WO2022092638A1 - Pyrimidin derivative and organic electroluminescent device comprising same - Google Patents
Pyrimidin derivative and organic electroluminescent device comprising same Download PDFInfo
- Publication number
- WO2022092638A1 WO2022092638A1 PCT/KR2021/014275 KR2021014275W WO2022092638A1 WO 2022092638 A1 WO2022092638 A1 WO 2022092638A1 KR 2021014275 W KR2021014275 W KR 2021014275W WO 2022092638 A1 WO2022092638 A1 WO 2022092638A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mmol
- compound
- synthesis
- reaction
- filtered
- Prior art date
Links
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 93
- 239000012044 organic layer Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims description 164
- 239000000463 material Substances 0.000 claims description 31
- 239000011368 organic material Substances 0.000 claims description 29
- 150000003230 pyrimidines Chemical class 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 2
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 198
- 238000003786 synthesis reaction Methods 0.000 description 187
- 230000015572 biosynthetic process Effects 0.000 description 186
- 239000007787 solid Substances 0.000 description 163
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 150
- 238000006243 chemical reaction Methods 0.000 description 122
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 120
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 111
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 93
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 78
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 63
- 239000012153 distilled water Substances 0.000 description 59
- 238000010992 reflux Methods 0.000 description 53
- 238000003756 stirring Methods 0.000 description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 235000019439 ethyl acetate Nutrition 0.000 description 39
- 239000011541 reaction mixture Substances 0.000 description 39
- 238000010898 silica gel chromatography Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 37
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 24
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 21
- -1 anthracene aromatic hydrocarbon Chemical class 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 19
- 239000011259 mixed solution Substances 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 17
- 239000008213 purified water Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 230000005525 hole transport Effects 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 11
- 239000008247 solid mixture Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CEBAHYWORUOILU-UHFFFAOYSA-N (4-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=C(C#N)C=C1 CEBAHYWORUOILU-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 7
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 7
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QMHZLIQDPHMKFM-UHFFFAOYSA-N C(#N)C1=CC=C(C=C1)B(O)O.C(#N)C1=CC=C(C=C1)B(O)O Chemical compound C(#N)C1=CC=C(C=C1)B(O)O.C(#N)C1=CC=C(C=C1)B(O)O QMHZLIQDPHMKFM-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- SNRCKKQHDUIRIY-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloromethane;dichloropalladium;iron(2+) Chemical compound [Fe+2].ClCCl.Cl[Pd]Cl.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 SNRCKKQHDUIRIY-UHFFFAOYSA-L 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 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 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- PFWWZGINJSDVGU-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1.C1CCNCC1 PFWWZGINJSDVGU-UHFFFAOYSA-N 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- HIZVCIIORGCREW-UHFFFAOYSA-N 1,4-dioxene Chemical compound C1COC=CO1 HIZVCIIORGCREW-UHFFFAOYSA-N 0.000 description 1
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
- AELBZZMQJAJEJW-UHFFFAOYSA-N 1-bromo-9-phenylcarbazole Chemical compound BrC1=CC=CC(C2=CC=CC=C22)=C1N2C1=CC=CC=C1 AELBZZMQJAJEJW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 description 1
- WNEXSUAHKVAPFK-UHFFFAOYSA-N 2,8-dibromodibenzothiophene Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3SC2=C1 WNEXSUAHKVAPFK-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- DDQJKLTYOLGRMF-UHFFFAOYSA-N 2-bromodibenzofuran Chemical compound C1=CC=C2C3=CC(Br)=CC=C3OC2=C1.C1=CC=C2C3=CC(Br)=CC=C3OC2=C1 DDQJKLTYOLGRMF-UHFFFAOYSA-N 0.000 description 1
- SOSPMXMEOFGPIM-UHFFFAOYSA-N 3,5-dibromopyridine Chemical compound BrC1=CN=CC(Br)=C1 SOSPMXMEOFGPIM-UHFFFAOYSA-N 0.000 description 1
- JTTLAEJDHYIANN-UHFFFAOYSA-N 3,6-dibromo-9H-carbazole Chemical compound BrC=1C=CC=2NC3=CC=C(C=C3C2C1)Br.BrC=1C=CC=2NC3=CC=C(C=C3C2C1)Br JTTLAEJDHYIANN-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- VQECNCYPOZVWGG-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarbonitrile Chemical compound Brc1cc(cc(c1)C#N)C#N.Brc1cc(cc(c1)C#N)C#N VQECNCYPOZVWGG-UHFFFAOYSA-N 0.000 description 1
- ZQVLPMNLLKGGIU-UHFFFAOYSA-N 5-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)N=C1 ZQVLPMNLLKGGIU-UHFFFAOYSA-N 0.000 description 1
- NGUVGKAEOFPLDT-UHFFFAOYSA-N 5-bromopyridine-3-carbaldehyde Chemical compound BrC1=CN=CC(C=O)=C1 NGUVGKAEOFPLDT-UHFFFAOYSA-N 0.000 description 1
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 1
- KCOYLRXCNKJSSC-UHFFFAOYSA-N 9h-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 KCOYLRXCNKJSSC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VJVXTZZFVPAXJB-UHFFFAOYSA-N BrC1=CC2=C(OC3=C2C=C(C=C3)Br)C=C1.BrC1=CC3=C(OC2=C3C=C(C=C2)Br)C=C1 Chemical compound BrC1=CC2=C(OC3=C2C=C(C=C3)Br)C=C1.BrC1=CC3=C(OC2=C3C=C(C=C2)Br)C=C1 VJVXTZZFVPAXJB-UHFFFAOYSA-N 0.000 description 1
- VVPGELKKZYSPBH-UHFFFAOYSA-N BrC1=CC2=C(SC3=C2C=C(C=C3)Br)C=C1.BrC1=CC3=C(SC2=C3C=C(C=C2)Br)C=C1 Chemical compound BrC1=CC2=C(SC3=C2C=C(C=C3)Br)C=C1.BrC1=CC3=C(SC2=C3C=C(C=C2)Br)C=C1 VVPGELKKZYSPBH-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MTDNUZUQTFFKGW-UHFFFAOYSA-N ClC1=CC=C(C=C1)B(O)O.ClC1=CC=C(C=C1)B(O)O Chemical compound ClC1=CC=C(C=C1)B(O)O.ClC1=CC=C(C=C1)B(O)O MTDNUZUQTFFKGW-UHFFFAOYSA-N 0.000 description 1
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005872 benzooxazolyl group Chemical group 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001716 carbazoles Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DSSBJZCMMKRJTF-UHFFFAOYSA-N dibenzofuran-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3OC2=C1 DSSBJZCMMKRJTF-UHFFFAOYSA-N 0.000 description 1
- GOXNHPQCCUVWRO-UHFFFAOYSA-N dibenzothiophen-4-ylboronic acid Chemical compound C12=CC=CC=C2SC2=C1C=CC=C2B(O)O GOXNHPQCCUVWRO-UHFFFAOYSA-N 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KSFLRAXQXWZQBA-UHFFFAOYSA-L dipotassium;1,4-dioxane;carbonate Chemical compound [K+].[K+].[O-]C([O-])=O.C1COCCO1 KSFLRAXQXWZQBA-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
Definitions
- the present invention relates to a specific pyrimidine derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having high luminous efficiency and a pyrimidine derivative therefor.
- OLED Organic Light Emitting Diodes
- the basic structure of an OLED display is, in general, an anode, a hole injection layer (HIL), a hole transporting layer (HTL), a light emitting layer (Emission Layer, EML), an electron transporting layer (Electron Transporting Layer, ETL), and a multilayer structure of a cathode, and a sandwich structure in which an electron organic multilayer film is formed between two electrodes.
- HIL hole injection layer
- HTL hole transporting layer
- EML emission Layer
- ETL electron transporting layer
- the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material.
- An organic light emitting device using an organic light emitting phenomenon typically has a structure including an anode and a cathode and an organic material layer therebetween.
- the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
- Such an organic light emitting device When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It lights up when it falls to the ground state.
- Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.
- a material used as an organic material layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like, according to functions.
- the light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials required to realize a better natural color.
- a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.
- the material constituting the organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is made of a stable and efficient material.
- the present inventors have repeatedly researched and found a specific pyrimidine derivative compound, and when it is used as a material for forming an organic layer of an organic electronic device, it will show effects such as an increase in device efficiency, a decrease in driving voltage, and an increase in stability. found out that it can
- An object of the present invention is to provide the above specific pyrimidine derivative compound and an organic electronic device using the same.
- a pyrimidine derivative represented by the following formula (1).
- Ar 1 , Ar 2 and Ar 3 are each independently a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,
- L is substituted or unsubstituted It is a heteroarylene group having 5 or more and 20 or less carbon atoms
- Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
- p is an integer from 0 to 2
- an organic electroluminescent device comprising the specific pyrimidine derivative.
- an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, wherein the organic material layer includes the specific pyrimidine derivative.
- the pyrimidine derivative is selected from the group consisting of an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function, and a light emitting layer constituting the organic material layer.
- An organic electroluminescent device is provided, characterized in that it is included in any one layer.
