KR20190073009A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents
Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof Download PDFInfo
- Publication number
- KR20190073009A KR20190073009A KR1020170174237A KR20170174237A KR20190073009A KR 20190073009 A KR20190073009 A KR 20190073009A KR 1020170174237 A KR1020170174237 A KR 1020170174237A KR 20170174237 A KR20170174237 A KR 20170174237A KR 20190073009 A KR20190073009 A KR 20190073009A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- sub
- mmol
- formula
- ring
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 97
- 239000010410 layer Substances 0.000 claims description 91
- 125000003118 aryl group Chemical group 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000000623 heterocyclic group Chemical group 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 125000001931 aliphatic group Chemical group 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000005842 heteroatom Chemical group 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 18
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- -1 X 2 is NL 5 -Ar 6 Inorganic materials 0.000 claims description 10
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000005567 fluorenylene group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052722 tritium Inorganic materials 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 150000003413 spiro compounds Chemical class 0.000 claims description 2
- 239000011368 organic material Substances 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 105
- 239000000047 product Substances 0.000 description 57
- 230000015572 biosynthetic process Effects 0.000 description 50
- 238000003786 synthesis reaction Methods 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000000463 material Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 0 *C(CCCC1C2C3CCCCCC2)(CCC1*3I*)N Chemical compound *C(CCCC1C2C3CCCCCC2)(CCC1*3I*)N 0.000 description 24
- 239000007858 starting material Substances 0.000 description 23
- 238000000434 field desorption mass spectrometry Methods 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 21
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001308 synthesis method Methods 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229960001866 silicon dioxide Drugs 0.000 description 12
- 101000933374 Gallus gallus Brain-specific homeobox/POU domain protein 3 Proteins 0.000 description 11
- 102100026459 POU domain, class 3, transcription factor 2 Human genes 0.000 description 10
- 108010072897 transcription factor Brn-2 Proteins 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000010189 synthetic method Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- BSWVSKQCYPFXJF-UHFFFAOYSA-N 2,4-dichloro-[1]benzothiolo[3,2-d]pyrimidine Chemical compound C1=CC=C2C3=NC(Cl)=NC(Cl)=C3SC2=C1 BSWVSKQCYPFXJF-UHFFFAOYSA-N 0.000 description 4
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 description 3
- CBJHFGQCHKNNJY-UHFFFAOYSA-N 4-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2Br CBJHFGQCHKNNJY-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- RRCMGJCFMJBHQC-UHFFFAOYSA-N (2-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Cl RRCMGJCFMJBHQC-UHFFFAOYSA-N 0.000 description 2
- MOWXJLUYGFNTAL-DEOSSOPVSA-N (s)-[2-chloro-4-fluoro-5-(7-morpholin-4-ylquinazolin-4-yl)phenyl]-(6-methoxypyridazin-3-yl)methanol Chemical compound N1=NC(OC)=CC=C1[C@@H](O)C1=CC(C=2C3=CC=C(C=C3N=CN=2)N2CCOCC2)=C(F)C=C1Cl MOWXJLUYGFNTAL-DEOSSOPVSA-N 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- VFFRLRQQWXGEBX-UHFFFAOYSA-N 1-aminonaphthalene-2-carboxylic acid Chemical compound C1=CC=C2C(N)=C(C(O)=O)C=CC2=C1 VFFRLRQQWXGEBX-UHFFFAOYSA-N 0.000 description 2
- UICAYKZNZSFYNU-UHFFFAOYSA-N 2,4-dichloro-[1]benzofuro[2,3-d]pyrimidine Chemical compound ClC=1N=C(C2=C(N1)OC1=C2C=CC=C1)Cl UICAYKZNZSFYNU-UHFFFAOYSA-N 0.000 description 2
- PJRGCJBBXGNEGD-UHFFFAOYSA-N 2-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Br)C=C3NC2=C1 PJRGCJBBXGNEGD-UHFFFAOYSA-N 0.000 description 2
- WQGRAXGAXSNSDL-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-naphthalen-1-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC2=CC=CC=C12 WQGRAXGAXSNSDL-UHFFFAOYSA-N 0.000 description 2
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 2
- FRYRJNHMRVINIZ-UHFFFAOYSA-N B1CCOO1 Chemical compound B1CCOO1 FRYRJNHMRVINIZ-UHFFFAOYSA-N 0.000 description 2
- NZVIMERNEXCZCL-UHFFFAOYSA-N C1=C(C=CC2=CC=CC=C12)N1C2=CC=CC=C2C=2C=CC=C(C12)B1OC(C(O1)(C)C)(C)C Chemical compound C1=C(C=CC2=CC=CC=C12)N1C2=CC=CC=C2C=2C=CC=C(C12)B1OC(C(O1)(C)C)(C)C NZVIMERNEXCZCL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- GCEJRTXWCUDQJM-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(ccc(-c2ccc(C(c3ccccc3-3)c(cc4)cc5c4c(cccc4)c4[n]5-c4ccccc4)c-3c2)c2)c2c2c1cccc2 Chemical compound c(cc1)ccc1-[n]1c(ccc(-c2ccc(C(c3ccccc3-3)c(cc4)cc5c4c(cccc4)c4[n]5-c4ccccc4)c-3c2)c2)c2c2c1cccc2 GCEJRTXWCUDQJM-UHFFFAOYSA-N 0.000 description 2
- ZAYDYNVXBIQORO-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1-[n]1c(ccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2cccc(-c3ccccc3)c2)c2)c2c2c1cccc2 Chemical compound c(cc1)ccc1-c(cc1)ccc1-[n]1c(ccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2cccc(-c3ccccc3)c2)c2)c2c2c1cccc2 ZAYDYNVXBIQORO-UHFFFAOYSA-N 0.000 description 2
- RNOOJCLVQCVTOO-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1-c(cc1)ccc1-[n]1c(ccc(-c(cc2c3ccccc33)ccc2[n]3-c2ccccc2)c2)c2c2c1cccc2 Chemical compound c(cc1)ccc1-c(cc1)ccc1-c(cc1)ccc1-[n]1c(ccc(-c(cc2c3ccccc33)ccc2[n]3-c2ccccc2)c2)c2c2c1cccc2 RNOOJCLVQCVTOO-UHFFFAOYSA-N 0.000 description 2
- ZONFYJGZJQRNJB-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n]2c(ccc(-c3cc(-c4ccccc4C4c5cc(cccc6)c6cc5)c4cc3)c3)c3c3c2cccc3)nc(-c2c(cccc3)c3ccc2)n1 Chemical compound c(cc1)ccc1-c1nc(-[n]2c(ccc(-c3cc(-c4ccccc4C4c5cc(cccc6)c6cc5)c4cc3)c3)c3c3c2cccc3)nc(-c2c(cccc3)c3ccc2)n1 ZONFYJGZJQRNJB-UHFFFAOYSA-N 0.000 description 2
- KYYFFLQBMZRHNB-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c2ccccc2)nc(-[n]2c(ccc(-c(cc3c4ccccc44)ccc3[n]4-c3ccccc3)c3)c3c3c2cccc3)n1 Chemical compound c(cc1)ccc1-c1nc(-c2ccccc2)nc(-[n]2c(ccc(-c(cc3c4ccccc44)ccc3[n]4-c3ccccc3)c3)c3c3c2cccc3)n1 KYYFFLQBMZRHNB-UHFFFAOYSA-N 0.000 description 2
- VLBFLGCLSOPBII-UHFFFAOYSA-N c(cc1c2ccc3)ccc1[nH]c2c3-c(cccc1c2c3cccc2)c1[n]3-c1cc2ccccc2cc1 Chemical compound c(cc1c2ccc3)ccc1[nH]c2c3-c(cccc1c2c3cccc2)c1[n]3-c1cc2ccccc2cc1 VLBFLGCLSOPBII-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- NCMZPQRLZSTHFF-UHFFFAOYSA-N (5-chloro-2-phenylphenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=CC=C1C1=CC=CC=C1 NCMZPQRLZSTHFF-UHFFFAOYSA-N 0.000 description 1
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- IQFGNOVULCLFPH-UHFFFAOYSA-N 2-dibenzofuran-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C2C3=CC=CC=C3OC2=C1 IQFGNOVULCLFPH-UHFFFAOYSA-N 0.000 description 1
- MTQVNVJTIGCAFZ-UHFFFAOYSA-N 2-dibenzothiophen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C2C3=CC=CC=C3SC2=C1 MTQVNVJTIGCAFZ-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- QYNSRZKKGLCOOJ-UHFFFAOYSA-N 3,3,4,4-tetramethylpiperidine Chemical compound CC1(C)CCNCC1(C)C QYNSRZKKGLCOOJ-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- QLILRKBRWXALIE-UHFFFAOYSA-N 3-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CN=C1 QLILRKBRWXALIE-UHFFFAOYSA-N 0.000 description 1
- SPPZBAGKKBHZRW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-naphthalen-2-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=CC=C2)C2=C1 SPPZBAGKKBHZRW-UHFFFAOYSA-N 0.000 description 1
- YOZHUJDVYMRYDM-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-naphthalen-1-yl-n-phenylaniline Chemical compound C=1C=C(C=2C(=CC(NC=3C=CC=CC=3)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 YOZHUJDVYMRYDM-UHFFFAOYSA-N 0.000 description 1
- NYPHKCKUTARNAQ-UHFFFAOYSA-N 4-bromo-1-ethylsulfanyl-2-iodobenzene Chemical compound BrC1=CC(=C(C=C1)SCC)I NYPHKCKUTARNAQ-UHFFFAOYSA-N 0.000 description 1
- VZTIPRTUIVMKBK-UHFFFAOYSA-N 4-bromo-2-chloro-6-phenylpyrimidine Chemical compound BrC1=NC(=NC(=C1)C1=CC=CC=C1)Cl VZTIPRTUIVMKBK-UHFFFAOYSA-N 0.000 description 1
- UXIULWIJWDJDQD-UHFFFAOYSA-N 4-bromo-2-iodophenol Chemical compound OC1=CC=C(Br)C=C1I UXIULWIJWDJDQD-UHFFFAOYSA-N 0.000 description 1
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 1
- KCBWAFJCKVKYHO-UHFFFAOYSA-N 6-(4-cyclopropyl-6-methoxypyrimidin-5-yl)-1-[[4-[1-propan-2-yl-4-(trifluoromethyl)imidazol-2-yl]phenyl]methyl]pyrazolo[3,4-d]pyrimidine Chemical compound C1(CC1)C1=NC=NC(=C1C1=NC=C2C(=N1)N(N=C2)CC1=CC=C(C=C1)C=1N(C=C(N=1)C(F)(F)F)C(C)C)OC KCBWAFJCKVKYHO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VQLXKJLKLNGTQF-UHFFFAOYSA-N 9-(3-phenylphenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=C(C=CC=2)C=2C=CC=CC=2)C=2C3=CC=CC=2)C3=C1 VQLXKJLKLNGTQF-UHFFFAOYSA-N 0.000 description 1
- WGAVHWLZSBXTLO-UHFFFAOYSA-N 9-(4-phenylphenyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C2C3=CC=CC=C3N(C=3C=CC(=CC=3)C=3C=CC=CC=3)C2=C1 WGAVHWLZSBXTLO-UHFFFAOYSA-N 0.000 description 1
- ZQVXGZDSERJQTC-UHFFFAOYSA-N 9-(4-phenylphenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C3=CC=CC=2)C3=C1 ZQVXGZDSERJQTC-UHFFFAOYSA-N 0.000 description 1
- UBASCOPZFCGGAV-UHFFFAOYSA-N 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC=CC=2)C=2C3=CC=CC=2)C3=C1 UBASCOPZFCGGAV-UHFFFAOYSA-N 0.000 description 1
- SWWDVJROWRAWMB-UHFFFAOYSA-N Brc1c2[s]c(c(N(c3ccccc3)c3ccccc3)ccc3)c3c2ccc1 Chemical compound Brc1c2[s]c(c(N(c3ccccc3)c3ccccc3)ccc3)c3c2ccc1 SWWDVJROWRAWMB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- KBXKSJRMXDSRSV-YLHCSOALSA-N C(/C(/c(cc1)cc2c1c(cccc1)c1[s]2)=C/c(cc1)cc2c1c1cc(N(c3ccccc3)c3ccccc3)ccc1[s]2)c1ccccc1 Chemical compound C(/C(/c(cc1)cc2c1c(cccc1)c1[s]2)=C/c(cc1)cc2c1c1cc(N(c3ccccc3)c3ccccc3)ccc1[s]2)c1ccccc1 KBXKSJRMXDSRSV-YLHCSOALSA-N 0.000 description 1
- SIYSWAWVXPLKPV-UHFFFAOYSA-N C(C(c(cc1)cc2c1[s]c1ccccc21)c1cccc(c2ccc3)c1[s]c2c3N(c1ccccc1)c1ccccc1)c(cc1)ccc1-c1ccccc1 Chemical compound C(C(c(cc1)cc2c1[s]c1ccccc21)c1cccc(c2ccc3)c1[s]c2c3N(c1ccccc1)c1ccccc1)c(cc1)ccc1-c1ccccc1 SIYSWAWVXPLKPV-UHFFFAOYSA-N 0.000 description 1
- OQMIOLYRKLTBQG-UHFFFAOYSA-N C(C(c(cc1)ccc1-c1ccccc1)c(cc1)cc2c1c(cccc1)c1[s]2)c(cc1)cc2c1[s]c1cccc(N(c3ccccc3)c3ccccc3)c21 Chemical compound C(C(c(cc1)ccc1-c1ccccc1)c(cc1)cc2c1c(cccc1)c1[s]2)c(cc1)cc2c1[s]c1cccc(N(c3ccccc3)c3ccccc3)c21 OQMIOLYRKLTBQG-UHFFFAOYSA-N 0.000 description 1
- CMGBNQVEXLZEGA-UHFFFAOYSA-N C(C(c(cccc1c2ccc3)c1[s]c2c3N(c1ccccc1)c1ccccc1)c1cc2ccccc2c2ccccc12)c(cc1)cc2c1[o]c1c2cccc1 Chemical compound C(C(c(cccc1c2ccc3)c1[s]c2c3N(c1ccccc1)c1ccccc1)c1cc2ccccc2c2ccccc12)c(cc1)cc2c1[o]c1c2cccc1 CMGBNQVEXLZEGA-UHFFFAOYSA-N 0.000 description 1
- SAONSIROGNDRDL-UHFFFAOYSA-N C(C(c1ccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c2c1)c1c2[s]c3ccccc3c2ccc1)c(cc1c2c3)ccc1[o]c2ccc3N(c1ccccc1)c(cccc1)c1-c(cccc1)c1-c1ccccc1 Chemical compound C(C(c1ccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c2c1)c1c2[s]c3ccccc3c2ccc1)c(cc1c2c3)ccc1[o]c2ccc3N(c1ccccc1)c(cccc1)c1-c(cccc1)c1-c1ccccc1 SAONSIROGNDRDL-UHFFFAOYSA-N 0.000 description 1
- MUMCMDDMDQOBII-UHFFFAOYSA-N C(C(c1ccccc1)c1ccc2[s]c3ccccc3c2c1)c(cc1)cc(c2c3)c1[s]c2c(cccc1)c1c3N(c1ccccc1)c1ccccc1 Chemical compound C(C(c1ccccc1)c1ccc2[s]c3ccccc3c2c1)c(cc1)cc(c2c3)c1[s]c2c(cccc1)c1c3N(c1ccccc1)c1ccccc1 MUMCMDDMDQOBII-UHFFFAOYSA-N 0.000 description 1
- FIXKOFLDKMEEIG-UHFFFAOYSA-N C(C(c1ccccc1)c1cccc(c2c3)c1[s]c2c(cccc1)c1c3N(c1ccccc1)c1ccccc1)c(cc1)cc2c1[s]c1c2cccc1 Chemical compound C(C(c1ccccc1)c1cccc(c2c3)c1[s]c2c(cccc1)c1c3N(c1ccccc1)c1ccccc1)c(cc1)cc2c1[s]c1c2cccc1 FIXKOFLDKMEEIG-UHFFFAOYSA-N 0.000 description 1
- XHGMJKOZCGOGAU-UHFFFAOYSA-N C1(=CC=CC=C1)C1=NC(=CC(=C1)C1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC(=CC12)B1OC(C(O1)(C)C)(C)C)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C1=NC(=CC(=C1)C1=CC=C(C=C1)N1C2=CC=CC=C2C=2C=CC(=CC12)B1OC(C(O1)(C)C)(C)C)C1=CC=CC=C1 XHGMJKOZCGOGAU-UHFFFAOYSA-N 0.000 description 1
- MSBMEWUTHJICCY-UHFFFAOYSA-N C1Sc(c(N(c2ccccc2)c2ccc(c(ccc(N(c3ccccc3)c3cc(cccc4)c4cc3)c3)c3[s]3)c3c2)ccc2)c2-c2ccccc12 Chemical compound C1Sc(c(N(c2ccccc2)c2ccc(c(ccc(N(c3ccccc3)c3cc(cccc4)c4cc3)c3)c3[s]3)c3c2)ccc2)c2-c2ccccc12 MSBMEWUTHJICCY-UHFFFAOYSA-N 0.000 description 1
- JJEZIXZTFQATEF-UHFFFAOYSA-N CC(C)(c1c-2cccc1)c1c-2c(-c2cccc3c2ccc2c(c4ccccc4[n]4-c5cccc(-c6nc(-c7ccccc7)ccn6)c5)c4ccc32)ccc1-c(cccc1c2ccccc22)c1[n]2-c1ccccc1 Chemical compound CC(C)(c1c-2cccc1)c1c-2c(-c2cccc3c2ccc2c(c4ccccc4[n]4-c5cccc(-c6nc(-c7ccccc7)ccn6)c5)c4ccc32)ccc1-c(cccc1c2ccccc22)c1[n]2-c1ccccc1 JJEZIXZTFQATEF-UHFFFAOYSA-N 0.000 description 1
- BVYGQHMNVYVFPW-UHFFFAOYSA-N CC(C1)C=Cc(c2c3ccc(-c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)c2)c1[n]3-c1nc2ccccc2c(-c2ccccc2)n1 Chemical compound CC(C1)C=Cc(c2c3ccc(-c(cc4)cc(c5ccccc55)c4[n]5-c4ccccc4)c2)c1[n]3-c1nc2ccccc2c(-c2ccccc2)n1 BVYGQHMNVYVFPW-UHFFFAOYSA-N 0.000 description 1
