CN111315717A - 2, 3-substituted naphthylamine derivative organic luminescent compound and organic electroluminescent device - Google Patents
2, 3-substituted naphthylamine derivative organic luminescent compound and organic electroluminescent device Download PDFInfo
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- CN111315717A CN111315717A CN201880071653.5A CN201880071653A CN111315717A CN 111315717 A CN111315717 A CN 111315717A CN 201880071653 A CN201880071653 A CN 201880071653A CN 111315717 A CN111315717 A CN 111315717A
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- -1 3-substituted naphthylamine Chemical class 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims description 177
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims description 83
- 239000000126 substance Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000002346 layers by function Substances 0.000 claims description 5
- 125000003367 polycyclic group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 138
- 238000006243 chemical reaction Methods 0.000 description 80
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 75
- 238000002360 preparation method Methods 0.000 description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 46
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 35
- 239000011541 reaction mixture Substances 0.000 description 29
- 238000010992 reflux Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000012153 distilled water Substances 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 17
- 230000005525 hole transport Effects 0.000 description 15
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 14
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 7
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 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 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 2
- YRPIGRRBBMFFBE-UHFFFAOYSA-N 1-(4-bromophenyl)naphthalene Chemical compound C1=CC(Br)=CC=C1C1=CC=CC2=CC=CC=C12 YRPIGRRBBMFFBE-UHFFFAOYSA-N 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 2
- GUTJITRKAMCHSD-UHFFFAOYSA-N 9,9-dimethylfluoren-2-amine Chemical compound C1=C(N)C=C2C(C)(C)C3=CC=CC=C3C2=C1 GUTJITRKAMCHSD-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- VIJSPAIQWVPKQZ-BLECARSGSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-acetamido-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-4,4-dimethylpentanoyl]amino]-4-methylpentanoyl]amino]propanoyl]amino]-5-(diaminomethylideneamino)pentanoic acid Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(C)=O VIJSPAIQWVPKQZ-BLECARSGSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 description 1
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- VCUXVXLUOHDHKK-UHFFFAOYSA-N 2-(2-aminopyrimidin-4-yl)-4-(2-chloro-4-methoxyphenyl)-1,3-thiazole-5-carboxamide Chemical compound ClC1=CC(OC)=CC=C1C1=C(C(N)=O)SC(C=2N=C(N)N=CC=2)=N1 VCUXVXLUOHDHKK-UHFFFAOYSA-N 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- AYFJBMBVXWNYLT-UHFFFAOYSA-N 2-bromo-6-methoxynaphthalene Chemical compound C1=C(Br)C=CC2=CC(OC)=CC=C21 AYFJBMBVXWNYLT-UHFFFAOYSA-N 0.000 description 1
- JOFOVYQPOOUQHX-UHFFFAOYSA-N 2-bromo-7-methoxynaphthalene Chemical compound C1=CC(Br)=CC2=CC(OC)=CC=C21 JOFOVYQPOOUQHX-UHFFFAOYSA-N 0.000 description 1
- MHIHHDLETNVZHE-UHFFFAOYSA-N 2-bromo-9,9-dimethyl-7-phenylfluorene Chemical compound C1=C2C(C)(C)C3=CC(Br)=CC=C3C2=CC=C1C1=CC=CC=C1 MHIHHDLETNVZHE-UHFFFAOYSA-N 0.000 description 1
- WNXNWOBGPRKOJF-UHFFFAOYSA-N 2-bromo-9,9-diphenylfluorene Chemical compound C12=CC(Br)=CC=C2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 WNXNWOBGPRKOJF-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DFRAKBCRUYUFNT-UHFFFAOYSA-N 3,8-dicyclohexyl-2,4,7,9-tetrahydro-[1,3]oxazino[5,6-h][1,3]benzoxazine Chemical compound C1CCCCC1N1CC(C=CC2=C3OCN(C2)C2CCCCC2)=C3OC1 DFRAKBCRUYUFNT-UHFFFAOYSA-N 0.000 description 1
- AZFABGHLDGJASW-UHFFFAOYSA-N 3-bromodibenzofuran Chemical compound C1=CC=C2C3=CC=C(Br)C=C3OC2=C1 AZFABGHLDGJASW-UHFFFAOYSA-N 0.000 description 1
- FDPBPKDNWCZVQR-UHFFFAOYSA-N 3-bromodibenzothiophene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3SC2=C1 FDPBPKDNWCZVQR-UHFFFAOYSA-N 0.000 description 1
- RIPZSADLUWTEFQ-UHFFFAOYSA-N 4-(4-bromophenyl)dibenzofuran Chemical compound C1=CC(Br)=CC=C1C1=CC=CC2=C1OC1=CC=CC=C21 RIPZSADLUWTEFQ-UHFFFAOYSA-N 0.000 description 1
- RFTRFDMRINNTSI-UHFFFAOYSA-N 9,9-dimethyl-n-phenylfluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1NC1=CC=CC=C1 RFTRFDMRINNTSI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- HQAGDFJHKPSZHT-UHFFFAOYSA-N [4-(4-bromophenyl)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=C(Br)C=C1 HQAGDFJHKPSZHT-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- DLXLTJRXOBTRJQ-UHFFFAOYSA-N chloro(trityl)silane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)([SiH2]Cl)C1=CC=CC=C1 DLXLTJRXOBTRJQ-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical class [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YGBMCLDVRUGXOV-UHFFFAOYSA-N n-[6-[6-chloro-5-[(4-fluorophenyl)sulfonylamino]pyridin-3-yl]-1,3-benzothiazol-2-yl]acetamide Chemical compound C1=C2SC(NC(=O)C)=NC2=CC=C1C(C=1)=CN=C(Cl)C=1NS(=O)(=O)C1=CC=C(F)C=C1 YGBMCLDVRUGXOV-UHFFFAOYSA-N 0.000 description 1
- IOMMMLWIABWRKL-WUTDNEBXSA-N nazartinib Chemical compound C1N(C(=O)/C=C/CN(C)C)CCCC[C@H]1N1C2=C(Cl)C=CC=C2N=C1NC(=O)C1=CC=NC(C)=C1 IOMMMLWIABWRKL-WUTDNEBXSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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Abstract
The invention provides a novel 2, 3-substituted naphthylamine derivative organic compound.
