KR102088702B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents
Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof Download PDFInfo
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- KR102088702B1 KR102088702B1 KR1020190043518A KR20190043518A KR102088702B1 KR 102088702 B1 KR102088702 B1 KR 102088702B1 KR 1020190043518 A KR1020190043518 A KR 1020190043518A KR 20190043518 A KR20190043518 A KR 20190043518A KR 102088702 B1 KR102088702 B1 KR 102088702B1
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- organic
- compound
- water
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims description 47
- 125000000623 heterocyclic group Chemical group 0.000 claims description 37
- 239000011368 organic material Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000005567 fluorenylene group Chemical group 0.000 claims 1
- 108091008695 photoreceptors Proteins 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 101
- 238000006243 chemical reaction Methods 0.000 description 79
- 239000010410 layer Substances 0.000 description 70
- 230000015572 biosynthetic process Effects 0.000 description 65
- 238000003786 synthesis reaction Methods 0.000 description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000000047 product Substances 0.000 description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 48
- 238000004440 column chromatography Methods 0.000 description 46
- 239000000460 chlorine Substances 0.000 description 33
- 238000001308 synthesis method Methods 0.000 description 33
- 239000003960 organic solvent Substances 0.000 description 32
- 239000000376 reactant Substances 0.000 description 32
- 238000000434 field desorption mass spectrometry Methods 0.000 description 31
- 238000001914 filtration Methods 0.000 description 31
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 28
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 28
- -1 borate compound Chemical class 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 229910002027 silica gel Inorganic materials 0.000 description 24
- 239000000741 silica gel Substances 0.000 description 24
- 229960001866 silicon dioxide Drugs 0.000 description 24
- 239000012044 organic layer Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 238000002347 injection Methods 0.000 description 21
- 239000007924 injection Substances 0.000 description 21
- 238000000605 extraction Methods 0.000 description 20
- 238000002156 mixing Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 229910052805 deuterium Inorganic materials 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 125000003342 alkenyl group Chemical group 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 230000005525 hole transport Effects 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 7
- 125000005018 aryl alkenyl group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- PTPGZCQGDXUUAH-UHFFFAOYSA-N 2-bromo-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(Br)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 PTPGZCQGDXUUAH-UHFFFAOYSA-N 0.000 description 4
- PJRGCJBBXGNEGD-UHFFFAOYSA-N 2-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Br)C=C3NC2=C1 PJRGCJBBXGNEGD-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- NCXURQLSLMPACG-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1N=C2C(N1C1=CC=CC=C1)C=CC=C2 Chemical compound BrC1=CC=C(C=C1)C1N=C2C(N1C1=CC=CC=C1)C=CC=C2 NCXURQLSLMPACG-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 4
- QLYUAISAKGDXCW-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-diphenylpyrimidine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=N1 QLYUAISAKGDXCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LEHBLKHJWCNXKQ-UHFFFAOYSA-N 1-bromo-2-nitronaphthalene Chemical compound C1=CC=CC2=C(Br)C([N+](=O)[O-])=CC=C21 LEHBLKHJWCNXKQ-UHFFFAOYSA-N 0.000 description 2
- SBABEHDRJFHMEU-UHFFFAOYSA-N 2-bromo-1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=C(Br)C=CC2=C1 SBABEHDRJFHMEU-UHFFFAOYSA-N 0.000 description 2
- XHJCHUVWJCDJPN-UHFFFAOYSA-N 9-bromo-10-nitrophenanthrene Chemical compound C1=CC=C2C([N+](=O)[O-])=C(Br)C3=CC=CC=C3C2=C1 XHJCHUVWJCDJPN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- CZUAHTZGRXIRIF-UHFFFAOYSA-N 1-iodo-2-methylsulfinylnaphthalene Chemical compound IC1=C(C=CC2=CC=CC=C12)S(=O)C CZUAHTZGRXIRIF-UHFFFAOYSA-N 0.000 description 1
- NIKMXXDCBKHEFO-UHFFFAOYSA-N 11-bromo-9h-dibenzo[a,c]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=C(Br)C=C1N2 NIKMXXDCBKHEFO-UHFFFAOYSA-N 0.000 description 1
- NYLZJEBTWCYOLU-UHFFFAOYSA-N 18-bromo-21-oxapentacyclo[12.7.0.02,7.08,13.015,20]henicosa-1(14),2,4,6,8,10,12,15(20),16,18-decaene Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=C(Br)C=C1O2 NYLZJEBTWCYOLU-UHFFFAOYSA-N 0.000 description 1
- YRWMGOSKROWAIT-UHFFFAOYSA-N 2-(4-bromophenyl)-1h-benzimidazole Chemical compound C1=CC(Br)=CC=C1C1=NC2=CC=CC=C2N1 YRWMGOSKROWAIT-UHFFFAOYSA-N 0.000 description 1
- GPGIIKKUKINTGW-UHFFFAOYSA-N 2-bromo-4,6-diphenylpyrimidine Chemical compound N=1C(Br)=NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 GPGIIKKUKINTGW-UHFFFAOYSA-N 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- ACANBSQSSDKBLC-UHFFFAOYSA-N 2-iodo-1-methylsulfinylnaphthalene Chemical compound IC1=C(C2=CC=CC=C2C=C1)S(=O)C ACANBSQSSDKBLC-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- FKHKSWSHWLYDOI-UHFFFAOYSA-N 2-phenylbenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C=2C=CC=CC=2)=C1 FKHKSWSHWLYDOI-UHFFFAOYSA-N 0.000 description 1
- AZFABGHLDGJASW-UHFFFAOYSA-N 3-bromodibenzofuran Chemical compound C1=CC=C2C3=CC=C(Br)C=C3OC2=C1 AZFABGHLDGJASW-UHFFFAOYSA-N 0.000 description 1
- GHDBFGUOBVYEOV-UHFFFAOYSA-N 4-(4-bromophenyl)-2,6-diphenylpyrimidine Chemical compound C1=CC(Br)=CC=C1C1=CC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 GHDBFGUOBVYEOV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PKIVMQZYFXOABI-UHFFFAOYSA-N 9-bromo-11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=C(Br)C=C1N2 PKIVMQZYFXOABI-UHFFFAOYSA-N 0.000 description 1
- DVWYFTYCQHNUDZ-UHFFFAOYSA-N 9-bromo-7H-benzo[a]carbazole Chemical compound BrC=1C=C2N=C3C4=C(C=CC3=C2CC1)C=CC=C4 DVWYFTYCQHNUDZ-UHFFFAOYSA-N 0.000 description 1
- XXUFFPSSSSKMMT-UHFFFAOYSA-N 9-bromonaphtho[1,2-b][1]benzofuran Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=C(Br)C=C1O2 XXUFFPSSSSKMMT-UHFFFAOYSA-N 0.000 description 1
- YFDUWPBKHIYLBJ-UHFFFAOYSA-N 9-bromonaphtho[2,1-b][1]benzofuran Chemical compound C1=CC=CC2=C3C4=CC=C(Br)C=C4OC3=CC=C21 YFDUWPBKHIYLBJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- YLTHBZFPABWJQL-UHFFFAOYSA-N IC=1C2=CC=CC=C2C=2C=CC=CC=2C=1S(=O)C Chemical compound IC=1C2=CC=CC=C2C=2C=CC=CC=2C=1S(=O)C YLTHBZFPABWJQL-UHFFFAOYSA-N 0.000 description 1
- 208000006930 Pseudomyxoma Peritonei Diseases 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 125000006615 aromatic heterocyclic group Chemical group 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
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 150000001975 deuterium Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
-
- H01L51/0061—
-
- H01L51/0067—
-
- H01L51/0071—
-
- 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
-
- 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
Abstract
본 발명은 소자의 발광효율, 안정성 및 수명을 향상시킬 수 있는 오원자 헤테로 고리를 포함하는 신규 화합물 및 이를 이용한 유기전기소자, 그 전자 장치를 제공한다.The present invention provides a novel compound containing a five-membered hetero ring capable of improving the luminous efficiency, stability and lifespan of the device, and an organic electrical device using the same, and an electronic device thereof.
Description
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.
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 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function.
한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투 확산되는 것을 지연시키며, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 또한 정공 수송층 재료의 낮은 유리전이 온도는 소자 구동시에 박막 표면의 균일도가 무너지는 특성에 따라 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자의 형성에 있어서 증착방법이 주류를 이루고 있으며, 이러한 증착방법에 오랫동안 견딜 수 있는 재료 즉 내열성 특성이 강한 재료가 필요한 실정이다. On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, in the formation of OLED devices, a vapor deposition method is predominant, and a material capable of withstanding such a vapor deposition method for a long time, that is, a material having strong heat resistance characteristics is required.