- XYGQUBYSZHBZOD-UHFFFAOYSA-N CC(C1)C=Cc2c1[s]c(cc1)c2cc1N(c1ccccc1)c1c(c(cc(CC(c2ccccc2)c2ccccc2)c2c3cccc2)c3[s]2)c2ccc1 Chemical compound CC(C1)C=Cc2c1[s]c(cc1)c2cc1N(c1ccccc1)c1c(c(cc(CC(c2ccccc2)c2ccccc2)c2c3cccc2)c3[s]2)c2ccc1 XYGQUBYSZHBZOD-UHFFFAOYSA-N 0.000 description 1
- ZOCXBTXSZHIZDX-UHFFFAOYSA-N CC1(C)c(cc(cc2)-c3nc(-[n]4c(ccc(-c(cc5)cc(c6ccccc66)c5[n]6-c5ccccc5)c5)c5c5c4cccc5)nc(-c4cc5ccccc5c5c4cccc5)c3)c2-c2ccccc12 Chemical compound CC1(C)c(cc(cc2)-c3nc(-[n]4c(ccc(-c(cc5)cc(c6ccccc66)c5[n]6-c5ccccc5)c5)c5c5c4cccc5)nc(-c4cc5ccccc5c5c4cccc5)c3)c2-c2ccccc12 ZOCXBTXSZHIZDX-UHFFFAOYSA-N 0.000 description 1
- UOISACFGHVDOFI-UHFFFAOYSA-N CC1(C=CC=CC1)N(c1ccccc1)c1c2[s]c(c(N(c3ccccc3)c3cc4ccccc4c4ccccc34)ccc3)c3c2ccc1 Chemical compound CC1(C=CC=CC1)N(c1ccccc1)c1c2[s]c(c(N(c3ccccc3)c3cc4ccccc4c4ccccc34)ccc3)c3c2ccc1 UOISACFGHVDOFI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WYRSMKLWUKJUAY-UHFFFAOYSA-N Clc1c2c(c(N(c3ccccc3)c3ccccc3)ccc3)c3[s]c2ccc1 Chemical compound Clc1c2c(c(N(c3ccccc3)c3ccccc3)ccc3)c3[s]c2ccc1 WYRSMKLWUKJUAY-UHFFFAOYSA-N 0.000 description 1
- LUUGUZVTJFKCAD-UHFFFAOYSA-N Clc1nc(-c2ccccc2)c(c(cccc2)c2[o]2)c2n1 Chemical compound Clc1nc(-c2ccccc2)c(c(cccc2)c2[o]2)c2n1 LUUGUZVTJFKCAD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- GXFIJNNOECYQOJ-UHFFFAOYSA-N [2-[1-(1-methylpyrazol-4-yl)indol-4-yl]oxy-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound CN1N=CC(=C1)N1C=CC2=C(C=CC=C12)OC1=NC(=CC(=C1)CN)C(F)(F)F GXFIJNNOECYQOJ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- GQVWHWAWLPCBHB-UHFFFAOYSA-L beryllium;benzo[h]quinolin-10-olate Chemical compound [Be+2].C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21.C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21 GQVWHWAWLPCBHB-UHFFFAOYSA-L 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- LOJZGOWXAMZDMM-UHFFFAOYSA-N c(cc1)cc2c1[nH]c1c2ccc(-c2ccc(c3ccccc3[n]3-c4cc(cccc5)c5c5c4cccc5)c3c2)c1 Chemical compound c(cc1)cc2c1[nH]c1c2ccc(-c2ccc(c3ccccc3[n]3-c4cc(cccc5)c5c5c4cccc5)c3c2)c1 LOJZGOWXAMZDMM-UHFFFAOYSA-N 0.000 description 1
- BTSGANDRHVNPSX-UHFFFAOYSA-N c(cc1)ccc1-[n](c(c1c2)ccc2-c2cccc(-c(cc3)ccc3-c3cccc(-c(cc4)cc5c4c(cccc4)c4[nH]5)c3)c2)c2c1ncnc2 Chemical compound c(cc1)ccc1-[n](c(c1c2)ccc2-c2cccc(-c(cc3)ccc3-c3cccc(-c(cc4)cc5c4c(cccc4)c4[nH]5)c3)c2)c2c1ncnc2 BTSGANDRHVNPSX-UHFFFAOYSA-N 0.000 description 1
- JNIGFUXIZVCEED-UHFFFAOYSA-N c(cc1)ccc1-[n](c(cccc1)c1c1c2)c1ccc2-c1ccc(c2ccccc2[nH]2)c2c1 Chemical compound c(cc1)ccc1-[n](c(cccc1)c1c1c2)c1ccc2-c1ccc(c2ccccc2[nH]2)c2c1 JNIGFUXIZVCEED-UHFFFAOYSA-N 0.000 description 1
- FLCFKZHASTXZJE-UHFFFAOYSA-N c(cc1)ccc1-[n](c(cccc1)c1c1ccc2)c1c2-c1ccc2[nH]c(cccc3)c3c2c1 Chemical compound c(cc1)ccc1-[n](c(cccc1)c1c1ccc2)c1c2-c1ccc2[nH]c(cccc3)c3c2c1 FLCFKZHASTXZJE-UHFFFAOYSA-N 0.000 description 1
- AZHAHKVOKUHZES-UHFFFAOYSA-N c(cc1)ccc1-[n](c1ccccc11)c2c1c1ccccc1cc2-c1ccc2[nH]c3ccc(cccc4)c4c3c2c1 Chemical compound c(cc1)ccc1-[n](c1ccccc11)c2c1c1ccccc1cc2-c1ccc2[nH]c3ccc(cccc4)c4c3c2c1 AZHAHKVOKUHZES-UHFFFAOYSA-N 0.000 description 1
- BQPORLJWPUAUJW-UHFFFAOYSA-N c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2-c1cc(-c(cccc2)c2-c2cc(-c3ccnc4c3[nH]c3c4nccc3)ccc2)ccc1 Chemical compound c(cc1)ccc1-[n](c1ccccc1c1c2)c1ccc2-c1cc(-c(cccc2)c2-c2cc(-c3ccnc4c3[nH]c3c4nccc3)ccc2)ccc1 BQPORLJWPUAUJW-UHFFFAOYSA-N 0.000 description 1
- KJOHUQVSLRCMDB-UHFFFAOYSA-N c(cc1)ccc1-[n]1c2c(cccc3)c3ccc2c2cc(-c3ccc(c4cnccc4[nH]4)c4c3)ccc12 Chemical compound c(cc1)ccc1-[n]1c2c(cccc3)c3ccc2c2cc(-c3ccc(c4cnccc4[nH]4)c4c3)ccc12 KJOHUQVSLRCMDB-UHFFFAOYSA-N 0.000 description 1
- GNJRHORDMKIWCB-UHFFFAOYSA-N c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3[nH]c3ccccc43)ccc2c2ccccc12 Chemical compound c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3[nH]c3ccccc43)ccc2c2ccccc12 GNJRHORDMKIWCB-UHFFFAOYSA-N 0.000 description 1
- HACGLSDYLNVAII-UHFFFAOYSA-N c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3c(cccc3)c3[nH]4)ccc2c2ccccc12 Chemical compound c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3c(cccc3)c3[nH]4)ccc2c2ccccc12 HACGLSDYLNVAII-UHFFFAOYSA-N 0.000 description 1
- JHDZULHXNINNTD-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3c(cccc3)c3[nH]4)ccc2c2ccccc12 Chemical compound c(cc1)ccc1-c(cc1)ccc1-[n]1c2cc(-c(cc3)cc4c3c(cccc3)c3[nH]4)ccc2c2ccccc12 JHDZULHXNINNTD-UHFFFAOYSA-N 0.000 description 1
- JOIQELZZCRVGHA-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1-c1cc2ccccc2c2c1ccc(-c(cc1)cc(c3c4cccc3)c1[n]4-c1nc(-c3cccc4c3[s]c3ccccc43)nc(-c3ccccc3)n1)c2 Chemical compound c(cc1)ccc1-c(cc1)ccc1-c1cc2ccccc2c2c1ccc(-c(cc1)cc(c3c4cccc3)c1[n]4-c1nc(-c3cccc4c3[s]c3ccccc43)nc(-c3ccccc3)n1)c2 JOIQELZZCRVGHA-UHFFFAOYSA-N 0.000 description 1
- INZDXNPCAGZAGP-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c(cc1)cc2c1c(cccc1)c1[s]2)c1ccc(c(ccc(N(c2ccccc2)c2ccccc2)c2)c2[s]2)c2c1 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c(cc1)cc2c1c(cccc1)c1[s]2)c1ccc(c(ccc(N(c2ccccc2)c2ccccc2)c2)c2[s]2)c2c1 INZDXNPCAGZAGP-UHFFFAOYSA-N 0.000 description 1
- DFVLLCFJUCXPJV-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c1ccc2[o]c(cccc3)c3c2c1)c(cc1)cc2c1c1cc(N(c3ccccc3)c3ccccc3)ccc1[s]2 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c1ccc2[o]c(cccc3)c3c2c1)c(cc1)cc2c1c1cc(N(c3ccccc3)c3ccccc3)ccc1[s]2 DFVLLCFJUCXPJV-UHFFFAOYSA-N 0.000 description 1
- JXOMKAOEYVOUTN-UHFFFAOYSA-N c(cc1)ccc1-c(cc1c2c3)ccc1[s]c2ccc3N(c1ccccc1)c(cc1)cc2c1c(ccc(N(c1ccccc1)c1ccccc1)c1)c1[s]2 Chemical compound c(cc1)ccc1-c(cc1c2c3)ccc1[s]c2ccc3N(c1ccccc1)c(cc1)cc2c1c(ccc(N(c1ccccc1)c1ccccc1)c1)c1[s]2 JXOMKAOEYVOUTN-UHFFFAOYSA-N 0.000 description 1
- PSJBQCQKTOFNHL-UHFFFAOYSA-N c(cc1)ccc1-c(ccc(N(c1ccccc1)c1ccc(c(ccc(N(c2ccccc2)c2ccccc2)c2)c2[s]2)c2c1)c1)c1-c1ccccc1 Chemical compound c(cc1)ccc1-c(ccc(N(c1ccccc1)c1ccc(c(ccc(N(c2ccccc2)c2ccccc2)c2)c2[s]2)c2c1)c1)c1-c1ccccc1 PSJBQCQKTOFNHL-UHFFFAOYSA-N 0.000 description 1
- JXEORUICFABCLD-UHFFFAOYSA-N c(cc1)ccc1-c1c(c2ccccc2[o]2)c2nc(-[n](c2ccccc2c2ccc3)c2c3-c(cccc2c3c4cccc3)c2[n]4-c2cc(cccc3)c3cc2)n1 Chemical compound c(cc1)ccc1-c1c(c2ccccc2[o]2)c2nc(-[n](c2ccccc2c2ccc3)c2c3-c(cccc2c3c4cccc3)c2[n]4-c2cc(cccc3)c3cc2)n1 JXEORUICFABCLD-UHFFFAOYSA-N 0.000 description 1
- DVZCPZDUTJXHTQ-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-[n](c(cccc2)c2c2c3)c2ccc3-c2c3[nH]c(cccc4)c4c3ccc2)ccc1 Chemical compound c(cc1)ccc1-c1cc(-[n](c(cccc2)c2c2c3)c2ccc3-c2c3[nH]c(cccc4)c4c3ccc2)ccc1 DVZCPZDUTJXHTQ-UHFFFAOYSA-N 0.000 description 1
- RAFYTMQVEPNKKI-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-[n](c(cccc2)c2c2c3)c2ccc3-c2ccc(c3ccccc3[nH]3)c3c2)ccc1 Chemical compound c(cc1)ccc1-c1cc(-[n](c(cccc2)c2c2c3)c2ccc3-c2ccc(c3ccccc3[nH]3)c3c2)ccc1 RAFYTMQVEPNKKI-UHFFFAOYSA-N 0.000 description 1
- LTJMYWIVLHFGAP-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-[n]2c3cc(-c(cc4)cc5c4c(cccc4)c4[nH]5)ccc3c3ccccc23)cc(-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c1cc(-[n]2c3cc(-c(cc4)cc5c4c(cccc4)c4[nH]5)ccc3c3ccccc23)cc(-c2ccccc2)c1 LTJMYWIVLHFGAP-UHFFFAOYSA-N 0.000 description 1
- LFXQHKOEBHOYNV-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c2ccccc2)cc(-[n](c2ccccc2c2c3)c2c(cccc2)c2c3-c2ccc(c3ccccc3[nH]3)c3c2)c1 Chemical compound c(cc1)ccc1-c1cc(-c2ccccc2)cc(-[n](c2ccccc2c2c3)c2c(cccc2)c2c3-c2ccc(c3ccccc3[nH]3)c3c2)c1 LFXQHKOEBHOYNV-UHFFFAOYSA-N 0.000 description 1
- GPHJZFWXYBGOHA-UHFFFAOYSA-N c(cc1)ccc1-c1cccc(-[n]2c(c(-c3ccc4[nH]c(cccc5)c5c4c3)ccc3)c3c3ccccc23)c1 Chemical compound c(cc1)ccc1-c1cccc(-[n]2c(c(-c3ccc4[nH]c(cccc5)c5c4c3)ccc3)c3c3ccccc23)c1 GPHJZFWXYBGOHA-UHFFFAOYSA-N 0.000 description 1
- LXZNPPMWXNQKMH-UHFFFAOYSA-N c(cc1)ccc1-c1cccc(N(c2ccc3[o]c(cccc4)c4c3c2)c(cc2)cc3c2c2cc(N(c4ccccc4)c4ccccc4)ccc2[s]3)c1 Chemical compound c(cc1)ccc1-c1cccc(N(c2ccc3[o]c(cccc4)c4c3c2)c(cc2)cc3c2c2cc(N(c4ccccc4)c4ccccc4)ccc2[s]3)c1 LXZNPPMWXNQKMH-UHFFFAOYSA-N 0.000 description 1
- CABDGCWLTYQXBD-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-[n]2c(ccc(-c(cc3)cc(c4c(cccc5)c5cnc44)c3[n]4-c3ccccc3)c3)c3c3c2cccc3)nc(-c2ccccc2)n1 Chemical compound c(cc1)ccc1-c1nc(-[n]2c(ccc(-c(cc3)cc(c4c(cccc5)c5cnc44)c3[n]4-c3ccccc3)c3)c3c3c2cccc3)nc(-c2ccccc2)n1 CABDGCWLTYQXBD-UHFFFAOYSA-N 0.000 description 1
- OMESJIYQVHJSKE-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c2cccc(-[n]3c(c4cccc(-c5cccc6c5ccc(c5c7cccc5)c6[n]7-c5ccccc5)c4cc4)c4c4ccccc34)c2)nc(-c2ccccc2)n1 Chemical compound c(cc1)ccc1-c1nc(-c2cccc(-[n]3c(c4cccc(-c5cccc6c5ccc(c5c7cccc5)c6[n]7-c5ccccc5)c4cc4)c4c4ccccc34)c2)nc(-c2ccccc2)n1 OMESJIYQVHJSKE-UHFFFAOYSA-N 0.000 description 1
- RIGBKVNDTWUOIR-UHFFFAOYSA-N c(cc1)ccc1-c1nc([s]c2ccccc22)c2c(-c2cc(-[n]3c4cc(-c(cc5)cc6c5c(c5ccccc5c5ccccc55)c5[nH]6)c(cccc5)c5c4c4ccccc34)ccc2)n1 Chemical compound c(cc1)ccc1-c1nc([s]c2ccccc22)c2c(-c2cc(-[n]3c4cc(-c(cc5)cc6c5c(c5ccccc5c5ccccc55)c5[nH]6)c(cccc5)c5c4c4ccccc34)ccc2)n1 RIGBKVNDTWUOIR-UHFFFAOYSA-N 0.000 description 1
- WOIZWPTZDJCVQI-UHFFFAOYSA-N c(cc1)ccc1N(c1cc2ccccc2cc1)c1cccc2c1[o]c1c2cccc1N(c(cc1)cc2c1[o]c1c2cccc1)c1cc2ccccc2cc1 Chemical compound c(cc1)ccc1N(c1cc2ccccc2cc1)c1cccc2c1[o]c1c2cccc1N(c(cc1)cc2c1[o]c1c2cccc1)c1cc2ccccc2cc1 WOIZWPTZDJCVQI-UHFFFAOYSA-N 0.000 description 1
- GAMBVZSNLPBNOD-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c(cc1)cc([s]c2c3)c1c2ccc3N(c1ccccc1)c1ccc2[o]c(cccc3)c3c2c1 Chemical compound c(cc1)ccc1N(c1ccccc1)c(cc1)cc([s]c2c3)c1c2ccc3N(c1ccccc1)c1ccc2[o]c(cccc3)c3c2c1 GAMBVZSNLPBNOD-UHFFFAOYSA-N 0.000 description 1
- GLZYIUUAULTPAH-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c1c2[s]c(c(N(c3ccccc3)c3cc4ccccc4c4ccccc34)ccc3)c3c2ccc1 Chemical compound c(cc1)ccc1N(c1ccccc1)c1c2[s]c(c(N(c3ccccc3)c3cc4ccccc4c4ccccc34)ccc3)c3c2ccc1 GLZYIUUAULTPAH-UHFFFAOYSA-N 0.000 description 1
- CZNYHWJAVBUBDO-UHFFFAOYSA-N c(cc1)ccc1N(c1ccccc1)c1cccc([s]c2ccc3)c1c2c3N(c1ccccc1)c1ccc2[s]c(cccc3)c3c2c1 Chemical compound c(cc1)ccc1N(c1ccccc1)c1cccc([s]c2ccc3)c1c2c3N(c1ccccc1)c1ccc2[s]c(cccc3)c3c2c1 CZNYHWJAVBUBDO-UHFFFAOYSA-N 0.000 description 1
- MZKZCGLQGDKMBI-UHFFFAOYSA-N c(cc1)ccc1Nc1ccc2[s]c3ccccc3c2c1 Chemical compound c(cc1)ccc1Nc1ccc2[s]c3ccccc3c2c1 MZKZCGLQGDKMBI-UHFFFAOYSA-N 0.000 description 1
- WZQZWYDNXVVFOP-UHFFFAOYSA-N c1ccc(C(c2ccccc2-c2c3)(c2ccc3N(c2ccccc2)c2cccc(c3ccc4)c2[o]c3c4N(c2ccccc2)c2ccccc2)c2ccccc2)cc1 Chemical compound c1ccc(C(c2ccccc2-c2c3)(c2ccc3N(c2ccccc2)c2cccc(c3ccc4)c2[o]c3c4N(c2ccccc2)c2ccccc2)c2ccccc2)cc1 WZQZWYDNXVVFOP-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000007243 oxidative cyclization reaction Methods 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000006476 reductive cyclization reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- GDQBPBMIAFIRIU-UHFFFAOYSA-N thieno[2,3-c]pyridine Chemical compound C1=NC=C2SC=CC2=C1 GDQBPBMIAFIRIU-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H01L51/0067—
-
- H01L51/0072—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multi-layered structure made of different materials, and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.
헤테로원자를 포함하고 있는 비스타입의 고리화합물의 경우 물질 구조에 따른 특성의 차이가 매우 커서 유기전기소자의 재료로 다양한 층에 적용되고 있다. 특히 환의 개수 및 fused 위치, 헤테로원자의 종류와 배열에 따라 밴드 갭(HOMO, LUMO), 전기적 특성, 화학적 특성, 물성 등이 상이한 특징을 갖고 있어, 이를 이용한 다양한 유기전기소자의 층에 대한 적용 개발이 진행되어 왔다.In the case of the cyclic compounds of the vicinal structure containing heteroatoms, the difference in properties depending on the material structure is very large and is applied to various layers of organic electronic devices. Especially, it has various characteristics such as band gap (HOMO, LUMO), electrical characteristic, chemical property, physical properties depending on the number of rings and fused position and heteroatom type and arrangement, Has progressed.
인광 발광 도펀트 재료를 이용하는 인광형 유기전기소자에 있어서 호스트 물질의 LUMO, 및 HOMO level은 유기전기소자의 효울 및 수명에 매우 큰 영향을 주는 요인으로서 발광층 내 전자 및 정공 주입을 효율적으로 조절 가능하냐에 따라 발광층 내 charge balance 조절, 도펀트 ?칭(quenching) 및 정공수송층 계면에서의 발광으로 인한 효율 저하 및 수명 저하를 방지할 수 있다.The LUMO and HOMO levels of the host material in the phosphorescent organic electroluminescent device using the phosphorescent dopant material have a great influence on the efficiency and lifetime of the organic electroluminescent device, It is possible to prevent deterioration in efficiency and lifetime due to charge balance control, dopant quenching in the light emitting layer, and light emission at the interface of the hole transporting layer.
형광 및 인광 발광용 호스트 물질의 경우 최근들어 TADF(Thermal activatied delayed fluorescent), Exciplex 등을 이용한 유기전기소자의 효율 증가 및 수명 증가 등을 연구하고 있으며, 특히 호스트 물질에서 도펀트 물질로의 에너지 전달 방법 규명에 많은 연구가 진행되고 있다.In the case of host materials for fluorescence and phosphorescent luminescence, the efficiency and lifetime increase of organic electronic devices using TADF (Thermal Activated Delayed Fluorescent) and Exciplex have been studied. Especially, the method of energy transfer from a host material to a dopant material Many studies are underway.
TADF (Thermal activated delayed fluorescent), exciplex에 대한 발광층 내 에너지 전달 규명은 여러 가지 방법들이 있지만, PL lifetime (TRTP) 측정법으로 손쉽게 확인할 수 있다.The energy transfer in the light emitting layer for TADF (thermally activated delayed fluorescent) and exciplex can be easily confirmed by the PL lifetime (TRTP) measurement method.