- the pyrimidine derivative compound according to the present invention may be used as a material for an organic layer of an organic light emitting device.
- the organic light-emitting device using a pyrimidine derivative compound introduced with a specific heteroarylene group into pyrimidine as a material for an organic material layer exhibits excellent characteristics such as high efficiency, low voltage and long life.
- the specific compound described in the present invention can improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light emitting device by introducing a cyano group.
- FIG. 1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment of the present invention.
- aryl refers to a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together.
- heteroaryl refers to an aryl group (or ring) comprising 1 to 4 heteroatoms selected from N, O and S (in each separate ring in the case of multiple rings), wherein the nitrogen and sulfur atoms are Optionally oxidized and the nitrogen atom(s) optionally quaternized.
- the heteroaryl group may be attached to the remainder of the molecule through a carbon or heteroatom.
- the aryl includes single or fused ring systems comprising suitably 4 to 7, preferably 5 or 6 ring atoms in each ring. In addition, it includes a structure in which one or more aryl is bonded through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, pyrenyl, fluoranthenyl, etc. including, but not limited to.
- the heteroaryl includes 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl fused with one or more benzene rings, which may be partially saturated. Also included are structures in which one or more heteroaryls are bonded through a chemical bond.
- the heteroaryl group includes a divalent aryl group in which a heteroatom in the ring is oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
- heteroaryl examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl, such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl,
- substituted in the expression “substituted or unsubstituted” means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced with the same or a different substituent.
- Useful substituents include, but are not limited to:
- substituents include -F; -Cl; -Br; -CN; -NO 2 ; -OH; -F, -Cl, -Br, -CN, -NO 2 or a C1-C20 alkyl group unsubstituted or substituted with -OH; -F, -Cl, -Br, -CN, -NO 2 or a C1-C20 alkoxy group unsubstituted or substituted with -OH; C1 ⁇ C20 alkyl group, C1 ⁇ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH C6 ⁇ C30 aryl group unsubstituted or substituted; C1 ⁇ C20 alkyl group, C1 ⁇ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH unsubstituted or substituted C6 ⁇ C30 hetero
- the pyrimidine derivative according to an embodiment of the present invention may be represented by the following formula (1).
- Ar 1 , Ar 2 and Ar 3 are each independently a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,
- L is substituted or unsubstituted It is a heteroarylene group having 5 or more and 20 or less carbon atoms
- Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
- p is an integer from 0 to 2
- Chemical Formula 1 may be represented by Chemical Formula 2 below.
- L is a substituted or unsubstituted, pyridine group; dibenzofuran group; dibenzothiophene group; a carbazole group; quinoline group; and an isoquinoline group; is any one of
- Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted carbazole group;
- Ar 3 and p are as defined in Formula 1 above.
- Ar 3 is a phenyl group substituted with cyano; phenyl group; and a pyridyl group; any one selected from
- the pyrimidine derivative of Formula 1 of the present invention is a pyrimidine derivative represented by Formula 3 below.
- the compound represented by Formula 1 of the present invention is not limited to the compounds of Formula 3 below.
- the pyrimidine derivative represented by Formula 1 can be synthesized using a known organic synthesis method.
- a method for synthesizing the pyrimidine derivative can be easily recognized by those skilled in the art with reference to Preparation Examples to be described later.
- an organic electroluminescent device comprising the pyrimidine derivative represented by Formula 1 above.
- the pyrimidine derivative of Formula 1 may be used in any one of the organic layers constituting the organic electroluminescent device, and is particularly useful as an electron transport layer material.
- the organic electroluminescent device includes an anode, a cathode, and one or more organic material layers disposed between these electrodes.
- the organic layer includes at least one pyrimidine derivative represented by Formula 1 above.
- the organic material layer includes a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function. It may include one or more layers selected from the group consisting of a functional layer having at the same time.
- the pyrimidine derivative may be included in at least one selected from the group consisting of an emission layer, an organic material layer disposed between the anode and the emission layer, and an organic material layer disposed between the emission layer and the cathode.
- the pyrimidine derivative may be included in any one or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, and a functional layer having both a hole injection function and a hole transport function.
- the pyrimidine derivative may be included in the organic material layer as a single material or a combination of different materials.
- the pyrimidine derivative may be used in a mixture with a conventionally known compound such as a light emitting layer, a hole transport layer, and a hole injection layer.
- the organic electroluminescent device is an anode / light emitting layer / cathode, anode / hole injection layer / light emitting layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode, or anode / hole injection layer / hole transport layer It may have a structure of /light emitting layer/electron transport layer/electron injection layer/cathode.
- the organic electroluminescent device is a functional layer / light emitting layer / electron transport layer / cathode having an anode / hole injection function and a hole transport function at the same time, or an anode / a functional layer / light emitting layer / electron transport layer / having a hole injection function and a hole transport function at the same time It may have an electron injection layer/cathode structure, but is not limited thereto.
- FIG. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
- the organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
- PVD physical vapor deposition
- an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed thereon. Then, it can be prepared by depositing a material that can be used as a cathode thereon.
- an organic electroluminescent device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
- the organic layer may be prepared by using various polymer materials, not by a deposition method, but by a solution process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method.
- a solution process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method.
- the organic electroluminescent device according to the present invention may be a top emission type, a back emission type or a double-sided emission type depending on the material used.
- the obtained compound was purified by silica gel column chromatography (n-Hex:Toluene) and then solidified with MeOH to obtain 28.2 g (yield: 47.6%) of the compound as a white solid (intermediate (15)).
- reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (Hex/EA) to obtain 77.9 g of a white solid compound (intermediate (20)) (yield: 68.5%).
- reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (Hex/EA) to obtain 35.5 g of a white solid compound (intermediate (21)) (yield: 37.3%, purity: 99.4%) got it
- reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (CHCl 3 /EtOH) to obtain 14.4 g (yield: 31.8%) of the compound as a white solid (intermediate (23)).
- reaction After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure.
- the reaction mixture was purified by silica gel column chromatography (CHCl 3 ), solidified with a mixed solution (DCM/MeOH), and filtered to obtain 51.1 g (yield: 86.4%) of the compound as a white solid (intermediate (25)).
- reaction mixture was purified by silica gel column chromatography (CHCl 3 :EA), solidified with hexane, and filtered to obtain 35.1 g (yield: 71.5%) of the compound as a yellow solid (intermediate (30)).
- reaction mixture was purified by silica gel column chromatography (Toluene) and solidified with a mixed solution (Hex/EA) to obtain 23.4 g (yield: 64.9%) of the compound as a white solid (intermediate (31)).
- reaction mixture was dissolved in chloroform, filtered through silica gel, and the solvent was concentrated under reduced pressure.
- the obtained reaction mixture was solidified with hexane to obtain 76.0 g (yield: 99.6%) of a white solid compound (intermediate (32)).
- the obtained reaction product was dissolved in dimethylformamide under reflux, and then laid over silica, celite and magnesium sulfate in that order, followed by filtration and concentration.
- the obtained reaction product was solidified with dimethylformamide to obtain 8.8 g (yield: 32.9%) of the compound (intermediate (35)) as a gray solid.
- reaction mixture was purified by column chromatography (Hex:CHCl 3 ) and solidified with a mixed solvent (DCM/EtOH) to obtain 6.9 g (yield: 64.9%) of the compound (intermediate (46)) as a white solid.
- Synthesis example 1 Synthesis of compound 3-1 (LT20-30-183)
- Synthesis example 2 Synthesis of compound 3-2 (LT20-30-150)
- Synthesis example 3 Synthesis of compound 3-3 (LT20-35-197)
- the obtained solid compound was purified by silica gel column chromatography (Hexanes:Chloroform), and then solidified with methanol to obtain 2.5 g (yield: 30.0%) of compound 3-3 (LT20-35-197) as a white solid.
- Synthesis example 4 Synthesis of compound 3-5 (LT20-30-207)
- intermediate (2) 4.0 g (8.6 mmol), intermediate (30) 2.6 g (10.3 mmol), Pd(PPh 3 ) 4 497.7 mg (430.7 ⁇ mol), K 3 PO 4 5.5 g (25.8 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried.
- Synthesis example 5 Synthesis of compound 3-8 (LT20-30-169)
- intermediate (2) 3.5 g (7.5 mmol), intermediate (25) 2.5 g (8.3 mmol), Pd(PPh 3 ) 4 435.5 mg (376.9 ⁇ mol), K 3 PO 4 4.8 g (22.6 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried.
- Synthesis example 6 Synthesis of compound 3-12 (LT20-30-243)
- intermediate (2) 3.5 g (7.5 mmol), intermediate (31) 2.5 g (9.0 mmol), Pd(PPh 3 ) 4 435.5 mg (376.9 ⁇ mol), K 3 PO 4 4.8 g (22.6 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried.
- the dried solid was purified by column chromatography (CHCl 3 :EA) and solidified with a mixed solution (DCM/EtOH) to obtain 1.1 g (yield: 27.0%) of compound 3-12 (LT20-30-243) as a white solid. .