전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to sufficiently exhibit the excellent characteristics of the above-described organic electric device, materials constituting an organic material layer in the device, for example, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently performed, and thus, the development of a new material is still required.
본 발명은 소자의 높은 발광효율, 낮은 구동전압, 고내열성, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다. An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime, and an organic electric device using the same and its electronic device.
일측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by the following formula.
다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.
본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다. By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.
도 2는 본 발명의 일 측면에 따른 화학식을 나타낸다.1 is an exemplary view of an organic electroluminescent device according to the present invention.
2 shows a chemical formula according to an aspect of the present invention.
이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known structures or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".
한편, 본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소, 염소, 브롬, 및 요오드를 포함한다. On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise specified.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkyl" or "alkyl group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto unless otherwise specified.
본 발명에 사용된 용어 "알케닐" 또는 "알키닐"은 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 여기에 제한되는 것은 아니다. The terms "alkenyl" or "alkynyl" used in the present invention have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and are 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 indicated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
본 발명에 사용된 용어 "알콕시기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkoxy group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto, unless otherwise specified.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified.
본 발명에서 아릴기 또는 아릴렌기는 단일환 또는 복소환의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 링을 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다. In the present invention, the aryl group or arylene group means a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene 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 3 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다.As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 3 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes a heterocycle as well as a single ring, and may be formed by combining adjacent groups.
본 발명에 사용된 용어 "헤테로시클로알킬", "헤테로고리기"는 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다. 또한, "헤테로고리기"는 헤테로원자를 포함하는 지환족 및/또는 방향족을 의미할 수 있다.The terms "heterocycloalkyl" and "heterocyclic group" used in the present invention include one or more heteroatoms, have 2 to 60 carbon atoms, and include heterocycles as well as monocycles, unless otherwise specified. , Adjacent groups may be formed by combining. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic group containing heteroatoms.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 및 Si를 나타낸다. The term “heteroatom” as used herein refers to N, O, S, P and Si unless otherwise noted.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "포화 또는 불포화 고리"는 포화 또는 불포화 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 헤테로고리를 의미한다.Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
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 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, 및 C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다. Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 arylthiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, deuterium substituted C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C 5 to C 20 heterocyclic groups, and is not limited to these substituents.
도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 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.Referring to FIG. 1, the organic
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다. The organic material layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 sequentially on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light-emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 may also serve as a hole blocking layer.
또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다. In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.
상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 캐핑층의 재료로 사용될 수 있다.The compound according to the present invention applied to the organic layer is the material of the host or dopant or capping layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the light emitting layer 150 Can be used as
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 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form the anode 120, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer is less by a method such as a solution process or a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), not a deposition method using various polymer materials. It can be prepared by a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.
본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double side emission type according to the material used.
또한, 본 발명에 따른 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a device for monochrome or white illumination.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 구동하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for driving the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, a compound according to an aspect of the present invention will be described.
본 발명의 일측면에 따른 화합물은 하기 화학식 1로 표시된다.The compound according to an aspect of the present invention is represented by the following Chemical Formula 1.
<화학식 1><
상기 화학식에서,In the above formula,
R1~R4 및 R7~R10는 ⅰ) 서로 독립적으로, 수소, 중수소, 할로겐, C6~C60의 아릴기, 플루오렌일기, C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로 고리기, -L-N(R’)(R”), C1~C50의 알킬기, C2~C20의 알켄일기, C1~C30의 알콕시기 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택되거나, 또는 ⅱ) 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성한다.(이때, 고리를 형성하지 않는 기는 ⅰ)에서 정의된 것과 같음)R 1 to R 4 and R 7 to R 10 are iii) independently of each other, hydrogen, deuterium, halogen, C 6 to C 60 aryl group, fluorenyl group, C 3 to C 60 aliphatic ring and C 6 to C 60 Fused ring group of the aromatic ring of 60 , C 2 ~ C 60 heterocyclic group including at least one hetero atom of O, N, S, Si and P, -LN (R ') (R "), C 1 -C 50 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 30 alkoxy group and C 6 ~ C 30 aryloxy group is selected from the group consisting of, or, or ii) adjacent groups are bonded to each other at least To form a ring (where the group that does not form a ring is as defined in 것과))
단, R1~R4가 모두 수소일 경우 R7~R10 중 적어도 하나는 수소가 아니며, R7~R10가 모두 수소일 경우 R1~R4 중 적어도 하나는 수소가 아니다. 즉, R1~R10이 동시에 수소인 경우는 제외한다.However, R 1 ~ R 4, when the work both hydrogen R 7 ~ R 10, at least one is not hydrogen, R 7 ~ if R 10 is one both hydrogen R 1 ~ R 4 at least one is not hydrogen. That is, the case where R 1 to R 10 are hydrogen at the same time is excluded.
또한, ⅱ)에서, R1~R4 및 R7~R10 중 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성한다 함은, R1과 R2끼리, R2와 R3끼리, R3와 R4끼리, R7과 R8끼리, R8과 R9끼리 및/또는 R9와 R10끼리 서로 결합하여 고리를 형성하는 것을 말한다. 이때, 이웃한 기끼리 서로 결합하여 고리를 형성한다는 자체가 중요하므로, 이들이 어떤 치환기이고 어떤 반응을 통해 고리가 형성되는지에 의해 본 발명의 권리범위가 제한되지는 않는다. 이때, 고리는 공지의 다른 반응(Heck reaction이나 Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764 등에 기재된 반응)에 의해 형성될 수도 있을 것이다.In addition, in ii), the adjacent groups among R 1 to R 4 and R 7 to R 10 combine with each other to form at least one ring, R 1 and R 2 , R 2 and R 3 , R Refers to a combination of 3 and R 4 , R 7 and R 8 , R 8 and R 9, and / or R 9 and R 10 to form a ring. At this time, since it is important that the adjacent groups combine with each other to form a ring, the scope of the present invention is not limited by what substituents they are and through which reaction the ring is formed. At this time, the ring is another known reaction (Heck reaction or Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764, etc.).
R1~R4 및 R7~R10 중 이웃한 기끼리 서로 결합하여 형성된 고리는 단환 또는 다환의 방향족고리 또는 헤테로 원자를 적어도 하나 포함하는 헤테로고리일 수 있을 뿐만 아니라 방향족고리와 지방족 고리가 융합된 형태일 수도 있다. 예시적으로, R1과 R10 중 이웃한 기끼리 서로 결합하여 벤젠, 나프탈렌, 페난트렌 등과 같은 방향족고리를 형성할 수 있는데, 이때 형성되는 방향족고리의 핵탄소수는 6 내지 60인 것이 바람직하다. 예컨대, R7과 R8이 서로 결합하여 벤젠고리를 형성하고, R9와 R10이 서로 결합하여 벤젠고리를 형성하면 이들이 결합된 모핵의 벤젠링과 함께 페난트렌 형태가 형성될 수 있을 것이다.The ring formed by combining adjacent groups among R 1 to R 4 and R 7 to R 10 may be a monocyclic or polycyclic aromatic ring or a heterocycle containing at least one hetero atom, as well as an aromatic ring and an aliphatic ring fused It may be in the form of. Illustratively, adjacent groups among R 1 and R 10 may be combined with each other to form an aromatic ring such as benzene, naphthalene, and phenanthrene, wherein the number of nuclear carbon atoms in the aromatic ring formed is preferably 6 to 60. For example, when R 7 and R 8 combine with each other to form a benzene ring, and R 9 and R 10 combine with each other to form a benzene ring, the phenanthrene form may be formed together with the benzene rings of the parent nuclei to which they are bonded.
또한, R1~R4 및 R7~R10 중 이웃한 기끼리 서로 결합하여 싸이오펜, 퓨란, 피리딘, 인돌, 퀴놀린 등과 같은 헤테로고리를 형성할 수 있는데, 이때 핵탄소수는 2 내지 60일 수 있다. 또한, 다환고리인 경우 서로 융합된(fused) 형태일 수도 있고 복수개의 환이 서로 융합되지 않은 형태일 수도 있으며, 융합된 형태와 비융합된 형태가 혼합된 환일 수도 있다.In addition, neighboring groups among R 1 to R 4 and R 7 to R 10 may combine with each other to form heterocycles such as thiophene, furan, pyridine, indole, quinoline, etc., wherein the number of nuclear carbon atoms may be 2 to 60 days. have. In addition, in the case of a polycyclic ring, it may be a fused form, a plurality of rings may be a form that is not fused to each other, or a ring in which a fused form and a non-fused form are mixed.