TRTP (Time resolved transient PL) 측정법은 펄스 광원을 호스트 박막에 조사한 후, 시간에 따른 스펙트럼의 감소(Decay time)를 관찰하는 방식으로서 에너지 전달 및 발광 지연시간 관찰을 통해 에너지 전달 방식을 규명할 수 있는 측정방법이다. 상기 TRTP 측정은 형광과 인광의 구분 및 mixed 호스트 물질 내에서의 에너지 전달방식, exciplex 에너지 전달방식, TADF 에너지 전달 방식 등을 구분해 줄 수 있는 측정법이다.The TRTP (Time Resolved Transient PL) measurement method is a method of observing a decay time of a pulse light source on a host thin film, and observing energy transmission and emission delay time, It is a measurement method. The TRTP measurement is a method of distinguishing between fluorescence and phosphorescence, energy transfer in a mixed host material, exciplex energy transfer, and TADF energy transfer.
이처럼 호스트 물질로부터 도펀트 물질로 에너지가 전달되는 방식에 따라 효율 및 수명에 영향을 주는 다양한 요인들이 존재하며, 물질에 따라 에너지 전달 방식이 상이하여, 아직까지 안정되고 효율적인 유기전기소자용 호스트 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광층의 호스트 물질에 대한 개발이 절실히 요구되고 있다.There are various factors affecting the efficiency and lifetime depending on the manner in which the energy is transferred from the host material to the dopant material, and the energy transfer method differs depending on the material, so that the stable and efficient host material for the organic electric device Is not sufficiently achieved. Therefore, development of new materials is continuously required, and development of a host material for a light emitting layer is urgently required.
본 발명은 상기와 같은 인광 호스트 물질의 문제점을 해결하기 위하여 제안된 것으로, 인광 도펀트를 포함하는 인광 발광형 유기전기소자의 호스트 물질에 대한 HOMO level 조절을 통한 발광층 내 charge balance 조절 및 효율, 수명을 향상시킬 수 있는 화합물 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.The present invention has been proposed in order to solve the problems of the above-mentioned phosphorescent host material, and it is an object of the present invention to provide a phosphorescent light emitting organic electroluminescent device including a phosphorescent dopant by controlling the HOMO level of the host material, An organic electroluminescent device using the same, and an electronic device therefor.
본 발명은 인광 발광형 유기전기소자의 발광층 내 효율적인 정공 주입을 조절하기 위해 주성분으로서 특정의 제 1호스트 재료에 특정의 제 2호스트 재료를 조합하여 함유함으로써, 발광층과 인접층의 에너지 장벽을 작게 할 수 있고, 발광층 내 charge balance를 최대화 시켜 유기전기소자의 고효율, 고수명을 제공하는 것이다.In order to control the efficient hole injection in the light emitting layer of the phosphorescence emitting organic electroluminescent device, the present invention includes a specific first host material in combination with a specific second host material as a main component, thereby reducing the energy barrier of the light emitting layer and the adjacent layer And maximize the charge balance in the light emitting layer, thereby providing high efficiency and long life of the organic electric device.
본 발명은 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은, 발광층을 포함하고, 상기 발광층은 하기 화학식 1로 표시되는 제 1호스트 화합물 및 하기 화학식 2로 표시되는 제 2호스트 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.The organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, And a second host compound represented by the following formula (2): < EMI ID = 2.0 >
또한, 본 발명은 상기 화학식들로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.The present invention also provides organic electronic devices using the compounds represented by the above formulas and electronic devices thereof.
본 발명에 따른 혼합물을 인광 호스트 물질로 이용함으로써, 유기전기소자의 높은 발광효율, 낮은 구동전압을 달성할 수 있으며, 또한 소자의 수명을 크게 향상시킬 수 있다.By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve a high luminous efficiency and a low driving voltage of the organic electroluminescent device, and also to greatly improve the lifetime of the device.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.
이하, 본 발명의 실시예를 참조하여 상세하게 설명한다. 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성 요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성 요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."
본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다: As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 사이클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.
본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다. The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.
본 발명에 사용된 용어 "헤테로알킬기"는 알킬기를 구성하는 탄소원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.
본 발명에 사용된 용어 "알켄일기", "알케닐기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다.The term "alkenyl group "," alkenyl group ", or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups , But is not limited thereto.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다.The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.
본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.
본 발명에 사용된 용어 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.
본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다.The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.
접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다. The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.
본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다.The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다.As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.
또한 "헤테로고리기"는 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. The "heterocyclic group" may also include a ring containing SO 2 in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다.Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화고리를 포함한다.Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다.Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "카르보닐"이란 -COR'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20 의 알킬기, 탄소수 6 내지 30 의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.
다른 설명이 없는 한, 본 발명에 사용된 용어 "에테르"란 -R-O-R'로 표시되는 것이며, 여기서 R 또는 R'은 각각 서로 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕실기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알켄일기, C2~C20의 알킨일기, C3~C20의 시클로알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C for use in the present invention 20 alkoxy group, C 1 ~ C 20 alkyl amine group, C 1 ~ C 20 alkyl thiophene group, C 6 ~ C 20 aryl thiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C of 20 alkynyl, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C 2 to C 20 heterocyclic group.
또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하는 것을 의미하는데, 즉 a가 0인 경우는 벤젠고리를 형성하는 탄소에 모두 수소가 결합된 것을 의미하며, 이때 탄소에 결합된 수소의 표시를 생략하고 화학식이나 화합물을 기재할 수 있다. a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.When a is an integer of 0, the substituent R 1 is absent. That is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. In this case, And the chemical formula or compound may be described. When a is an integer of 1, one substituent R < 1 > is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3, R < 1 > And when a is an integer of 4 to 6, it bonds to the carbon of the benzene ring in a similar manner, while the indication of the hydrogen bonded to the carbon forming the benzene ring is omitted.
이하, 본 발명의 일 측면에 따른 화합물 및 이를 포함하는 유기전기소자에 대하여 설명한다. Hereinafter, a compound according to one aspect of the present invention and an organic electronic device including the same will be described.
본 발명은제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광성 발광층으로서 화학식 1로 표시되는 제 1 호스트 화합물 및 화학식 2로 표시되는 제 2 호스트 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.The organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, 1 < / RTI > and a second host compound represented by the general formula (2).
{상기 화학식 1 및 화학식 2에서,{In the above Chemical Formulas 1 and 2,
X1은 S 또는 O이고, X < 1 > is S or O,
X2는 N-L5-Ar6, O, S 또는 CRaRb이고,X 2 is NL 5 -Ar 6 , O, S or CR a R b ,
A, B, C, D, E 및 F는 서로 독립적으로 C6-C20의 아릴기, C2-C20의 헤테로고리기이며,A, B, C, D, E and F independently of one another are a C 6 -C 20 aryl group, a C 2 -C 20 heterocyclic group,
Ra 및 Rb는 서로 독립적으로 수소, 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택되며, 또는 Ra와 Rb는 서로 결합하여 스파이로(spiro) 화합물을 형성할 수 있으며,R a and R b are independently of each other hydrogen, deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group and a C 6 -C 30 aryloxy group, or R a and R b may combine with each other to form a spiro compound,
Ar1 내지 Ar6은 서로 독립적으로 C6-C60의 아릴기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택되고, 또는 Ar1 내지 Ar6은 서로 결합하여 고리를 형성할 수 있고,Ar 1 to Ar 6 are each independently a C 6 to C 60 aryl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C 6 -C 60 aromatic ring and a C 3 -C 60 aliphatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; And a C 6 -C 30 aryloxy group; or Ar 1 is selected from the group consisting of Ar 1 To Ar < 6 > may combine with each other to form a ring,
L1 내지 L5는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 C3-C60의 지방족고리기;로 이루어진 군에서 선택되며,L 1 to L 5 independently represent a single bond; C 6 -C 60 arylene groups; A fluorenylene group; A C 2 -C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; And a C 3 -C 60 aliphatic cyclic group;
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 지방족고리기, 융합고리기, 알킬기, 알케닐기, 알콕시기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}The aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fluorenylene group, the aliphatic cyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkoxy group and the aryloxy group are respectively deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C 1 -C 20 ; A C 1 -C 20 alkoxyl group; A C 1 -C 20 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 6 -C 20 aryl group; A C 6 -C 20 aryl group substituted by deuterium; A fluorenyl group; A C 2 -C 20 heterocyclic group; A C 3 -C 20 cycloalkyl group; An arylalkyl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms and an arylalkenyl group having 8 to 20 carbon atoms, and these substituents may be further bonded to each other to form a ring, Ring " refers to a fused ring consisting of a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 heterocyclic ring or a combination thereof, including saturated or unsaturated rings.
구체적으로 본 발명은 상기 A, B, C, D, E, 및 F가 서로 독립적으로 하기 화학식 a-1 내지 화학식 a-7로 이루어진 군에서 선택되는 어느 하나로 표시되는 화합물을 포함한다.Specifically, the present invention includes compounds wherein A, B, C, D, E and F are independently selected from the group consisting of the following formulas a-1 to a-7.
{상기 화학식 a-1 내지 화학식 a-7에서,(In formulas (a-1) to (a-7)
Z1 내지 Z48은 서로 독립적으로 CRc 또는 N이고, Z 1 to Z 48 independently of one another are CR c or N,
단, L1 내지 L3에 결합하고 있는 Z1 내지 Z48은 탄소(C)이며,Provided that Z 1 to Z 48 bonded to L 1 to L 3 are carbon (C)
Rc는 상기에서 Ra의 정의와 동일하고,R c is the same as defined above for R a ,
*는 축합되는 위치를 나타낸다.}* Indicates the position to be condensed.
또한 본 발명은 상기 L1 내지 L5가 하기 화학식 b-1 내지 b-13 중에 어느 하나로 표시되는 화합물을 제공한다.The present invention also provides a compound wherein L 1 to L 5 are each represented by any one of the following formulas b-1 to b-13.
화학식 b-11 화학식 b-12 화학식 b-13Formula b-11 Formula b-12 Formula b-13
{상기 화학식 b-1 내지 화학식 b-13에서,(In the formulas (b-1) to (b-13)
Y는 N-L6-Ar7, O, S, 또는 CRdRe이고, Y is NL 6 -Ar 7 , O, S, or CR d R e ,
L6은 상기에서 L4의 정의와 동일하고,L 6 is as defined above for L 4 ,
Ar7은 상기에서 Ar5의 정의와 동일하고,Ar 7 is as defined above for Ar 5 ,
Rd 및 Re는 상기에서 Ra의 정의와 동일하며,R d and R e are as defined above for R a ,
a, c, d, e은 서로 독립적으로 0 내지 4의 정수이고 b은 0 내지 6의 정수이고,a, c, d and e are each independently an integer of 0 to 4 and b is an integer of 0 to 6,
f 및 g은 서로 독립적으로 0~3의 정수이고, h는 0 내지 2의 정수이며 i는 0 또는 1의 정수이고,f and g are independently an integer of 0 to 3, h is an integer of 0 to 2, i is an integer of 0 or 1,
R1 내지 R3은 서로 독립적으로 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기 및 -La-N(Rf)(Rg)로 이루어진 군에서 선택되고, 또는 상기 a, b, c, d, e, f 및 g가 2 이상인 경우, 및 h가 2인 경우는 각각 복수로서 서로 동일하거나 상이하며 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 이웃한 R1과 R2 또는 R2과 R3은 서로 결합하여 방향족 고리 또는 헤테로방향족 고리를 형성할 수 있고,R 1 to R 3 independently of one another are hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; When C 6 is selected from the group consisting of -C 30 aryloxy, and -L a -N (R f) ( R g), or wherein a, b, c, d, e, f and g is two or more, And when h is 2, a plurality of R 1 s, a plurality of R 2 s, a plurality of R 3 s or adjacent R 1 s and R 2 s or R 2 s and R 3 s bonded to each other An aromatic ring or a heteroaromatic ring,
여기서 상기 La는 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 C3-C60의 지방족 탄화수소기로 이루어진 군에서 선택되며, 상기 Rf 및 Rg는 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되고,Wherein L a is a single bond; C 6 -C 60 arylene groups; A fluorenylene group; A C 2 -C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; And C 3 -C 60 aliphatic hydrocarbon groups, wherein R f and R g are independently selected from the group consisting of C 6 -C 60 aryl groups; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring,
Z49, Z50 및 Z51은 서로 독립적으로 CRh 또는 N이고, Z49, Z50 및 Z51 중 적어도 하나는 N이며,Z 49 , Z 50 and Z 51 independently of one another are CR h or N, and at least one of Z 49 , Z 50 and Z 51 is N,
Rh은 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되고, 이웃한 R1과 Rh는 서로 결합하여 방향족 고리 또는 헤테로방향족 고리를 형성할 수 있다.}R h is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; And a C 6 -C 30 aryloxy group, and adjacent R 1 and R h may be bonded to each other to form an aromatic ring or a heteroaromatic ring.
또한 본 발명은 상기 화학식 1로 나타내는 제 1 호스트 화합물이 하기 화학식 3 내지 화학식 5 중 어느 하나로 표시되는 화합물을 포함한다.The present invention also relates to a compound represented by any one of the following general formulas (3) to (5), wherein the first host compound represented by the general formula (1)
{상기 화학식 3 내지 화학식 5에서,{In the above Chemical Formulas 3 to 5,
X1, A, B, L1, L2, Ar2 내지 Ar4는 상기에서 정의된 바와 같고,X 1 , A, B, L 1 , L 2 , Ar 2 to Ar 4 are as defined above,
G 및 H는 상기에서 A의 정의와 동일하고,G and H are the same as defined above for A,
W는 N-L8-Ar8, O, S, 또는 CRiRj이고, W is NL 8 -Ar 8 , O, S, or CR i R j ,
L7 및 L8은 상기에서 L4의 정의와 동일하고, L 7 and L 8 are as defined above for L 4 ,
Ar8은 상기에서 Ar5의 정의와 동일하고,Ar 8 is as defined above for Ar 5 ,
Ri 및 Rj는 상기에서 Ra의 정의와 동일하며,R i and R j are as defined above for R a ,
2개의 Ar8은 각각 동일하거나 상이하고, 2개의 W는 각각 동일하거나 상이하고, Two Ar 8 s are the same or different, and two W s are the same or different,
2개의 G은 각각 동일하거나 상이하고, 2개의 H는 각각 동일하거나 상이하다.}Two G's are the same or different, and two H's are each the same or different.
또한 본 발명은 상기 화학식 1로 나타내는 제 1 호스트 화합물이 하기 화학식 6으로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.The present invention also provides an organic electroluminescent device, wherein the first host compound represented by Formula 1 comprises a compound represented by Formula 6 below.
{상기 화학식 6에서,{In the above formula (6)
X1, Ar2 내지 Ar4 및 Z1 내지 Z4는 상기에서 정의된 바와 같고,X 1 , Ar 2 to Ar 4 and Z 1 to Z 4 are as defined above,
W는 N-L8-Ar8, O, S, 또는 CRiRj이고, W is NL 8 -Ar 8 , O, S, or CR i R j ,
L8은 상기 L4의 정의와 동일하고,L 8 is the same as the definition of L 4 above,
Ar8은 상기 Ar5의 정의와 동일하고,Ar 8 has the same definition as Ar 5 above,
Ri 및 Rj는 상기 Ra의 정의와 동일하다.}R i and R j are as defined above for R a .
바람직하게는, 화학식 3 내지 화학식 5의 X1, W는 서로 독립적으로 O 또는 S인 것을 특징으로 하는 유기전기소자를 제공한다.Preferably, X1 and W in the general formulas (3) to (5) are independently O or S, respectively.
본 발명에서 상기 화학식 2로 나타내는 제2호스트 화합물은 하기 화학식 7 내지 화학식 10 중 어느 하나로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.In the present invention, the second host compound represented by the general formula (2) includes a compound represented by any one of the following general formulas (7) to (10).
{상기 화학식 7 내지 화학식 10에서,{In the above Chemical Formulas 7 to 10,
C, D, E, F, L3 내지 L5, Ar5, Ar6, Ra, Rb는 상기에서 정의된 바와 동일하다.}C, D, E, F, L 3 to L 5 , Ar 5 , Ar 6 , R a and R b are as defined above.
보다 상세하게는, 본 발명은 상기 화학식 1로 나타내는 제 1호스트 화합물이 하기 화합물 1-1 내지 화합물 1-175 을 포함한다.More specifically, the first host compound represented by Formula 1 includes the following Compounds 1-1 to 1-175.
또한 본 발명에서 상기 화학식 2로 나타내는 제 2호스트 화합물은 하기 화합물 2-1 내지 화합물 2-135을 포함한다.In the present invention, the second host compound represented by Formula 2 includes the following Compounds 2-1 to 2-135.
도 1을 참조하여 설명하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(120)과 제 2전극(180) 사이에 화학식 1로 표시되는 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.1, an
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 발광보조층(151), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 전자수송보조층, 버퍼층(141) 등을 더 포함할 수 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있다.The organic layer includes a
또한, 미도시하였지만 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다.Further, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic layer.
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when energy level and T1 value between each organic material layer, and the intrinsic characteristics (mobility, interfacial characteristics, etc.) of the material are optimized, long life and high efficiency can be achieved at the same time.
본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 또한, 정공수송층(140)과 발광층(150) 사이에 발광보조층(151)을, 발광층(150)과 전자수송층(160) 사이에 전자수송보조층을 추가로 더 형성할 수 있다. The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, a positive
이에 따라, 본 발명은 상기 제 1전극과 발광층 사이에 1층 이상의 정공수송대역층을 포함하고, 상기 정공수송대역층은 정공수송층, 발광보조층 또는 이 둘을 모두 포함하며, 상기 정공수송대역층이 상기 화학식 1로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.Accordingly, the present invention provides a light emitting device comprising at least one hole transporting band layer between the first electrode and a light emitting layer, wherein the hole transporting band layer includes a hole transporting layer, a light emitting auxiliary layer or both, And an organic electroluminescent device including the compound represented by the formula (1).
또한 본 발명은 상기 화학식 1 및 상기 화학식 2로 나타내는 화합물이 1:9 내지 9:1 중 어느 하나의 비율로 혼합되어 상기 발광층에 포함되는 유기전기소자를 제공하며, 바람직하게는 1:9 내지 5:5로, 보다 바람직하게는 2:8 또는 3:7 비율로 혼합되어 상기 발광층에 포함된다.Also, the present invention provides an organic electroluminescent device wherein the compound represented by Formula 1 and the compound represented by Formula 2 are mixed in a ratio of 1: 9 to 9: 1 and included in the light emitting layer, : 5, more preferably in a ratio of 2: 8 or 3: 7 and contained in the light emitting layer.
본 발명은 상기 유기전기소자에서 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율개선층을 더 포함하는 유기전기소자를 제공한다.The organic electroluminescent device may further include a light efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic layer or one side of the one side of the second electrode opposite to the organic layer, Thereby providing an organic electric device.
또한 본 발명에서 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되며, 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다. In the present invention, the organic material layer may be formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process. Therefore, the scope of the present invention is not limited by the forming method.
본 발명의 일 실시예에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다.WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.
또한 본 발명은 상기한 유기전기소자를 포함하는 디스플레이장치 ; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다. The present invention also relates to a display device including the above organic electroluminescent device; And a control unit for driving the display device.
또 다른 측면에서 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치를 본 발명에서 제공한다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말기일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.In another aspect, the present invention provides an electronic device characterized in that the organic electric device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device. At this time, the electronic device may be a current or a future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하에서, 본 발명의 상기 화학식 1 및 2로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (2) and the production example of the organic electronic device of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto .
[[ 합성예Synthetic example 1] One]
본 발명에 따른 화학식 1로 표시되는 화합물(final product 1)은 하기 반응식 1과 같이 Sub 1과 Sub 2를 반응시켜 합성되며, 이에 한정되는 것은 아니다. X1, A, B, L1, L2, Ar1 내지 Ar4는 상기 화학식 1에서 정의된 것과 동일하며, Hal1은 Br 또는 Cl이다.The compound of formula (1) according to the present invention is synthesized by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto. X 1 , A, B, L 1 , L 2 , Ar 1 to Ar 4 are the same as defined in Formula 1, and Hal 1 is Br or Cl.