- Synthesis example 7 Synthesis of compound 3-13 (LT20-30-185)
- Synthesis example 8 Synthesis of compound 3-16 (LT20-30-201)
- Synthesis example 9 Synthesis of compound 3-19 (LT20-30-167)
- Synthesis example 10 Synthesis of compound 3-20 (LT20-30-195)
- Synthesis example 11 Synthesis of compound 3-28 (LT20-30-262)
- Synthesis example 12 Synthesis of compound 3-29 (LT20-35-210)
- Synthesis example 14 Synthesis of compound 3-51 (LT20-30-193)
- Synthesis example 15 Synthesis of compound 3-53 (LT20-30-216)
- Synthesis example 16 Synthesis of compound 3-58 (LT20-30-253)
- Synthesis example 17 Synthesis of compound 3-59 (LT20-30-198)
- Synthesis example 18 Synthesis of compound 3-60 (LT20-30-179)
- Synthesis example 19 Synthesis of compound 3-62 (LT20-30-244)
- Synthesis example 20 Synthesis of compound 3-65 (LT20-30-147)
- Synthesis example 21 Synthesis of compound 3-71 (LT20-30-285)
- reaction mixture was dissolved in chloroform, filtered through silica gel to remove the solvent, and then solidified with hot chloroform to obtain 1.3 g (yield: 27.2%) of compound 3-71 (LT20-30-285) as a white solid.
- Synthesis example 22 Synthesis of compound 3-75 (LT20-30-263)
- intermediate (6) 3.5 g (7.5 mmol), intermediate (31) 2.5 g (9.0 mmol), Pd(PPh 3 ) 4 261.3 mg (226.1 ⁇ mol), K 2 CO 3 3.1 g (22.6 mmol) ), 40 mL of toluene, 10 mL of ethanol, and 10 mL of distilled water were mixed, followed by reaction at 90° C. for one day. After the reaction was completed, it was cooled to room temperature, and 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water, methanol, and ethyl acetate.
- reaction mixture was cooled to room temperature, filtered, and the obtained reaction mixture was dissolved in chloroform, filtered through silica gel, concentrated under reduced pressure, and solidified with chloroform/methanol, 2.3 g of compound 3-76 (LT20-30-218) as a white solid ( Yield: 65.4%) was obtained.
- Synthesis example 24 Synthesis of compound 3-79 (LT20-30-217)
- Synthesis example 25 Synthesis of compound 3-82 (LT20-30-169)
- Synthesis example 26 Synthesis of compound 3-83 (LT20-30-204)
- reaction mixture was cooled to room temperature and filtered, and the obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol/hexane, and compound 3-83 as a white solid (LT20-30- 204) 2.7 g (yield: 87.3%) was obtained.
- Synthesis example 27 Synthesis of compound 3-142 (LT20-30-293)
- reaction mixture was cooled to room temperature, filtered with purified water, and the resulting reaction mixture was dissolved in methylene chloride, filtered through silica gel, and solidified with chloroform/methanol, and compound 3-142 as a white solid (LT20-30-293) ) to obtain 2.4 g (yield: 34.6%).
- Synthesis example 28 Synthesis of compound 3-146 (LT20-30-199)
- Synthesis example 29 Synthesis of compound 3-162 (LT20-30-287)
- Synthesis example 30 Synthesis of compound 3-169 (LT20-30-289)
- Synthesis example 31 Synthesis of compound 3-170 (LT20-30-305)
- Synthesis example 32 Synthesis of compound 3-171 (LT20-30-215)
- Synthesis example 33 Synthesis of compound 3-173 (LT20-30-304)
- Synthesis example 34 Synthesis of compound 3-175 (LT20-30-298)
- Synthesis example 35 Synthesis of compound 3-179 (LT20-30-309)
- Synthesis example 36 Synthesis of compound 3-184 (LT20-30-303)
- Synthesis example 37 Synthesis of compound 3-193 (LT20-30-290)
- reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with ethyl acetate to obtain 1.6 g (yield: 56.5%) of compound 3-193 (LT20-30-290) as a white solid.
- Synthesis example 38 Synthesis of compound 3-255 (LT20-30-258)
- Synthesis example 39 Synthesis of compound 3-269 (LT20-30-200)
- Synthesis example 40 Synthesis of compound 3-277 (LT20-30-286)
- Synthesis example 41 Synthesis of compound 3-278 (LT20-35-283)
- Synthesis example 42 Synthesis of compound 3-292 (LT20-30-296)
- Synthesis example 43 Synthesis of compound 3-376 (LT20-30-288)
- Synthesis example 44 Synthesis of compound 3-380 (LT20-30-306)
- Synthesis example 45 Synthesis of compound 3-381 (LT20-35-313)
- ITO a transparent electrode
- 2-TNATA is a hole injection layer
- NPB is a hole transport layer
- ⁇ -ADN is a host of the light emitting layer
- Pyrene-CN is a blue fluorescent dopant
- Liq is an electron injection layer.
- Al was used as the cathode. The structures of these compounds are as follows.
- Comparative Example 1 ITO / 2-TNATA (60 nm) / NPB (20 nm) / ⁇ -ADN: 10% Pyrene-CN (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Al ( 100 nm)
- Blue fluorescent organic light emitting diode ITO 180 nm
- 2-TNATA 60 nm
- NPB 20 nm
- ⁇ -ADN:Pyrene-CN 10% (30 nm)
- electron transport layer (30 nm)
- Liq (2 nm) / Al 100 nm
- the ITO electrode Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 2 ⁇ 10 - 2 Torr at 125 W for 2 minutes. Organic materials were deposited at a vacuum degree of 9 ⁇ 10 - 7 Torr, Liq was 0.1 ⁇ /sec, ⁇ -ADN was 0.18 ⁇ /sec, and Pyrene-CN was simultaneously deposited at 0.02 ⁇ /sec, and the remaining organic materials were all 1 Deposited at a rate of ⁇ /sec.
- the device After the device was manufactured, it was encapsulated in a glove box filled with nitrogen gas to prevent the device from contacting air and moisture. After forming the barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.
- Comparative Example 1 a device was manufactured in the same manner as in Comparative Example, except that each compound shown in Table 1 was used instead of using REF01 (Alq 3 ).
- Table 1 shows the electroluminescence characteristics of the organic light emitting devices prepared in Comparative Example 1, Comparative Example 2, and Examples 1-45.
- Example 1 REF01(Alq 3 ) 6.60 5.10 91.78 Comparative Example 2 REF02 5.11 6.18 94.15
- Example 1 3-1 (LT20-30-183) 3.56 8.43 99.29
- Example 2 3-2 (LT20-30-150) 3.97 6.76 98.64
- Example 3 3-3 (LT20-35-197) 4.00 6.82 98.61
- Example 4 3-5 (LT20-30-207) 3.73 6.67 99.52
- Example 5 3-8 (LT20-30-169) 3.43 7.89 99.65
- Example 6 3-12 (LT20-30-243) 4.15 6.68 98.47
- Example 7 3-13 (LT20-30-185) 3.40 7.28 98.95
- Example 8 3-16 (LT20-30-201) 3.33 7.74 99.77
- Example 9 3-19 (LT20-30-167) 3.50 8.30 99.06
- Example 10 3-20 (LT20-30-195) 3.32 8.04 99.56
- Example 11 3-28 (LT20-30-262) 3.85 7.27 100.62
- Example 21 When comparing Comparative Example 2 (REF02) and Example 21 (Compound 3-71) from Table 1 above, the chemical structures of the two compounds are similar, but the compound of Example 21 is pyrimidine to heteroarylene (pyridine) and by improving electron injection and electron mobility according to the introduction of a cyano group and balancing holes and electrons, low voltage (3.32 compared to 5.11 (V)), high efficiency (6.87 compared to 6.18 (cd/A)) and long life (101.68 (%) compared to 94.15).
- the pyrimidine derivative compound substituted with a heteroallylene group according to the present invention can be generally used as a material for an organic material layer of an organic electronic device including an organic light emitting device, and an organic electronic device including an organic light emitting device using the same can have efficiency, driving voltage, It can be seen that excellent characteristics such as stability are exhibited.
- the compound according to the present invention exhibits high efficiency characteristics due to excellent hole-electron balancing ability and electron transport ability.
- the pyrimidine derivative compound according to the present invention can be used to improve the quality of an organic electroluminescent device by being used in the organic layer of the organic electroluminescent device.
- the organic electroluminescent device When the compound is used in the organic material layer, the organic electroluminescent device exhibits the original characteristics and at the same time, the lifespan can be improved by the characteristics of the compound.
Abstract
Provided is a pyrimidin derivative substantially contributing to the driving voltage, efficiency and extended life of an organic electroluminescent device. The organic electroluminescent device according to the present invention comprises: an anode; a cathode; and one or more organic layers disposed between the anode and cathode and comprising an electron transport layer, wherein the organic layers or electron transport layer comprise a pyrimidin derivative expressed by chemical formula 1 of the present invention.
Description
본 발명은 특정의 피리미딘 유도체 및 이를 포함한 유기 전계발광 소자에 관한 것으로, 특히 발광 효율이 높은 유기 전계발광 소자 및 이를 위한 피리미딘 유도체에 관한 것이다.The present invention relates to a specific pyrimidine derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having high luminous efficiency and a pyrimidine derivative therefor.