한편, R5 및 R6는 서로 독립적으로, 수소, 중수소, 할로겐, C6~C60의 아릴기, 플루오렌일기, C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로 고리기, -L-N(R’)(R”), C1~C50의 알킬기, C2~C20의 알켄일기, C1~C30의 알콕시기 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택될 수 있다.On the other hand, R 5 and R 6 are independently of each other, fusion of hydrogen, deuterium, halogen, C 6 ~ C 60 aryl group, fluorenyl group, C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring C 2 ~ C 60 heterocyclic group containing at least one heteroatom of the ring group, O, N, S, Si and P, -LN (R ') (R ”), C 1 ~ C 50 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 30 alkoxy group and may be selected from the group consisting of C 6 ~ C 30 aryloxy group.
상기 화학식에서, X 및 Y는 서로 독립적으로 S, O 또는 -Si(R11)(R12)이다. 여기서, R11과 R12는 서로 독립적으로 수소, C6~C60의 아릴기, 플루오렌일기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, 또는 C1~C50의 알킬기일 수 있다. 한편, m과 n 각각은 0 또는 1일 수 있으나, m과 n이 모두 0인 경우는 제외한다. 즉, m+n=1 이상의 정수이어야 하므로, X, Y 중 적어도 하나는 반드시 존재해야 한다.In the above formula, X and Y are independently of each other S, O or -Si (R 11 ) (R 12 ). Here, R 11 and R 12 are independently of each other hydrogen, C 6 ~ C 60 C 2 ~ C 60 containing at least one heteroatom of the aryl group, fluorenyl group, O, N, S, Si and P Heterocyclic group, or may be a C 1 ~ C50 alkyl group. Meanwhile, each of m and n may be 0 or 1, except when m and n are both 0. That is, since m + n = 1 must be an integer, at least one of X and Y must exist.
L은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 2가의 지방족 탄화수소기;로 이루어진 군에서 선택된다. 이때, 단일결합을 제외한 기는 니트로기, 시아노기, 할로겐기, C1~C20의 알킬기, C6~C20의 아릴기, C2~C20의 헤테로고리기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환될 수 있다.L is a single bond; C 6 ~ C 60 Arylene group; Fluorylene group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And a divalent aliphatic hydrocarbon group; is selected from the group consisting of. At this time, the group excluding the single bond is a nitro group, cyano group, halogen group, C 1 ~ C 20 alkyl group, C 6 ~ C 20 aryl group, C 2 ~ C 20 heterocyclic group, C 1 ~ C 20 alkoxy It may be substituted with one or more substituents selected from the group consisting of groups and amino groups.
또한, Ar1은 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기, 플루오렌일기 또는 -N(R’)(R”)이고,In addition, Ar 1 is C 2 ~ C 60 heterocyclic group containing at least one hetero atom of O, N, S, Si and P, C 6 ~ C 60 aryl group, fluorenyl group or -N (R ') (R ”),
상기 R'과 R"은 서로 독립적으로 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기 또는 플루오렌일기이다.R 'and R "are independently of each other O, N, S, Si and P, C 2 ~ C 60 heterocyclic group containing at least one heteroatom, C 6 ~ C 60 aryl group or fluorenyl group to be.
한편, 상기 R1~R10, Ar1, R', R", R11 및 R12가 아릴기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기, C2~C20의 알카인일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Meanwhile, when R 1 to R 10 , Ar 1 , R ', R ", R 11 and R 12 are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C 1 ~ C 20 alkylthio, C 1 ~ C 20 alkoxyl group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 6 ~ C 20 Aryl group, C 6 ~ C 20 aryl group substituted with deuterium, C 2 ~ C 20 heterocyclic group, C 3 ~ C 20 cycloalkyl group, C 7 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C 8 ~ C 20 arylalkenyl groups,
상기 R1~R10, Ar1, R', R", R11 및 R12가 헤테로고리기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, 니트로기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Wherein R 1 ~ R 10 , Ar 1 , R ', R ", R 11 and R 12 are heterocyclic groups, they are deuterium, halogen, silane group, cyano group, nitro group, alkoxyl group of C 1 ~ C 20 , C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 6 ~ C 20 aryl group, substituted with deuterium C 6 ~ C 20 aryl group, C 2 ~ C 20 heterocyclic group, C 3 to C 20 cycloalkyl group, C 7 to C 20 It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C 8 ~ C 20 arylalkenyl groups,
상기 R1~R10, Ar1, R', R", R11 및 R12가 플루오렌일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알킬기, C2~C20의 알켄일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Wherein R 1 ~ R 10 , Ar 1 , R ', R ", R 11 and R 12 are fluorenyl groups, they are deuterium, halogen, silane group, cyano group, C 1 ~ C 20 alkyl group, C 2 ~ for C 20 alkenyl group, C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, from the group consisting of a cycloalkyl group of C 2 ~ C 20 heterocyclic group and C 3 ~ C 20 of Can be substituted with one or more selected substituents,
상기 R1~R1O이 융합고리기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기, C2~C20의 알카인일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Wherein R 1 ~ R 1O When the fused ring group, which is heavy hydrogen, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C 1 ~ C 20 coming of the alkylthio, C 1 ~ alkoxy group of C 20 , an aryl group of C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 of the alkynyl group, a C 6 ~ C 20 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 20 of, C 2 ~ C 20 heterocyclic group, C 3 ~ C 20 cycloalkyl group, C 7 ~ C 20 of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C 8 ~ C 20 arylalkenyl groups,
상기 R1~R12가 알킬기인 경우, 이는 할로겐, 실란기, 붕소기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When R 1 ~ R 12 is an alkyl group, it is a halogen, silane group, boron group, cyano group, C 1 ~ C 20 alkoxyl group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 6 to C 20 aryl group, substituted with deuterium, C 6 to C 20 aryl group, C 2 to C 20 heterocyclic group, C 7 to C 20 It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C 8 ~ C 20 arylalkenyl groups,
상기 R1~R10이 알켄일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When R 1 ~ R 10 is an alkenyl group, it is deuterium, halogen, silane group, cyano group, C 1 ~ C 20 alkoxyl group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 6 to C 20 aryl group, substituted with deuterium C 6 to C 20 aryl group, C 2 ~ C 20 heterocyclic group, C 3 ~ C 20 cycloalkyl group, C 7 ~ C 20 of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C 8 ~ C 20 arylalkenyl groups,
상기 R1~R10이 알콕실기인 경우, 이는 중수소, 할로겐, 실란기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When the R 1 ~ R 10 is an alkoxy group, which is heavy hydrogen, a halogen, a silane group, a C 1 ~ C 20 alkyl group, C 6 ~ C 20 aryl group, a C 6 ~ C 20 substituted with a heavy hydrogen of the aryl group, C 2 ~ C 20 heterocyclic group and C 3 ~ C 20 cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,
상기 R1~R10이 아릴옥시기인 경우, 이는 중수소, 실란기, 시아노기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Wherein R 1 ~ R 10 is an aryloxy group cases, this deuterium, a silane group, a cyano group, C of 1 ~ C 20 alkyl group, a C 6 ~ C 20 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 20 aryl group , C 2 ~ C 20 heterocyclic group and C 3 ~ C 20 cycloalkyl group may be substituted with one or more substituents selected from the group consisting of.
상기 화학식 1은, n=0인 경우 하기 화학식 2와 같이, m=0인 경우에는 하기 화학식 3과 같이 표시될 수 있다.
<화학식 2> <화학식 3> <Formula 2> <Formula 3>
, ,
상기 화학식에서, R1~R10, X, Y, L 및 Ar1은 화학식 1에서 정의된 것과 같다.In the above formula, R 1 to R 10 , X, Y, L and Ar 1 are as defined in
또한, 상기 화학식 2에서, R1~R4가 모두 수소인 경우 하기 화학식 2와 같이, R1과 R2가 서로 결합하여 벤젠고리를 형성하고 R3과 R4가 수소인 경우에는 하기 화학식 5와 같이, R1과 R2가 수소이고, R3과 R4가 서로 결합하여 벤젠고리를 형성하면 하기 화학식 6과 같이, R1과 R2가 서로 결합하여 벤젠고리를 형성함과 동시에 R3과 R4가 서로 결합하여 벤젠고리를 형성할 경우에는 하기 화학식 7과 같이 표시될 수 있을 것이다.In addition, in the above Chemical Formula 2, when R 1 to R 4 are both hydrogen, as shown in Chemical Formula 2, when R 1 and R 2 are combined with each other to form a benzene ring, and when R 3 and R 4 are hydrogen, the following Chemical Formula 5 As shown in the following formula 6, when R 1 and R 2 are hydrogen and R 3 and R 4 are combined with each other to form a benzene ring, R 1 and R 2 combine with each other to form a benzene ring, and at the same time R 3 When R 4 and R 4 combine with each other to form a benzene ring, it may be represented as in the following Chemical Formula 7.