<반응식 1><Reaction Scheme 1>
I. Sub 1의 합성I. Synthesis of Sub 1
상기 반응식 1의 Sub 1은 하기 반응식 2의 반응경로에 의해 합성되며, 이에 한정되는 것은 아니다.Sub 1 of Reaction Scheme 1 is synthesized by the reaction path of Reaction Scheme 2 below, but is not limited thereto.
<반응식 2><Reaction Scheme 2>
1. Sub 1-1 1. Sub 1-1 합성예Synthetic example
출발물질인 Sub 2-1 (15.22 g, 89.94 mmol)을 둥근바닥플라스크에 toluene (750ml)으로 녹인 후에, Sub 1-1-c (CAS Registry Number: 669773-34-6) (46.14 g, 134.91 mmol), Pd2(dba)3 (2.47 g, 2.70 mmol), P(t-Bu)3 (1.46 g, 7.19 mmol), NaOt-Bu (25.93 g, 269.81 mmol)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 23.61 g (수율: 61%)를 얻었다.Sub 1-1-c (CAS Registry Number: 669773-34-6) (46.14 g, 134.91 mmol) was dissolved in toluene (750 ml) in a round bottom flask, ), Pd 2 (dba) 3 (2.47 g, 2.70 mmol), P ( t- Bu) 3 (1.46 g, 7.19 mmol) and NaO t- Bu (25.93 g, 269.81 mmol) . After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 23.61 g (yield: 61%) of the product.
2. Sub 1-3 2. Sub 1-3 합성예Synthetic example
출발물질인 Sub 2-12 (13.94 g, 63.57 mmol)에 Sub 1-3-e (CAS Registry Number: 201138-91-2) (31.08 g, 95.35 mmol), Pd2(dba)3 (1.75 g, 1.91 mmol) P(t-Bu)3 (1.03 g, 5.09 mmol), NaOt-Bu (18.33 g, 190.71 mmol), toluene (530ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 19.78 g (수율: 67%)를 얻었다.Sub-1-3-e (CAS Registry Number: 201138-91-2) (31.08 g, 95.35 mmol) and Pd 2 (dba) 3 (1.75 g, 95.35 mmol) were added to Sub 2-12 (13.94 g, 63.57 mmol) 1.91 mmol) was added P ( t- Bu) 3 (1.03 g, 5.09 mmol), NaO t- Bu (18.33 g, 190.71 mmol) and toluene (530 ml) Yield: 67%).
3. Sub 1-5 3. Sub 1-5 합성예Synthetic example
(1) Sub 1-5-a의 합성(1) Synthesis of Sub 1-5-a
출발물질인 (2-bromo-6-iodophenyl)(ethyl)sulfane (9.94 g, 28.98 mmol)을 둥근바닥플라스크에 THF (100ml)로 녹인 후에, (4-chlorophenyl)boronic acid (4.53 g, 28.98 mmol), Pd(PPh3)4 (1.00 g, 0.87 mmol), NaOH (2.32 g, 57.96 mmol), 물 (50ml)을 첨가하고 80 ℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 8.55 g (수율: 90%)을 얻었다.(4-chlorophenyl) boronic acid (4.53 g, 28.98 mmol) was dissolved in THF (100 ml) in a round bottom flask. , and Pd (PPh 3) was added 4 (1.00 g, 0.87 mmol) , NaOH (2.32 g, 57.96 mmol), water (50ml) and stirred at 80 ℃. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.55 g (yield: 90%) of the product.
(2) Sub 1-5-b의 합성(2) Synthesis of Sub 1-5-b
상기 합성에서 얻어진 Sub 1-5-a (8.55 g, 26.09 mmol)에 acetic acid (90ml)를 넣고 35% hydrogen peroxide (H2O2) (2.66 g, 78.28 mmol)을 넣고 상온에서 교반한다. 반응이 종료되면 NaOH 수용액으로 중화시킨 뒤, EA로 추출하고 물로 닦아주었다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column을 이용하여 분리하여 생성물 8.70 g (97%)을 얻었다.Acetic acid (90 ml) was added to Sub 1-5-a (8.55 g, 26.09 mmol) obtained in the above synthesis, and 35% hydrogen peroxide (H 2 O 2 ) (2.66 g, 78.28 mmol) was added thereto and stirred at room temperature. After the reaction was completed, the reaction solution was neutralized with aqueous NaOH solution, extracted with EA, and wiped with water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was separated using a silicagel column to obtain 8.70 g (97%) of the product.
(3) Sub 1-5-c의 합성(3) Synthesis of Sub 1-5-c
상기 합성에서 얻어진 Sub 1-5-b (8.70 g, 25.32 mmol)에 sulfuric acid (H2SO4) (50ml)를 넣고 상온에서 교반한다. 반응이 종료되면 NaOH 수용액으로 중화시킨 뒤, MC로 추출하고 물로 닦아주었다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column을 이용하여 분리하여 생성물 7.16 g (95%)을 얻었다.Sulfuric acid (H 2 SO 4 ) (50 ml) was added to Sub 1-5-b (8.70 g, 25.32 mmol) obtained in the above synthesis and stirred at room temperature. After the reaction was completed, it was neutralized with aqueous NaOH solution, extracted with MC and wiped with water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was separated using a silicagel column to obtain 7.16 g (95%) of the product.
(4) Sub 1-5의 합성(4) Synthesis of Sub 1-5
상기 합성에서 얻어진 Sub 1-5-c (7.16 g, 24.06 mmol)을 둥근바닥플라스크에 toluene (240ml)으로 녹인 후에, Sub 2-11 (5.28 g, 24.06 mmol), Pd2(dba)3 (0.66 g, 0.72 mmol), P(t-Bu)3 (0.49 g, 2.41 mmol), NaOt-Bu (4.62 g, 48.12 mmol)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 8.08 g (수율: 77%)를 얻었다.Sub 1-5-11 (5.28 g, 24.06 mmol), Pd 2 (dba) 3 (0.66 g, 24.06 mmol) was dissolved in toluene (240 ml) in a round bottom flask, g, 0.72 mmol), P ( t- Bu) 3 (0.49 g, 2.41 mmol) and NaO t- Bu (4.62 g, 48.12 mmol) were added and stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.08 g (yield: 77%) of the product.
4. Sub 1-17 4. Sub 1-17 합성예Synthetic example
(1) Sub 1-17-a의 합성(1) Synthesis of Sub 1-17-a
출발물질인 (4-bromo-2-iodophenyl)(ethyl)sulfane (10.65 g, 31.05 mmol)에 (4-chloro-[1,1'-biphenyl]-2-yl)boronic acid (7.22 g, 31.05 mmol), Pd(PPh3)4 (1.08 g, 0.93 mmol), NaOH (2.48 g, 62.10 mmol), THF (100ml), 물 (50ml)을 첨가하고 상기 Sub 1-5-a 합성법을 사용하여 생성물 9.90 g (수율: 79%)를 얻었다.To a solution of the starting material (4-bromo-2-iodophenyl) (ethyl) sulfane (10.65 g, 31.05 mmol) was added (4-chloro- [1,1'- biphenyl] -2- yl) boronic acid (7.22 g, 31.05 mmol ), Pd (PPh 3) 4 (1.08 g, 0.93 mmol), NaOH (2.48 g, 62.10 mmol), was added to THF (100ml), water (50ml) and use the Sub-1-5 a synthetic product 9.90 g (yield: 79%).
(2) Sub 1-17-b의 합성(2) Synthesis of Sub 1-17-b
상기 합성에서 얻어진 Sub 1-17-a (9.90 g, 24.52 mmol), acetic acid (80ml), 35% hydrogen peroxide (H2O2) (2.50 g, 73.56 mmol)을 상기 Sub 1-5-b의 합성법을 사용하여 생성물 9.78 g (95%)을 얻었다.Sub-1-17-a (9.90 g, 24.52 mmol), acetic acid (80 ml) and 35% hydrogen peroxide (H 2 O 2 ) (2.50 g, 73.56 mmol) 9.78 g (95%) of the product was obtained using the synthetic method.
(3) Sub 1-17-c의 합성(3) Synthesis of Sub 1-17-c
상기 합성에서 얻어진 Sub 1-17-b (9.78 g, 23.30 mmol), sulfuric acid (H2SO4) (50ml)를 상기 Sub 1-5-c의 합성법을 사용하여 생성물 7.84 g (90%)을 얻었다.Sub-1-17-b (9.78 g, 23.30 mmol) and sulfuric acid (H 2 SO 4 ) (50 ml) obtained in the above synthesis were reacted with 7.84 g (90%) of the product .
(4) Sub 1-17의 합성(4) Synthesis of Sub 1-17
상기 합성에서 얻어진 Sub 1-17-c (7.84 g, 20.98 mmol)에 Sub 2-78 (7.02 g, 20.98 mmol), Pd2(dba)3 (0.58 g, 0.63 mmol) P(t-Bu)3 (0.42 g, 2.10 mmol), NaOt-Bu (4.03 g, 41.96 mmol), toluene (210ml)을 첨가하고 상기 Sub 1-5 합성법을 사용하여 생성물 10.79 g (수율: 82%)를 얻었다.Obtained in the above Synthesis Sub 1-17-c (7.84 g, 20.98 mmol) in Sub 2-78 (7.02 g, 20.98 mmol ), Pd 2 (dba) 3 (0.58 g, 0.63 mmol) P (t -Bu) 3 (0.42 g, 2.10 mmol), NaO t- Bu (4.03 g, 41.96 mmol) and toluene (210 ml) were added and the Sub 1-5 synthetic procedure was used to obtain 10.79 g (yield: 82%) of the product.
5. Sub 1-82 5. Sub 1-82 합성예Synthetic example
출발물질인 Sub 2-1 (16.48 g, 97.38 mmol)에 Sub 1-82-c (CAS Registry Number: 83834-10-0) (49.96 g, 146.07 mmol), Pd2(dba)3 (2.68 g, 2.92 mmol) P(t-Bu)3 (1.58 g, 7.79 mmol), NaOt-Bu (28.08 g, 292.15 mmol), toluene (810ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 26.40 g (수율: 63%)를 얻었다.Sub-1-82-c (CAS Registry Number: 83834-10-0) (49.96 g, 146.07 mmol), Pd 2 (dba) 3 (2.68 g, 2.8 mmol) P ( t- Bu) 3 (1.58 g, 7.79 mmol), NaO t- Bu (28.08 g, 292.15 mmol) and toluene (810 ml) Yield: 63%).
6. Sub 1-102 6. Sub 1-102 합성예Synthetic example
(1) Sub 1-102-d의 합성(1) Synthesis of Sub 1-102-d
출발물질인 4-bromo-2-iodophenol (39.85 g, 133.32 mmol)에 (2-chlorophenyl)boronic acid (20.85 g, 133.32 mmol), Pd(PPh3)4 (4.62 g, 4.00 mmol), NaOH (10.67 g, 266.64 mmol), THF (440ml), 물 (220ml)을 첨가하고 상기 Sub 1-5-a 합성법을 사용하여 생성물 28.73 g (수율: 76%)를 얻었다.The starting material, 4-bromo-2-iodophenol in (39.85 g, 133.32 mmol) ( 2-chlorophenyl) boronic acid (20.85 g, 133.32 mmol), Pd (PPh 3) 4 (4.62 g, 4.00 mmol), NaOH (10.67 g, 266.64 mmol), THF (440 ml) and water (220 ml), and 28.73 g (Yield: 76%) of the product was obtained using the Sub 1-5-a synthesis method.
(2) Sub 1-102-e의 합성(2) Synthesis of Sub 1-102-e
상기 합성에서 얻어진 Sub 1-102-d (28.73 g, 101.32 mmol)에 Pd(OAc)2 (2.27 g, 10.13 mmol), 3-nitropyridine (1.26 g, 10.13 mmol), BzOOtBu (tert-butyl peroxybenzoate) (39.36 g, 202.65 mmol), C6F6 (hexafluorobenzene) (150ml), DMI (N,N'-dimethylimidazolidinone) (100ml)을 넣고 90℃에서 3시간 환류시킨다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, EA로 추출하고 물로 닦아준다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column을 이용하여 분리하여 생성물 13.69 g (48%)을 얻었다.Pd (OAc) 2 (2.27 g, 10.13 mmol), 3-nitropyridine (1.26 g, 10.13 mmol) and BzOO t Bu (tert-butyl peroxybenzoate) were added to Sub 1-102-d (28.73 g, 101.32 mmol) ) (39.36 g, 202.65 mmol), C 6 F 6 (hexafluorobenzene) (150 ml) and DMI (N, N'-dimethylimidazolidinone) (100 ml) were added and refluxed at 90 ° C. for 3 hours. When the reaction is complete, the reaction temperature is cooled to room temperature, extracted with EA, and wiped with water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was separated by silicagel column to obtain 13.69 g (48%) of product.
(3) Sub 1-102의 합성(3) Synthesis of Sub 1-102
상기 합성에서 얻어진 Sub 1-102-e (13.69 g, 48.63 mmol)에 Sub 2-29 (13.39 g, 48.63 mmol), Pd2(dba)3 (1.34 g, 1.46 mmol) P(t-Bu)3 (0.98 g, 4.86 mmol), NaOt-Bu (9.35 g, 97.25 mmol), toluene (490ml)을 첨가하고 상기 Sub 1-5 합성법을 사용하여 생성물 19.67 g (수율: 85%)를 얻었다.The Sub 1-102-e (13.69 g, 48.63 mmol) obtained in the above Synthesis Sub 2-29 (13.39 g, 48.63 mmol ), Pd 2 (dba) 3 (1.34 g, 1.46 mmol) P (t -Bu) 3 (0.98 g, 4.86 mmol), NaO t- Bu (9.35 g, 97.25 mmol) and toluene (490 ml) were added and the Sub 1-5 synthetic method was used to obtain 19.67 g of the product (yield: 85%).
7. Sub 1-104 7. Sub 1-104 합성예Synthetic example
출발물질인 Sub 2-1 (9.15 g, 54.04 mmol)에 Sub 1-104-c (CAS Registry Number: 31574-87-5) (27.73 g, 81.07 mmol), Pd2(dba)3 (1.48 g, 1.62 mmol) P(t-Bu)3 (0.87 g, 4.32 mmol), NaOt-Bu (15.58 g, 162.13 mmol), toluene (450ml)을 첨가하고 상기 Sub 1-1 합성법을 사용하여 생성물 15.12 g (수율: 65%)를 얻었다.Sub-1-104-c (CAS Registry Number: 31574-87-5) (27.73 g, 81.07 mmol) and Pd 2 (dba) 3 (1.48 g, 1.62 mmol) P ( t- Bu) 3 (0.87 g, 4.32 mmol), NaO t- Bu (15.58 g, 162.13 mmol) and toluene (450 ml) Yield: 65%).
8. Sub 1-112 8. Sub 1-112 합성예Synthetic example
(1) Sub 1-112-a의 합성(1) Synthesis of Sub 1-112-a
출발물질인 (3-bromo-2-iodophenyl)(ethyl)sulfane (12.73 g, 37.11 mmol)에 (2-chlorophenyl)boronic acid (5.80 g, 37.11 mmol), Pd(PPh3)4 (1.29 g, 1.11 mmol), NaOH (2.97 g, 74.22 mmol), THF (120ml), 물 (60ml)을 첨가하고 상기 Sub 1-5-a 합성법을 사용하여 생성물 9.48 g (수율: 78%)를 얻었다.(2-chlorophenyl) boronic acid (5.80 g, 37.11 mmol) and Pd (PPh 3 ) 4 (1.29 g, 1.11 mmol) were added to the starting material (3-bromo- 2- iodophenyl) mmol), NaOH (2.97 g, 74.22 mmol), THF (120 ml) and water (60 ml) were added and 9.48 g of the product (yield: 78%) was obtained using the Sub 1-5-a synthesis method.
(2) Sub 1-112-b의 합성(2) Synthesis of Sub 1-112-b
상기 합성에서 얻어진 Sub 1-112-a (9.48 g, 28.93 mmol), acetic acid (95ml), 35% hydrogen peroxide (H2O2) (2.95 g, 86.80 mmol)을 상기 Sub 1-5-b의 합성법을 사용하여 생성물 9.74 g (98%)을 얻었다.Sub 1-112-a (9.48 g, 28.93 mmol), acetic acid (95 ml) and 35% hydrogen peroxide (H 2 O 2 ) (2.95 g, 86.80 mmol) 9.74 g (98%) of the product was obtained using the synthetic method.
(3) Sub 1-112-c의 합성(3) Synthesis of Sub 1-112-c
상기 합성에서 얻어진 Sub 1-112-b (9.74 g, 28.34 mmol), sulfuric acid (H2SO4) (60ml)를 상기 Sub 1-5-c의 합성법을 사용하여 생성물 7.76 g (92%)을 얻었다.Sub-1-112-b (9.74 g, 28.34 mmol) and sulfuric acid (H 2 SO 4 ) (60 ml) obtained in the above synthesis were reacted with 7.76 g (92%) of the product .
(4) Sub 1-112의 합성(4) Synthesis of Sub 1-112
상기 합성에서 얻어진 Sub 1-112-c (7.76 g, 26.08 mmol)에 Sub 2-1 (4.41 g, 26.08 mmol), Pd2(dba)3 (0.72 g, 0.78 mmol) P(t-Bu)3 (0.53 g, 2.61 mmol), NaOt-Bu (5.01 g, 52.15 mmol), toluene (260ml)을 첨가하고 상기 Sub 1-5 합성법을 사용하여 생성물 5.84 g (수율: 58%)를 얻었다.Obtained in the above Synthesis Sub 1-112-c (7.76 g, 26.08 mmol) in Sub 2-1 (4.41 g, 26.08 mmol ), Pd 2 (dba) 3 (0.72 g, 0.78 mmol) P (t -Bu) 3 (0.53 g, 2.61 mmol), NaO t- Bu (5.01 g, 52.15 mmol) and toluene (260 ml) were added to obtain 5.84 g of the product (yield: 58%).
Sub 1에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 1은 Sub 1에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1.
II. Sub 2의 합성II. Synthesis of Sub 2
상기 반응식 1의 Sub 2는 하기 반응식 3의 반응경로에 의해 합성(본 출원인의 한국등록특허 제 10-1251451호 (2013.04.05일자 등록공고)에 개시)될 수 있5으나, 이에 한정되는 것은 아니다.Sub 2 of Reaction Scheme 1 may be synthesized by the reaction path of the following Reaction Scheme 3 (disclosed in Korean Patent No. 10-1251451 of the present applicant (published on April 3, 2013)), but is not limited thereto .
Z1은 Ar1 또는 Ar3이고, Z2는 Ar2 또는 Ar4이다.Z 1 is Ar 1 or Ar 3 , and Z 2 is Ar 2 or Ar 4 .
<반응식 3><Reaction Scheme 3>
Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 2는 Sub 2에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 2 may be, but not limited to, the following compounds, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 2.
III. Final Product 1 합성III. Final Product 1 Composite
Sub 1 (1 당량)을 둥근바닥플라스크에 Toluene으로 녹인 후에, Sub 2 (1 당량), Pd2(dba)3 (0.03 당량), (t-Bu)3P (1.00 당량), NaOt-Bu (2 당량)을 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 Final product 1을 얻었다.Sub 1 (1 eq) was dissolved in toluene in a round bottom flask and Sub 2 (1 eq), Pd 2 (dba) 3 (0.03 eq.), ( T- Bu) 3 P (1.00 eq.) And NaO t- Bu (2 eq.) Were stirred at 100 < 0 > C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain final product 1.
본 발명 화합물 1-30, 1-32, 1-35, 1-37, 1-67, 1-80, 1-86, 1-94, 1-111. 1-119, 1-133은 본 출원인의 한국등록특허 제 10-1668448호 (2016.10.17일자 등록공고), 한국등록특허 제 10-1789998호 (2017.10.19일자 등록공고)에 개시된 합성방법으로 제조되었다.1-30, 1-32, 1-35, 1-37, 1-67, 1-80, 1-86, 1-94, 1-111 of the present invention. 1-119 and 1-133 are manufactured by the synthetic method disclosed in the Korean Registered Patent No. 10-1668448 (Registered on October 17, 2016) and Korean Patent No. 10-1789998 (Registered on October 19, 2017) .