디스플레이 산업에서 자기 발광 현상을 이용한 디스플레이로서 OLED(유기발광다이오드, Organic Light Emitting Diodes)가 주목받고 있다. OLED (Organic Light Emitting Diodes) is attracting attention as a display using self-luminescence in the display industry.
OLED에 있어, 1963년 Pope 등에 의하여 안트라센(Anthracene) 방향족 탄화수소의 단결정을 이용한 캐리어 주입형 전계발광(Electroluminescence; EL)의 연구가 최초로 시도되었다. 이러한 연구로부터 유기물에서 전하주입, 재결합, 여기자 생성, 발광 등의 기초적 메커니즘과 전기발광 특성 등이 이해되고 연구되어왔다. In OLED, a study of carrier injection electroluminescence (EL) using a single crystal of an anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, basic mechanisms such as charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescence characteristics have been understood and studied.
특히 발광 효율을 높이기 위해 소자의 구조 변화 및 물질 개발 등 다양한 접근이 이루어지고 있다[Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364]. In particular, in order to increase the luminous efficiency, various approaches are being made, such as changing the structure of the device and developing materials [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].
OLED 디스플레이의 기본적 구조는, 일반적으로 양극(Anode), 정공주입층(Hole Injection Layer, HIL), 정공수송층(Hole Transporting Layer, HTL), 발광층 (Emission Layer, EML), 전자수송층(Electron Transporting Layer, ETL), 그리고 음극(Cathode)의 다층 구조로 구성되며, 전자 유기 다층막이 두 전극 사이에 형성된 샌드위치 구조로 되어 있다. The basic structure of an OLED display is, in general, an anode, a hole injection layer (HIL), a hole transporting layer (HTL), a light emitting layer (Emission Layer, EML), an electron transporting layer (Electron Transporting Layer, ETL), and a multilayer structure of a cathode, and a sandwich structure in which an electron organic multilayer film is formed between two electrodes.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환해주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이들 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등을 포함할 수 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon typically has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면, 양극에서는 정공이, 음극에서는 전자가 유기물층으로 주입되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이러한 유기 발광 소자는 자발광, 고휘도, 고효율, 낮은 구동전압, 넓은 시야각, 높은 콘트라스트, 고속 응답성 등의 특성을 갖는 것으로 알려져 있다.When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It lights up when it falls to the ground state. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.
유기 발광 소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공 주입 재료, 정공 수송 재료, 전자 수송 재료, 전자 주입 재료 등으로 분류될 수 있다. A material used as an organic material layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like, according to functions.
발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 좀 더 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료가 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도판트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도판트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도판트로 수송되어 효율이 높게 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials required to realize a better natural color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.
전술한 유기 발광 소자가 갖는 우수한 특징들을 충분히 발현하기 위해, 소자 내 유기물층을 이루는 물질, 예컨대 정공 주입 물질, 정공 수송 물질, 발광 물질, 전자 수송 물질, 전자 주입 물질 등이, 안정하고 효율적인 재료에 의하여 뒷받침되어야 한다. In order to sufficiently express the excellent characteristics of the above-described organic light emitting device, the material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is made of a stable and efficient material. should be supported
아직까지 안정하고 효율적인 유기 발광 소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서 새로운 재료의 개발이 계속 요구되고 있다. The development of a stable and efficient organic material for an organic light emitting device has not been sufficiently developed. Therefore, the development of new materials continues to be required.
본 발명자들은 예의 연구를 거듭하여, 특정의 피리미딘 유도체 화합물을 발견하고, 이를 유기 전자 소자의 유기물층을 형성하는 재료로 사용하는 경우에 소자의 효율 상승, 구동 전압 하강 및 안정성 상승 등의 효과를 나타낼 수 있음을 알아냈다. The present inventors have repeatedly researched and found a specific pyrimidine derivative compound, and when it is used as a material for forming an organic layer of an organic electronic device, it will show effects such as an increase in device efficiency, a decrease in driving voltage, and an increase in stability. found out that it can
본 발명은 상기 특정의 피리미딘 유도체 화합물 및 이를 이용한 유기 전자 소자를 제공하는 것을 목적으로 한다.An object of the present invention is to provide the above specific pyrimidine derivative compound and an organic electronic device using the same.
본 발명의 일 측면에 의하면, 하기 화학식 1로 표시되는 피리미딘 유도체를 제공한다. According to one aspect of the present invention, there is provided a pyrimidine derivative represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에 있어서, In Formula 1,
Ar1, Ar2 및 Ar3는 각각 독립적으로 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 1 , Ar 2 and Ar 3 are each independently a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,
L 은 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴렌기이고,L is substituted or unsubstituted It is a heteroarylene group having 5 or more and 20 or less carbon atoms,
Ar4 는 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나, 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
p는 0 내지 2의 정수이고, p is an integer from 0 to 2,
p가 2일 경우 복수의 Ar4는 같거나 상이하다. When p is 2, a plurality of Ar 4 are the same or different.
본 발명의 다른 측면에 의하면, 상기 특정의 피리미딘 유도체를 포함하는 유기 전계발광 소자가 제공된다.According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the specific pyrimidine derivative.
본 발명의 또 다른 측면에 의하면, 제1 전극, 제2 전극, 및 상기 전극들 사이에 배치된 1층 이상의 유기물층을 포함하되, 상기 유기물층은 상기 특정의 피리미딘 유도체를 포함하는 유기 전계발광 소자가 제공된다. According to another aspect of the present invention, an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, wherein the organic material layer includes the specific pyrimidine derivative. provided
본 발명의 또 다른 측면에 의하면, 상기 피리미딘 유도체가 상기 유기물층을 구성하는 전자저지층, 전자수송층, 전자주입층, 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층 및 발광층으로 이루어진 군 중에서의 선택된 어느 1층에 포함되는 것을 특징으로 하는 유기 전계발광 소자가 제공된다.According to another aspect of the present invention, the pyrimidine derivative is selected from the group consisting of an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function, and a light emitting layer constituting the organic material layer. An organic electroluminescent device is provided, characterized in that it is included in any one layer.
본 발명에 따른 피리미딘 유도체 화합물은 유기 발광 소자의 유기물층의 재료로 사용될 수 있다.The pyrimidine derivative compound according to the present invention may be used as a material for an organic layer of an organic light emitting device.
또한, 본 발명에 따라 피리미딘에 특정의 헤테로아릴렌기를 도입한 피리미딘 유도체 화합물을 유기물층의 재료로 이용한 유기 발광 소자는, 고효율, 저전압 및 장수명 등의 우수한 특성을 나타낸다.In addition, according to the present invention, the organic light-emitting device using a pyrimidine derivative compound introduced with a specific heteroarylene group into pyrimidine as a material for an organic material layer exhibits excellent characteristics such as high efficiency, low voltage and long life.
본 발명에 기재된 특정의 화합물은 시아노기를 도입함으로써, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다.The specific compound described in the present invention can improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light emitting device by introducing a cyano group.
도 1은 본 발명의 일 실시예에 따른 유기 발광 소자의 개략적인 단면도이다. 1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment of the present invention.
본 명세서에서 용어 "아릴"은 다른 의미로 명시되지 않는 한, 함께 융합 또는 공유 결합된 단일 고리 또는 다중 고리(1개 내지 3개의 고리)일 수 있는 다중불포화, 방향족, 탄화수소 치환기를 의미한다.As used herein, unless otherwise specified, the term "aryl" refers to a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together.
"헤테로아릴"이란 용어는 (다중 고리의 경우 각각의 별도의 고리에서) N, O 및 S로부터 선택되는 1 내지 4개의 이종원자를 포함하는 아릴 기(또는 고리)를 의미하고, 질소 및 황 원자는 경우에 따라 산화되고, 질소 원자(들)은 경우에 따라 4차화된다. 헤테로아릴 기는 탄소 또는 이종원자를 통해 분자의 나머지에 결합될 수 있다.The term "heteroaryl" refers to an aryl group (or ring) comprising 1 to 4 heteroatoms selected from N, O and S (in each separate ring in the case of multiple rings), wherein the nitrogen and sulfur atoms are Optionally oxidized and the nitrogen atom(s) optionally quaternized. The heteroaryl group may be attached to the remainder of the molecule through a carbon or heteroatom.
상기 아릴은 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함한다. 또한, 하나 이상의 아릴이 화학결합을 통하여 결합되어 있는 구조도 포함한다. 상기 아릴의 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐, 플루오레닐, 페난트릴, 트라이페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 파이렌일, 플루오란텐일 등을 포함하지만, 이에 한정되지 않는다.The aryl includes single or fused ring systems comprising suitably 4 to 7, preferably 5 or 6 ring atoms in each ring. In addition, it includes a structure in which one or more aryl is bonded through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, pyrenyl, fluoranthenyl, etc. including, but not limited to.