Description
Technical Field
The present invention relates to 2, 3-substituted naphthylamine derivative organic light emitting compounds and organic electroluminescent devices comprising the same.
Background
An electroluminescent device (EL device) is a self-luminous display device and has the advantages of high response speed and wide viewing angle. In 1987, Eastman Kodak for the first time developed an organic electroluminescent device using a low-molecular aromatic diamine and an aluminum complex as a light emitting layer material (appl. phys. lett.51, 913, 1987).
The most important factor determining the luminous efficiency in the organic electroluminescent device is a light emitting material in which a phosphorescent material can theoretically improve the luminous efficiency to 4 times that of a fluorescent material. Iridium (III) complexes and carbazoles have been widely known as phosphorescent light-emitting materials so far, and recently, new phosphorescent materials are being studied.
The principle of the organic electroluminescence phenomenon is that when an organic thin film layer is present between a cathode and an anode, electrons and holes are injected into the organic thin film layer from the cathode and the anode, respectively, when a voltage is applied between the two electrodes. The electrons and holes injected into the organic thin film layer are recombined to form excitons (exiton), which return to the ground state again to emit light. An organic electroluminescent device using this principle may be generally composed of a cathode and an anode with organic thin film layers therebetween, such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer.
Most of materials used for the organic electroluminescent device are pure organic substances or complexes formed by complexing organic substances and metals, and can be classified into hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials and the like according to the application. Among them, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state at the time of oxidation is mainly used. On the other hand, an organic material having an n-type property, that is, an organic substance that is easily reduced and has an electrochemically stable state at the time of reduction, is mainly used as the electron injecting material or the electron transporting material. The light emitting layer material mainly uses a material having both p-type and n-type properties, that is, preferably, a material having a stable form in both an oxidized and reduced state, and preferably, a material having high light emission efficiency that converts it into light when forming excitons. Therefore, there is a need in the art to develop new organic materials that meet the above requirements.
Disclosure of Invention
Problems to be solved by the invention
An embodiment of the present invention provides a 2, 3-substituted naphthylamine derivative compound having appropriate energy levels, electrochemical stability, and thermal stability.
Another embodiment of the present invention provides an organic electroluminescent device comprising a 2, 3-substituted naphthylamine derivative compound.
Means for solving the problems
In an embodiment of the present invention, there is provided a 2, 3-substituted naphthylamine derivative organic compound represented by the following chemical formula a:
chemical formula a:
in the above-mentioned chemical formula, the metal oxide,
L1is a single bond, phenylene or biphenylene,
L2is a single bond, phenylene or biphenylene,
Ar1is substituted or unsubstituted heteroaryl of C3-C60, alkyl of C1-C30 or aryl of C6-C30 when Ar is1When substituted, the substituent is at least one selected from the group consisting of C1-C30 alkyl groups, C6-C30 aryl groups, C5-C30 heteroaryl groups, substituted or unsubstituted silyl (sily) groups, and combinations thereof, and when the silyl group is substituted, the second substituent is a C6-C30 aryl group, provided that when Ar is substituted1When it is C1-C30 alkyl, L1Is not a single bond, but is,
Ar2is substituted or unsubstituted aryl of C6-C30 or substituted or unsubstituted heteroaryl of C3-C60, Ar2The substituent when substituted is at least one selected from the group consisting of deuterium, cyano, nitrile, halogen, alkyl groups of C1 to C12, aryl groups of C6 to C60, heteroaryl groups of C3 to C60, and combinations thereof.
R1And R2Independently represent hydrogen, deuterium, cyano, nitrile, halogen, C1-C12 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and R is1And R2The substituent when substituted is one selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C5-C30 heteroaryl, and combinations thereof,
x is oxygen, sulfur, C (R)3R4) Or is absent, R3And R4Are the same or different and are respectively and independently hydrogen, alkyl of C1-C20 and aryl of C5-C30, R is3And R4Each of which may be linked to a carbon capable of bonding in a ring of a polycyclic ring containing the above-mentioned X to form a saturated or unsaturated condensed ring.
Effects of the invention
The 2, 3-substituted naphthylamine derivative compound can satisfactorily satisfy the conditions required for a substance usable in an organic electroluminescent device, for example, appropriate energy levels, electrochemical stability, thermal stability and the like, and can exert various effects depending on the substituent in the requirements of the organic electroluminescent device.
Drawings
Fig. 1 to 3 are life characteristic evaluation graphs showing measurement results of the organic electroluminescent devices manufactured in examples 1 to 17 and comparative examples 1 to 5.
Detailed Description
Hereinafter, examples of the present invention will be described in detail. However, this is provided by way of example only and the invention is not limited thereto, the scope of which is defined by the scope of the invention claimed in the foregoing.
In the present specification, unless otherwise defined, the case of "substituted" includes the case of being substituted by a substituent selected from the group consisting of an alkyl group of C1 to C12, an amino group, a nitrile group, a cycloalkyl group of C3 to C7, an alkenyl group of C2 to C12, a cycloalkenyl group of C3 to C7, an alkynyl group of C2 to C50, a cycloalkynyl group of C2 to C50, a cyano group, an alkoxy group of C1 to C12, an aryl group of C6 to C60, an aralkyl group of C7 to C60, and a combination thereof.
In the present specification, unless otherwise defined, "a combination thereof" means that two or more substituents are bonded through a linking group, or two or more substituents are bonded through condensation.
In the present specification, unless otherwise defined, "hetero" means that a hetero atom is contained in one compound or substituent, and the hetero atom may be one selected from the group consisting of N, O, S, P and a combination thereof. For example, the case where one compound or substituent described above contains one to three hetero atoms and the remainder is carbon may be mentioned.
And, in the present specification,
refers to moieties attached to the same or different atoms or chemical formulas.
In one embodiment of the present invention, there is provided a novel 2, 3-substituted naphthylamine derivative organic compound represented by the following chemical formula a.