1. 1-1 1. 1-1 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-1 (5.97 g, 13.87 mmol)을 둥근바닥플라스크에 toluene (140ml)으로 녹인 후에, Sub 2-17 (3.74 g, 13.87 mmol), Pd2(dba)3 (0.38 g, 0.42 mmol), P(t-Bu)3 (0.28 g, 1.39 mmol), NaOt-Bu (2.67 g, 27.74 mmol)을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 6.09 g (수율: 71%)를 얻었다.Sub 1-1 (5.74 g, 13.87 mmol) obtained in the above synthesis was dissolved in toluene (140 ml) in a round bottom flask, Sub 2-17 (3.74 g, 13.87 mmol) and Pd 2 (dba) 3 (0.38 g, 0.42 mmol), P ( t- Bu) 3 (0.28 g, 1.39 mmol) and NaO t- Bu (2.67 g, 27.74 mmol) were added and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 6.09 g of the product (yield: 71%).
2. 1-2 2. 1-2 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-1 (5.29 g, 12.29 mmol)에 Sub 2-37 (4.32 g, 12.29 mmol), Pd2(dba)3 (0.34 g, 0.37 mmol) P(t-Bu)3 (0.25 g, 1.23 mmol), NaOt-Bu (2.36 g, 24.58 mmol), toluene (125ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 6.81 g (수율: 79%)를 얻었다.Obtained in the above Synthesis Sub 1-1 (5.29 g, 12.29 mmol ) in Sub 2-37 (4.32 g, 12.29 mmol ), Pd 2 (dba) 3 (0.34 g, 0.37 mmol) P (t -Bu) 3 (0.25 g, 1.23 mmol), NaO t- Bu (2.36 g, 24.58 mmol) and toluene (125 ml) were added to the reaction mixture to obtain 6.81 g of the product (yield: 79%).
3. 1-4 3. 1-4 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-3 (6.13 g, 13.20 mmol)에 Sub 2-41 (4.08 g, 13.20 mmol), Pd2(dba)3 (0.36 g, 0.40 mmol) P(t-Bu)3 (0.27 g, 1.32 mmol), NaOt-Bu (2.54 g, 26.40 mmol), toluene (130ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 7.32 g (수율: 80%)를 얻었다.Obtained in the above Synthesis Sub 1-3 (6.13 g, 13.20 mmol ) in Sub 2-41 (4.08 g, 13.20 mmol ), Pd 2 (dba) 3 (0.36 g, 0.40 mmol) P (t -Bu) 3 (0.27 g, 1.32 mmol), NaO t- Bu (2.54 g, 26.40 mmol) and toluene (130 ml) were added.
4. 1-10 4. 1-10 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-5 (5.56 g, 12.75 mmol)에 Sub 2-43 (4.28 g, 12.75 mmol), Pd2(dba)3 (0.35 g, 0.38 mmol) P(t-Bu)3 (0.26 g, 1.28 mmol), NaOt-Bu (2.45 g, 25.51 mmol), toluene (130ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 8.06 g (수율: 86%)를 얻었다.The Sub 1-5 (5.56 g, 12.75 mmol ) obtained in the above Synthesis Sub 2-43 (4.28 g, 12.75 mmol ), Pd 2 (dba) 3 (0.35 g, 0.38 mmol) P (t -Bu) 3 (0.26 g, 1.28 mmol), NaO t- Bu (2.45 g, 25.51 mmol) and toluene (130 ml) were added to the reaction mixture to obtain 8.06 g of the product (yield: 86%).
5. 1-24 5. 1-24 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-17 (6.18 g, 9.85 mmol)에 Sub 2-1 (1.67 g, 9.85 mmol), Pd2(dba)3 (0.27 g, 0.30 mmol) P(t-Bu)3 (0.20 g, 0.99 mmol), NaOt-Bu (1.89 g, 19.71 mmol), toluene (100ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 5.62 g (수율: 75%)를 얻었다.The Sub 1-17 (6.18 g, 9.85 mmol ) obtained in the above Synthesis Sub 2-1 (1.67 g, 9.85 mmol ), Pd 2 (dba) 3 (0.27 g, 0.30 mmol) P (t -Bu) 3 (0.20 g, 0.99 mmol), NaO t- Bu (1.89 g, 19.71 mmol) and toluene (100 ml) were added to the reaction mixture to obtain 5.62 g of the product (yield: 75%).
6. 1-122 6. 1-122 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-82 (5.05 g, 11.73 mmol)에 Sub 2-49 (4.12 g, 11.73 mmol), Pd2(dba)3 (0.32 g, 0.35 mmol) P(t-Bu)3 (0.24 g, 1.17 mmol), NaOt-Bu (2.26 g, 23.47 mmol), toluene (120ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 7.65 g (수율: 93%)를 얻었다.Obtained in the above Synthesis Sub 1-82 (5.05 g, 11.73 mmol ) in Sub 2-49 (4.12 g, 11.73 mmol ), Pd 2 (dba) 3 (0.32 g, 0.35 mmol) P (t -Bu) 3 (0.24 g, 1.17 mmol), NaO t- Bu (2.26 g, 23.47 mmol) and toluene (120 ml) were added to the reaction mixture to obtain 7.65 g of the product (yield: 93%).
7. 1-125 7. 1-125 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-82 (5.20 g, 12.08 mmol)에 Sub 2-40 (3.13 g, 12.08 mmol), Pd2(dba)3 (0.33 g, 0.36 mmol) P(t-Bu)3 (0.24 g, 1.21 mmol), NaOt-Bu (2.32 g, 24.17 mmol), toluene (120ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 6.69 g (수율: 91%)를 얻었다.Obtained in the above Synthesis Sub 1-82 (5.20 g, 12.08 mmol ) in Sub 2-40 (3.13 g, 12.08 mmol ), Pd 2 (dba) 3 (0.33 g, 0.36 mmol) P (t -Bu) 3 (0.24 g, 1.21 mmol), NaO t- Bu (2.32 g, 24.17 mmol) and toluene (120 ml) were added to the reaction mixture to obtain 6.69 g of the product (yield: 91%).
8. 1-141 8. 1-141 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-102 (6.26 g, 13.15 mmol)에 Sub 2-1 (2.23 g, 13.15 mmol), Pd2(dba)3 (0.36 g, 0.39 mmol) P(t-Bu)3 (0.27 g, 1.32 mmol), NaOt-Bu (2.53 g, 26.30 mmol), toluene (130ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 6.57 g (수율: 82%)를 얻었다.Obtained in the above Synthesis Sub 1-102 (6.26 g, 13.15 mmol ) in Sub 2-1 (2.23 g, 13.15 mmol ), Pd 2 (dba) 3 (0.36 g, 0.39 mmol) P (t -Bu) 3 (0.27 g, 1.32 mmol), NaO t- Bu (2.53 g, 26.30 mmol) and toluene (130 ml) were added to the reaction mixture to obtain 6.57 g of the product (yield: 82%).
9. 1-146 9. 1-146 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-104 (6.12 g, 14.22 mmol)에 Sub 2-83 (5.84 g, 14.22 mmol), Pd2(dba)3 (0.39 g, 0.43 mmol) P(t-Bu)3 (0.29 g, 1.42 mmol), NaOt-Bu (2.73 g, 28.43 mmol), toluene (140ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 8.00 g (수율: 74%)를 얻었다.Sub-83 (5.84 g, 14.22 mmol), Pd 2 (dba) 3 (0.39 g, 0.43 mmol) and P ( t- Bu) 3 (0.29 g, 1.42 mmol), NaO t- Bu (2.73 g, 28.43 mmol) and toluene (140 ml) were added to the reaction mixture to obtain 8.00 g (yield: 74%) of the product.
10. 1-158 10. 1-158 합성예Synthetic example
상기 합성에서 얻어진 Sub 1-112 (5.75 g, 14.90 mmol)에 Sub 2-29 (4.10 g, 14.90 mmol), Pd2(dba)3 (0.41 g, 0.45 mmol) P(t-Bu)3 (0.30 g, 1.49 mmol), NaOt-Bu (2.86 g, 29.80 mmol), toluene (150ml)을 첨가하고 상기 1-1 합성법을 사용하여 생성물 6.24 g (수율: 67%)를 얻었다.Obtained in the above Synthesis Sub 1-112 (5.75 g, 14.90 mmol ) in Sub 2-29 (4.10 g, 14.90 mmol ), Pd 2 (dba) 3 (0.41 g, 0.45 mmol) P (t -Bu) 3 (0.30 g, 1.49 mmol), NaO t- Bu (2.86 g, 29.80 mmol) and toluene (150 ml) were added to the reaction mixture to obtain 6.24 g of the product (yield: 67%).
한편, 상기와 같은 합성예에 따라 제조된 본 발명의 화합물 1-1 내지 1-175의 FD-MS 값은 하기 표 3과 같다.The FD-MS values of the compounds 1-1 to 1-175 of the present invention prepared according to the above Synthesis Examples are shown in Table 3 below.
[[ 합성예Synthetic example 2] 2]
본 발명에 따른 화학식 2로 표시되는 화합물(final product 2)은 하기 반응식 4 와 같이 Sub 3과 Sub 4를 반응시켜 합성되며, 이에 한정되는 것은 아니다. X2, C, D, E, F, L3, L4, Ar5는 화학식 2에서 정의된 것과 동일하며, Hal2는 Br 또는 Cl이다.The final product 2 represented by the formula 2 according to the present invention is synthesized by reacting Sub 3 and Sub 4 as shown in Reaction Scheme 4, but is not limited thereto. X 2 , C, D, E, F, L 3 , L 4 and Ar 5 are the same as defined in formula (2), and Hal 2 is Br or Cl.
<반응식 4><Reaction Scheme 4>
I. Sub 3의 합성I. Synthesis of Sub 3
상기 반응식 4의 Sub 3은 하기 반응식 5의 반응경로에 의해 합성되며, 이에 한정되는 것은 아니다.Sub 3 of Scheme 4 is synthesized by the reaction path of Scheme 5 below, but is not limited thereto.
<반응식 5><Reaction Scheme 5>
Sub 3 의 합성에서 사용되는 출발물질인 카바졸 유도체는 본 출원인의 한국등록특허 제 10-1535606호 (2015.07.03일자 등록공고), 한국출원특허 2012-0152002 (2012.12.24일자 출원), 한국출원특허 2016-0025426 (2016.03.03 일자 출원)에 개시된 합성방법으로 제조되었다.The carbazole derivative, which is a starting material used in the synthesis of Sub 3, is disclosed in Korean Patent No. 10-1535606 (Registered on May 3, 2015), Korean Patent Application No. 2012-0152002 (filed on December 24, 2012) Was prepared by the synthetic method disclosed in patent 2016-0025426 (filed March 23, 2013).
Sub 3의 합성에서 사용되는 출발물질인 다이벤조싸이오펜 유도체 또는 다이벤조퓨란은 본 출원인의 한국출원특허 2014-0074261 (2014.06.18일자 출원)에 개시된 합성방법으로 제조되었다.The dibenzothiophene derivative or the dibenzofuran, which is the starting material used in the synthesis of Sub 3, was prepared by the synthetic method disclosed in Korean Patent Application No. 2014-0074261 (filed on Apr. 18, 2014) of the present applicant.
Sub 3의 합성에서 사용되는 출발물질인 플루오렌 유도체는 본 출원인의 한국출원특허 2013-0056221 (2013.05.20일자 출원), 한국출원특허 2015-0083505 (2015.06.12일자 출원)에 개시된 합성방법으로 제조되었다.The fluorene derivative, which is a starting material used in the synthesis of Sub 3, can be produced by the synthesizing method disclosed in Korean Patent Application No. 2013-0056221 (filed on May 20, 201) and Korean Patent Application No. 2015-0083505 (filed on June 20, 2015) .
1. Sub 3-1 1. Sub 3-1 합성예Synthetic example
출발물질인 3-bromo-9H-carbazole (47.03 g, 191.09 mmol)를 둥근바닥플라스크에 THF (850ml)로 녹인 후에, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (70.57 g, 191.09 mmol), Pd(PPh3)4 (6.62 g, 5.73 mmol), K2CO3 (79.23 g, 573.28 mmol), 물 (425ml)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 64.79 g (수율: 83%)을 얻었다.The starting material, 3-bromo-9 H -carbazole ( 47.03 g, 191.09 mmol) was dissolved in the THF (850ml) in a round bottom flask, 9-phenyl-3- (4,4,5,5 -tetramethyl-1, 3,2-dioxaborolan-2-yl) -9 H -carbazole (70.57 g, 191.09 mmol), Pd (PPh 3) 4 (6.62 g, 5.73 mmol), K 2 CO 3 (79.23 g, 573.28 mmol), water (425 ml) was added and stirred at 80 < 0 > C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 64.79 g (yield: 83%) of the product.
2. Sub 3-19 2. Sub 3-19 합성예Synthetic example
출발물질인 4-bromo-9H-carbazole (16.11 g, 65.46 mmol)에 9-([1,1'-biphenyl]-4-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (29.15 g, 65.46 mmol), Pd(PPh3)4 (2.27 g, 1.96 mmol), K2CO3 (27.14 g, 196.38 mmol), THF (290ml), 물 (145ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 24.43 g (수율: 77%)을 얻었다.The starting material, 4-bromo-9 H -carbazole ( 16.11 g, 65.46 mmol) in 9 - ([1,1'-biphenyl] -4-yl) -3- (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl ) -9 H -carbazole (29.15 g, 65.46 mmol), Pd (PPh 3) 4 (2.27 g, 1.96 mmol), K 2 CO 3 (27.14 g, 196.38 mmol), THF (290 ml) and water (145 ml) were added, and 24.43 g of the product (yield: 77%) was obtained using the above Sub 3-1 synthesis method.
3. Sub 3-44 3. Sub 3-44 합성예Synthetic example
출발물질인 4-bromo-9H-carbazole (16.57 g, 67.33 mmol)에 9-(4-(2,6-diphenylpyridin-4-yl)phenyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (40.30 g, 67.33 mmol), Pd(PPh3)4 (2.33 g, 2.02 mmol), K2CO3 (27.91 g, 201.98 mmol), THF (300ml), 물 (150ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 26.62 g (수율: 62%)을 얻었다.The starting material, 4-bromo-9 H -carbazole ( 16.57 g, 67.33 mmol) to 9- (4- (2,6-diphenylpyridin- 4-yl) phenyl) -2- (4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) -9 H -carbazole (40.30 g, 67.33 mmol), Pd (PPh 3) 4 (2.33 g, 2.02 mmol), K 2 CO 3 (27.91 g, 201.98 mmol ), THF (300 ml) and water (150 ml) were added, and 26.62 g (yield: 62%) of the product was obtained using the Sub 3-1 synthesis method.
4. Sub 3-46 4. Sub 3-46 합성예Synthetic example
출발물질인 1-bromo-9H-carbazole (17.21 g, 69.93 mmol)에 9-(naphthalen-2-yl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (29.32 g, 69.93 mmol), Pd(PPh3)4 (2.42 g, 2.10 mmol), K2CO3 (28.99 g, 209.78 mmol), THF (300ml), 물 (150ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 18.60 g (수율: 58%)을 얻었다.To the starting material, 1-bromo-9 H -carbazole (17.21 g, 69.93 mmol) was added 9- (naphthalen-2-yl) -1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl) -9 H -carbazole ( 29.32 g, 69.93 mmol), Pd (PPh 3) 4 (2.42 g, 2.10 mmol), K 2 CO 3 (28.99 g, 209.78 mmol), THF (300ml), water ( 150 ml) was added and 18.60 g (yield: 58%) of the product was obtained using the Sub 3-1 synthesis method.
5. Sub 3-57 5. Sub 3-57 합성예Synthetic example
출발물질인 3-bromo-9H-carbazole (20.53 g, 83.42 mmol)에 9-([1,1'-biphenyl]-3-yl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (37.15 g, 83.42 mmol), Pd(PPh3)4 (2.89 g, 2.50 mmol), K2CO3 (34.59 g, 250.25 mmol), THF (370ml), 물 (185ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 21.83 g (수율: 54%)을 얻었다.To the starting material, 3-bromo-9 H -carbazole (20.53 g, 83.42 mmol) was added 9 - ([1,1'-biphenyl] -3-yl) -1- (4,4,5,5-tetramethyl- , 3,2-dioxaborolan-2-yl ) -9 H -carbazole (37.15 g, 83.42 mmol), Pd (PPh 3) 4 (2.89 g, 2.50 mmol), K 2 CO 3 (34.59 g, 250.25 mmol), THF (370 ml) and water (185 ml) were added, and 21.83 g of the product (yield: 54%) was obtained using the Sub 3-1 synthesis method.
6. Sub 3-62 6. Sub 3-62 합성예Synthetic example
출발물질인 2-bromo-9H-carbazole (13.78 g, 55.99 mmol)에 9-([1,1'-biphenyl]-4-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (24.94 g, 55.99 mmol), Pd(PPh3)4 (1.94 g, 1.68 mmol), K2CO3 (23.21 g, 167.97 mmol), THF (250ml), 물 (125ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 23.06 g (수율: 85%)을 얻었다.The starting material, 2-bromo-9 H -carbazole ( 13.78 g, 55.99 mmol) in 9 - ([1,1'-biphenyl] -4-yl) -2- (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl ) -9 H -carbazole (24.94 g, 55.99 mmol), Pd (PPh 3) 4 (1.94 g, 1.68 mmol), K 2 CO 3 (23.21 g, 167.97 mmol), THF (250 ml) and water (125 ml) were added, and 23.06 g (Yield: 85%) of the product was obtained using the above Sub 3-1 synthesis method.
7. Sub 3-74 7. Sub 3-74 합성예Synthetic example
출발물질인 2-bromo-9H-carbazole (19.10 g, 77.61 mmol)에 9-([1,1'-biphenyl]-3-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (34.56 g, 77.61 mmol), Pd(PPh3)4 (2.69 g, 2.33 mmol), K2CO3 (32.18 g, 232.82 mmol), THF (340ml), 물 (170ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 33.10 g (수율: 88%)을 얻었다.The starting material, 2-bromo-9 H -carbazole ( 19.10 g, 77.61 mmol) in 9 - ([1,1'-biphenyl] -3-yl) -3- (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl ) -9 H -carbazole (34.56 g, 77.61 mmol), Pd (PPh 3) 4 (2.69 g, 2.33 mmol), K 2 CO 3 (32.18 g, 232.82 mmol), THF (340 ml) and water (170 ml) were added, and 33.10 g (yield: 88%) of the product was obtained using the above Sub 3-1 synthesis method.
8. Sub 3-92 8. Sub 3-92 합성예Synthetic example
출발물질인 4-bromo-9H-carbazole (15.12 g, 61.44 mmol)에 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[4,5]thieno[2,3-c]pyridine (19.12 g, 61.44 mmol), Pd(PPh3)4 (2.13 g, 1.84 mmol), K2CO3 (25.47 g, 184.31 mmol), THF (270ml), 물 (140ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 14.86 g (수율: 69%)을 얻었다.The starting material, 4-bromo-9 H -carbazole 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [4,5] in (15.12 g, 61.44 mmol) thieno [2,3-c] pyridine ( 19.12 g, 61.44 mmol), Pd (PPh 3) 4 (2.13 g, 1.84 mmol), K 2 CO 3 (25.47 g, 184.31 mmol), THF (270ml), water ( 140 ml) was added, and 14.86 g (yield: 69%) of the product was obtained using the Sub 3-1 synthesis method.
9. Sub 3-96 9. Sub 3-96 합성예Synthetic example
출발물질인 1-bromo-9H-carbazole (16.61 g, 67.49 mmol)에 2-(9,9-diphenyl-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (29.99 g, 67.49 mmol), Pd(PPh3)4 (2.34 g, 2.02 mmol), K2CO3 (27.98 g, 202.47 mmol), THF (300ml), 물 (150ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 24.81 g (수율: 76%)을 얻었다.The starting material, 1-bromo-9 H -carbazole ( 16.61 g, 67.49 mmol) 2- (9,9-diphenyl-9 H -fluoren-4-yl) to -4,4,5,5-tetramethyl-1, a 3,2-dioxaborolane (29.99 g, 67.49 mmol), Pd (PPh 3) 4 (2.34 g, 2.02 mmol), K 2 CO 3 (27.98 g, 202.47 mmol), THF (300ml), water (150ml) was added And 24.81 g (yield: 76%) of the product was obtained using the Sub 3-1 synthesis method.