또한, 상기 화학식 2에서, R7~R10이 모두 수소인 경우 하기 화학식 8와 같이, R7과 R8이 서로 결합하여 벤젠고리를 형성하고 R9과 R10이 수소인 경우에는 하기 화학식 9와 같이, R1과 R2가 수소이고 R3과 R4가 서로 결합하여 벤젠고리를 형성하면 하기 화학식 10과 같이, R7과 R8이 서로 결합하여 벤젠고리를 형성함과 동시에 R9와 R10이 서로 결합하여 벤젠고리를 형성할 경우에는 하기 화학식 11과 같이 표시될 수 있을 것이다.In addition, in Chemical Formula 2, when R 7 to R 10 are both hydrogen, as shown in Chemical Formula 8, R 7 and R 8 combine with each other to form a benzene ring, and when R 9 and R 10 are hydrogen, Chemical Formula 9 As shown in the following formula (10), when R 1 and R 2 are hydrogen and R 3 and R 4 are combined with each other to form a benzene ring, R 7 and R 8 combine with each other to form a benzene ring, and at the same time R 9 and When R 10 is combined with each other to form a benzene ring, it may be represented by the following formula (11).
유사하게, 상기 화학식 3은 하기 화학식 중 하나로 표시될 수 있을 것이다.Similarly, Chemical Formula 3 may be represented by one of the following Chemical Formulas.
보다 구체적으로, 상기 화학식들은 하기 화합물 중 하나일 수 있을 것이다.More specifically, the formulas may be one of the following compounds.
이하, 상기 화학식으로 표시되는 본 발명 화합물의 합성예 및 유기전기소자의 제조예에 대하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis example of the compound of the present invention represented by the above formula and the production example of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.
합성예Synthetic example
예시적으로 본 발명에 따른 화합물은 하기 합성예 1 또는 2에 의해 제조될 수 있으며, R1~R4, R7~R10 중 이웃한 기끼리 서로 결합하여 고리를 형성할 경우에는 하기 합성예 3 또는 4 등에 의해 제조될 수 있을 것이다. 이때, 고리는 공지의 다른 반응(Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764 등에 기재된 반응)에 의해 형성될 수도 있을 것이다.Illustratively, the compound according to the present invention may be prepared by Synthesis Examples 1 or 2 below, and when adjacent groups among R 1 to R 4 and R 7 to R 10 are bonded to each other to form a ring, the following Synthesis Example 3 or 4, and the like. At this time, the ring is another known reaction (Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764, and the like).
<합성예 1><Synthesis Example 1>
<합성예 2><Synthesis Example 2>
<합성예 3><Synthesis Example 3>
<합성예 4><Synthesis Example 4>
보다 구체적으로, 본 발명의 화합물은 하기 반응식 1에 의해 제조될 수 있다.More specifically, the compound of the present invention can be prepared by
Products 합성법 예시Products Synthesis Example
본 발명에 따른 화합물(final product)은 하기 반응식 1과 같이 Sub 1 내지 Sub 14 중 하나와 Sub 15를 반응시켜 제조될 수 있다.The final product according to the present invention may be prepared by reacting one of
<반응식 1><
상기 출발물질(Sub 1~Sub 14 물질 등)은 하기 반응식에 의해 제조될 수 있지만, 이미 설명한 것과 같이 합성예 1 및 합성예 2 등에 의해 제조될 수도 있다. 따라서, 하기에서 설명하는 Sub 물질의 제조는 어디까지나 합성예에 지나지 아니하며, 이들 합성예에 의해 본 발명의 권리범위가 제한되지는 않는다.The starting materials (
1-1. Sub 1 합성법 예시(X 또는 Y가 S인 경우)1-1.
<반응식 2><Reaction Scheme 2>
(1) Sub1-1 합성법(1) Sub1-1 synthesis method
합성한 중간체 A와 R1~R4로 치환된 2-bromocarbazole, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub1-1을 얻었다. The synthesized intermediate A and 2-bromocarbazole, Ph (PPh 3 ), NaCO 3 substituted with R 1 to R 4 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub1-1.
(2) Sub 1 합성법(2)
Sub 1-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1을 얻었다. Sub 1-1 was dissolved in a trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired
1-2. Sub 1' 합성법 예시(X 또는 Y가 O인 경우)1-2. Sub 1 'Synthesis Example (When X or Y is O)
<반응식 3><Scheme 3>
* *
(1) Sub 1-2합성(1) Sub 1-2 synthesis
3-bromodibenzo[b,d]furan (1당량)을 DMF에 녹인 후에, 비스피나콜라토다이보론 (1.1당량), Pd (dppf)Cl2 촉매 (0.03당량), KOAc (3당량)을 순서대로 첨가한 후 24시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 silicagel column 및 재결정을 걸쳐서 분리한 후 Sub 1-2를 얻었다.After dissolving 3-bromodibenzo [b, d] furan (1 eq.) In DMF, bispinacolatodiboron (1.1 eq.), Pd (dppf) Cl 2 catalyst (0.03 eq.), And KOAc (3 eq.) Were added in this order. After stirring for 24 hours to synthesize a borate compound, the obtained compound was separated over a silicagel column and recrystallization to obtain Sub 1-2.
(2) Sub 1-3 합성(2) Sub 1-3 synthesis
얻은 Sub 1-2 (1당량)와 R1~4로 치환된 1-bromo-2-nitrobenzene(1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-3을 얻었다.The obtained Sub 1-2 (1 eq.) And 1-bromo-2-nitrobenzene (1 eq.) Substituted with R 1-4 , Pd (PPh 3 ) 4 (0.03 eq.), K 2 CO 3 (3 eq.) Are anhydrous. After dissolving in THF and a small amount of water, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 1-3.
(3) Sub 1' 합성예(3) Sub 1 'Synthesis Example
얻은 Sub 1-3(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1'를 얻었다.The obtained Sub 1-3 (1 eq.) And triphenylphosphine (2.5 eq.) Were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 1 '.
Sub 1 및 Sub 1'의 예시는 다음과 같으나 이에 한정되는 것은 아니며, 이들의 FD-MS 값은 표 1과 같다.Examples of
2. Sub 2 합성법 예시 <반응식 4> 2. Sub 2 Synthesis Example <Scheme 4>
(1) Sub 2-2 합성법(1) Sub 2-2 synthesis method
Sub 2-1을 무수 THF에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane)을 천천히 적가하고 난 후, 반응물을 0℃에서 1시간 동안 교반시켰다. 이후, 반응물의 온도를 -78℃로 낮추고, trimethyl borate를 적가하고 난 후, 상온에서 12시간 동안 교반시켰다. 반응이 종결되면 2N-HCl 수용액을 넣고, 30분간 교반시킨 후, ether로 추출하였다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 2-2를 얻었다. Sub 2-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Thereafter, the temperature of the reaction product was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 2-2 by column chromatography.
(2) Sub 2-3 합성법(2) Sub 2-3 synthesis method
Sub 2-2와 R1~R4로 치환된 1-bromo-2-nitrobenzene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 2-3를 얻었다.Sub 2-2 and 1-bromo-2-nitrobenzene, Pd (PPh 3 ) 4 , K 2 CO 3 substituted with R 1 to R 4 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 2-3 using column chromatography.
(3) Sub 2 합성법(3) Sub 2 synthesis method
Sub 2-3과 triphenylphosphine을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 2를 얻었다.Sub 2-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 2.
Sub 2의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 2 are as follows, but are not limited thereto.
3. Sub 3 합성법 예시 <반응식 5> 3. Sub 3 Synthesis Example <Scheme 5>
(1) Sub3-1 합성법(1) Sub3-1 synthesis method
합성한 중간체 A와 9-bromo-7H-benzocarbazole, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub3-1을 얻었다. The synthesized intermediate A, 9-bromo-7H-benzocarbazole, Ph (PPh 3 ) and NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product by column chromatography to obtain the desired Sub3-1.
(2) Sub 3 합성법(2) Sub 3 synthesis method
Sub 3-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 3을 얻었다. Sub 3-1 was dissolved in a trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 3.
<반응식 6><Scheme 6>
(3) Sub 3-2 합성(3) Sub 3-2 synthesis
얻은 Sub 1-2 (1당량)와 1-bromo-2-nitronaphthalene (1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 3-1를 얻었다.The obtained Sub 1-2 (1 eq), 1-bromo-2-nitronaphthalene (1 eq), Pd (PPh 3 ) 4 (0.03 eq), K 2 CO 3 (3 eq) were dissolved in anhydrous THF and a small amount of water. After reflux, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 3-1.
(4) Sub 3' 합성예(4) Sub 3 'Synthesis Example
얻은 Sub 3-2(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 3'를 얻었다.The obtained Sub 3-2 (1 eq.) And triphenylphosphine (2.5 eq.) Were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 3 '.