상기 헤테로아릴은 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 융합된 다환식 헤테로아릴을 포함하며, 부분적으로 포화될 수도 있다. 또한, 하나 이상의 헤테로아릴이 화학결합을 통하여 결합되어 있는 구조도 포함된다. 상기 헤테로아릴기는 고리 내 헤테로원자가 산화되거나 4원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다.The heteroaryl includes 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl fused with one or more benzene rings, which may be partially saturated. Also included are structures in which one or more heteroaryls are bonded through a chemical bond. The heteroaryl group includes a divalent aryl group in which a heteroatom in the ring is oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
상기 헤테로아릴의 구체적인 예로 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 포함하지만, 이에 한정되지 않는다.Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl, such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl polycyclic heteroaryls such as , phenanthridinyl, benzodioxolyl and their corresponding N-oxides (e.g., pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, However, the present invention is not limited thereto.
본 명세서에 기재된 "치환 또는 비치환된"이라는 표현에서 "치환"은 탄화수소 내의 수소 원자 하나 이상이 각각, 서로 독립적으로, 동일하거나 상이한 치환기로 대체되는 것을 의미한다. 유용한 치환기는 다음을 포함하지만 이에 제한되지 않는다.As used herein, "substituted" in the expression "substituted or unsubstituted" means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced with the same or a different substituent. Useful substituents include, but are not limited to:
이러한 치환기는, -F; -Cl; -Br; -CN; -NO2; -OH; -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C1~C20 알킬기; -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C1~C20 알콕시기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C6~C30 아릴기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C6~C30 헤테로아릴기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C5~C20 사이클로알킬기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C5~C30 헤테로사이클로알킬기; 및 -N(G1)(G2)으로 표시되는 기로 이루어진 군으로부터 선택된 하나 이상일 수 있다. 이때, 상기 G1 및 G2는 서로 독립적으로 각각 수소; C1~C10 알킬기; 또는 C1~C10 알킬기로 치환되거나 비치환된 C6~C30 아릴기일 수 있다.Such substituents include -F; -Cl; -Br; -CN; -NO 2 ; -OH; -F, -Cl, -Br, -CN, -NO 2 or a C1-C20 alkyl group unsubstituted or substituted with -OH; -F, -Cl, -Br, -CN, -NO 2 or a C1-C20 alkoxy group unsubstituted or substituted with -OH; C1~ C20 alkyl group, C1~ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH C6~ C30 aryl group unsubstituted or substituted; C1~ C20 alkyl group, C1~ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH unsubstituted or substituted C6~ C30 heteroaryl group; C1~ C20 alkyl group, C1~ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH unsubstituted or substituted C5~ C20 cycloalkyl group; C1~ C20 alkyl group, C1~ C20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 or -OH unsubstituted or substituted C5~ C30 heterocycloalkyl group; And it may be at least one selected from the group consisting of -N (G1) (G2). In this case, G1 and G2 are each independently hydrogen; C1~ C10 alkyl group; Or it may be a C6-C30 aryl group unsubstituted or substituted with a C1-C10 alkyl group.
이하, 본 발명에 대해 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명의 일 실시예에 따른 피리미딘 유도체는 하기 화학식 1로 표시될 수 있다.The pyrimidine derivative according to an embodiment of the present invention may be represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에 있어서, In Formula 1,
Ar1, Ar2 및 Ar3는 각각 독립적으로 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 1 , Ar 2 and Ar 3 are each independently a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,
L 은 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴렌기이고,L is substituted or unsubstituted It is a heteroarylene group having 5 or more and 20 or less carbon atoms,
Ar4 는 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나, 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms,
p는 0 내지 2의 정수이고, p is an integer from 0 to 2,
p가 2일 경우 복수의 Ar4는 같거나 상이하다.When p is 2, a plurality of Ar 4 are the same or different.
본 발명의 일 실시예에 따르면 상기 화학식 1은 하기 화학식 2로 표시될 수 있다. According to an embodiment of the present invention, Chemical Formula 1 may be represented by Chemical Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2에 있어서,In Formula 2,
L 은 치환 또는 비치환된, 피리딘기; 디벤조퓨란기; 디벤조티오펜기; 카바졸기; 퀴놀린기; 및 아이소퀴놀린기; 중 어느 하나이며,L is a substituted or unsubstituted, pyridine group; dibenzofuran group; dibenzothiophene group; a carbazole group; quinoline group; and an isoquinoline group; is any one of
Ar4 은 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기; 또는 치환 또는 비치환된 카바졸기;이고,Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted carbazole group;
Ar3 및 p는 상기 화학식 1에서 정의된 것과 같다. Ar 3 and p are as defined in Formula 1 above.
본 발명의 일 실시예에 따르면 상기 화학식 1에서,According to an embodiment of the present invention, in Formula 1,
Ar3 은 시아노가 치환된 페닐기; 페닐기; 및 피리딜기; 중에서 선택되는 어느 하나이다.Ar 3 is a phenyl group substituted with cyano; phenyl group; and a pyridyl group; any one selected from
본 발명의 상기 화학식 1의 피리미딘 유도체는 하기 화학식 3으로 표시되는 피리미딘 유도체이다. 그러나 본 발명의 화학식 1로 표시되는 화합물이 하기 화학식 3의 화합물들로 한정되지 않는다.The pyrimidine derivative of Formula 1 of the present invention is a pyrimidine derivative represented by Formula 3 below. However, the compound represented by Formula 1 of the present invention is not limited to the compounds of Formula 3 below.
[화학식 3][Formula 3]
상기 화학식 1로 표시되는 피리미딘 유도체는 공지의 유기 합성방법을 이용하여 합성이 가능하다. 상기 피리미딘 유도체의 합성방법은 후술하는 제조예를 참조하여 당업자에게 용이하게 인식될 수 있다.The pyrimidine derivative represented by Formula 1 can be synthesized using a known organic synthesis method. A method for synthesizing the pyrimidine derivative can be easily recognized by those skilled in the art with reference to Preparation Examples to be described later.
또한, 본 발명에 따르면, 상기 화학식 1로 표시되는 피리미딘 유도체를 포함하는 유기 전계발광 소자가 제공된다. In addition, according to the present invention, there is provided an organic electroluminescent device comprising the pyrimidine derivative represented by Formula 1 above.
상기 화학식 1의 피리미딘 유도체는 유기 전계발광 소자를 구성하는 유기물층의 어느 하나에 사용될 수 있는데, 특히 전자수송층 재료로 유용하다.The pyrimidine derivative of Formula 1 may be used in any one of the organic layers constituting the organic electroluminescent device, and is particularly useful as an electron transport layer material.
또한, 본 발명에 따른 유기 전계발광 소자는 양극, 음극 및 이들 전극 사이에 배치된 1층 이상의 유기물층을 포함한다. 상기 유기물층은 상기 화학식 1로 표시되는 피리미딘 유도체를 하나 이상 포함한다.In addition, the organic electroluminescent device according to the present invention includes an anode, a cathode, and one or more organic material layers disposed between these electrodes. The organic layer includes at least one pyrimidine derivative represented by Formula 1 above.
상기 유기물층은 정공주입층, 정공수송층, 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층, 버퍼층, 전자저지층, 발광층, 정공저지층, 전자수송층, 전자주입층, 및 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 1층 이상을 포함할 수 있다.The organic material layer includes a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function. It may include one or more layers selected from the group consisting of a functional layer having at the same time.
예를 들어, 상기 피리미딘 유도체는 발광층, 양극과 발광층 사이에 배치된 유기물층 및 발광층과 음극 사이에 배치된 유기물층으로 이루어진 군 중에서 선택되는 적어도 어느 하나에 포함될 수 있다. 바람직하게는, 상기 피리미딘 유도체는 발광층, 정공주입층, 정공수송층, 및 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 어느 1층 이상에 포함될 수 있다. 상기 피리미딘 유도체는 단일 물질 또는 서로 다른 물질의 조합으로서 상기 유기물층에 포함될 수 있다. 또는 상기 피리미딘 유도체는 발광층, 정공수송층 및 정공주입층 등에 종래 알려진 화합물과 혼합되어 사용될 수 있다. For example, the pyrimidine derivative may be included in at least one selected from the group consisting of an emission layer, an organic material layer disposed between the anode and the emission layer, and an organic material layer disposed between the emission layer and the cathode. Preferably, the pyrimidine derivative may be included in any one or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, and a functional layer having both a hole injection function and a hole transport function. The pyrimidine derivative may be included in the organic material layer as a single material or a combination of different materials. Alternatively, the pyrimidine derivative may be used in a mixture with a conventionally known compound such as a light emitting layer, a hole transport layer, and a hole injection layer.
본 발명에 따른 유기 전계발광소자는 양극/발광층/음극, 양극/정공주입층/발광층/음극, 양극/정공주입층/정공수송층/발광층/전자수송층/음극, 또는 양극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/음극의 구조를 가질 수 있다. 또는 상기 유기 전계발광소자는 양극/정공주입 기능 및 정공수송 기능을 동시에 갖는 기능층/발광층/전자수송층/음극, 또는 양극/정공주입 기능 및 정공 수송 기능을 동시에 갖는 기능층/발광층/전자수송층/전자주입층/음극의 구조를 가질 수 있지만 이에 한정되는 것은 아니다.The organic electroluminescent device according to the present invention is an anode / light emitting layer / cathode, anode / hole injection layer / light emitting layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode, or anode / hole injection layer / hole transport layer It may have a structure of /light emitting layer/electron transport layer/electron injection layer/cathode. Alternatively, the organic electroluminescent device is a functional layer / light emitting layer / electron transport layer / cathode having an anode / hole injection function and a hole transport function at the same time, or an anode / a functional layer / light emitting layer / electron transport layer / having a hole injection function and a hole transport function at the same time It may have an electron injection layer/cathode structure, but is not limited thereto.