10. Sub 3-112 10. Sub 3-112 합성예Synthetic example
출발물질인 3-bromo-9H-carbazole (18.40 g, 74.76 mmol)에 2-(dibenzo[b,d]thiophen-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (23.19 g, 74.76 mmol), Pd(PPh3)4 (2.59 g, 2.24 mmol), K2CO3 (31.00 g, 224.29 mmol), THF (320ml), 물 (160ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 21.42 g (수율: 82%)을 얻었다.The starting material, 3-bromo-9 H -carbazole ( 18.40 g, 74.76 mmol) in 2- (dibenzo [b, d] thiophen-3-yl) -4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (23.19 g, 74.76 mmol) , Pd (PPh 3) 4 (2.59 g, 2.24 mmol), K 2 CO 3 (31.00 g, 224.29 mmol), THF (320ml), was added water (160ml) and the Sub Using the 3-1 synthesis method, 21.42 g of the product (yield: 82%) was obtained.
11. Sub 3-113 11. Sub 3-113 합성예Synthetic example
출발물질인 3-bromo-9H-carbazole (17.19 g, 69.85 mmol)에 2-(dibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20.55 g, 69.85 mmol), Pd(PPh3)4 (2.42 g, 2.10 mmol), K2CO3 (28.96 g, 209.54 mmol), THF (300ml), 물 (150ml)을 첨가하고 상기 Sub 3-1 합성법을 사용하여 생성물 18.63 g (수율: 80%)을 얻었다.The starting material, 3-bromo-9 H -carbazole ( 17.19 g, 69.85 mmol) in 2- (dibenzo [b, d] furan-3-yl) -4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (20.55 g, 69.85 mmol) , Pd (PPh 3) 4 (2.42 g, 2.10 mmol), K 2 CO 3 (28.96 g, 209.54 mmol), was added to THF (300ml), water (150ml) and the Sub 3-1 Using the synthetic method, 18.63 g (yield: 80%) of the product was obtained.
Sub 3에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 4는 Sub 3에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 3 may be, but not limited to, the following compounds, and Table 4 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 3.
II. Sub 4의 합성II. Synthesis of Sub 4
상기 반응식 4의 Sub 4는 하기 반응식 6의 반응경로에 의해 합성되며, 이에 한정되는 것은 아니다. 이때, Hal2 및 Hal3은 Br 또는 Cl이다.Sub 4 of Scheme 4 is synthesized by the reaction path of Scheme 6 below, but is not limited thereto. Wherein Hal 2 and Hal 3 are Br or Cl.
<반응식 6><Reaction Scheme 6>
1. Sub 4-37 1. Sub 4-37 합성예Synthetic example
출발물질인 4-bromo-2-chloro-6-phenylpyrimidine (CAS Registry Number: 1412955-57-7) (21.85 g, 81.07 mmol)을 둥근바닥플라스크에 THF (280ml)로 녹인 후에, 4,4,5,5-tetramethyl-2-(naphthalen-2-yl)-1,3,2-dioxaborolane (CAS Registry Number: 256652-04-7) (22.66 g, 89.17 mmol), Pd(PPh3)4 (3.75 g, 3.24 mmol), K2CO3 (33.61 g, 243.20 mmol), 물 (140ml)을 첨가하고 90℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 19.52 g (수율: 76%)를 얻었다.The starting material, 4-bromo-2-chloro-6-phenylpyrimidine (CAS Registry Number: 1412955-57-7) (21.85 g, 81.07 mmol) was dissolved in 280 ml of THF in a round bottom flask, , 5-tetramethyl-2- (naphthalen -2-yl) -1,3,2-dioxaborolane (CAS Registry Number: 256652-04-7) (22.66 g, 89.17 mmol), Pd (PPh 3) 4 (3.75 g, 3.24 mmol), K 2 CO 3 (33.61 g, 243.20 mmol) and water (140 ml) were added and stirred at 90 ° C. After completion of the reaction, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 19.52 g of the product (yield: 76%).
2. Sub 4-46 2. Sub 4-46 합성예Synthetic example
출발물질인 1,4-dibromobenzene (CAS Registry Number: 106-37-6) (17.80 g, 75.45 mmol)에 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine (CAS Registry Number: 1402237-88-0) (29.73 g, 83.00 mmol), Pd(PPh3)4 (3.49 g, 3.02 mmol), K2CO3 (31.28 g, 226.36 mmol), THF (260ml), 물 (130ml)을 첨가하고 상기 Sub 4-37 합성법을 사용하여 생성물 21.33 g (수율: 73%)를 얻었다.1,4-dibromobenzene (CAS Registry Number: 106-37-6) (17.80 g, 75.45 mmol) was added to the starting material 2,4-diphenyl-6- (4,4,5,5- 2-dioxaborolan-2-yl) pyrimidine (CAS Registry Number: 1402237-88-0) (29.73 g, 83.00 mmol), Pd (PPh 3) 4 (3.49 g, 3.02 mmol), K 2 CO 3 (31.28 g, 226.36 mmol), THF (260 ml) and water (130 ml) were added, and 21.33 g of the product (yield: 73%) was obtained using the Sub 4-37 synthesis method described above.
3. Sub 4-68 3. Sub 4-68 합성예Synthetic example
(1) Sub 4-I-68 합성(1) Sub 4-I-68 synthesis
출발물질인 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol)를 둥근바닥플라스크에 urea (CAS Registry Number: 57-13-6) (168.69 g, 2808.75 mmol)와 함께 넣고 160℃에서 교반하였다. TLC로 반응을 확인한 후, 100℃까지 냉각시키고 물 (200ml)을 첨가하여 1시간 동안 교반하였다. 반응이 완료되면 생성된 고체를 감압여과하고 물로 세척 후 건조하여 생성물 63.86 g (수율: 75%)를 얻었다.The starting material, 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was added to a round bottom flask with urea (CAS Registry Number: 57-13-6) 2808.75 mmol) and stirred at 160 < 0 > C. After the reaction was confirmed by TLC, the reaction mixture was cooled to 100 ° C, water (200 ml) was added, and the mixture was stirred for 1 hour. After completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water, and then dried to obtain 63.86 g (yield: 75%) of the product.
(2) Sub 4-II-68 합성(2) Sub 4-II-68 Synthesis
상기 합성에서 얻어진 Sub 4-I-68 (63.86 g, 300.94 mmol)을 둥근바닥플라스크에 POCl3 (200ml)를 상온에서 녹인 후에, N,N-Diisopropylethylamine (97.23 g, 752.36 mmol)을 천천히 적가시킨 후, 90℃에서 교반하였다. 반응이 완료되면 농축 한 후 얼음물 (500ml)을 넣고 상온에서 1시간 동안 교반하였다. 생성된 고체를 감압여과하고 건조하여 생성물 67.47 g (수율: 90%)를 얻었다. N , N- Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise to the round bottom flask of Sub 4-I-68 (63.86 g, 300.94 mmol) obtained in the above synthesis by dissolving POCl 3 , And stirred at 90 ° C. After completion of the reaction, the reaction mixture was concentrated, and then ice water (500 ml) was added thereto, followed by stirring at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g (yield: 90%) of the product.
(3) Sub 4-68 합성(3) Sub 4-68 Synthesis
상기 합성에서 얻어진 Sub 4-II-68 (27.05 g, 108.60 mmol)에 4,4,5,5-tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane (CAS Registry Number: 68716-52-9) (30.36 g, 119.45 mmol), Pd(PPh3)4 (5.02 g, 4.34 mmol), K2CO3 (45.03 g, 325.79 mmol), THF (380ml), 물 (190ml)을 첨가하고 상기 Sub 4-37 합성법을 사용하여 생성물 22.21 g (수율: 60%)를 얻었다.4,4,5,5-tetramethyl-2- (naphthalen-1-yl) -1,3,2-dioxaborolane (CAS Registry Number: 68716-52-9) (30.36 g, 119.45 mmol ), Pd (PPh 3) 4 (Yield: 60%) of the product using the Sub 4-37 synthesis method, to which was added potassium carbonate (5.02 g, 4.34 mmol), K 2 CO 3 (45.03 g, 325.79 mmol), THF (380 ml) .
4. Sub 4-86 4. Sub 4-86 합성예Synthetic example
출발물질인 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (CAS Registry Number: 160199-05-3) (38.00 g, 148.95 mmol)에 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (CAS Registry Number: 24388-23-6) (33.44 g, 163.84 mmol), Pd(PPh3)4 (6.88 g, 5.96 mmol), K2CO3 (61.76 g, 446.85 mmol), THF (520ml), 물 (260ml)을 첨가하고 상기 Sub 4-37 합성법을 사용하여 생성물 17.68 g (수율: 40%)를 얻었다.The starting material, 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (CAS Registry Number: 160199-05-3) (38.00 g, 148.95 mmol) -2-phenyl-1,3,2-dioxaborolane ( CAS Registry Number: 24388-23-6) (33.44 g, 163.84 mmol), Pd (PPh 3) 4 (6.88 g, 5.96 mmol), K 2 CO 3 ( 61.76 g, 446.85 mmol), THF (520 ml) and water (260 ml) were added, and 17.68 g (Yield: 40%) of the product was obtained using the Sub 4-37 synthesis method.
5. Sub 4-88 5. Sub 4-88 합성예Synthetic example
출발물질인 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (CAS Registry Number: 160199-05-3) (35.15 g, 137.78 mmol)에 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 947770-80-1) (44.58 g, 151.56 mmol), Pd(PPh3)4 (6.37 g, 5.51 mmol), K2CO3 (57.13 g, 413.33 mmol), THF (480ml), 물 (240ml)을 첨가하고 상기 Sub 4-37 합성법을 사용하여 생성물 22.92 g (수율: 43%)를 얻었다.(Dibenzo [b, d] pyrimidin-2-one) was added to the starting material 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (CAS Registry Number: 160199-05-3) (35.15 g, 137.78 mmol) (CAS Registry furan-2-yl ) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Number: 947770-80-1) (44.58 g, 151.56 mmol), Pd (PPh 3) 4 (Yield: 43%) of the product using the Sub-4-37 synthetic method, to which was added potassium carbonate (6.37 g, 5.51 mmol), K 2 CO 3 (57.13 g, 413.33 mmol), THF (480 ml) .
6. Sub 4-92 6. Sub 4-92 합성예Synthetic example
출발물질인 2,4-dichlorobenzofuro[2,3-d]pyrimidine (CAS Registry Number: 1801325-92-7) (41.43 g, 173.30 mmol)에 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (CAS Registry Number: 24388-23-6) (38.90 g, 190.63 mmol), Pd(PPh3)4 (8.01 g, 6.93 mmol), K2CO3 (71.86 g, 519.91 mmol), THF (600ml), 물 (300ml)을 첨가하고 상기 Sub 4-37 합성법을 사용하여 생성물 18.49 g (수율: 38%)를 얻었다.4,4,5,5-tetramethyl-2-phenyl-1 (4,4,5,5-tetramethylpiperidine) was added to the starting material, 2,4- dichlorobenzofuro [2,3-d] pyrimidine (CAS Registry Number: 1801325-92-7) , 3,2-dioxaborolane (CAS Registry Number : 24388-23-6) (38.90 g, 190.63 mmol), Pd (PPh 3) 4 (8.01 g, 6.93 mmol), K 2 CO 3 (71.86 g, 519.91 mmol) , THF (600 ml) and water (300 ml) were added, and 18.49 g (yield: 38%) of the product was obtained using the Sub 4-37 synthesis method.
Sub 4에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 5는 Sub 4에 속하는 일부 화합물의 FD-MS(Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.The compound belonging to Sub 4 may be, but not limited to, the following compounds, and Table 5 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 4.
III. Final Product 2 합성III. Final Product 2 Composite
Sub 3 (1 당량)을 둥근바닥플라스크에 Toluene으로 녹인 후에, Sub 4 (1.1 당량), Pd2(dba)3 (0.03 당량), (t-Bu)3P (0.06 당량), NaOt-Bu (3 당량)을 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Final product 2를 얻었다.After Sub 3 (1 eq.) Was dissolved in toluene in a round bottom flask, Sub 4 (1.1 eq.), Pd 2 (dba) 3 (0.03 eq.), ( T- Bu) 3 P (0.06 eq.) And NaO t- Bu (3 eq.) Were stirred at 100 < 0 > C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain final product 2.
1. 2-2 1. 2-2 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (8.62 g, 21.10 mmol)을 둥근바닥플라스크에 toluene (220ml)으로 녹인 후에, Sub 4-11 (CAS Registry Number: 1762-84-1) (7.18 g, 23.21 mmol), Pd2(dba)3 (0.58 g, 0.63 mmol), P(t-Bu)3 (0.26 g, 1.27 mmol), NaOt-Bu (6.08 g, 63.30 mmol)을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 10.62 g (수율: 79%)를 얻었다.Sub-4-1 (CAS Registry Number: 1762-84-1) (7.18 g, 23.21 mmol) was dissolved in toluene (220 ml) in a round bottom flask, and Sub 3-1 (8.62 g, 21.10 mmol) , Pd 2 (dba) 3 (0.58 g, 0.63 mmol), P ( t- Bu) 3 (0.26 g, 1.27 mmol) and NaO t- Bu (6.08 g, 63.30 mmol) were added and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.62 g (yield: 79%) of the product.
2. 2-3 2. 2-3 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (7.49 g, 18.34 mmol)에 Sub 4-30 (CAS Registry Number: 94994-62-4) (6.50 g, 20.17 mmol), Pd2(dba)3 (0.50 g, 0.55 mmol) P(t-Bu)3 (0.22 g, 1.10 mmol), NaOt-Bu (5.29 g, 55.01 mmol), toluene (195ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 10.01 g (수율: 84%)를 얻었다.Sub 4-30 (CAS Registry Number: 94994-62-4) (6.50 g, 20.17 mmol) and Pd 2 (dba) 3 (0.50 g, 0.55 mmol) were added to Sub 3-1 (7.49 g, 18.34 mmol) mmol) P (t -Bu) 3 (0.22 g, 1.10 mmol), NaO t -Bu (5.29 g, 55.01 mmol), was added to toluene (195ml) using the product 2-2 synthesis 10.01 g (yield: 84%).
3. 2-4 3. 2-4 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (7.55 g, 18.48 mmol)에 Sub 4-50 (CAS Registry Number: 80984-79-8) (6.35 g, 20.33 mmol), Pd2(dba)3 (0.51 g, 0.55 mmol) P(t-Bu)3 (0.22 g, 1.11 mmol), NaOt-Bu (5.33 g, 55.45 mmol), toluene (195ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 10.17 g (수율: 86%)를 얻었다.Sub-4-50 (CAS Registry Number: 80984-79-8) (6.35 g, 20.33 mmol), Pd 2 (dba) 3 (0.51 g, 0.55 mmol) was added to Sub 3-1 (7.55 g, 18.48 mmol) mmol) P (t -Bu) 3 (0.22 g, 1.11 mmol), NaO t -Bu (5.33 g, 55.45 mmol), was added to toluene (195ml) using the product 2-2 synthesis 10.17 g (yield: 86%).
4. 2-10 4. 2-10 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (8.10 g, 19.83 mmol)에 Sub 4-61 (CAS Registry Number: 29874-83-7) (5.25 g, 21.81 mmol), Pd2(dba)3 (0.54 g, 0.59 mmol) P(t-Bu)3 (0.24 g, 1.19 mmol), NaOt-Bu (5.72 g, 59.49 mmol), toluene (210ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 9.84 g (수율: 81%)를 얻었다.(CAS Registry Number: 29874-83-7) (5.25 g, 21.81 mmol), Pd 2 (dba) 3 (0.54 g, 0.59 mmol) was added to Sub 3-1 (8.10 g, 19.83 mmol) mmol) P ( t- Bu) 3 (0.24 g, 1.19 mmol), NaO t- Bu (5.72 g, 59.49 mmol) and toluene (210 ml) 81%).
5. 2-14 5. 2-14 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (9.93 g, 24.31 mmol)에 Sub 4-74 (CAS Registry Number: 7065-92-1) (6.44 g, 26.74 mmol), Pd2(dba)3 (0.67 g, 0.73 mmol) P(t-Bu)3 (0.30 g, 1.46 mmol), NaOt-Bu (7.01 g, 72.93 mmol), toluene (255ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 9.98 g (수율: 67%)를 얻었다.Sub-4-74 (CAS Registry Number: 7065-92-1) (6.44 g, 26.74 mmol) and Pd 2 (dba) 3 (0.67 g, 0.73 mmol) were added to Sub 3-1 (9.93 g, 24.31 mmol) mmol) P (t -Bu) 3 (0.30 g, 1.46 mmol), NaO t -Bu (7.01 g, 72.93 mmol), was added to toluene (255ml) and the product was 9.98 using the synthetic method 2-2 g (yield: 67%).
6. 2-19 6. 2-19 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-1 (6.44 g, 15.76 mmol)에 Sub 4-86 (5.15 g, 17.34 mmol), Pd2(dba)3 (0.43 g, 0.47 mmol) P(t-Bu)3 (0.19 g, 0.95 mmol), NaOt-Bu (4.55 g, 47.29 mmol), toluene (165ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 8.96 g (수율: 85%)를 얻었다.Obtained in the above Synthesis Sub 3-1 (6.44 g, 15.76 mmol ) in Sub 4-86 (5.15 g, 17.34 mmol ), Pd 2 (dba) 3 (0.43 g, 0.47 mmol) P (t -Bu) 3 (0.19 g, 0.95 mmol), NaO t- Bu (4.55 g, 47.29 mmol) and toluene (165 ml) were added and the product 2. 2-2 was used to obtain 8.96 g (yield: 85%) of the product.
7. 2-31 7. 2-31 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-19 (10.28 g, 21.21 mmol)에 Sub 4-74 (CAS Registry Number: 7065-92-1) (5.62 g, 23.33 mmol), Pd2(dba)3 (0.58 g, 0.64 mmol) P(t-Bu)3 (0.26 g, 1.27 mmol), NaOt-Bu (6.12 g, 63.64 mmol), toluene (225ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 9.35 g (수율: 64%)를 얻었다.Sub-4-74 (CAS Registry Number: 7065-92-1) (5.62 g, 23.33 mmol) and Pd 2 (dba) 3 (0.58 g, 0.64 mmol) were added to Sub 3-19 (10.28 g, 21.21 mmol) mmol) P ( t- Bu) 3 (0.26 g, 1.27 mmol), NaO t- Bu (6.12 g, 63.64 mmol) and toluene (225 ml) 64%).
8. 2-54 8. 2-54 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-44 (9.12 g, 14.30 mmol)에 Sub 4-36 (CAS Registry Number: 56181-49-8) (4.89 g, 15.73 mmol), Pd2(dba)3 (0.39 g, 0.43 mmol) P(t-Bu)3 (0.17 g, 0.86 mmol), NaOt-Bu (4.12 g, 42.90 mmol), toluene (150ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 8.69 g (수율: 70%)를 얻었다.Sub-4-36 (CAS Registry Number: 56181-49-8) (4.89 g, 15.73 mmol) and Pd 2 (dba) 3 (0.39 g, 0.43 mmol) were added to Sub 3-44 mmol) P ( t- Bu) 3 (0.17 g, 0.86 mmol), NaO t- Bu (4.12 g, 42.90 mmol) and toluene (150 ml) 70%).
9. 2-60 9. 2-60 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-46 (9.45 g, 20.61 mmol)에 Sub 4-92 (6.36 g, 22.67 mmol), Pd2(dba)3 (0.57 g, 0.62 mmol) P(t-Bu)3 (0.25 g, 1.24 mmol), NaOt-Bu (5.94 g, 61.82 mmol), toluene (215ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 9.12 g (수율: 63%)를 얻었다.P ( t- Bu) 3 (0.25 g, 0.62 mmol) and Pd 2 (dba) 3 (6.36 g, 22.67 mmol) were added to Sub 3-46 (9.45 g, 20.61 mmol) g, 1.24 mmol), NaO t- Bu (5.94 g, 61.82 mmol) and toluene (215 ml) were added and the product was obtained using 9.2 g (yield: 63%).