Sub 3의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 3 are as follows, but are not limited thereto.
4. Sub 4 합성법 예시 <반응식 7> 4. Sub 4 Synthesis Example <Scheme 7>
(1) Sub 4-1 합성법(1) Sub 4-1 synthesis method
Sub 2-2와 R1~R4로 치환된 1-bromo-2-nitronaphthalene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 2-3를 얻었다.1-bromo-2-nitronaphthalene, Pd (PPh 3 ) 4 , K 2 CO 3 substituted with Sub 2-2 and R 1 to R 4 was dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 2-3 using column chromatography.
(2) Sub 4 합성법(2) Sub 4 synthesis method
Sub 4-1과 triphenylphosphine을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 4를 얻었다.Sub 4-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 4.
Sub 4의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 4 are as follows, but are not limited thereto.
5. Sub 5 합성법 예시 <반응식 8> 5. Sub 5 Synthesis Example <Scheme 8>
(1) Sub 5-1 합성법(1) Sub 5-1 synthesis method
합성한 중간체 A와 9-bromo-11H-benzo[a]carbazole, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 5-1을 얻었다. The synthesized intermediate A, 9-bromo-11H-benzo [a] carbazole, Ph (PPh 3 ) and NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 5-1.
(2) Sub 5 합성법(2) Sub 5 synthesis method
Sub 5-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 5를 얻었다. Sub 5-1 was dissolved in a trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 5.
<반응식 9><Scheme 9>
(3) Sub 5-2 합성(3) Sub 5-2 synthesis
얻은 Sub 1-2 (1당량)와 2-bromo-1-nitronaphthalene (1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 5-2를 얻었다.The obtained Sub 1-2 (1 eq), 2-bromo-1-nitronaphthalene (1 eq), Pd (PPh 3 ) 4 (0.03 eq), K 2 CO 3 (3 eq) were dissolved in anhydrous THF and a small amount of water. After reflux, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 5-2.
(4) Sub 5' 합성예(4) Sub 5 'Synthesis Example
얻은 Sub 5-2(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 5'를 얻었다.The obtained Sub 5-2 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 5 '.
Sub 5의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 5 are as follows, but are not limited thereto.
6. Sub 6 합성법 예시 <반응식 10> 6. Sub 6 Synthesis Example <Scheme 10>
(1) Sub 6-1 합성법(1) Sub 6-1 synthesis method
Sub 2-2와 2-bromo-1-nitronaphthalene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 6-1을 얻었다.Sub 2-2 and 2-bromo-1-nitronaphthalene, Pd (PPh 3 ) 4 , K 2 CO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. The water in the reaction was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated to obtain the desired Sub 6-1 by column chromatography.
(2) Sub 6 합성법(2) Sub 6 synthesis method
Sub 6-1과 triphenylphosphine을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 6을 얻었다.Sub 6-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain desired Sub 6.
Sub 6의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 6 are as follows, but are not limited thereto.
7. Sub 7 합성법 예시 <반응식 11> 7. Sub 7 Synthesis Example <Scheme 11>
(1) Sub 7-1 합성법(1) Sub 7-1 synthesis method
합성한 중간체 A와 11-bromo-9H-dibenzo[a,c]carbazole, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 7-1을 얻었다. The synthesized intermediate A and 11-bromo-9H-dibenzo [a, c] carbazole, Ph (PPh 3 ), NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7-1.
(2) Sub 7 합성법(2) Sub 7 synthesis method
Sub 7-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 7을 얻었다. Sub 7-1 was dissolved in a trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7.
<반응식 12><Reaction Scheme 12>
(3) Sub 7-2 합성(3) Sub 7-2 synthesis
얻은 Sub 1-2 (1당량)와 9-bromo-10-nitrophenanthrene (1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 7-2를 얻었다.Dissolve the obtained Sub 1-2 (1 eq), 9-bromo-10-nitrophenanthrene (1 eq), Pd (PPh 3 ) 4 (0.03 eq), K 2 CO 3 (3 eq) in anhydrous THF and a small amount of water After reflux, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7-2.
(4) Sub 7' 합성예(4) Sub 7 'Synthesis Example
얻은 Sub 7-2(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 7'를 얻었다.The obtained Sub 7-2 (1 eq.) And triphenylphosphine (2.5 eq.) Were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 7 '.
Sub 7의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 7 are as follows, but are not limited thereto.
* *
8. Sub 8 합성법 예시 <반응식 13> 8. Sub 8 Synthesis Example <Scheme 13>
(1) Sub 8-1 합성법(1) Sub 8-1 synthesis method
Sub 2-2와 9-bromo-10-nitrophenanthrene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 8-1을 얻었다.Sub 2-2 and 9-bromo-10-nitrophenanthrene, Pd (PPh 3 ) 4 , K 2 CO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 8-1 by column chromatography.
(2) Sub 8 합성법(2) Sub 8 synthesis method
Sub 8-1과 triphenylphosphine을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 8을 얻었다.Sub 8-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 8.
Sub 8의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 8 are as follows, but are not limited thereto.
9. Sub 9 합성법 예시 <반응식 14> 9. Sub 9 Synthesis Example <Scheme 14>
(1) Sub 9-1 합성법(1) Sub 9-1 synthesis method
R1~R4로 치환된 2-bromocarbazole과 1-iodo-2-(methylsulfinyl)naphthalene, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 9-1을 얻었다. 2-Bromocarbazole substituted with R 1 to R 4 and 1-iodo-2- (methylsulfinyl) naphthalene, Ph (PPh 3 ), NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 9-1.
(2) Sub 9 합성법(2) Sub 9 synthesis method
Sub 9-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 9를 얻었다. Sub 9-1 was dissolved in a trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resultant product using column chromatography to obtain the desired Sub 9.
<반응식 15><Reaction Scheme 15>
(3) Sub 9-2합성(3) Sub 9-2 synthesis
R5~6으로 치환된 9-bromonaphtho[2,1-b]benzofuran (1당량)을 DMF에 녹인 후에, 비스피나콜라토다이보론 (1.1당량), Pd (dppf)Cl2 촉매 (0.03당량), KOAc (3당량)을 순서대로 첨가한 후 24시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 silicagel column 및 재결정을 걸쳐서 분리한 후 Sub 9-2를 얻었다.After dissolving 9-bromonaphtho [2,1-b] benzofuran (1 eq.) Substituted with R 5-6 in DMF, bispinacolatodiboron (1.1 eq.), Pd (dppf) Cl 2 catalyst (0.03 eq.), After adding KOAc (3 equivalents) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated over a silicagel column and recrystallization to obtain Sub 9-2.
(4) Sub 9-3 합성(4) Sub 9-3 synthesis
얻은 Sub 9-2 (1당량)와 R1~4로 치환된 1-bromo-2-nitrobenzene(1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 9-3을 얻었다.The obtained Sub 9-2 (1 eq.) And 1-bromo-2-nitrobenzene (1 eq.) Substituted with R 1-4 , Pd (PPh 3 ) 4 (0.03 eq.), K 2 CO 3 (3 eq.) Were anhydrous. After dissolving in THF and a small amount of water, the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 9-3.
(5) Sub 9' 합성예(5) Sub 9 'Synthesis Example
얻은 Sub 9-3(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 9'를 얻었다.The obtained Sub 9-3 (1 eq.) And triphenylphosphine (2.5 eq.) Were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 9 '.
Sub 9의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 9 are as follows, but are not limited thereto.
10. Sub 10 합성법 예시 <반응식 16> 10. Sub 10 Synthesis Example <Scheme 16>
(1) Sub 10-2 합성법(1) Sub 10-2 synthesis method
Sub 10-1을 무수 THF에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane)을 천천히 적가하고 난 후, 반응물을 0℃에서 1시간 동안 교반시켰다. 이후, 반응물의 온도를 -78℃로 낮추고, trimethyl borate를 적가하고 난 후, 상온에서 12시간 동안 교반시켰다. 반응이 종결되면 2N-HCl 수용액을 넣고, 30분간 교반시킨 후, ether로 추출하였다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 10-2를 얻었다. Sub 10-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Thereafter, the temperature of the reaction product was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 10-2 using column chromatography.
(2) Sub 10-3 합성법(2) Sub 10-3 synthesis method
Sub 10-2와 R1~R4로 치환된 1-bromo-2-nitrobenzene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 10-3를 얻었다.Sub 10-2 and 1-bromo-2-nitrobenzene, Pd (PPh 3 ) 4 , K 2 CO 3 substituted with R 1 to R 4 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 10-3 using column chromatography.
(3) Sub 10 합성법(3) Sub 10 synthesis method
Sub 10-3과 triphenylphosphine을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 10을 얻었다.Sub 10-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 10.