도 1은 본 발명의 일 실시예에 따른 유기 전계발광 소자의 개략적인 단면도이다.1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
상기 유기 전계발광 소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예를 들어, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 전계발광 소자를 만들 수도 있다.The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed thereon. Then, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic electroluminescent device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
한편, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정(solution process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법으로 제조될 수 있다.On the other hand, the organic layer may be prepared by using various polymer materials, not by a deposition method, but by a solution process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method.
본 발명에 따른 유기 전계발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be a top emission type, a back emission type or a double-sided emission type depending on the material used.
이하 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나 본 명세서에 따른 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 출원의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 출원의 실시예들은 당 업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.
[제조예] [Production Example]
중간체 intermediate
합성예Synthesis example
1: 중간체(2)의 합성 1: Synthesis of intermediate (2)
(중간체(1)의 합성)(Synthesis of Intermediate (1))
1구 2 L 플라스크에 1,2-다이페닐에탄-1-온(1,2-diphenylethan-1-one) 40.0 g(203.8 mmol)과 5-브로모니코틴알데하이드(5-bromonicotinaldehyde) 37.9 g(203.8 mmol)을 톨루엔 750 mL에 혼합한 후, 120℃에서 2일 동안 교반하였다. 반응이 종료된 후, 상온에서 물을 넣고 에틸아세테이트로 추출하고 유기층을 NaHCO3 수용액에 씻어서 감압 증류하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 노란색 고체의 화합물(중간체(1)) 61.0 g(수율: 81.2%)을 얻었다.In a 1-neck 2 L flask, 40.0 g (203.8 mmol) of 1,2-diphenylethan-1-one and 37.9 g (203.8) of 5-bromonicotinaldehyde mmol) was mixed with 750 mL of toluene, followed by stirring at 120° C. for 2 days. After the reaction was completed, water was added at room temperature, extracted with ethyl acetate, and the organic layer was washed with NaHCO 3 aqueous solution and distilled under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 61.0 g (yield: 81.2%) of the compound (intermediate (1)) as a yellow solid.
(중간체(2)의 합성)(Synthesis of Intermediate (2))
1구 2 L 플라스크에 중간체(1) 61.0 g(167.5 mmol), 벤자미딘 염산염(Benzamidine hydrochloride) 27.0 g(172.5 mmol)을 에탄올 840 mL에 혼합한 후, NaOH 20.1 g(502.4 mmol)을 넣고 3일 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 물을 넣어 교반하였다. 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3:EA) 여과하고 에탄올로 고체화하여, 흰색 고체의 화합물(중간체(2)) 26.6 g(수율: 34.2%)을 얻었다.In a 1-neck 2 L flask, 61.0 g (167.5 mmol) of the intermediate (1) and 27.0 g (172.5 mmol) of benzamidine hydrochloride were mixed in 840 mL of ethanol, and 20.1 g (502.4 mmol) of NaOH was added thereto 3 It was stirred at reflux for one day. After the reaction was completed, it was cooled to room temperature, and water was added and stirred. The solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 :EA), and solidified with ethanol to obtain 26.6 g (yield: 34.2%) of the compound as a white solid (intermediate (2)).
중간체 intermediate
합성예Synthesis example
2: 중간체(4)의 합성 2: Synthesis of intermediate (4)
(중간체(3)의 합성)(Synthesis of Intermediate (3))
1구 1 L 플라스크에서 6-브로모피콜린알데하이드(6-bromopicolinaldehyde) 28.4 g(152.9 mmol), 1,2-다이페닐에타논(1,2-diphenylethanone) 30.0 g(152.9 mmol), 피페리딘(Piperidine) 2.6 g(30.6 mmol), AcOH 9.2 g(152.9 mmol) 및 톨루엔 382 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 포화 탄산수소나트륨 수용액과 에틸아세테이트를 넣고 추출하였다. 유기층은 무수 황산 마그네슘으로 건조하여 감압 하에 용매를 제거하였다. 얻어진 반응물을 혼합용액(EtOH:EtOAc)으로 고체화하여 아이보리색 고체의 화합물(중간체(3))을 39.4 g(수율: 70.9%)을 얻었다.In a 1-neck 1 L flask, 6-bromopicolinaldehyde 28.4 g (152.9 mmol), 1,2-diphenylethanone 30.0 g (152.9 mmol), piperidine ( Piperidine) 2.6 g (30.6 mmol), AcOH 9.2 g (152.9 mmol) and 382 mL of toluene were mixed, followed by stirring under reflux for 1 day. After the reaction was completed, it was cooled to room temperature, and a saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added and extracted. The organic layer was dried over anhydrous magnesium sulfate to remove the solvent under reduced pressure. The obtained reactant was solidified with a mixed solution (EtOH:EtOAc) to obtain 39.4 g (yield: 70.9%) of the compound (intermediate (3)) as an ivory solid.
(중간체(4)의 합성)(Synthesis of Intermediate (4))
1구 1 L 플라스크에서 중간체(3) 34.0 g(93.3 mmol), 벤지미다미드 염산염(benzimidamide hydrochloride) 17.5 g(112.0 mmol), NaOH 11.2 g(279.9 mmol) 및 에탄올 311 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 생성된 고체를 여과하고 에탄올로 세척하여 흰색 고체의 화합물(중간체(4))을 19.1 g(수율: 44.1%)을 얻었다.Intermediate in 1-neck 1 L flask (3) After mixing 34.0 g (93.3 mmol), 17.5 g (112.0 mmol) of benzimidamide hydrochloride, 11.2 g (279.9 mmol) of NaOH and 311 mL of ethanol, the mixture was stirred under reflux for 1 day. After completion of the reaction, the reaction was cooled to room temperature, and the resulting solid was filtered and washed with ethanol to obtain 19.1 g (yield: 44.1%) of the compound as a white solid (intermediate (4)).
중간체 intermediate
합성예Synthesis example
3: 중간체(6)의 합성 3: Synthesis of intermediate (6)
(중간체(5)의 합성)(Synthesis of Intermediate (5))
2구 500 mL 플라스크에서 1,2-디페닐에타논(1,2-diphenylethanone) 20 g(101.9 mmol), 5-브로모피콜린알데히드(5-bromopicolinaldehyde) 18.9 g(101.9 mmol), 피페리딘(Piperidine) 2 mL(20.3 mmol), AcOH 5.9 mL(101.9 mmol) 및 톨루엔 240 mL를 혼합한 후, 110℃에서 하루 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 정제수를 넣고 에틸아세테이트로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하고 용매를 감압 농축하였다. 얻어진 반응 혼합물을 메탄올/헥산으로 고체화하여, 흰색 고체의 화합물(중간체(5)) 15.7 g(수율: 42.4%)을 얻었다.In a 2-neck 500 mL flask, 1,2-diphenylethanone 20 g (101.9 mmol), 5-bromopicolinaldehyde 18.9 g (101.9 mmol), piperidine ( Piperidine) 2 mL (20.3 mmol), AcOH 5.9 mL (101.9 mmol) and toluene 240 mL were mixed, followed by reaction at 110° C. for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure. The obtained reaction mixture was dissolved in chloroform, filtered through silica gel, and the solvent was concentrated under reduced pressure. The obtained reaction mixture was solidified with methanol/hexane to obtain 15.7 g (yield: 42.4%) of a white solid compound (intermediate (5)).
(중간체(6)의 합성)(Synthesis of Intermediate (6))
2구 250 mL 플라스크에 중간체(5) 10 g(27.4 mmol), 벤지미다미드 염산염(benzimidamide hydrochloride) 8.6 g(54.9 mmol), K2CO3 7.6 g(54.9 mmol) 및 1,4-디옥센 160 mL를 혼합한 후, 100℃에서 3일 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 정제수를 넣고 에틸아세테이트로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하고 용매를 감압 농축하였다. 얻어진 반응 혼합물을 디클로로메탄/메탄올로 고체화하여, 흰색 고체의 화합물(중간체(6)) 5.3 g(수율: 41.6%)을 얻었다.In a 2-neck 250 mL flask, 10 g (27.4 mmol) of Intermediate (5), 8.6 g (54.9 mmol) of benzimidamide hydrochloride, 7.6 g (54.9 mmol) of K 2 CO 3 and 1,4-dioxene 160 After mixing mL, the reaction was carried out at 100° C. for 3 days. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure. The obtained reaction mixture was dissolved in chloroform, filtered through silica gel, and the solvent was concentrated under reduced pressure. The obtained reaction mixture was solidified with dichloromethane/methanol to obtain 5.3 g (yield: 41.6%) of a white solid compound (intermediate (6)).