Chemical formula a:
in the above-mentioned chemical formula, the metal oxide,
L1is a single bond, phenylene or biphenylene,
L2is a single bond, phenylene or biphenylene,
Ar1is a substituted or unsubstituted heteroaryl group of C3-C60, an alkyl group of C1-C30 or an aryl group of C6-C30, the above Ar1The substituent(s) when substituted is (are) at least one member selected from the group consisting of C1-C30 alkyl groups, C6-C30 aryl groups, C5-C30 heteroaryl groups, substituted or unsubstituted silyl groups and combinations thereof, and the second substituent(s) when the silyl group(s) is (are) substituted is (are) C6-C30 aryl groups, provided that Ar when Ar is1When the alkyl group is a C1-C30 group, L1Is not a single bond, but is,
Ar2is substituted or unsubstituted aryl of C6-C30 or substituted or unsubstituted heteroaryl of C3-C60, Ar2The substituent when substituted is at least one selected from the group consisting of deuterium, cyano, nitrile, halogen, C1-C12 alkyl, C6-C60 aryl, C3-C60 heteroaryl, and combinations thereof,
R1and R2Are respectively and independently hydrogen, deuterium, cyano, nitrile, halogen radical, C1-C12
Alkyl, substituted or unsubstituted aryl with C6-C60, and substituted or unsubstituted heteroaryl with C3-C601And R2The substituent when substituted is one selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C5-C30 heteroaryl, and combinations thereof,
x is oxygen, sulfur, C (R)3R4) Or is absent, R3And R4Are the same or different and are respectively and independently hydrogen, alkyl of C1-C20 and aryl of C5-C30, R is3And R4May be linked to a carbon capable of bonding during reduction of a polycyclic ring containing the above X to form a saturated or unsaturated condensed ring, respectively.
For example, the saturated or unsaturated condensed ring may be a condensed form of a polycyclic ring containing the X and a cyclic ring having C3 to C7. The condensed form means that the two rings, i.e., the polycyclic ring containing X and the rings of C3 to C7 have at least two reduced forms in total.
The compound of the above chemical formula a may be one selected from the group consisting of compounds represented by the following chemical formulas a-1, a-2, a-3 and a-4:
chemical formula a-1:
chemical formula a-2:
chemical formula a-3:
chemical formula a-4:
in the above chemical formula, R1、R2、R3、R4、L1、L2、X、Ar1And Ar2The same as defined in the above chemical formula a.
Specifically, Ar1May be phenyl, tolyl, naphthyl, biphenyl, triphenyl (Terphenyl), phenanthryl, fluorenyl, spirofluorenyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, pyridyl, phenylnaphthyl, phenylfluorenyl, phenyldibenzofuranyl, phenyldibenzothienyl, phenylphenanthrenyl, tetraphenylsilyl or biphenyltriphenylsilyl.
Specifically, L is as defined above1And L2May each independently be one of groups represented by the following structural formulae:
for example, the 2, 3-substituted naphthylamine derivative compound represented by the above chemical formula a may be one of the following compounds 1 to 156.
TABLE 1
When the above-mentioned 2, 3-substituted naphthylamine derivative compound is used as a material for an organic electroluminescent device, the conditions required for a substance usable for an organic electroluminescent device, such as appropriate energy level, electrochemical stability, thermal stability and the like, can be satisfactorily satisfied, and various actions required in the organic electroluminescent device can be exhibited depending on the substituent.
In another embodiment of the present invention, there is provided an organic electroluminescent device in which at least one organic thin film layer is interposed between a cathode and an anode, the organic thin film layer has a multi-layer structure including at least one light-emitting layer, and at least one layer in the organic thin film layer other than the light-emitting layer contains the above 2, 3-substituted naphthylamine derivative organic compound alone or a mixture of two or more of the above 2, 3-substituted naphthylamine derivative organic compounds.
The above-mentioned 2, 3-substituted naphthylamine derivative organic compound contained in the organic thin film layer of the above-mentioned organic electroluminescent device is a compound represented by the above-mentioned chemical formula a, the detailed description of which is as described above.
The organic thin film layer may include a hole transport region interposed between the cathode and the light emitting layer, and the hole transport region may include at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a buffer layer, and an electron blocking layer.
The hole transport region may contain the above-mentioned 2, 3-substituted naphthylamine derivative organic compound. Specifically, at least one of the functional layer, the buffer layer, and the electron blocking layer may contain the 2, 3-substituted naphthylamine derivative organic compound.
In one example, the above-mentioned 2, 3-substituted naphthylamine derivative organic compound can be used as a substance of an electron blocking layer, a hole transporting layer or a hole injecting layer in a material for an organic electroluminescent device. That is, the organic thin film layer containing the above 2, 3-substituted naphthylamine derivative organic compound may be a light-emitting layer, an electron blocking layer, a hole transporting layer or a hole injecting layer.
The organic thin film layer may include one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a functional layer, a buffer layer, an electron blocking layer, a light emitting layer hole blocking layer, an electron transport layer, an electron injection layer, and a combination thereof, in addition to the layer including the 2, 3-substituted naphthylamine derivative organic compound.
The light-emitting layer, the hole injection layer, the hole transport layer, the functional layer, the buffer layer, the electron blocking layer, the light-emitting layer hole blocking layer electron transport layer, the electron injection layer, and the like, which form the organic thin film layer, may be formed using well-known materials, respectively, or at least one or more of them may contain one or more 2, 3-substituted naphthylamine derivative organic compounds represented by the above chemical formula a.
The detailed description of the 2, 3-substituted naphthylamine derivative organic compound represented by the chemical formula a contained in the organic thin film layer is as described above.
Hereinafter, examples of the present invention and comparative examples are described. The following embodiment is only one embodiment of the present invention, and the present invention is not limited to the following embodiment.
Examples
The following synthesis examples and comparative examples are specifically illustrated, but the present invention is not limited to the following reaction examples and examples. In the following synthesis examples, the intermediate compounds are labeled with a series of numbers added to the number of the final product. For example, Compound 1 is labeled with a compound, and an intermediate of the above compound is labeled with [1-1] or the like. In the present specification, the numbers of the compounds are denoted by the numbers of the chemical formulae shown in table 1 above. For example, the compound represented as 1 in table 1 represents compound 1.
Synthesis example 1: preparation of the Compounds
Reaction formula 1:
preparation of intermediate Compound [5-2]
A1L reaction flask was charged with 30g (148.51mmol) of compound [5-1], 34.9g (222.76mmol) of bromobenzene, 1.7g (1.49mmol) of tetrakis (triphenylphosphine) palladium, 30.8g (222.76mmol) of potassium carbonate, 300ml of toluene, 150ml of distilled water, and stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to prepare 31.7g (91%) of an intermediate compound [5-2] as a white solid.
Preparation of intermediate Compound [5-3]
A1L reaction flask was charged with 30g (128.05mmol) of the compound [5-2] and 300ml of methylene chloride, and 14.81ml (235.09mmol) of boron tribromide was slowly dropped thereinto at a temperature of 0 ℃ and stirred for 2 hours, and then the reaction mixture was slowly dropped thereinto a sodium hydrogencarbonate solution. Extraction was performed using ethyl acetate and distilled water, and the extract was treated with anhydrous magnesium sulfate, filtered, and after concentrating the filtrate under reduced pressure, recrystallization was performed using dichloromethane and hexane to prepare 25.9g (92%) of an intermediate compound [5-3] as a white solid.
Preparation of intermediate Compound [5-4]
A1L reaction flask was charged with 25g (113.49mmol) of compound [5-3], 250ml of methylene chloride, and 13.7ml (170.24mmol) of pyridine, and 22.9ml (136.19mmol) of trifluoromethanesulfonate was added slowly at a temperature of 0 ℃. After stirring at room temperature for 2 hours, 100ml of distilled water was slowly added, and the mixture was extracted with dichloromethane and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then recrystallized from dichloromethane and hexane to prepare 33.9g (85%) of an intermediate compound [5-4] as a white solid.
Preparation of intermediate Compound [5-5]
Into a 1L reaction flask were charged 33g (93.66mmol) of compound [5-4], 18.38g (93.66mmol) of 9, 9-dimethylfluoren-2-amine, 0.86g (0.94mmol) of tris (dibenzylideneacetone) dipalladium, 0.43ml (1.87mmol) of tris (tert-butyl) phosphine, 13.5g (140.49mmol) of sodium tert-butoxide, 330ml of toluene, and stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 23.9g (62%) of an intermediate compound [5-5] as a yellow solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 23g (55.89mmol) of the compound [5-5], 13.03g (55.89mmol) of 4-bromobiphenyl, 0.51g (0.56mmol) of tris (dibenzylideneacetone) dipalladium, 0.26ml (1.12mmol) of tris (tert-butyl) phosphine, 8.06g (83.84mmol) of sodium tert-butoxide, 230ml of toluene, and stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 19.8g (63%) of the objective compound as a pale yellow solid.
Synthesis example 2: preparation of the Compounds
Reaction formula 2:
preparation of intermediate Compound [10-1]
Into a 500ml reaction flask were charged 20g (56.76mmol) of the compound [5-4], 8.9g (62.47mmol) of naphthalen-1-amine, 1.04g (1.14mmol) of tris (dibenzylideneacetone) dipalladium, 0.53ml (2.28mmol) of tris (tert-butyl) phosphine, 8.18g (85.14mmol) of sodium tert-butoxide, 200ml of toluene, and stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 13.1g (65%) of an intermediate compound [10-1] as a pale yellow solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 13g (36.68mmol) of compound [10-1], 17.49g (44.02mmol) of 2-bromo-9, 9-diphenylfluorene, 0.67g (0.73mmol) of tris (dibenzylideneacetone) dipalladium, 0.34ml (1.46mmol) of tris (tert-butyl) phosphine, 7.93g (mmol) of sodium tert-butoxide, 130ml of toluene, and stirred under reflux for 16 hours. After the reaction was completed, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 15.7g (63%) of the objective compound as a pale yellow solid.
Synthesis example 3: preparation of the Compounds
Reaction formula 3:
preparation of intermediate Compound [15-1]
Into a 500ml reaction flask were charged 20g (56.76mmol) of the compound [5-4], 5.82g (62.47mmol) of aniline, 1.04g (1.14mmol) of tris (dibenzylideneacetone) dipalladium, 0.53ml (2.28mmol) of tris (tert-butyl) phosphine, 8.18g (85.14mmol) of sodium tert-butoxide, 200ml of toluene, and stirred under reflux for 20 hours. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the mixture was treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 9.89g (59%) of an intermediate compound [15-1] as a yellow solid.
Preparation of the Compounds
Into a 250ml reaction flask were charged 9g (30.47mmol) of compound [15-1], 12.77g (36.56mmol) of 2-bromo-9, 9-dimethyl-7-phenylfluorene, 0.56g (0.61mmol) of tris (dibenzylideneacetone) dipalladium, 0.28ml (1.22mmol) of tris (tert-butyl) phosphine, 4.39g (45.71mmol) of sodium tert-butoxide, 90ml of toluene, and stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 12.5g (73%) of the objective compound as a pale yellow solid.
Synthesis example 4: preparation of the Compounds
Reaction formula 4:
preparation of intermediate Compound [19-1]
Into a 500ml reaction flask were charged 20g (84.35mmol) of 2-bromo-6-methoxynaphthalene, 10.29g (88.56mmol) of phenylboronic acid, 1.95g (1.69mmol) of tetrakis (triphenylphosphine) palladium, 17.49g (126.53mmol) of potassium carbonate, 200ml of toluene, 60ml of distilled water, and stirred under reflux for 14 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 18.4g (93%) of an intermediate compound [19-1] as a white solid.
Preparation of intermediate Compound [19-2]
In a 500ml reaction flask, 18g (76.83mmol) of the compound [19-1] was dissolved in 180ml of anhydrous tetrahydrofuran, followed by stirring at-78 ℃. 36.88ml (92.19mmol) of n-butyllithium (2.5M in hexane) were added dropwise at the same temperature, and after 30 minutes 10.28ml (92.19mmol) of trimethyl borate were added dropwise. After the reaction temperature was raised to room temperature and extracted with ethyl acetate and a saturated ammonia solution, the reaction mixture was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, followed by recrystallization from methylene chloride and hexane to prepare 15.4g (72%) of an intermediate compound [19-2] as a white solid.
Preparation of intermediate Compound [19-3]
A500 ml reaction flask was charged with 15g (53.94mmol) of compound [19-2], 10.16g (64.73mmol) of bromobenzene, 1.25g (1.08mmol) of tetrakis (triphenylphosphine) palladium, 11.18g (80.91mmol) of potassium carbonate, 150ml of toluene, 45ml of distilled water, and stirred under reflux for 18 hours. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the mixture was treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 14.7g (88%) of an intermediate compound [19-3] as a white solid.