10. 2-67 10. 2-67 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-57 (8.30 g, 17.13 mmol)에 Sub 4-51 (CAS Registry Number: 2011776-79-5) (6.82 g, 18.84 mmol), Pd2(dba)3 (0.47 g, 0.51 mmol) P(t-Bu)3 (0.21 g, 1.03 mmol), NaOt-Bu (4.94 g, 51.38 mmol), toluene (180ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 10.36 g (수율: 79%)를 얻었다.Sub-4-51 (CAS Registry Number: 2011776-79-5) (6.82 g, 18.84 mmol) and Pd 2 (dba) 3 (0.47 g, 0.51 mmol) were added to Sub 3-57 (8.30 g, 17.13 mmol) 10.36 g (Yield: 95%) of the product was obtained using the above 2-2 synthesis method by adding P ( t- Bu) 3 (0.21 g, 1.03 mmol), NaO t- Bu (4.94 g, 51.38 mmol) 79%).
11. 2-73 11. 2-73 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-62 (11.01 g, 22.72 mmol)에 Sub 4-53 (CAS Registry Number: 1646152-18-2) (10.30 g, 24.99 mmol), Pd2(dba)3 (0.62 g, 0.68 mmol) P(t-Bu)3 (0.28 g, 1.36 mmol), NaOt-Bu (6.55 g, 68.16 mmol), toluene (240ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 12.61 g (수율: 68%)를 얻었다.Sub-53 (CAS Registry Number: 1646152-18-2) (10.30 g, 24.99 mmol) and Pd 2 (dba) 3 (0.62 g, 0.68 mmol) were added to Sub 3-62 (11.01 g, 22.72 mmol) mmol), P ( t- Bu) 3 (0.28 g, 1.36 mmol), NaO t- Bu (6.55 g, 68.16 mmol) and toluene (240 ml) 68%).
12. 2-84 12. 2-84 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-74 (9.03 g, 18.63 mmol)에 Sub 4-37 (7.40 g, 20.50 mmol), Pd2(dba)3 (0.51 g, 0.56 mmol) P(t-Bu)3 (0.23 g, 1.12 mmol), NaOt-Bu (5.37 g, 55.90 mmol), toluene (195ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 12.40 g (수율: 87%)를 얻었다.Obtained in the above Synthesis Sub 3-74 (9.03 g, 18.63 mmol ) in Sub 4-37 (7.40 g, 20.50 mmol ), Pd 2 (dba) 3 (0.51 g, 0.56 mmol) P (t -Bu) 3 (0.23 g, 1.12 mmol), NaO t- Bu (5.37 g, 55.90 mmol) and toluene (195 ml) were added to the reaction mixture to obtain 12.40 g of the product (yield: 87%).
13. 2-112 13. 2-112 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-92 (7.28 g, 20.77 mmol)에 Sub 4-68 (7.79 g, 22.85 mmol), Pd2(dba)3 (0.57 g, 0.62 mmol) P(t-Bu)3 (0.25 g, 1.25 mmol), NaOt-Bu (5.99 g, 62.32 mmol), toluene (220ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 8.43 g (수율: 62%)를 얻었다.P ( t- Bu) 3 (0.25 g, 0.62 mmol), Sub 4-68 (7.79 g, 22.85 mmol), Pd 2 (dba) 3 (0.57 g, 0.62 mmol) was added to Sub 3-92 (7.28 g, 20.77 mmol) g, 1.25 mmol), NaO t- Bu (5.99 g, 62.32 mmol) and toluene (220 ml) were added and the product 2:2 was used to obtain 8.43 g of the product (yield: 62%).
14. 2-116 14. 2-116 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-96 (10.07 g, 20.82 mmol)에 Sub 4-61 (CAS Registry Number: 29874-83-7) (5.51 g, 22.90 mmol), Pd2(dba)3 (0.57 g, 0.62 mmol) P(t-Bu)3 (0.25 g, 1.25 mmol), NaOt-Bu (6.00 g, 62.47 mmol), toluene (220ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 9.31 g (수율: 65%)를 얻었다.Sub-4-61 (CAS Registry Number: 29874-83-7) (5.51 g, 22.90 mmol) and Pd 2 (dba) 3 (0.57 g, 0.62 mmol) were added to Sub 3-96 (10.07 g, 20.82 mmol) mmol) P ( t- Bu) 3 (0.25 g, 1.25 mmol), NaO t- Bu (6.00 g, 62.47 mmol) and toluene (220 ml) 65%).
15. 2-131 15. 2-131 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-112 (8.83 g, 25.27 mmol)에 Sub 4-88 (10.75 g, 27.80 mmol), Pd2(dba)3 (0.69 g, 0.76 mmol) P(t-Bu)3 (0.31 g, 1.52 mmol), NaOt-Bu (7.29 g, 75.80 mmol), toluene (265ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 12.73 g (수율: 72%)를 얻었다.Obtained in the above Synthesis Sub 3-112 (8.83 g, 25.27 mmol ) in Sub 4-88 (10.75 g, 27.80 mmol ), Pd 2 (dba) 3 (0.69 g, 0.76 mmol) P (t -Bu) 3 (0.31 g, 1.52 mmol), NaO t- Bu (7.29 g, 75.80 mmol) and toluene (265 ml) were added to the reaction mixture to obtain 12.73 g (yield: 72%) of the product.
16. 2-133 16. 2-133 합성예Synthetic example
상기 합성에서 얻어진 Sub 3-113 (6.84 g, 20.52 mmol)에 Sub 4-46 (8.74 g, 22.57 mmol), Pd2(dba)3 (0.56 g, 0.62 mmol) P(t-Bu)3 (0.25 g, 1.23 mmol), NaOt-Bu (5.92 g, 61.55 mmol), toluene (215ml)을 첨가하고 상기 2-2 합성법을 사용하여 생성물 10.11 g (수율: 77%)를 얻었다.P ( t- Bu) 3 (0.25 g, 0.62 mmol) and Pd 2 (dba) 3 (8.74 g, 22.57 mmol) were added to Sub 3-113 (6.84 g, 20.52 mmol) g, 1.23 mmol), NaO t- Bu (5.92 g, 61.55 mmol) and toluene (215 ml) were added and 10.11 g (yield: 77%) of the product was obtained using the 2-2 synthesis method.
한편, 상기와 같은 합성예에 따라 제조된 본 발명의 화합물 2-1 내지 2-135의 FD-MS 값은 하기 표 6과 같다.The FD-MS values of the compounds 2-1 to 2-135 of the present invention prepared according to the above Synthesis Examples are shown in Table 6 below.
한편, 상기에서는 화학식 1 및 화학식 2로 표시되는 본 발명의 예시적 합성예를 설명하였지만, 이들은 모두 Buchwald-Hartwig cross coupling 반응, Miyaura boration 반응, Suzuki cross-coupling 반응, Intramolecular acid-induced cyclization 반응 (J. mater. Chem . 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization 반응 (Org . Lett . 2011, 13, 5504) 및 PPh3-mediated reductive cyclization 반응 (J. Org . Chem. 2005, 70, 5014.)등에 기초한 것으로 구체적 합성예에 명시된 치환기 이외에 화학식 1 및 화학식 2에 정의된 다른 치환기 (X1, X2, L1 내지 L4, Ar1 내지 Ar5, A, B, C, D, E 및 F등의 치환기)가 결합되더라도 상기 반응이 진행된다는 것을 당업자라면 쉽게 이해할 수 있을 것이다.On the other hand, the In been described an exemplary composite of the present invention represented by Formula 1 and Formula 2, all of Buchwald-Hartwig cross coupling reaction, Miyaura boration reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (J . mater. Chem. 1999, 9 , 2095.), Pd (II) -catalyzed oxidative cyclization reaction (Org. Lett. 2011, 13 , 5504) , and PPh 3 -mediated reductive cyclization reaction (J. Org. Chem. 2005, 70, 5014.) or the like in addition to the substituents specifically set forth in synthetic example formulas (1) and the other substituents (X 1, X 2 are defined in formula (2), based on L 1 to L 4, Ar 1 to Ar 5, a, B, C , D, E, and F) are bonded to each other, the reaction proceeds.
유기전기소자의 제조평가Evaluation of manufacturing of organic electric device
[[ 실시예Example 1] 내지 [ 1] to [ 실시예Example 137] 137] 적색유기전기발광소자Red organic electroluminescent device ( ( 발광층The light- 혼합 인광호스트) Mixed phosphorescent host)
먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 정공주입층으로서 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (이하 NPB로 약기함)을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공수송층 상부에 호스트로서 화학식 1 (제 1 호스트)과 화학식 2 (제 2 호스트)로 표시되는 본 발명 화합물(표 7에 기재)을3:7로 혼합한 혼합물을 사용하였으며, 도판트로서는 (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate]을 5% 중량으로 도핑함으로써 상기 정공수송층 위에 30nm 두께의 발광층을 증착하였다. 정공저지층으로 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 Bis(10-hydroxybenzo[h]quinolinato)beryllium (이하 BeBq2로 약칭함)을 50 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전기발광소자를 제조하였다.First, a 4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] triphenylamine (abbreviated as 2-TNATA) film was vacuum deposited on the ITO layer (anode) (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as NPB) (Shown in Table 7) represented by Formula 1 (first host) and Formula 2 (second host) as a host were immersed in a 3: 7 was doped with 5 wt% of (piq) 2 Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] as a dopant to form a 30 nm thick light emitting layer on the hole transport layer (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer , Electronic To the transport layer Bis (10-hydroxybenzo [h] quinolinato) beryllium ( hereinafter referred to as BeBq 2) was formed in 50 nm thick, and since, depositing a halogenated alkali metal, LiF to the electron injection layer to 0.2 nm thickness, Subsequently, Al was deposited to a thickness of 150 nm and used as a cathode to produce an organic electroluminescent device.
[[ 비교예Comparative Example 1] 내지 [ 1] to [ 비교예Comparative Example 3] 3]
화학식 2로 표시되는 본 발명 화합물(표 7에 기재)을 단독으로 호스트로 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic EL device was prepared in the same manner as in Example 1 except that the compound of the present invention represented by the formula (2) (described in Table 7) was used as a host alone.
[[ 비교예Comparative Example 4] 4]
비교화합물 v1과 본 발명 화합물 2-4를 혼합하여 호스트로 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescence device was fabricated in the same manner as in Example 1 except that Comparative Compound v1 and Compound 2-4 of the present invention were mixed and used as a host.
본 발명의 실시예 1 내지 실시예 137 및 비교예 1 내지 비교예 4에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch) 사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 2500cd/m2 기준휘도에서 맥사이언스사의 수명측정장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 7과 같다.A forward bias DC voltage was applied to the organic electroluminescent devices manufactured in Examples 1 to 137 and Comparative Examples 1 to 4, and electroluminescence (EL) characteristics were measured with a photoresearch PR-650 And the T95 lifetime was measured at a luminance of 2500 cd / m < 2 > through a lifetime measuring device of Mac Science Inc., and the measurement results are shown in Table 7 below.
(V)Driving voltage
(V)
(mA/cm2)electric current
(mA / cm 2)
(cd/m2)Luminance
(cd / m < 2 &
(cd/A)efficiency
(cd / A)
T(95)life span
T (95)
상기 표 7의 결과로부터 알 수 있듯이, 화학식 1과 화학식 2로 표시되는 본 발명의 유기전기발광소자용 재료를 혼합하여 인광 호스트로 사용할 경우 (실시예 1 내지 실시예 137), 단일물질을 사용한 소자(비교예 1 내지 비교예 3)이거나 비교화합물 v1과 본 발명 화합물 2-4를 혼합하여 인광호스트로 사용한 소자(비교예 4)보다 구동전압, 효율 및 수명을 현저히 개선시키는 것을 확인 할 수 있다.As can be seen from the results of Table 7, when the organic electroluminescence device material of the present invention represented by the formulas (1) and (2) is mixed to be used as a phosphorescent host (Examples 1 to 137) (Comparative Example 1 to Comparative Example 3), or Comparative Compound v1 and Compound 2-4 of the present invention were mixed to remarkably improve driving voltage, efficiency, and lifetime, compared with the device using as a phosphorescent host (Comparative Example 4).
특히, 단독물질을 사용한 비교예 1 내지 비교예 3보다 비교화합물 v1과 본 발명 화합물 2-4를 혼합하여 인광호스트로 사용한 비교예 4가 좀 더 높은 효율을 나타내는 것을 확인 할 수 있으며, 상기 비교예 4의 경우보다 본 발명 화합물인 화학식 1과 화학식 2의 화합물을 혼합하여 호스트로 사용한 실시예 1 내지 실시예 137이 현저히 높은 효율 및 수명을 나타내는 것을 확인할 수 있다.Particularly, it can be confirmed that Comparative Example 4 using Comparative Compound v1 and Compound 2-4 as a phosphorescent host by mixing the compound of Comparative Example v1 with the compound of Comparative Example 1, which is a single substance, shows a higher efficiency, It can be confirmed that Examples 1 to 137 using the compounds of the present invention as a host by mixing the compounds of the formulas (1) and (2) with the compounds of the present invention exhibited remarkably high efficiency and long life.
본 발명자들은 상기 실험결과를 근거로 화학식 1의 물질과 화학식 2의 물질을 혼합한 물질의 경우 각각 물질에 대한 특성 이외의 다른 신규한 특성을 갖는다고 판단하여, 화학식 1의 물질, 화학식 2의 물질, 본 발명 혼합물을 각각 사용하여 PL lifetime을 측정하였다. 그 결과 본 발명 화합물인 화학식 1과 화학식 2를 혼합하였을 경우 단독 화합물일 때와 달리 새로운 PL 파장이 형성되는 것을 확인할 수 있었으며, 새롭게 형성된 PL 파장의 감소 및 소멸 시간은 화학식 1 및 화학식 2 물질 각각의 감소 및 소멸시간 보다 작게는 약 60배에서 많게는 약 360배까지 증가하는 하는 것을 확인할 수 있었다. 이는 본 발명화합물을 혼합하여 사용할 경우 각각의 물질이 갖는 에너지 준위를 통해 전자와 정공이 이동되는 것뿐만 아니라, 혼합으로 인하여 형성된 새로운 에너지 준위를 갖는 신규 영역에(exciplex) 의한 전자, 정공 이동 또는 에너지 전달로 효율 및 수명이 증가하는 것으로 판단된다. 이는 결과적으로 상기 본 발명 혼합물을 사용할 경우 혼합 박막이 exciplex 에너지 전달 및 발광 프로세스를 보이는 중요한 예라고 할 수 있다.On the basis of the above experimental results, the inventors of the present invention have found that a substance obtained by mixing a substance of the formula (1) and a substance of the formula (2) has novel characteristics other than those of the substance, , And the mixture of the present invention was used to measure PL lifetime. As a result, it was confirmed that a new PL wavelength was formed when the compounds of the present invention were combined with the compounds of the formulas (1) and (2), and the newly formed PL wavelength was reduced and the decay time was Decrease and decay time from about 60 times to about 360 times. When mixed with the compound of the present invention, not only electrons and holes are moved through the energy level of each substance, but also electrons, holes, or energy (exciplex) due to exciplex in a new region having a new energy level It is considered that the efficiency and life span of the transmission line are increased. As a result, when the mixture of the present invention is used, the mixed thin film is an important example showing the exciplex energy transfer and light emitting process.
또한 본 발명의 조합이 우수한 이유는 electron 뿐만 아니라 hole에 대한 안정성, 높은 T1 등의 특징이 있는 화학식 2로 표시되는 비스타입의 헤테로고리 화합물에 hole 특성이 강한 화학식 1로 표시되는 화합물을 혼합할 경우, 높은 T1과 높은 LUMO 에너지 값으로 인해 전자 블로킹 능력이 향상되고, 발광층에 더 많은 hole이 빠르고 쉽게 이동하게 된다. 이에 따라 정공과 전자의 발광층 내 charge balance가 증가되어 정공수송층 계면이 아닌 발광층 내부에서 발광이 잘 이루지고, 그로 인해 HTL 계면에 열화 또한 감소하여 소자 전체의 구동 전압, 효율 그리고 수명이 극대화 된다고 판단된다. 즉, 결론적으로 화학식 1과 화학식 2의 조합이 전기 화학적으로 시너지 작용을 하여 소자 전체의 성능을 향상된 것으로 사료된다.The reason why the combination of the present invention is superior is that when a compound represented by the general formula (1) having a hole property stronger than that of the bis-type heterocyclic compound represented by the general formula (2) , The electron blocking ability is improved due to the high T1 and high LUMO energy value, and more holes are moved to the emissive layer quickly and easily. As a result, the charge balance in the light emitting layer of holes and electrons is increased, so that light emission is well performed inside the light emitting layer rather than at the interface of the hole transporting layer, and deterioration is further reduced in the HTL interface, thereby maximizing the driving voltage, efficiency and lifetime of the device . That is, it is concluded that the combination of the formula (1) and the formula (2) is electrochemically synergistic to improve the performance of the device as a whole.
[[ 실시예Example 138] 내지 [ 138] to [ 실시예Example 140] 140] 혼합비율 별By mixing ratio 적색유기전기발광소자Red organic electroluminescent device ( ( 발광층The light- 혼합 인광호스트) Mixed phosphorescent host)
표 8에 기재된 대로 물질의 혼합비율을 다르게 사용한 것을 제외하고는 상기 실시예 4와 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescence device was fabricated in the same manner as in Example 4, except that the mixing ratios of the materials were changed as shown in Table 8.
[[ 실시예Example 141] 내지 [ 141] to [ 실시예Example 143] 143] 혼합비율 별By mixing ratio 적색유기전기발광소자Red organic electroluminescent device ( ( 발광층The light- 혼합 인광호스트) Mixed phosphorescent host)
표 8에 기재된 대로 물질의 혼합비용을 다르게 사용한 것을 제외하고는 상기 실시예 136과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescence device was fabricated in the same manner as in Example 136 except that the mixing cost of the materials was changed as described in Table 8.
본 발명의 실시예 4, 실시예 136, 실시예 138 내지 실시예 143에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch) 사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 2500cd/m2 기준휘도에서 맥사이언스사의 수명측정장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 8과 같다.A forward bias DC voltage was applied to the organic electroluminescent devices manufactured in Example 4, Example 136, and Examples 138 to 143, and electroluminescence (EL) characteristics were measured with photoresearch PR-650 And the T95 lifetime was measured at a luminance of 2500 cd / m < 2 > through a lifetime measuring device of Mac Science Inc., and the measurement results are shown in Table 8 below.
(제1호스트:
제2호스트)Mixing ratio
(First host:
Second host)
전압
(V)Driving
Voltage
(V)
(mA/cm2)electric current
(mA / cm 2)
(cd/m2)Luminance
(cd / m < 2 &
(cd/A)efficiency
(cd / A)
T(95)life span
T (95)
상기 표 8과 같이 본 발명의 화합물의 혼합물을 비율 별(2:8, 3:7, 4:6, 5:5)로 소자를 제작하여 측정하였다. 화합물 1-37과 화합물 2-4의 혼합물 결과에서는 2:8, 3:7로 혼합 했을 경우 구동전압, 효율 및 수명 등의 결과가 유사하게 우수했지만 4:6, 5:5의 혼합비율의 경우는 제 1호스트의 비율이 증가하면서 구동전압, 효율 및 수명의 결과가 점점 떨어지는 것을 확인 할 수 있다. 이러한 결과는 화합물 1-136과 화합물 2-111을 혼합한 경우에도 동일한 양상을 띄었다. 이는 2:8, 3:7과 같이 hole 특성이 강한 화학식 1로 표시되는 화합물이 적정한 양이 혼합될 경우, 발광층 내 charge balance가 극대화되기 때문이라고 판단된다.As shown in Table 8, the mixture of the compound of the present invention was measured by fabricating the device at a ratio of 2: 8, 3: 7, 4: 6, 5: 5. As a result of the mixture of the compound 1-37 and the compound 2-4, when the mixture was mixed at 2: 8 and 3: 7, the results such as the driving voltage, the efficiency and the lifetime were comparable, but in the case of the mixing ratio of 4: 6 and 5: The efficiency of the driving voltage, the efficiency and the lifetime are gradually decreased as the ratio of the first host increases. These results were the same even when the compound 1-136 and the compound 2-111 were mixed. It is considered that this is because the charge balance in the light emitting layer is maximized when an appropriate amount of the compound represented by the formula (1) having strong hole properties such as 2: 8 and 3: 7 is mixed.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시 예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시 예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.