중간체 intermediate
합성예Synthesis example
4: 중간체(8)의 합성 4: Synthesis of intermediate (8)
(중간체(7)의 합성)(Synthesis of Intermediate (7))
1구 1 L 플라스크에서 벤즈이미다미드 염산염(benzimidamide hydrochloride) 50.0 g(319.3 mmol)을 증류수(water) 128 mL와 혼합한 후, NaOH 12.8 g(319.3 mmol)을 증류수 30 mL에 녹여 적가하였다. 에틸 3-옥소-3-페닐프로판오에이트 (ethyl 3-oxo-3-phenylpropanoate) 64.4 g(335.3 mmol)과 에탄올 140 mL를 적가한 후, 18시간 상온에서 교반하였다. 반응이 종결된 후, 생성된 고체를 여과하고, 다이에틸이서와 에탄올로 세척하고 건조하여 아이보리색 고체의 화합물 (중간체(7)) 45.9 g(수율: 57.9%)을 얻었다.In a 1-neck 1 L flask, 50.0 g (319.3 mmol) of benzimidamide hydrochloride was mixed with 128 mL of distilled water, and then 12.8 g (319.3 mmol) of NaOH was dissolved in 30 mL of distilled water and added dropwise. 64.4 g (335.3 mmol) of ethyl 3-oxo-3-phenylpropanoate and 140 mL of ethanol were added dropwise, followed by stirring at room temperature for 18 hours. After the reaction was completed, the resulting solid was filtered, washed with diethyl ether and ethanol, and dried to obtain 45.9 g (yield: 57.9%) of the compound as an ivory solid (Intermediate (7)).
(중간체(8)의 합성)(Synthesis of Intermediate (8))
1구 2 L 플라스크에서 중간체(7) 45.9 g(184.9 mmol)와 아세틱산(Acetic acid) 1.2 L를 혼합한 후, NBS 49.4 g(277.4 mmol)을 적가하였다. 반응물을 상온에서 18시간 교반한 후, 증류수를 첨가하였다. 디클로로메탄으로 추출한 후, 분리된 유기층을 무수황산나트륨으로 건조, 감압 증류하였다. 얻은 화합물을 에탄올에서 결정화하고, 여과, 건조하여 흰색 고체의 화합물(중간체(8)) 51.8 g(수율: 85.6%)을 얻었다.In a 1-neck 2 L flask, 45.9 g (184.9 mmol) of the intermediate (7) and 1.2 L of acetic acid were mixed, and then 49.4 g (277.4 mmol) of NBS was added dropwise. After the reaction was stirred at room temperature for 18 hours, distilled water was added. After extraction with dichloromethane, the separated organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure. The obtained compound was crystallized in ethanol, filtered and dried to obtain 51.8 g (yield: 85.6%) of the compound as a white solid (intermediate (8)).
중간체 intermediate
합성예Synthesis example
5: 중간체(10)의 합성 5: Synthesis of intermediate (10)
(중간체(9)의 합성)(Synthesis of Intermediate (9))
1구 2 L 플라스크에서 중간체(8) 41.8 g(127.8 mmol), 페닐보론산 (phenylboronic acid) 20.3 g(166.1 mmol), Pd(PPh3)4 14.8 g(12.8 mmol), Na2CO3 40.6 g(383.4 mmol), 디옥산 1 L 및 증류수 213 mL를 혼합한 후, 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 증류수를 첨가한 후 상온에서 3시간 교반하였다. 생성된 고체를 여과한 후, 증류수로 세척하였다. 얻어진 고체를 건조하여 노란색 고체의 화합물(중간체(9)) 33.3 g(수율: 80.4%)을 얻었다.Intermediate (8) 41.8 g (127.8 mmol), phenylboronic acid 20.3 g (166.1 mmol), Pd(PPh 3 ) 4 14.8 g (12.8 mmol), Na 2 CO 3 40.6 g in a 1-neck 2 L flask (383.4 mmol), 1 L of dioxane and 213 mL of distilled water were mixed, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature, distilled water was added, and the mixture was stirred at room temperature for 3 hours. The resulting solid was filtered and washed with distilled water. The obtained solid was dried to obtain 33.3 g (yield: 80.4%) of a yellow solid compound (intermediate (9)).
(중간체(10)의 합성)(Synthesis of Intermediate (10))
1구 2 L 플라스크에서 중간체(9) 33.3 g(102.7 mmol)을 디옥산(Dioxane) 514 mL와 혼합한 후, POCl3 95.9 mL(1.0 mol)를 상온에서 천천히 적가한 후, 3시간 교반, 환류하였다. 반응이 종결된 후, 상온으로 냉각하고, 얼음물에 반응물을 천천히 적가하였다. 포화수용액 Na2CO3를 pH 6까지 천천히 적가한 후, 디클로로메탄으로 추출하였다. 분리된 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에서 증류하였다. 얻어진 화합물을 실리카겔 컬럼크로마토 그래피 (Hexanes:DCM)로 정제하고, 메탄올로 고체화하여 흰색 고체의 화합물(중간체(10))을 27.1 g(수율: 77.0%)을 얻었다.After mixing 33.3 g (102.7 mmol) of the intermediate (9) with 514 mL of Dioxane in a 1-neck 2 L flask, POCl 3 95.9 mL (1.0 mol) was slowly added dropwise at room temperature, stirred for 3 hours, and refluxed. After the reaction was completed, it was cooled to room temperature, and the reactant was slowly added dropwise to ice water. A saturated aqueous solution of Na 2 CO 3 was slowly added dropwise to pH 6, followed by extraction with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes:DCM) and solidified with methanol to obtain 27.1 g (yield: 77.0%) of the compound as a white solid (intermediate (10)).
중간체 intermediate
합성예Synthesis example
6: 중간체(12)의 합성 6: Synthesis of intermediate (12)
(중간체(11)의 합성)(Synthesis of intermediate (11))
1구 2 L 플라스크에서 중간체(8) 40.0 g(122.3 mmol), (4-시아노페닐)보론산 ((4-cyanophenyl)boronic acid) 23.4 g(158.9 mmol), Pd(PPh3)4 14.1 g(12.2 mmol), Na2CO3 38.9 g(366.8 mmol), 디옥산 1 L 및 증류수 210 mL를 혼합한 후, 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 증류수를 첨가한 후 상온에서 3시간 교반하였다. 생성된 고체를 여과한 후 증류수로 세척하였다. 얻어진 고체를 건조하여 노란색 고체의 화합물(중간체(11)) 29.7 g(수율: 69.5%)을 얻었다.In a 1-neck 2 L flask, 40.0 g (122.3 mmol) of Intermediate (8), 23.4 g (158.9 mmol) of (4-cyanophenyl)boronic acid, 14.1 g of Pd(PPh 3 ) 4 (12.2 mmol), Na 2 CO 3 38.9 g (366.8 mmol), 1 L of dioxane and 210 mL of distilled water were mixed, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature, distilled water was added, and the mixture was stirred at room temperature for 3 hours. The resulting solid was filtered and washed with distilled water. The obtained solid was dried to obtain 29.7 g (yield: 69.5%) of a yellow solid compound (intermediate (11)).
(중간체(12)의 합성)(Synthesis of Intermediate (12))
1구 2 L 플라스크에 중간체(11) 29.7 g(85.0 mmol)을 디옥산(Dioxane) 437mL와 혼합한 후, POCl3 81.5 mL(0.8 mol)를 상온에서 천천히 적가한 후, 3시간 교반, 환류하였다. 반응이 종결된 후, 상온으로 냉각하고, 얼음물에 반응물을 천천히 적가하였다. 포화수용액 Na2CO3를 pH 6까지 천천히 적가한 뒤, 디클로로메탄으로 추출하였다. 분리된 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에서 증류하였다. 얻어진 화합물을 실리카겔 컬럼크로마토그래피 (Hexanes:DCM)로 정제하고, 메탄올로 고체화하여 흰색 고체의 화합물(중간체(12))을 21.3 g(수율: 68.1%)을 얻었다.After mixing 29.7 g (85.0 mmol) of the intermediate (11) with 437 mL of dioxane in a 1-neck 2 L flask, POCl 3 81.5 mL (0.8 mol) was slowly added dropwise at room temperature, stirred for 3 hours, and refluxed. After the reaction was completed, it was cooled to room temperature, and the reactant was slowly added dropwise to ice water. A saturated aqueous solution of Na 2 CO 3 was slowly added dropwise to pH 6, followed by extraction with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes:DCM) and solidified with methanol to obtain 21.3 g (yield: 68.1%) of the compound as a white solid (intermediate (12)).