Preparation of intermediate Compound [19-4]
A500 ml reaction flask was charged with 14g (45.11mmol) of the compound [19-3] and 140ml of methylene chloride, and 5.22ml (54.13mmol) of boron tribromide was slowly dropped thereinto at a temperature of 0 ℃ and stirred for 2 hours, after which the reaction mixture was slowly dropped into a sodium hydrogencarbonate solution. Extraction was performed using methylene chloride and distilled water, and the extract was treated with anhydrous magnesium sulfate, filtered, and after concentrating the filtrate under reduced pressure, recrystallized using methylene chloride and hexane, 13.4g (91%) of an intermediate compound [19-4] was prepared as a white solid.
Preparation of intermediate Compound [19-5]
Into a 500ml reaction vessel were charged 13g (43.87mmol) of the compound [19-4], 130ml of methylene chloride and 5.31ml (65.81mmol) of pyridine, and 8.63ml (52.64mmol) of trifluoromethanesulfonate was added slowly at a temperature of 0 ℃. After stirring at room temperature for 2 hours, 50ml of distilled water was slowly added, and the mixture was extracted with dichloromethane and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then recrystallized from dichloromethane and hexane to prepare 15.2g (81%) of an intermediate compound [19-5] as a white solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 15g (35.01mmol) of the compound [19-5], 13.92g (38.51mmol) of N- (4-biphenyl) -9, 9-dimethyl-fluoro-2-amine, 0.64g (0.7mmol) of tris (dibenzylideneacetone) dipalladium, 0.33ml (1.4mmol) of tris (tert-butyl) phosphine, 5.05g (52.52mmol) of sodium tert-butoxide, 150ml of toluene, and stirred under reflux for 16 hours. After the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 14.5g (65%) of the objective compound as a pale yellow solid.
Synthesis example 5: preparation of the Compounds
Reaction formula 5:
preparation of intermediate Compound [21-1]
An intermediate compound [21-1] was prepared in the same manner as in Synthesis example 4, using 2-bromo-7-methoxynaphthalene in a yield of 42%.
Preparation of the Compounds
Into a 250ml reaction flask were charged 12g (28.01mmol) of the compound [21-1], 12.15g (33.61mmol) of N- (4-biphenyl) -9, 9-dimethyl-fluoro-2-amine, 0.51g (0.56mmol) of tris (dibenzylideneacetone) dipalladium, 0.26ml (1.12mmol) of tris (tert-butyl) phosphine, 4.04g (42.02mmol) of sodium tert-butoxide, 120ml portions of toluene, and stirred at reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 11.1g (62%) of the objective compound as a pale yellow solid.
Synthesis example 6: preparation of the Compounds
Reaction formula 6:
preparation of intermediate Compound [26-1]
An intermediate compound [26-1] was prepared in the same manner as in Synthesis example 1, using compound [5-1] and 1-bromonaphthalene in a yield of 65%.
Preparation of the Compounds
Into a 500ml reaction flask were charged 15g (37.28mmol) of compound [26-1], 16.17g (44.74mmol) of N- (4-biphenyl) -9, 9-dimethyl-fluoro-2-amine, 0.69g (0.75mmol) of tris (dibenzylideneacetone) dipalladium, 0.35ml (1.49mmol) of tris (tert-butyl) phosphine, 5.37g (55.92mmol) of sodium tert-butoxide, 150ml of toluene, and stirred at reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 13.9g (61%) of the title compound as a beige solid.
Synthesis example 7: preparation of the Compounds
Reaction formula 7:
preparation of the Compounds
A250 ml reaction flask was charged with 10g (24.29mmol) of the compound [5-5], 9.42g (29.15mmol) of 4- (4-bromophenyl) dibenzo [ b, d ] furan, 0.44g (0.48mmol) of tris (dibenzylideneacetone) dipalladium, 0.22ml (0.97mmol) of tris (tert-butyl) phosphine, 3.5g (36.43mmol) of sodium tert-butoxide, 100ml of toluene, and stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 10.6g (67%) of the title compound as a beige solid.
Synthesis example 8: preparation of the Compounds
Reaction formula 8:
preparation of intermediate Compound [49-1]
In a 500ml reaction flask, 20g (64.11mmol) of 4, 4' -dibromobiphenyl was dissolved in 200ml of anhydrous tetrahydrofuran, followed by stirring at a temperature of-78 ℃. 25.64ml (64.11mmol) of n-butyllithium (2.5M in hexane) were added dropwise at the same temperature, and after 30 minutes 22.68g (76.93mmol) of chlorotritylsilane were added dropwise. The reaction temperature was raised to room temperature, extraction was performed using ethyl acetate and saturated pure water, and then the reaction mixture was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and then recrystallized from methylene chloride and hexane to prepare 17.6g (56%) of an intermediate compound [49-1] as a white solid.
Preparation of the Compounds
A500 ml reaction flask was charged with 17g (34.59mmol) of compound [49-1], 14.95g (36.32mmol) of compound [5-5], 0.63g (.0.69mmol) of tris (dibenzylideneacetone) dipalladium, 0.32ml (1.38mmol) of tris (tert-butyl) phosphine, 4.98g (51.89mmol) of sodium tert-butoxide, 170ml of toluene, and stirred at reflux for 18 hours. After the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 19.9g (70%) of the objective compound as a pale yellow solid.
Synthesis example 9: preparation of the Compounds
Reaction formula 9:
preparation of the Compounds
A250 ml reaction flask was charged with 10g (24.29mmol) of compound [5-5], 8.25g (29.15mmol) of 1- (4-bromophenyl) naphthalene, 0.44g (0.48mmol) of tris (dibenzylideneacetone) dipalladium, 0.23ml (0.97mmol) of tris (tert-butyl) phosphine, 3.5g (36.43mmol) of sodium tert-butoxide, 100ml of toluene, and stirred at reflux for 16 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 10.1g (68%) of the title compound as a beige solid.
Synthesis example 10: preparation of the Compounds
Reaction formula 10:
preparation of intermediate Compound [77-1]
Into a 500ml reaction flask were charged 20g (56.76mmol) of compound [5-4], 11.53g (68.11mmol) of biphenyl-4-amine, 1.04g (1.14mmol) of tris (dibenzylideneacetone) dipalladium, 0.53ml (2.27mmol) of tris (tert-butyl) phosphine, 8.18g (85.14mmol) of sodium tert-butoxide, 200ml of toluene, and stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 15.4g (73%) of an intermediate compound [77-1] as a beige solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 15g (40.38mmol) of compound [77-1], 11.97g (48.46mmol) of 3-bromodibenzo [ b, d ] furan, 0.74g (0.81mmol) of tris (dibenzylideneacetone) dipalladium, 0.38ml (1.62mmol) of tris (tert-butyl) phosphine, 5.82g (60.57mmol) of sodium tert-butoxide, 150ml of toluene, and stirred under reflux for 24 hours. After the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 13.5g (62%) of the title compound as a beige solid.
Synthesis example 11: preparation of the Compounds
Reaction formula 11:
preparation of the Compounds
A250 ml reaction flask was charged with 10g (26.92mmol) of the compound [77-1], 8.51g (32.31mmol) of 3-bromodibenzo [ b, d ] thiophene, 0.49g (0.54mmol) of tris (dibenzylideneacetone) dipalladium, 0.25ml (1.07mmol) of tris (tert-butyl) phosphine, 3.88g (40.38mmol) of sodium tert-butoxide, 100ml of toluene, and stirred under reflux for 14 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 9.9g (69%) of the title compound as a beige solid.
Synthesis example 12: preparation of the Compounds
Reaction formula 12:
preparation of intermediate Compound [82-1]
Into a 500ml reaction flask were charged 20g (56.76mmol) of the compound [5-4], 12.54g (62.43mmol) of 4-bromophenylboronic acid, 1.32g (1.14mmol) of tetrakis (triphenylphosphine) palladium, 11.77g (85.14mmol) of potassium carbonate, 200ml of toluene, 80ml of distilled water, and stirred under reflux for 10 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 17.5g (86%) of an intermediate compound [82-1] as a white solid.
Preparation of intermediate Compound [82-2]
Into a 500ml reaction flask were charged 17g (47.32mmol) of compound [82-1], 11.88g (56.78mmol) of 9, 9-dimethylfluoren-2-amine, 0.87g (0.95mmol) of tris (dibenzylideneacetone) dipalladium, 0.43ml (1.89mmol) of tris (tert-butyl) phosphine, 6.82g (70.98mmol) of sodium tert-butoxide, 170ml of toluene, and stirred under reflux for 20 hours. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the mixture was treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 14.7g (59%) of an intermediate compound [82-2] as a beige solid.
Preparation of the Compounds
Into a 250ml reaction flask were charged 14g (28.71mmol) of the compound [82-2], 7.13g (34.45mmol) of 1-bromonaphthalene, 0.52g (0.57mmol) of tris (dibenzylideneacetone) dipalladium, 0.27ml (1.15mmol) of tris (tert-butyl) phosphine, 4.14g (43.07mmol) of sodium tert-butoxide, 140ml of toluene, and stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 12.7g (72%) of the title compound as a beige solid.
Synthesis example 13: preparation of the Compounds
Reaction formula 13:
preparation of the Compounds
Into a 500ml reaction flask were charged 20g (55.67mmol) of compound [82-1], 24.15g (66.81mmol) of N- (4-biphenyl) -9, 9-dimethyl-fluoro-2-amine, 1.02g (1.11mmol) of tris (dibenzylideneacetone) dipalladium, 0.52ml (2.23mmol) of tris (tert-butyl) phosphine, 8.03g (83.51mmol) of sodium tert-butoxide, 200ml of toluene, and stirred under reflux for 16 hours. After the reaction was completed, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 22.4g (63%) of the objective compound as a beige solid.
Synthesis example 14: preparation of the Compounds
Equation 14:
preparation of intermediate Compound [100-1]
An intermediate compound [100-1] was prepared in the same manner as in Synthesis example 11, using compound [5-1] and 1-bromo-3-methylbenzene in a yield of 56%.
Preparation of the Compounds
Into a 500ml reaction flask were charged 15g (40.18mmol) of the compound [100-1], 17.43g (48.22mmol) of N- (4-biphenyl) -9, 9-dimethyl-fluoro-2-amine, 0.74g (0.81mmol) of tris (dibenzylideneacetone) dipalladium, 0.37ml (1.61mmol) of tris (tert-butyl) phosphine, 5.79g (60.27mmol) of sodium tert-butoxide, 150ml of toluene, and stirred at reflux for 18 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 15.2g (58%) of the objective compound as a pale yellow solid.
Synthesis example 15: preparation of the Compounds
Equation 15:
preparation of intermediate Compound [102-1]
Into a 500ml reaction flask were charged 20g (46.68mmol) of the compound [19-5], 10.31g (51.35mmol) of 4-bromophenylboronic acid, 1.07g (0.93mmol) of tetrakis (triphenylphosphine) palladium, 9.68g (70.02mmol) of potassium carbonate, 200ml of toluene, 80ml of distilled water, and stirred under reflux for 8 hours. After completion of the reaction, extraction was performed with ethyl acetate and distilled water, and the mixture was treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 18.7g (92%) of an intermediate compound [102-1] as a white solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 18g (41.35mmol) of the compound [102-1], 14.16g (49.62mmol) of 9, 9-dimethyl-N-phenylfluoren-2-amine, 0.76g (0.83mmol) of tris (dibenzylideneacetone) dipalladium, 0.38ml (1.65mmol) of tris (tert-butyl) phosphine, 5.96g (62.03mmol) of sodium tert-butoxide, 180ml of toluene, and stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 17.2g (65%) of the objective compound as a yellow solid.
Synthesis example 16: preparation of the Compounds
Equation 16:
preparation of intermediate compound [134-1]
Into a 500ml reaction flask were charged 20g (55.67mmol) of compound [82-1], 10.36g (61.24mmol) of biphenyl-4-amine, 1.02g (1.11mmol) of tris (dibenzylideneacetone) dipalladium, 0.52ml (2.23mmol) of tris (tert-butyl) phosphine, 8.03g (83.51mmol) of sodium tert-butoxide, 200ml of toluene, and stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 18.19g (73%) of an intermediate compound [134-1] as a beige solid.