100 : 유기전기소자 110 : 기판
120 : 제 1전극(양극) 130 : 정공주입층
140 : 정공수송층 141 : 버퍼층
150 : 발광층 151 : 발광보조층
160 : 전자수송층 170 : 전자주입층
180 : 제 2전극(음극)100: organic electric element 110: substrate
120: First electrode (anode) 130: Hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)
Claims (15)
{상기 화학식 1 및 화학식 2에서,
X1은 S 또는 O이고,
X2는 N-L5-Ar6, O, S 또는 CRaRb이고,
A, B, C, D, E 및 F는 서로 독립적으로 C6-C20의 아릴기, C2-C20의 헤테로고리기이며,
Ra 및 Rb는 서로 독립적으로 수소, 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택되며, 또는 Ra와 Rb는 서로 결합하여 스파이로(spiro) 화합물을 형성할 수 있으며,
Ar1 내지 Ar6은 서로 독립적으로 C6-C60의 아릴기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택되고, 또는 Ar1 내지 Ar6은 서로 결합하여 고리를 형성할 수 있고,
L1 내지 L5는 서로 독립적으로 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 C3-C60의 지방족 탄화수소기;로 이루어진 군에서 선택되며,
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 융합고리기, 알킬기, 알케닐기, 알콕시기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}
1. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes a light emitting layer, And a second host compound represented by the general formula (2).
{In the above Chemical Formulas 1 and 2,
X < 1 > is S or O,
X 2 is NL 5 -Ar 6 , O, S or CR a R b ,
A, B, C, D, E and F independently of one another are a C 6 -C 20 aryl group, a C 2 -C 20 heterocyclic group,
R a and R b are independently of each other hydrogen, deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group and a C 6 -C 30 aryloxy group, or R a and R b may combine with each other to form a spiro compound,
Ar 1 to Ar 6 are each independently a C 6 to C 60 aryl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C 6 -C 60 aromatic ring and a C 3 -C 60 aliphatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; And a C 6 -C 30 aryloxy group; or Ar 1 is selected from the group consisting of Ar 1 To Ar < 6 > may combine with each other to form a ring,
L 1 to L 5 independently represent a single bond; C 6 -C 60 arylene groups; A fluorenylene group; A C 2 -C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; And a C 3 -C 60 aliphatic hydrocarbon group,
Here, the aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fluorenylene group, the fused ring group, the alkyl group, the alkenyl group, the alkoxy group and the aryloxy group each may be substituted with deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C 1 -C 20 ; A C 1 -C 20 alkoxyl group; A C 1 -C 20 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 6 -C 20 aryl group; A C 6 -C 20 aryl group substituted by deuterium; A fluorenyl group; A C 2 -C 20 heterocyclic group; A C 3 -C 20 cycloalkyl group; An arylalkyl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms and an arylalkenyl group having 8 to 20 carbon atoms, and these substituents may be further bonded to each other to form a ring, Ring " refers to a fused ring consisting of a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 heterocyclic ring or a combination thereof, including saturated or unsaturated rings.
{상기 화학식 a-1 내지 화학식 a-7에서,
Z1 내지 Z48은 서로 독립적으로 CRc 또는 N이고,
단, L1 내지 L3에 결합하고 있는 Z1 내지 Z48은 탄소(C)이며,
Rc는 상기 청구항 1에서 Ra의 정의와 동일하고,
*는 축합되는 위치를 나타낸다.}
The method according to claim 1, wherein A, B, C, D, E, and F in Formula 1 or 2 are independently selected from the group consisting of the following Formulas a-1 to a-7 .
(In formulas (a-1) to (a-7)
Z 1 to Z 48 independently of one another are CR c or N,
Provided that Z 1 to Z 48 bonded to L 1 to L 3 are carbon (C)
R c is the same as defined in R a in claim 1,
* Indicates the position to be condensed.
화학식 b-11 화학식 b-12 화학식 b-13
{상기 화학식 b-1 내지 화학식 b-13에서,
Y는 N-L6-Ar7, O, S, 또는 CRdRe이고,
L6은 상기 청구항 1에서 L4의 정의와 동일하고,
Ar7은 상기 청구항 1에서 Ar5의 정의와 동일하고,
Rd 및 Re는 상기 청구항 1에서 Ra의 정의와 동일하며,
a, c, d, e은 서로 독립적으로 0 내지 4의 정수이고 b은 0 내지 6의 정수이고,
f 및 g은 서로 독립적으로 0~3의 정수이고, h는 0 내지 2의 정수이며 i는 0 또는 1의 정수이고,
R1 내지 R3은 서로 독립적으로 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기 및 -La-N(Rf)(Rg)로 이루어진 군에서 선택되고, 또는 상기 a, b, c, d, e, f 및 g가 2 이상인 경우, 및 h가 2인 경우는 각각 복수로서 서로 동일하거나 상이하며 복수의 R1끼리 혹은 복수의 R2끼리 혹은 복수의 R3끼리 혹은 이웃한 R1과 R2 또는 R2과 R3은 서로 결합하여 방향족 고리 또는 헤테로방향족 고리를 형성할 수 있고,
여기서 상기 La는 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 C3-C60의 지방족 탄화수소기로 이루어진 군에서 선택되며, 상기 Rf 및 Rg는 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되고,
Z49, Z50 및 Z51은 서로 독립적으로 CRh 또는 N이고, Z49, Z50 및 Z51 중 적어도 하나는 N이며,
Rh은 수소; 중수소; 삼중수소; 할로겐; 시아노기; 나이트로기; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기로 이루어진 군에서 선택되고, 이웃한 R1과 Rh는 서로 결합하여 방향족 고리 또는 헤테로방향족 고리를 형성할 수 있다.}
The organic electroluminescent device according to claim 1, wherein L 1 to L 5 in the formula (1) or (2) are represented by any one of the following formulas (b-1) to (b-13).
Formula b-11 Formula b-12 Formula b-13
(In the formulas (b-1) to (b-13)
Y is NL 6 -Ar 7 , O, S, or CR d R e ,
L 6 are the same as defined in L 4 in the claim 1,
Ar 7 has the same definition as Ar 5 in claim 1,
R d and R e are the same as defined for R a in claim 1,
a, c, d and e are each independently an integer of 0 to 4 and b is an integer of 0 to 6,
f and g are independently an integer of 0 to 3, h is an integer of 0 to 2, i is an integer of 0 or 1,
R 1 to R 3 independently of one another are hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; When C 6 is selected from the group consisting of -C 30 aryloxy, and -L a -N (R f) ( R g), or wherein a, b, c, d, e, f and g is two or more, And when h is 2, a plurality of R 1 s, a plurality of R 2 s, a plurality of R 3 s or adjacent R 1 s and R 2 s or R 2 s and R 3 s bonded to each other An aromatic ring or a heteroaromatic ring,
Wherein L a is a single bond; C 6 -C 60 arylene groups; A fluorenylene group; A C 2 -C 60 heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; And C 3 -C 60 aliphatic hydrocarbon groups, wherein R f and R g are independently selected from the group consisting of C 6 -C 60 aryl groups; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring,
Z 49 , Z 50 and Z 51 independently of one another are CR h or N, and at least one of Z 49 , Z 50 and Z 51 is N,
R h is hydrogen; heavy hydrogen; Tritium; halogen; Cyano; A nitro group; An aryl group of C 6 -C 60 ; A fluorenyl group; Heterocyclic group of O, N, S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C 3 -C 60 aliphatic ring and a C 6 -C 60 aromatic ring; A C 1 -C 50 alkyl group; An alkenyl group of C 2 -C 20 ; A C 2 -C 20 alkynyl group; A C 1 -C 30 alkoxyl group; And a C 6 -C 30 aryloxy group, and adjacent R 1 and R h may be bonded to each other to form an aromatic ring or a heteroaromatic ring.
{상기 화학식 3 내지 화학식 5에서,
X1, A, B, L1, L2, Ar2 내지 Ar4는 상기 청구항 1에서 정의된 바와 같고,
G 및 H는 상기 청구상 1에서 A의 정의와 동일하고,
W는 N-L8-Ar8, O, S, 또는 CRiRj이고,
L7 및 L8은 상기 청구항 1에서 L4의 정의와 동일하고,
Ar8은 상기 청구항 1에서 Ar5의 정의와 동일하고,
Ri 및 Rj는 상기 청구항 1에서 Ra의 정의와 동일하며,
2개의 Ar8은 각각 동일하거나 상이하고, 2개의 W는 각각 동일하거나 상이하고,
2개의 G은 각각 동일하거나 상이하고, 2개의 H는 각각 동일하거나 상이하다.}
The organic electroluminescent device according to claim 1, wherein the first host compound represented by Formula 1 is represented by any one of the following Formulas (3) - (5).
{In the above Chemical Formulas 3 to 5,
X 1 , A, B, L 1 , L 2 , Ar 2 to Ar 4 are as defined in claim 1,
G and H are the same as defined in claim 1 above,
W is NL 8 -Ar 8 , O, S, or CR i R j ,
L 7 and L 8 have the same definitions as L 4 in claim 1,
Ar 8 has the same definition as Ar 5 in claim 1,
R i and R j are the same as defined in R a in claim 1,
Two Ar 8 s are the same or different, and two W s are the same or different,
Two G's are the same or different, and two H's are each the same or different.
{상기 화학식 6에서,
X1, Ar2 내지 Ar4는 상기 청구항 1에서 정의된 바와 같고,
Z1 내지 Z4는 서로 독립적으로 CRc 또는 N이고,
단, N에 결합하고 있는 Z1 내지 Z4는 탄소(C)이며,
Rc는 상기 청구항 1에서 Ra의 정의와 동일하고,
W는 N-L8-Ar8, O, S, 또는 CRiRj이고,
L8은 상기 청구항 1에서 L4의 정의와 동일하고,
Ar8은 상기 청구항 1에서 Ar5의 정의와 동일하고,
Ri 및 Rj는 상기 청구항 1에서 Ra의 정의와 동일하다.}
The organic electroluminescent device according to claim 4, wherein the first host compound represented by Formula 1 is represented by Formula 6 below.
{In the above formula (6)
X 1 , Ar 2 to Ar 4 are as defined in claim 1,
Z 1 to Z 4 are independently of each other CR c or N,
Provided that Z 1 to Z 4 bonded to N are carbon (C)
R c is the same as defined in R a in claim 1,
W is NL 8 -Ar 8 , O, S, or CR i R j ,
L 8 is the same as the definition of L 4 in the claim 1,
Ar 8 has the same definition as Ar 5 in claim 1,
R i and R j are as defined in R a in claim 1.
The organic electroluminescent device according to claim 4, wherein X 1 and W in the general formulas (3) to (5) are independently O or S.
{상기 화학식 7 내지 화학식 10에서,
C, D, E, F, L3 내지 L5, Ar5, Ar6, Ra, Rb는 상기 청구항 1에서 정의된 바와 동일하다.}
The organic electroluminescent device according to claim 1, wherein the second host compound represented by Formula 2 is represented by any of Formulas 7 to 10 below.
{In the above Chemical Formulas 7 to 10,
C, D, E, F, L 3 to L 5 , Ar 5 , Ar 6 , R a and R b are the same as defined in claim 1.
The organic electroluminescent device according to claim 1, wherein the first host compound represented by Formula 1 is any one of the following Compounds 1-1 to 1-175.
The organic electroluminescent device according to claim 1, wherein the second host compound represented by Formula 2 is any one of the following Compounds 2-1 to 2-135.
The organic electroluminescent device of claim 1, further comprising at least one hole transporting band layer between the first electrode and the light emitting layer, wherein the hole transporting band layer comprises a hole transporting layer, a light emitting auxiliary layer or both, The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device comprises a compound represented by the general formula (1).
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 1: 9 to 9: 1 and included in the light emitting layer.
The organic electroluminescent device according to claim 1, wherein the compound represented by Formula 1 and Formula 2 are mixed in a ratio of 1: 9 to 5: 5 and included in the light emitting layer.
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 2: 8 or 3: 7 and included in the light emitting layer.
A display device comprising the organic electroluminescent device according to claim 1, and a control part for driving the display device.
15. The electronic device according to claim 14, wherein the organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020170174237A KR102501667B1 (en) | 2017-12-18 | 2017-12-18 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020170174237A KR102501667B1 (en) | 2017-12-18 | 2017-12-18 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20190073009A true KR20190073009A (en) | 2019-06-26 |
KR102501667B1 KR102501667B1 (en) | 2023-02-21 |
Family
ID=67105292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020170174237A KR102501667B1 (en) | 2017-12-18 | 2017-12-18 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR102501667B1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190097577A (en) * | 2018-02-12 | 2019-08-21 | 엘티소재주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
KR20210023773A (en) * | 2019-08-22 | 2021-03-04 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
KR20210023774A (en) * | 2019-08-22 | 2021-03-04 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
KR20210089523A (en) * | 2020-01-08 | 2021-07-16 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
WO2021145651A1 (en) * | 2020-01-14 | 2021-07-22 | 덕산네오룩스 주식회사 | Compound for organic electrical element, organic electrical element using same, and electronic device thereof |
WO2022050592A1 (en) * | 2020-09-04 | 2022-03-10 | 엘티소재주식회사 | Heterocyclic compound and organic light-emitting element comprising same |
CN115093402A (en) * | 2022-08-29 | 2022-09-23 | 吉林奥来德光电材料股份有限公司 | Organic compound and preparation method and application thereof |
WO2023083269A1 (en) * | 2021-11-11 | 2023-05-19 | 中国科学院上海药物研究所 | Aromatic heterocyclic compound and application thereof |
WO2024014932A1 (en) * | 2022-07-15 | 2024-01-18 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic diode, composition for organic optoelectronic diode, organic optoelectronic diode and display device |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101170666B1 (en) | 2009-03-03 | 2012-08-07 | 덕산하이메탈(주) | Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof |
JP2013102220A (en) * | 2006-03-17 | 2013-05-23 | Konica Minolta Inc | Organic electroluminescent element, display device and illuminating device |
WO2014067614A1 (en) * | 2012-10-31 | 2014-05-08 | Merck Patent Gmbh | Electronic device |
JP2014116454A (en) * | 2012-12-10 | 2014-06-26 | Konica Minolta Inc | Organic electroluminescent element material and organic electroluminescent element |
KR20140105913A (en) * | 2013-02-25 | 2014-09-03 | 주식회사 두산 | Organic electro luminescence device |
KR20160043505A (en) * | 2014-10-13 | 2016-04-21 | 유니버셜 디스플레이 코포레이션 | Novel compounds and uses in devices |
KR20160141359A (en) * | 2015-05-27 | 2016-12-08 | 삼성디스플레이 주식회사 | Organic light-emitting device |
KR20170061768A (en) * | 2015-11-26 | 2017-06-07 | 삼성디스플레이 주식회사 | Organic light emitting device |
WO2017170812A1 (en) * | 2016-03-31 | 2017-10-05 | コニカミノルタ株式会社 | Luminescent thin film and organic electroluminescent element |
-
2017
- 2017-12-18 KR KR1020170174237A patent/KR102501667B1/en active IP Right Grant
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013102220A (en) * | 2006-03-17 | 2013-05-23 | Konica Minolta Inc | Organic electroluminescent element, display device and illuminating device |
KR101170666B1 (en) | 2009-03-03 | 2012-08-07 | 덕산하이메탈(주) | Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof |
WO2014067614A1 (en) * | 2012-10-31 | 2014-05-08 | Merck Patent Gmbh | Electronic device |
KR20150079911A (en) * | 2012-10-31 | 2015-07-08 | 메르크 파텐트 게엠베하 | Electronic device |
KR101963104B1 (en) * | 2012-10-31 | 2019-03-28 | 메르크 파텐트 게엠베하 | Electronic device |
JP2014116454A (en) * | 2012-12-10 | 2014-06-26 | Konica Minolta Inc | Organic electroluminescent element material and organic electroluminescent element |
KR20140105913A (en) * | 2013-02-25 | 2014-09-03 | 주식회사 두산 | Organic electro luminescence device |
KR20160043505A (en) * | 2014-10-13 | 2016-04-21 | 유니버셜 디스플레이 코포레이션 | Novel compounds and uses in devices |
KR20160141359A (en) * | 2015-05-27 | 2016-12-08 | 삼성디스플레이 주식회사 | Organic light-emitting device |
KR20170061768A (en) * | 2015-11-26 | 2017-06-07 | 삼성디스플레이 주식회사 | Organic light emitting device |
WO2017170812A1 (en) * | 2016-03-31 | 2017-10-05 | コニカミノルタ株式会社 | Luminescent thin film and organic electroluminescent element |
KR102146445B1 (en) * | 2016-03-31 | 2020-08-20 | 코니카 미놀타 가부시키가이샤 | Luminous thin film and organic electroluminescent device |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190097577A (en) * | 2018-02-12 | 2019-08-21 | 엘티소재주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
KR20210023773A (en) * | 2019-08-22 | 2021-03-04 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
KR20210023774A (en) * | 2019-08-22 | 2021-03-04 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
KR20210089523A (en) * | 2020-01-08 | 2021-07-16 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
WO2021145651A1 (en) * | 2020-01-14 | 2021-07-22 | 덕산네오룩스 주식회사 | Compound for organic electrical element, organic electrical element using same, and electronic device thereof |
WO2022050592A1 (en) * | 2020-09-04 | 2022-03-10 | 엘티소재주식회사 | Heterocyclic compound and organic light-emitting element comprising same |
EP4212519A4 (en) * | 2020-09-04 | 2024-08-07 | Lt Mat Co Ltd | Heterocyclic compound and organic light-emitting element comprising same |
WO2023083269A1 (en) * | 2021-11-11 | 2023-05-19 | 中国科学院上海药物研究所 | Aromatic heterocyclic compound and application thereof |
WO2024014932A1 (en) * | 2022-07-15 | 2024-01-18 | 삼성에스디아이 주식회사 | Compound for organic optoelectronic diode, composition for organic optoelectronic diode, organic optoelectronic diode and display device |
CN115093402A (en) * | 2022-08-29 | 2022-09-23 | 吉林奥来德光电材料股份有限公司 | Organic compound and preparation method and application thereof |
CN115093402B (en) * | 2022-08-29 | 2022-12-02 | 吉林奥来德光电材料股份有限公司 | Organic compound and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
KR102501667B1 (en) | 2023-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102501667B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR102170190B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR102293436B1 (en) | Display device using a composition for organic electronic element, and an organic electronic element thereof | |
US11367839B2 (en) | Compound for organic electric element, organic electric element using the same, and an electronic device thereof | |
EP4303218A2 (en) | Benzo[b]naphtho[2,3-d]furanyl- or benzo[b]naphtho[2,3-d]thiophenyl-triazine compounds for organic electronic elements | |
KR102502430B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
US11205755B2 (en) | Compound for organic electronic element, organic electronic element using same, and electronic device thereof | |
KR102329807B1 (en) | Display device using a composition for organic electronic element, and an organic electronic element thereof | |
KR102152194B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
US11271165B2 (en) | Compound for organic electric element, organic electric element using same, and electronic device comprising same organic electronic element | |
KR102342493B1 (en) | Display device using a composition for organic electronic element, and an organic electronic element thereof | |
KR102211338B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
US11495747B2 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20180013713A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20180008286A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR101934385B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20190040176A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR102543685B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR102403160B1 (en) | An organic electronic element comprising compound for organic electronic element and an electronic device thereof | |
KR20190098020A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20200084172A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
US20220029104A1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20200046339A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR102654639B1 (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
KR20200037544A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant |