example 1] One]
실시예 1 내지 15 및 비교예 1, 2에서 각각 제작한 청색 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율, 발광파장을 측정하였고, 그 결과를 하기 표 1에 나타내었다.The driving voltage, current efficiency and emission wavelength at the current density of 10 mA / cm 2 were measured for the blue organic electroluminescent devices fabricated in Examples 1 to 15 and Comparative Examples 1 and 2, Respectively.
상기 표 1에 나타낸 바와 같이, 본 발명의 화합물을 전자 수송층에 사용한 청색 유기 전계 발광 소자(실시예 1 내지 13)는 종래의 Alq3를 전자 수송층에 사용한 청색 유기 전계 발광 소자(비교예 1) 및 전자 수송층이 없는 청색 유기 전계 발광 소자(비교예 2)에 비해 구동전압, 발광피크 및 전류효율 면에서 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 1 above, the blue organic electroluminescent devices (Examples 1 to 13) using the compound of the present invention as the electron transporting layer (Comparative Examples 1 and 2) using conventional Alq 3 as the electron transporting layer and the blue organic electroluminescent devices Emitting layer and the blue organic electroluminescent device without the electron transport layer (Comparative Example 2).
[[ 실시예Example 16 내지 34] 청색 유기 16 to 34] Blue organic 전계Field 발광 소자의 제작 Fabrication of light emitting device
합성예에서 합성된 화합물 6, 15, 22, 28, 32, 39, 58, 67, 71, 74, 94, 102, 110, 116, 130, 152, 160, 173, 175를 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 아래의 과정에 따라 청색 유기 전계 발광 소자를 제작하였다.The compound 6, 15, 22, 28, 32, 39, 58, 67, 71, 74, 94, 102, 110, 116, 130, 152, 160, 173, 175 synthesized in Synthesis Example was subjected to high purity After sublimation purification, a blue organic electroluminescent device was fabricated according to the following procedure.
먼저, 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.First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) And the substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (㈜두산전자, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (㈜두산전자, 30nm)/ 화합물 6, 15, 22, 28, 32, 39, 58, 67, 71, 74, 94, 102, 110, 116, 130, 152, 160, 173, 175 (5 nm)/Alq3 (25 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제조하였다.NPN (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30 nm) / Compound 6, 15, 22, 28 (5 nm) / Alq 3 (25 nm) / LiF (1 nm) / Al (2 nm), 32, 39, 58, 67, 71, 74, 94, 102, 200 nm) were stacked in this order to fabricate an organic electroluminescent device.
[[ 비교예Comparative Example 3] 청색 유기 3] Blue organic 전계Field 발광 소자의 제조 Manufacturing of light emitting device
전자수송 보조층 물질로서 화합물 6을 사용하지 않고, 전자 수송층 물질인 Alq3를 25 nm 대신 30 nm로 증착하는 것을 제외하고는, 상기 실시예 16과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was fabricated in the same manner as in Example 16 except that Compound 6 was not used as an electron transporting auxiliary layer material and Alq 3 , which is an electron transporting layer material, was deposited at 30 nm instead of 25 nm .
[[ 평가예Evaluation example 2] 2]
실시예 16 내지 34 및 비교예 3에서 각각 제조된 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 발광파장, 전류효율을 측정하였고, 그 결과를 하기 표 2에 나타내었다.The driving voltage, light emission wavelength and current efficiency at the current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 16 to 34 and Comparative Example 3, respectively, and the results are shown in Table 2 below.
상기 표2에 나타낸 바와 같이, 본 발명의 화합물을 전자수송 보조층에 사용한 청색 유기 전계 발광 소자(실시예 16 내지 34)는 전자수송 보조층이 없는 청색 유기 전계 발광 소자(비교예 3)에 비해 전류 효율, 발광피크 및 구동전압 면에서 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 2, the blue organic electroluminescent devices (Examples 16 to 34) using the compound of the present invention as the electron transporting auxiliary layer (Examples 16 to 34) were superior to the blue organic electroluminescent devices without the electron transporting auxiliary layer Current efficiency, emission peak, and driving voltage.
Claims (11)
[화학식 1]
상기 화학식 1에서,
X는 O 또는 N(R1)이고;
Z1 내지 Z12는 각각 독립적으로 N 또는 C(R2)이나, 상기 Z1 내지 Z12 중 적어도 하나는 N이며;
m은 0 내지 4의 정수이며;
Ar1은 하기 화학식 2로 표시되는 치환기이고, 상기 Ar1이 복수 개인 경우 이들은 서로 동일하거나 상이하며;
R1은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;
R2는 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고, 상기 R2가 복수 개인 경우 이들은 서로 동일하거나 상이하며;
상기 R1 및 R2의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하며;
[화학식 2]
상기 화학식 2에서,
*은 결합이 이루어지는 부분을 의미하고;
L1 및 L2는 각각 독립적으로 단일결합, C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며;
R3은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되며;
상기 L1 및 L2의 아릴렌기 및 헤테로아릴렌기와, 상기 R3의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.A compound represented by the following formula (1):
[Chemical Formula 1]
In Formula 1,
X is O or N (R < 1 >);
Each of Z 1 to Z 12 is independently N or C (R 2 ), or at least one of Z 1 to Z 12 is N;
m is an integer from 0 to 4;
Ar 1 is a substituent represented by the following formula (2), and when a plurality of Ar 1 s are present, they are the same or different;
R 1 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
R 2 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R 2 s are the same or different, ;
The alkyl, aryl and heteroaryl groups of R 1 and R 2 are each independently selected from the group consisting of deuterium, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 6 to C 60 aryl, To 60 heteroaryl groups and C 6 to C 60 arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
(2)
In Formula 2,
* Denotes the part where the bond is made;
L 1 and L 2 are each independently selected from the group consisting of a single bond, a C 6 to C 18 arylene group and a heteroarylene group having 5 to 18 nucleus atoms;
R 3 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 ring atoms;
Wherein L 1, and arylene group of L 2 and a heteroarylene group, an alkyl group of said R 3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C substituted with 6 ~ C over a 60 aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ selected from the aryl group consisting of an amine group in the C 60 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other.
상기 화합물은 하기 화학식 3 내지 10 중 어느 하나로 표시되는, 화합물:
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 7]
[화학식 8]
[화학식 9]
[화학식 10]
상기 화학식 3 내지 10에서,
R4 내지 R14는 각각 독립적으로 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고;
상기 R4 내지 R14의 알킬기, 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하며;
R1, Ar1 및 m 각각은 제1항에서 정의된 바와 같다.The method according to claim 1,
Wherein said compound is represented by any one of the following formulas (3) to (10):
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
[Chemical formula 10]
In the above formulas 3 to 10,
R 4 to R 14 are each independently selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;
The alkyl, aryl and heteroaryl groups of R 4 to R 14 are each independently selected from the group consisting of deuterium, a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 6 to C 60 aryl group, To 60 heteroaryl groups and C 6 to C 60 arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
Each of R < 1 >, Ar < 1 > and m is as defined in claim 1 .
상기 화합물은 하기 화학식 11로 표시되는, 화합물:
[화학식 11]
상기 화학식 11에서,
X, Z1 내지 Z12 및 Ar1 각각은 제1항에서 정의된 바와 같다.The method according to claim 1,
Wherein said compound is represented by the following formula (11):
(11)
In Formula 11,
X, Z 1 to Z 12 and Ar 1 are each as defined in claim 1 .
상기 L1 및 L2는 각각 독립적으로 페닐렌기, 비페닐렌기, 나프탈레닐기, 플루오레닐기 및 카바졸릴기로 이루어진 군에서 선택되며,
상기 L1 및 L2의 페닐렌기, 비페닐렌기, 나프탈레닐기, 플루오레닐기 및 카바졸릴기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이한 화합물.The method according to claim 1,
Each of L 1 and L 2 is independently selected from the group consisting of a phenylene group, a biphenylene group, a naphthalenyl group, a fluorenyl group and a carbazolyl group,
Wherein L 1 and the phenyl group, a biphenyl of the L 2 group, a naphthyl Frontale group, a fluorenyl group and carbazolyl groups are each independently a heavy hydrogen, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C 6 ~ If C 60 aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ substituted by one substituent at least one selected from the group consisting of an aryl amine of the C 60 or is unsubstituted, substituted by a plurality of substituents, these are Are the same or different.
상기 Ar1은 하기 화학식 12 내지 14 중 어느 하나로 표시되는 치환기인 화합물:
[화학식 12]
[화학식 13]
[화학식 14]
상기 화학식 12 내지 14에서,
*은 결합이 이루어지는 부분을 의미하고;
R3은 제1항에서 정의된 바와 같다.The method according to claim 1,
Wherein Ar < 1 > is a substituent represented by any one of the following formulas (12) to (14):
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
In the above Formulas 12 to 14,
* Denotes the part where the bond is made;
R < 3 > is as defined in claim 1.
상기 R3은 피리미딘, 피라진, 트리아진, 이미다졸, 벤즈이미다졸, 페난트로이미다졸, 이미다조피리딘, 퀴나졸린 및 트리아졸로피리딘로 이루어진 군에서 선택되며,
상기 R3의 피리미딘, 피라진, 트리아진, 이미다졸, 벤즈이미다졸, 페난트로이미다졸, 이미다조피리딘, 퀴나졸린 및 트리아졸로피리딘은 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이한 화합물.The method according to claim 1,
Wherein R 3 is selected from the group consisting of pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine,
The pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine of R 3 are each independently selected from deuterium, a C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 6 ~ C 60 aryl group, nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ C is substituted by at least at 60 the group consisting of an aryl amine of the selected one more substituents or being unsubstituted , When they are substituted with a plurality of substituents, they are the same as or different from each other.
상기 R3은 하기 A1 내지 A13 중 어느 하나로 표시되는 치환기인 화합물:
상기 A1 내지 A13에서,
*은 결합이 이루어지는 부분을 의미하고;
p는 0 내지 3의 정수이며;
q는 0 내지 2의 정수이며;
R15는 C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 상기 R15가 복수 개인 경우 이들은 서로 동일하거나 상이하며;
R16은 수소, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며;
상기 R15 및 R16의 알킬기, 아릴기, 헤테로아릴기 및 아릴아민기는 각각 독립적으로 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이하다.The method according to claim 1,
Wherein R < 3 > is a substituent represented by any one of the following Al to A13:
In the above-mentioned A1 to A13,
* Denotes the part where the bond is made;
p is an integer from 0 to 3;
q is an integer from 0 to 2;
R 15 is selected from the group consisting of C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C 6 ~ with an aryl amine of the C 60 of the R 15 is When plural are the same or different from each other;
R 16 is selected from the group consisting of hydrogen, a C 1 to C 40 alkyl group, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having a C 6 to C 60 ;
The alkyl, aryl, heteroaryl and arylamine groups of R 15 and R 16 are each independently selected from the group consisting of deuterium, a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 6 to C 60 aryl group, A heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having 6 to 60 carbon atoms, and when they are substituted with a plurality of substituents, they are the same as or different from each other.
상기 R15는 C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고, 상기 R16은 수소, C1~C40의 알킬기, C6~C60의 아릴기 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되는 화합물.8. The method of claim 7,
Wherein R 15 is C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group and a nuclear atoms selected from 5 to 60 heteroaryl group the group consisting of, wherein R 16 is hydrogen, C alkyl group of 1 ~ C 40 , An aryl group having 6 to 60 carbon atoms, and a heteroaryl group having 5 to 60 nuclear atoms.
상기 화학식 1로 표시되는 화합물은 아래의 화합물로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물:
The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the group consisting of the following compounds:
상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항의 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.1. An organic electroluminescent device comprising: (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound represented by the general formula (1).
상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층, 전자 수송층, 전자 수송 보조층, 전자 주입층, 수명 개선층, 발광층 및 발광 보조층으로 이루어진 군에서 선택되는 유기 전계 발광 소자.11. The method of claim 10,
Wherein the organic compound layer containing the compound is selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron transporting layer, an electron transporting auxiliary layer, an electron injecting layer, a lifetime improving layer, a light emitting layer and a light emitting auxiliary layer.
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