Preparation of the Compounds
A500 ml reaction flask was charged with 18g (40.22mmol) of compound [134-1], 12.53g (44.24mmol) of 1- (4-bromophenyl) naphthalene, 0.74g (0.81mmol) of tris (dibenzylideneacetone) dipalladium, 0.37ml (1.61mmol) of tris (tert-butyl) phosphine, 5.79g (60.33mmol) of sodium tert-butoxide, 180ml of toluene, and stirred at reflux for 18 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to prepare 15.2g (58%) of the objective compound as a yellow solid.
Synthesis example 17: preparation of the Compounds
Equation 17:
preparation of intermediate Compound [150-1]
Into a 500ml reaction flask were charged 20g (56.76mmol) of the compound [5-4], 18.86g (68.11mmol) of 4' -bromobiphenyl-4-boronic acid, 1.31g (1.14mmol) of tetrakis (triphenylphosphine) palladium, 11.77g (85.14mmol) of potassium carbonate, 200ml of toluene, 80ml of distilled water, and stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using methylene chloride and hexane to prepare 21.7g (88%) of an intermediate compound [150-1] as a white solid.
Preparation of the Compounds
Into a 500ml reaction flask were charged 20g (45.94mmol) of the compound [150-1], 18.49g (55.13mmol) of 9, 9-dimethyl-N- (1-naphthalene) -fluoren-2-amine, 0.84g (0.92mmol) of tris (dibenzylideneacetone) dipalladium, 0.43ml (1.84mmol) of tris (tert-butyl) phosphine, 6.62g (68.91mmol) of sodium tert-butoxide, 200ml of toluene, and stirred at reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to prepare 21.2g (67%) of the title compound as a beige solid.
Compounds 1 to 156 were prepared according to the preparation methods of synthesis examples 1 to 17, and the results are shown in table 2 below.
TABLE 2
Comparative example Compound
Chemical formula b:
chemical formula c:
chemical formula d:
formula e:
comparative example 1
Using a compound f represented by the following chemical formula f as a fluorescent blue host compound, using a compound g represented by the following chemical formula g as a fluorescent blue dopant compound, and using 4, 4' -tris [ 2-naphthylphenylamino ] group]Triphenylamine (4, 4' -tris (N-naphthalen-2-yl) -N-phenylamido) -triphenylamine, 2-TNATA) as hole injection layer materialAn organic light-emitting device having a structure of ITO/4, 4', 4' -tris [ 2-naphthylphenylamino ] group was produced by using N, N '-di (naphthalene-1-yl) -N, N' -diphenylbenzidine (N, N '-di (naphthalene-1-yl) -N, N' -diphenylbenzidine, α -NPD) as a hole transport layer material]Triphenylamine (60nm)/N, N '-di (naphthalene-1-yl) -N, N' -diphenyl benzidine (30 nm)/compound f + compound g (30nm)/Alq3(25nm)/Liq(1nm)/Al(100nm)。
For the anode, Corning 15 Ω/cm2 
The ITO glass substrate was cut into a size of 25 mm. times.25 mm. times.0.7 mm, and was subjected to ultrasonic cleaning in acetone-isopropyl alcohol and pure water for 15 minutes and then subjected to ultraviolet ozone cleaning for 30 minutes. Vacuum evaporating 4, 4', 4' -tri [ 2-naphthyl phenylamino ] group on the substrate]Triphenylamine to form a hole injection layer having a thickness of 60 nm. N, N '-di (naphthalene-1-yl) -N, N' -diphenyl benzidine was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 30 nm. A compound represented by the formula f and a compound represented by the formula g (doping ratio: 4 wt%) were vacuum-deposited on the hole transport layer to form a light-emitting layer having a thickness of 30 nm. Then, Alq was vacuum-deposited on the light-emitting layer at a thickness of 25nm3The compound to form an electron transport layer. Liq (electron injection layer) of 1nm and Al (cathode) of 100nm were sequentially vacuum-deposited on the electron transport layer, thereby producing organic light-emitting devices as shown in Table 3. This was referred to as comparative sample 1.
Chemical formula f:
chemical formula g:
Alq3：
comparative examples 2 to 5
An organic light-emitting device having the following structure was manufactured using comparative example compound b, comparative example compound c, comparative example compound d, and comparative example compound e, respectively, in place of N, N '-di (naphthalene-1-yl) -N, N' -diphenylbenzidine as the hole transport layer compound in comparative example 1 above: ITO/4, 4', 4' -tris [ 2-naphthylphenylamino group]Triphenylamine (60 nm)/compound b, compound c, compound d, or compound e (30 nm)/compound f + compound g (30nm)/Alq3(25nm)/Liq(1nm)/Al(100nm)。
These were referred to as comparative examples 2 to 5.
Examples 1 to 17
Organic light-emitting devices were manufactured in the same manner as in comparative example 1, except that compound 5, compound 10, compound 15, compound 19, compound 21, compound 26, compound 47, compound 49, compound 51, compound 77, compound 78, compound 82, compound 84, compound 100, compound 102, compound 134, and compound 150 disclosed in table 1 above, which were subjected to sublimation purification, were each substituted for N, N '-di (naphthalen-1-yl) -N, N' -diphenylbenzidine used as a hole transport layer, and the results are shown in table 3. These are referred to as example 1 to example 17, respectively.
Evaluation example 1: evaluation of light emission characteristics and lifetime in comparative examples 1 to 5 and examples 1 to 17
For comparative examples 1 to 5 and examples 1 to 17, the emission peak and the emission efficiency were evaluated using a digital source meter (2400) of Keithley (Keithley) and a CS-2000 of Konica Minolta (Konica Minolta).
Using a life detection device M6000S from pulse sciences (mcscience), the initial brightness (L) was determined0) The time (LT97) until the luminance (L) reached 97% was measured for each of the samples with reference to 1000nit, and the results are shown in table 3 and fig. 1 to 3.
TABLE 3
As shown in table 3 above, examples 1 to 17 exhibited low voltage driving and improved light emission characteristics as compared with comparative examples 1 to 5.
Fig. 1, 2 and 3 are life characteristic evaluation graphs showing the above-described detection results of the organic electroluminescent devices manufactured in examples 1 to 17 and comparative examples 1 to 5.
As shown in table 3 above, examples 1 to 17 exhibited improved life characteristics as compared with comparative examples 1 to 5. In particular, the above compounds of 2, 3-substituted naphthylamine derivatives exhibit excellent performance and life.