Sub 10의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 10 are as follows, but are not limited thereto.
11. Sub 11 합성법 예시 <반응식 17> 11. Sub 11 Synthesis Example <Scheme 17>
(1) Sub 11-1 합성법(1) Sub 11-1 synthesis method
R1~R4로 치환된 2-bromocarbazole 와 2-iodo-1-(methylsulfinyl)naphthalene, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 11-1을 얻었다. 2-bromocarbazole substituted with R 1 to R 4 and 2-iodo-1- (methylsulfinyl) naphthalene, Ph (PPh 3 ), NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 11-1.
(2) Sub 11 합성법(2) Sub 11 synthesis method
Sub 11-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 11를 얻었다. Sub 11-1 was dissolved in a trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 11.
<반응식 18><Reaction Scheme 18>
(3) Sub 11-2합성(3) Sub 11-2 synthesis
R5~6으로 치환된 9-bromonaphtho[1,2-b]benzofuran (1당량)을 DMF에 녹인 후에, 비스피나콜라토다이보론 (1.1당량), Pd (dppf)Cl2 촉매 (0.03당량), KOAc (3당량)을 순서대로 첨가한 후 24시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 silicagel column 및 재결정을 걸쳐서 분리한 후 Sub 11-2를 얻었다.After dissolving 9-bromonaphtho [1,2-b] benzofuran (1 eq.) Substituted with R 5-6 in DMF, bispinacolatodiboron (1.1 eq.), Pd (dppf) Cl 2 catalyst (0.03 eq.), After adding KOAc (3 eq) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated over a silicagel column and recrystallization to obtain Sub 11-2.
(4) Sub 11-3 합성(4) Sub 11-3 synthesis
얻은 Sub 11-2 (1당량)와 R1~4로 치환된 1-bromo-2-nitrobenzene(1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 11-3을 얻었다.The obtained Sub 11-2 (1 eq.) And 1-bromo-2-nitrobenzene (1 eq.) Substituted with R 1-4 , Pd (PPh 3 ) 4 (0.03 eq.), K 2 CO 3 (3 eq.) Were anhydrous. After dissolving in THF and a small amount of water, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 11-3.
(5) Sub 11' 합성예(5) Sub 11 'Synthesis Example
얻은 Sub 11-3(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 11'를 얻었다.The obtained Sub 11-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 11 '.
Sub 11의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 11 are as follows, but are not limited thereto.
12. Sub 12 합성법 예시 <반응식 19> 12. Sub 12 Synthesis Example <Scheme 19>
(1) Sub 12-2 합성법(1) Sub 12-2 synthesis method
Sub 12-1을 무수 THF에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane)을 천천히 적가하고 난 후, 반응물을 0℃에서 1시간 동안 교반시켰다. 이후, 반응물의 온도를 -78℃로 낮추고, trimethyl borate를 적가하고 난 후, 상온에서 12시간 동안 교반시켰다. 반응이 종결되면 2N-HCl 수용액을 넣고, 30분간 교반시킨 후, ether로 추출하였다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 12-2를 얻었다. Sub 12-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Thereafter, the temperature of the reaction product was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 12-2 using column chromatography.
(2) Sub 12-3 합성법(2) Sub 12-3 synthesis method
Sub 12-2와 R1~R4로 치환된 1-bromo-2-nitrobenzene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 12-3를 얻었다.Sub 12-2 and 1-bromo-2-nitrobenzene, Pd (PPh 3 ) 4 , K 2 CO 3 substituted with R 1 to R 4 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 12-3 using column chromatography.
(3) Sub 12 합성법(3) Sub 12 synthesis method
Sub 12-3 (1당량)과 triphenylphosphine (2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 12를 얻었다.Sub 12-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 12.
Sub 12의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 12 are as follows, but are not limited thereto.
13. Sub 13 합성법 예시 <반응식 20> 13. Sub 13 Synthesis Example <Scheme 20>
(1) Sub 13-1 합성법(1) Sub 13-1 synthesis method
R1~R4로 치환된 2-bromocarbazole 와 9-iodo-10-(methylsulfinyl)phenanthrene, Ph(PPh3), NaCO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 13-1을 얻었다. 2-bromocarbazole substituted with R 1 to R 4 , 9-iodo-10- (methylsulfinyl) phenanthrene, Ph (PPh 3 ), NaCO 3 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 13-1.
(2) Sub 13 합성법(2) Sub 13 synthesis method
Sub 13-1을 trifluoromethanesulfonic acid 용매에 녹인 후, 상온에서 48시간 동안 교반시켰다. 반응이 종료되면 반응물을 물과 pyridine 의 혼합용매에 붓고, 20분 동안 환류시켰다. 반응물의 온도를 상온으로 식히고, CH2Cl2 로 추출하고 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 13을 얻었다. Sub 13-1 was dissolved in a trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reactant was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 and wiped. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 13.
<반응식 21><Reaction Scheme 21>
(3) Sub 13-2 합성(3) Sub 13-2 synthesis
R5~6으로 치환된 11-bromophenanthro[9,10-b]benzofuran (1당량)을 DMF에 녹인 후에, 비스피나콜라토다이보론 (1.1당량), Pd (dppf)Cl2 촉매 (0.03당량), KOAc (3당량)을 순서대로 첨가한 후 24시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 silicagel column 및 재결정을 걸쳐서 분리한 후 Sub 13-2를 얻었다.After dissolving 11-bromophenanthro [9,10-b] benzofuran (1 eq.) Substituted with R 5-6 in DMF, bispinacolatodiboron (1.1 eq.), Pd (dppf) Cl 2 catalyst (0.03 eq.), After adding KOAc (3 eq) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated over a silicagel column and recrystallization to obtain Sub 13-2.
(4) Sub 13-3 합성(4) Sub 13-3 synthesis
얻은 Sub 13-2 (1당량)와 R1~4로 치환된 1-bromo-2-nitrobenzene(1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 13-3을 얻었다.The obtained Sub 13-2 (1 eq.) And 1-bromo-2-nitrobenzene (1 eq.) Substituted with R 1-4 , Pd (PPh 3 ) 4 (0.03 eq.), K 2 CO 3 (3 eq.) Were anhydrous. After dissolving in THF and a small amount of water, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing a small amount of water with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 13-3.
(5) Sub 13' 합성예(5) Sub 13 'Synthesis Example
얻은 Sub 13-3(1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 13'를 얻었다.The obtained Sub 13-3 (1 eq.) And triphenylphosphine (2.5 eq.) Were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 13 '.
Sub 13의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 13 are as follows, but are not limited thereto.
14. Sub 14 합성법 예시 <반응식 22> 14. Sub 14 Synthesis Example <Scheme 22>
(1) Sub 14-2 합성법(1) Sub 14-2 synthesis method
Sub 14-1을 무수 THF에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane)을 천천히 적가하고 난 후, 반응물을 0℃에서 1시간 동안 교반시켰다. 이후, 반응물의 온도를 -78℃로 낮추고, trimethyl borate를 적가하고 난 후, 상온에서 12시간 동안 교반시켰다. 반응이 종결되면 2N-HCl 수용액을 넣고, 30분간 교반시킨 후, ether로 추출하였다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 14-2를 얻었다. Sub 14-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Thereafter, the temperature of the reaction product was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 14-2 using column chromatography.
(2) Sub 14-3 합성법(2) Sub 14-3 synthesis method
Sub 14-2와 R1~R4로 치환된 1-bromo-2-nitrobenzene, Pd(PPh3)4, K2CO3를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아 주었다. 무수 MgSO4로 반응물 내의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 14-3를 얻었다.Sub 14-2 and 1-bromo-2-nitrobenzene, Pd (PPh 3 ) 4 , K 2 CO 3 substituted with R 1 to R 4 were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. After removing the water in the reaction with anhydrous MgSO 4 and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 14-3 using column chromatography.
(3) Sub 14 합성법(3) Sub 14 synthesis method
Sub 14-3 (1당량)과 triphenylphosphine (2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압 증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 14를 얻었다.Sub 14-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 14.
Sub 14의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 14 are as follows, but are not limited thereto.
Sub 15의 예시는 다음과 같으나, 이에 한정되는 것은 아니다. Examples of Sub 15 are as follows, but are not limited thereto.
Products 합성 예시 : Sub 1, Sub 2, Sub 3, Sub 4, Sub 5, Sub 6, Sub 7, Sub 8, Sub 9, Sub 10, Sub 11, Sub 12, Sub 13 또는 Sub 14 중 하나 (1당량)와 Sub 15 (1.1당량)을 톨루엔에 넣고 Pd2(dba)3 (0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 Products를 얻었다. Product synthesis example:
(1) Product 16 합성 예시(1) Example of Product 16 synthesis
오원자 헤테로 화합물 (7.0g, 20mmol) 과 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.5g (수율 65%)를 얻었다.After mixing the five-membered hetero compound (7.0g, 20mmol) and 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.5 g (yield 65%).