Although the preferred embodiments of the present invention have been described in detail, the scope of the invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept defined by the above scope of the invention also belong to the scope of the invention.
Claims (8)
1. A 2, 3-substituted naphthylamine derivative organic compound represented by the following chemical formula a:
chemical formula a:
in the above-mentioned chemical formula, the metal oxide,
L1is a single bond, phenylene or biphenylene,
L2is a single bond, phenylene or biphenylene,
Ar1is a substituted or unsubstituted heteroaryl group of C3-C60, an alkyl group of C1-C30 or an aryl group of C6-C30, the above Ar1The substituent when substituted is selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C5-C30 heteroaryl, substituted or unsubstitutedAt least one unsubstituted silyl group, wherein the second substituent in the case where the silyl group is substituted is an aryl group having from C6 to C30, provided that Ar in the case where Ar is at least one member selected from the group consisting of1When the alkyl group is a C1-C30 group, L1Is not a single bond, but is,
Ar2is substituted or unsubstituted aryl of C6-C30 or substituted or unsubstituted heteroaryl of C3-C60, Ar2The substituent when substituted is at least one selected from the group consisting of deuterium, cyano, nitrile, halogen, C1-C12 alkyl, C6-C60 aryl, C3-C60 heteroaryl, and combinations thereof,
R1and R2Independently represent hydrogen, deuterium, cyano, nitrile, halogen, C1-C12 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and R is1And R2The substituent when substituted is one selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C5-C30 heteroaryl, and combinations thereof,
x is oxygen, sulfur, C (R)3R4) Or is absent, R3And R4Are the same or different and are respectively and independently hydrogen, alkyl of C1-C20 and aryl of C5-C30, R is3And R4Each of which is linked to a carbon capable of bonding during reduction of a polycyclic ring containing X described above to form a saturated or unsaturated fused ring.
2. The 2, 3-substituted naphthylamine derivative organic compound according to claim 1, wherein the compound of the formula a is one selected from the group consisting of compounds represented by the following formulae a-1, a-2, a-3 and a-4:
chemical formula a-1:
chemical formula a-2:
chemical formula a-3:
chemical formula a-4:
in the above chemical formula, R1、R2、R3、R4、L1、L2、X、Ar1And Ar2The same as defined in the above chemical formula a.
3. The 2, 3-substituted naphthylamine derivative organic compound of claim 1, wherein Ar is Ar1Is phenyl, tolyl, naphthyl, biphenyl, triphenyl, phenanthryl, fluorenyl, spirofluorenyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, pyridyl, phenylnaphthyl, phenylfluorenyl, phenyldibenzofuranyl, phenyldibenzothienyl, phenylphenanthryl, tetraphenylsilyl or biphenyltriphenylsilyl.
4. The 2, 3-substituted naphthylamine derivative organic compound as claimed in claim 1, wherein L is as defined above1And L2Each independently is one of the groups represented by the following structural formula:
5. the 2, 3-substituted naphthylamine derivative organic compound as claimed in claim 1, wherein the above formula a is one of the following 1 to 156:
6. the 2, 3-substituted naphthylamine derivative organic compound as claimed in claim 1, wherein the 2, 3-substituted naphthylamine derivative organic compound is used as an electron-blocking layer substance, a hole-transporting layer substance or a hole-injecting layer substance in a material for an organic electroluminescent device.
7. An organic electroluminescent device having at least one organic thin film layer interposed between a cathode and an anode, wherein the organic thin film layer has a multilayer structure including at least one light-emitting layer, and at least one of the organic thin film layers other than the light-emitting layer includes the 2, 3-substituted naphthylamine derivative organic compound according to any one of claims 1 to 6 alone or a mixture including two or more 2, 3-substituted naphthylamine derivative organic compounds according to any one of claims 1 to 6.
8. The device of claim 7, wherein the organic thin film layer is interposed between the cathode and the light emitting layer and includes a hole transporting region, and the hole transporting region includes at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, and an electron blocking layer.
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|---|---|---|---|---|
| CN110078631A (en) * | 2018-01-26 | 2019-08-02 | 三星显示有限公司 | Organic electroluminescence device and monoamine compound for organic electroluminescence device |
| CN111718269A (en) * | 2019-03-20 | 2020-09-29 | 三星显示有限公司 | Amine compound and organic light-emitting element including same |
| CN112028864A (en) * | 2019-06-04 | 2020-12-04 | 东进世美肯株式会社 | Compound for capping layer and organic light emitting device including the same |
| US11805697B2 (en) | 2018-01-26 | 2023-10-31 | Samsung Display Co., Ltd. | Organic electroluminescence device and monoamine compound for organic electroluminescence device |
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| WO2021193654A1 (en) * | 2020-03-25 | 2021-09-30 | 出光興産株式会社 | Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device |
| KR20230061616A (en) * | 2021-10-28 | 2023-05-09 | 엘티소재주식회사 | Amine compound and organic light emitting device comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078631A (en) * | 2018-01-26 | 2019-08-02 | 三星显示有限公司 | Organic electroluminescence device and monoamine compound for organic electroluminescence device |
| US11805697B2 (en) | 2018-01-26 | 2023-10-31 | Samsung Display Co., Ltd. | Organic electroluminescence device and monoamine compound for organic electroluminescence device |
| CN110078631B (en) * | 2018-01-26 | 2023-12-12 | 三星显示有限公司 | Organic electroluminescent device and monoamine compound for organic electroluminescent device |
| US11871656B2 (en) | 2018-01-26 | 2024-01-09 | Samsung Display Co., Ltd. | Organic electroluminescence device and monoamine compound for organic electroluminescence device |
| CN111718269A (en) * | 2019-03-20 | 2020-09-29 | 三星显示有限公司 | Amine compound and organic light-emitting element including same |
| US11849632B2 (en) | 2019-03-20 | 2023-12-19 | Samsung Display Co., Ltd. | Amine-based compound and organic light-emitting device including the same |
| CN112028864A (en) * | 2019-06-04 | 2020-12-04 | 东进世美肯株式会社 | Compound for capping layer and organic light emitting device including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019088517A1 (en) | 2019-05-09 |
| KR20190050525A (en) | 2019-05-13 |
| CN117417261A (en) | 2024-01-19 |
| KR102081739B1 (en) | 2020-02-26 |
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Application publication date: 20200619 |