(2) Product 32 합성 예시(2) Product 32 synthesis example
오원자 헤테로 화합물 (9.3g, 20mmol) 과 bromobenzene (3.8g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.4g (수율 68%)를 얻었다.After mixing the five-membered hetero compound (9.3g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively, and stirred and refluxed at 100 ° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.4 g (yield 68%).
(3) Product 60 합성 예시(3) Example of Product 60 synthesis
오원자 헤테로 화합물 (6.5g, 20mmol) 과 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.8g (수율 62%)를 얻었다.After mixing the five-membered hetero compound (6.5g, 20mmol) and 4- (4-bromophenyl) -2,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 7.8 g (yield 62%).
(4) Product 75 합성 예시(4) Product 75 synthesis example
오원자 헤테로 화합물 (6.5g, 20mmol) 과 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.5g (수율 63%)를 얻었다.After mixing the five-membered hetero compound (6.5g, 20mmol) and 2- (4-bromophenyl) -1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, Pd 2 (dba) 3 , After adding PPh 3 and NaOt-Bu, respectively, the mixture was refluxed with stirring at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.5 g (yield 63%).
(5) Product 82 합성 예시(5) Example of Product 82 synthesis
오원자 헤테로 화합물 (7.5g, 20mmol) 과 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.9g (수율 65%)를 얻었다.After mixing a 5-membered hetero compound (7.5g, 20mmol) and 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.9 g (yield 65%).
(6) Product 103 합성 예시(6) Example of Product 103 synthesis
오원자 헤테로 화합물 (7.5g, 20mmol) 과 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 8.1g (수율 63%)를 얻었다.After mixing the five-membered hetero compound (7.5g, 20mmol) and 2- (4-bromophenyl) -1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, Pd 2 (dba) 3 , After adding PPh 3 and NaOt-Bu, respectively, the mixture was refluxed with stirring at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.1 g (yield 63%).
(7) Product 105 합성 예시(7) Product 105 synthesis example
오원자 헤테로 화합물 (5.6g, 20mmol) 과 bromobenzene (3.8g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 5.0g (수율 70%)를 얻었다.After mixing the five-membered hetero compound (5.6g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively, and stirred and refluxed at 100 ° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 5.0 g (yield 70%).
(8) Product 200 합성 예시(8) Example of Product 200 synthesis
오원자 헤테로 화합물 (8.1g, 20mmol) 과 2-(4-bromophenyl)-benzoimidazole (6.6 g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.4g (수율 62%)를 얻었다.After mixing the five-membered hetero compound (8.1 g, 20 mmol) and 2- (4-bromophenyl) -benzoimidazole (6.6 g, 24 mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively. The mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.4 g (yield 62%).
(9) Product 211 합성 예시(9) Product 211 synthesis example
오원자 헤테로 화합물 (9.0g, 20mmol) 과 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 9.8g (수율 65%)를 얻었다.After mixing the five-membered hetero compound (9.0g, 20mmol) and 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 9.8 g (yield 65%).
(10) Product 225 합성 예시(10) Example of Product 225 synthesis
오원자 헤테로 화합물 (9.0g, 20mmol) 과 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 10.0g (수율 66%)를 얻었다.After mixing the five-membered hetero compound (9.0g, 20mmol) and 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 10.0 g (yield 66%).
(11) Product 231 합성 예시(11) Product 231 synthesis example
오원자 헤테로 화합물 (7.5g, 20mmol) 과 2-bromonaphthalene (5.0g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 6.8g (수율 68%)를 얻었다.After mixing the five-membered hetero compound (7.5 g, 20 mmol) and 2-bromonaphthalene (5.0 g, 24 mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively, and then stirred at 100 ° C. for 24 hours. Reflux. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 6.8 g (yield 68%).
(12) Product 255 합성 예시(12) Example of Product 255 synthesis
오원자 헤테로 화합물 (9.0g, 20mmol) 과 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 9.4g (수율 65%)를 얻었다.After mixing the five-membered hetero compound (9.0g, 20mmol) and 2- (4-bromophenyl) -1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, Pd 2 (dba) 3 , After adding PPh 3 and NaOt-Bu, respectively, the mixture was refluxed with stirring at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 9.4 g (yield 65%).
(13) Product 257 합성 예시(13) Product 257 synthesis example
오원자 헤테로 화합물 (5.5g, 20mmol) 과 bromobenzene (3.8g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 4.5g (수율 63%)를 얻었다.After mixing the five-membered hetero compound (5.5g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively, and stirred and refluxed at 100 ° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 4.5 g (yield 63%).
(14) Product 272 합성 예시(14) Product 272 synthesis example
오원자 헤테로 화합물 (7.0g, 20mmol) 과 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.5g (수율 65%)를 얻었다.After mixing the five-membered hetero compound (7.0g, 20mmol) and 2-brom-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.5 g (yield 65%).
(15) Product 288 합성 예시(15) Product 288 synthesis example
오원자 헤테로 화합물 (9.3g, 20mmol) 과 bromobenzene (3.8g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 7.4g (수율 68%)를 얻었다.After mixing the five-membered hetero compound (9.3g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively, and stirred and refluxed at 100 ° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.4 g (yield 68%).
(16) Product 315 합성 예시(16) Product 315 synthesis example
오원자 헤테로 화합물 (9.7g, 20mmol) 과 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 12.7g (수율 67%)를 얻었다.After mixing the five-membered hetero compound (9.7g, 20mmol) and 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 12.7 g (yield 67%).
(17) Product 324 합성 예시(17) Product 324 synthesis example
오원자 헤테로 화합물 (9.7g, 20mmol) 과 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 11.5g (수율 69%)를 얻었다.After mixing pentaatomic hetero compound (9.7g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 11.5 g (yield 69%).
(18) Product 339 합성 예시(18) Product 339 synthesis example
오원자 헤테로 화합물 (7.1g, 20mmol) 과 2-bromo-4,6-diphenylpyrimidine (7.5g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 7.2g (수율 61%)를 얻었다.After mixing the five-membered hetero compound (7.1g, 20mmol) and 2-bromo-4,6-diphenylpyrimidine (7.5g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , and NaOt-Bu were added, respectively. The mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.2 g (yield 61%).
(19) Product 359 합성 예시(19) Product 359 Synthesis Example
오원자 헤테로 화합물 (7.5g, 20mmol) 과 2-(4-bromophenyl)-1-phenyl-2,7a-dihydrobenzoimidazole (8.4g, 24mmol)을 톨루엔에 혼합 후에 Pd2(dba)3, PPh3, NaOt-Bu을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 8.0g (수율 62%)를 얻었다.After mixing the five-membered hetero compound (7.5g, 20mmol) and 2- (4-bromophenyl) -1-phenyl-2,7a-dihydrobenzoimidazole (8.4g, 24mmol) in toluene, Pd 2 (dba) 3 , PPh 3 , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.0 g (yield 62%).
유기전기소자의 제조평가Manufacturing evaluation of organic electric devices
[실험예 1](발광호스트에 적용)[Experimental Example 1] (applied to the light emitting host)
합성을 통해 얻은 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 정공주입층을 형성하였다. 이어서, 정공주입층 상에 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 -NPD로 약기함)을 20 nm 두께로 진공 증착하여 정공수송층을 형성하였다. 다음으로, 정공 수송층 상부에 본 발명의 화합물을 호스트 물질로, Ir(ppy)3 [tris(2-phenylpyridine)-iridium]을 도펀트 물질로 사용하여 95:5 중량으로 도핑하여 30nm 두께의 발광층을 증착하였다. 이어서 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 두께로 진공증착하여 정공저지층을 형성하고, 트리스(8-퀴놀리놀)알루미늄 (이하 Alq3로 약기함)을 40 nm 두께로 성막하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150 nm의 두께로 증착하여 음극을 형성함으로써 유기전계발광소자를 제조하였다.The organic electroluminescent device was manufactured according to a conventional method using the compound obtained through synthesis as a light emitting host material of the light emitting layer. First, on the ITO layer (anode) formed on the glass substrate, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum-deposited to form a hole injection layer with a thickness of 60 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. . Next, using a compound of the present invention as a host material and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as a dopant material on the hole transport layer, doped with a weight of 95: 5 to deposit a 30 nm thick light emitting layer Did. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole blocking layer, , Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was formed to a thickness of 40 nm to form an electron transport layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.
[비교예 1][Comparative Example 1]
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 비교 화합물 1을 발광호스트로 이용하여 발광층을 형성하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a light emitting layer was formed by using
<비교 화합물 1><
[비교예 2][Comparative Example 2]
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 비교 화합물 2을 발광호스트로 이용하여 발광층을 형성하였다.In the same manner as in Experimental Example 1, an organic electroluminescent device was manufactured, but instead of the compound of the present invention, a comparative compound 2 was used as a light emitting host to form a light emitting layer.
<비교 화합물 2> <Comparative Compound 2>
[비교예 3][Comparative Example 3]
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 비교 화합물 3을 발광호스트로 이용하여 발광층을 형성하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but instead of the compound of the present invention, Comparative Compound 3 was used as a light emitting host to form a light emitting layer.
<비교 화합물 3><Comparative Compound 3>
이와 같이 제조된 실시예 및 비교예 유기전기발광소자에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표 17은 발명에 따른 화합물을 적용한 실시예 및 비교예에 대한 소자제작 및 그 평가 결과를 나타낸 것으로, 실험예 1에 따라 제조된 유기전기소자를 실시예 1 내지 실시예 360으로 표시하였다.In the embodiment, prepared as examples and comparative examples the organic was applied with a forward bias DC voltage to the electroluminescent device Photo Research (photoresearch) 's were measured and electroluminescence (EL) properties by PR-650, from the measurement result 300cd / m 2 based on the luminance T95 life was measured using a life measurement equipment manufactured by Max Science. Table 17 below shows the device fabrication and evaluation results of the Examples and Comparative Examples to which the compounds according to the invention were applied, and the organic electric devices manufactured according to Experimental Example 1 are shown as Examples 1 to 360.
상기 표에서 확인한 것처럼 본 발명의 화합물의 경우 비교예 1 내지 비교예 3보다 높은 발광효율 및 높은 수명을 나타내며, 특히, 비교예 2, 비교예3 보다 낮은 비교적 낮은 구동전압과, 높은 효율, 높은 수명을 나타내고 있다. 이는 오원자헤테로고리 backbone에 치환기가 도입됨으로써 코어의 HOMO가 보다 깊어지며, HTL과의 알맞은 HOMO 값을 갖게 되어 hole mobility 를 빠르게 함으로써 수명이 증가된다고 판단되어지며, 또한 backbone의 치환기에 의한 LUMO의 전자밀도가 비 편재화됨으로써 높은 효율을 나타내는 것으로 판단된다.As shown in the above table, the compounds of the present invention show higher luminous efficiency and higher lifetime than Comparative Examples 1 to 3, in particular, comparatively lower driving voltages than Comparative Examples 2 and 3, and high efficiency and high lifetime. Is shown. It is judged that the introduction of a substituent on the backbone of the five-membered heterocycle makes the HOMO of the core deeper, has an appropriate HOMO value with the HTL, and increases the life of the hole by speeding up the hole mobility. It is judged that the density is non-localized and thus exhibits high efficiency.
본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 발광 호스트 재료로 사용되어 색순도, 높은 발광효율 및 수명을 현저히 개선시킬 수 있으며, 본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 정공주입층, 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층 등에 사용하더라도 동일한 효과를 얻을 수 있는 것은 자명하다.The organic light emitting device using the material for an organic light emitting device of the present invention can be used as a light emitting host material to significantly improve color purity, high luminous efficiency and lifespan, and the compounds of the present invention, other organic material layers of the organic light emitting device, For example, it is obvious that the same effect can be obtained even when used in a hole injection layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer.
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 설명 하기 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.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, 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 interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.
100: 유기전기소자 110: 기판
120: 제 1전극 130: 정공주입층
140: 정공수송층 141: 버퍼층
150: 발광층 151: 발광보조층
160: 전자수송층 170: 전자주입층
180: 제 2전극100: organic electric element 110: substrate
120: first electrode 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
Claims (12)
<화학식 1>
상기 화학식 1에서,
X 및 Y는 서로 독립적으로 S 또는 O이며,
m 및 n은 0 또는 1이고, m과 n 중에서 적어도 하나는 1이며,
R1~R4 및 R7~R10은 서로 독립적으로 수소; C6~C18의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C12의 헤테로 고리기; 및 C1~C10의 알킬기로 이루어진 군에서 선택되며,
단, R1~R4가 모두 수소인 경우 R7~R10 중 적어도 하나는 상기 아릴기, 플루오렌일기, 헤테로고리기 또는 알킬기이며, R7~R10가 모두 수소인 경우 R1~R4 중 적어도 하나는 상기 아릴기, 플루오렌일기, 헤테로고리기 또는 알킬기이며,
R5 및 R6은 수소이며,
L은 단일결합; C6~C18의 아릴렌기; 플루오렌일렌기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C12의 헤테로고리기로 이루어진 군에서 선택되며,
Ar1은 C6~C18의 아릴기; 플루오렌일기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C12의 헤테로고리기로 이루어진 군에서 선택되고,
단, L-Ar1은 N을 포함하는 C3~C12의 헤테로고리를 포함하며,
상기 R1~R4, R7~R10이 아릴기, 헤테로고리기 또는 플루오렌일기인 경우, 이들 각각은 C1~C20의 알킬기; C6~C20의 아릴기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,
상기 L이 아릴렌기, 헤테로고리기 또는 플루오렌일렌기인 경우, L은 C6~C20의 아릴기; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기 중에서 하나 이상의 치환기로 더 치환될 수 있고,
상기 Ar1이 아릴기, 헤테로고리기 또는 플루오렌일기인 경우, Ar1은 C6~C20의 아릴기; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기 중에서 하나 이상의 치환기로 더 치환될 수 있다.Compound represented by the formula (1):
<Formula 1>
In Chemical Formula 1,
X and Y are each independently S or O,
m and n are 0 or 1, at least one of m and n is 1,
R 1 to R 4 and R 7 to R 10 are each independently hydrogen; C 6 ~ C 18 aryl group; Fluorenyl group; C 3 ~ C 12 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C 1 ~ C 10 It is selected from the group consisting of an alkyl group,
However, when R 1 to R 4 are all hydrogen, at least one of R 7 to R 10 is the aryl group, a fluorenyl group, a heterocyclic group or an alkyl group, and when R 7 to R 10 are all hydrogen, R 1 to R At least one of 4 is the aryl group, fluorenyl group, heterocyclic group or alkyl group,
R 5 and R 6 are hydrogen,
L is a single bond; C 6 ~ C 18 arylene group; Fluorylene group; And O, N, S, Si and P is selected from the group consisting of a heterocyclic group of C 3 ~ C 12 containing at least one heteroatom,
Ar 1 is a C 6 ~ C 18 aryl group; Fluorenyl group; And C 3 to C 12 heterocyclic groups including at least one hetero atom from O, N, S, Si, and P,
However, L-Ar 1 includes a heterocyclic ring of C 3 ~ C 12 containing N,
R 1 ~ R 4 , When R 7 to R 10 are an aryl group, a heterocyclic group, or a fluorenyl group, each of these is an alkyl group of C 1 to C 20 ; C 6 ~ C 20 aryl group; And O, N, S, Si and P may be substituted with one or more substituents selected from the group consisting of C 2 ~ C 20 heterocyclic group containing a hetero atom,
When L is an arylene group, a heterocyclic group or a fluorenylene group, L is a C 6 ~ C 20 aryl group; Or it may be further substituted with one or more substituents from C 2 ~ C 20 heterocyclic group containing at least one hetero atom of O, N, S, Si and P,
When Ar 1 is an aryl group, a heterocyclic group or a fluorenyl group, Ar 1 is a C 6 ~ C 20 aryl group; Or it may be further substituted with one or more substituents from C 2 ~ C 20 heterocyclic groups containing at least one hetero atom of O, N, S, Si and P.
X는 O인 것을 특징으로 하는 화합물.According to claim 1,
X is O compound.
상기 화학식 1로 표시되는 화합물은 하기 화합물 중 하나인 것을 특징으로 하는 화합물:
According to claim 1,
The compound represented by Formula 1 is one of the following compounds:
상기 유기물층은 제1항의 화합물을 포함하는 것을 특징으로 하는 유기전기소자.In the organic electrical device including a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode,
The organic material layer is an organic electrical device comprising the compound of claim 1.
상기 유기물층은 발광층을 포함하며, 상기 화합물은 상기 발광층의 호스트물질로 사용되는 것을 특징으로 하는 유기전기소자.The method of claim 9,
The organic material layer includes a light emitting layer, and the compound is an organic electric device characterized in that it is used as a host material of the light emitting layer.
상기 디스플레이장치를 구동하는 제어부; 를 포함하는 전자장치.A display device comprising the organic electroluminescent device of claim 9; And
A control unit for driving the display device; Electronic device comprising a.
상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.The method of claim 11,
The organic electric device is an electronic device, characterized in that at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device.
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