중간체 intermediate
합성예Synthesis example
7: 중간체(14)의 합성 7: Synthesis of intermediate (14)
(중간체(13)의 합성)(Synthesis of Intermediate (13))
1구 2 L 플라스크에서 중간체(8) 40.0 g(122.3 mmol), 3-피리디닐보론산(3-Pyridinylboronic acid) 19.5 g(158.9 mmol), Pd(PPh3)4 14.1 g(12.2 mmol), Na2CO3 38.9 g(366.8 mmol), 디옥산 1 L 및 증류수 210 mL를 혼합한 후, 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 증류수를 첨가한 후 상온에서 3시간 교반하였다. 생성된 고체를 여과한 후 증류수로 세척하였다. 얻어진 고체를 건조하여 노란색 고체의 화합물(중간체(13)) 21.4 g(수율: 53.8%)을 얻었다.In a 1-neck 2 L flask, 40.0 g (122.3 mmol) of intermediate (8), 19.5 g (158.9 mmol) of 3-Pyridinylboronic acid, 14.1 g (12.2 mmol) of Pd(PPh 3 ) 4 , Na 2 CO 3 38.9 g (366.8 mmol), 1 L of dioxane and 210 mL of distilled water were mixed, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature, distilled water was added, and the mixture was stirred at room temperature for 3 hours. The resulting solid was filtered and washed with distilled water. The obtained solid was dried to obtain 21.4 g (yield: 53.8%) of a yellow solid compound (intermediate (13)).
(중간체(14)의 합성)(Synthesis of Intermediate (14))
1구 2 L 플라스크에서 중간체(13) 21.4 g(65.8 mmol)을 디옥산(Dioxane) 339mL와 혼합한 후, POCl3 62.3 mL(0.6 mol)를 상온에서 천천히 적가한 후, 3시간 교반, 환류하였다. 반응이 종결된 후, 상온으로 냉각하고, 얼음물에 반응물을 천천히 적가하였다. 포화수용액 Na2CO3를 pH 6까지 천천히 적가한 뒤, 디클로로메탄으로 추출하였다. 분리된 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에서 증류하였다. 얻어진 화합물을 실리카겔 컬럼크로마토 그래피 (Hexanes:DCM)로 정제하고, 메탄올로 고체화하여 흰색 고체의 화합물(중간체(14))을 13.2 g(수율: 58.4%)을 얻었다.After mixing 21.4 g (65.8 mmol) of the intermediate (13) with 339 mL of Dioxane in a 1-neck 2 L flask, POCl 3 62.3 mL (0.6 mol) was slowly added dropwise at room temperature, stirred for 3 hours, and refluxed. After the reaction was completed, it was cooled to room temperature, and the reactant was slowly added dropwise to ice water. A saturated aqueous solution of Na 2 CO 3 was slowly added dropwise to pH 6, followed by extraction with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes:DCM), and solidified with methanol to obtain 13.2 g (yield: 58.4%) of the compound as a white solid (intermediate (14)).
중간체 intermediate
합성예Synthesis example
8: 중간체(17)의 합성 8: Synthesis of intermediate (17)
(중간체(15)의 합성)(Synthesis of Intermediate (15))
3구 3 L 플라스크에서 2,8-디브로모디벤조퓨란(2,8-dibromodibenzo[b,d] furan) 70.0 g(214.7 mmol)에 THF 1.5 L를 혼합한 후, 1시간 동안 교반하였다. 혼합물을 -65℃로 냉각한 후, n-BuLi 94.4 mL(235.8 mmol, 2.5 M in hexane)를 1시간 동안 적가하였다. 얻어진 혼합물에 DMF 49.5 mL(641.6 mmol)를 -65℃에서 천천히 적가 한 후 15시간 동안 상온에서 교반하였다. 반응이 종결된 후 6 N HCl 1.5 L를 첨가한 후 Toluene과 물로 씻었다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(n-Hex:Toluene)로 정제한 후 MeOH로 고체화하여 흰색 고체의 화합물(중간체(15)) 28.2 g (수율: 47.6%)얻었다.In a 3-neck 3 L flask, 2,8-dibromodibenzofuran (2,8-dibromodibenzo[b,d] furan) 70.0 g (214.7 mmol) was mixed with 1.5 L of THF, followed by stirring for 1 hour. After the mixture was cooled to -65°C, 94.4 mL of n-BuLi (235.8 mmol, 2.5 M in hexane) was added dropwise over 1 hour. To the resulting mixture, 49.5 mL (641.6 mmol) of DMF was slowly added dropwise at -65°C, followed by stirring at room temperature for 15 hours. After the reaction was completed, 1.5 L of 6 N HCl was added and washed with toluene and water. The obtained compound was purified by silica gel column chromatography (n-Hex:Toluene) and then solidified with MeOH to obtain 28.2 g (yield: 47.6%) of the compound as a white solid (intermediate (15)).
(중간체(16)의 합성)(Synthesis of Intermediate (16))
1구 1 L 플라스크에서 중간체(15) 28.2 g (102.3 mmol), 1,2-디페닐에탄온 (1,2-diphenylethanone) 19.0 g (102.3 mmol), 피페리딘(Piperidine) 2.0 mL (20.4 mmol), AcOH 5.8 mL (102.3 mmol) 및 톨루엔 500 mL를 혼합한 후, 48시간 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 실리카 패드에 (CHCl3) 여과하고 용액을 제거하여, 갈색 액체의 화합물(중간체(16)) 44.6 g (수율: 96.2%)을 얻었다.In a 1-neck 1 L flask, 28.2 g (102.3 mmol) of intermediate (15), 19.0 g (102.3 mmol) of 1,2-diphenylethanone, 2.0 mL (20.4 mmol) of piperidine ), AcOH 5.8 mL (102.3 mmol) and toluene 500 mL were mixed, followed by stirring under reflux for 48 hours. After completion of the reaction, the reaction was cooled to room temperature, filtered through a silica pad (CHCl 3 ), and the solution was removed to obtain 44.6 g (yield: 96.2%) of the compound (intermediate (16)) as a brown liquid.
(중간체(17)의 합성)(Synthesis of Intermediate (17))
1구 1 L 플라스크에서 중간체(16) 20.0 g (44.1 mmol), 벤즈이미다마이드 염산염(benzimidamide hydrochloride) 7.2 g (45.9 mmol), NaOH 3.5 g (88.2 mmol) 및 에탄올 250 mL를 혼합한 후, 24시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에탄올을 제거하였다. 얻어진 화합물에 2-Methoxyethanol 300 mL를 혼합한 후, 20시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에탄올과 물로 씻어주며 여과하여, 노란색 고체의 화합물(중간체(17)) 11.0 g (수율: 45.1%)을 얻었다.After mixing 20.0 g (44.1 mmol) of intermediate (16), 7.2 g (45.9 mmol) of benzimidamide hydrochloride, 3.5 g (88.2 mmol) of NaOH and 250 mL of ethanol in a 1-neck 1 L flask, 24 Stir at reflux for hours. After the reaction was completed, it was cooled to room temperature, and ethanol was removed. After mixing 300 mL of 2-Methoxyethanol with the obtained compound, the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction was cooled to room temperature, washed with ethanol and water and filtered to obtain 11.0 g of a yellow solid compound (Intermediate (17)) (yield: 45.1%).
중간체 intermediate
합성예Synthesis example
9: 중간체(21)의 합성 9: Synthesis of intermediate (21)
(중간체(18)의 합성)(Synthesis of Intermediate (18))
4구 4 L 플라스크에서 1-브로모다이벤조[b,d]퓨란-4-아민(1-bromodibenzo [b,d]furan-4-amine) 90.0 g(343.4 mmol), 35.0% 염산 143.1 ml(1.4 mol) 및 증류수 400 ml를 혼합한 후, 0℃에서 교반하였다. 내부온도를 4℃ 이하를 유지하며 NaNO2 30.8 g(446.4 mmol)을 증류수 125 ml에 녹여 천천히 적가 후, 1시간 유지하였다. 5℃ 이하를 유지하며 KI 114 g(686.8 mmol)을 증류수 125 ml에 녹여 천천히 적가 후, 1시간 교반하였다. 상온으로 온도를 올린 후 하루 동안 반응시켰다. 반응이 종료되면 반응물에 NaS2O3 수용액을 넣어 중화 후 에틸아세테이트로 추출하였다. 분리한 유기층을 무수 황산마그네슘으로 건조, 여과하고 감압 증류한 후 얻어진 고체 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여, 흰색 고체의 화합물(중간체(18)) 65.9 g (수율: 51.4%)얻었다.In a 4-neck 4 L flask, 1-bromodibenzo [b, d ]furan-4-amine (1-bromodibenzo [ b,d ]furan-4-amine) 90.0 g (343.4 mmol), 35.0% hydrochloric acid 143.1 ml (1.4 mol) and 400 ml of distilled water were mixed, followed by stirring at 0°C. While maintaining the internal temperature below 4℃, NaNO 2 30.8 g (446.4 mmol) was dissolved in 125 ml of distilled water, slowly added dropwise, and maintained for 1 hour. 114 g (686.8 mmol) of KI was dissolved in 125 ml of distilled water while maintaining 5° C. or lower, and then slowly added dropwise, followed by stirring for 1 hour. After raising the temperature to room temperature, the reaction was carried out for one day. When the reaction was completed, an aqueous solution of NaS 2 O 3 was added to the reaction mixture, neutralized, and extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the resulting solid mixture was purified by silica gel column chromatography (Hex) to obtain 65.9 g (yield: 51.4%) of the white solid compound (Intermediate (18)). .
(중간체(19)의 합성)(Synthesis of Intermediate (19))
2구 2 L 플라스크에서 중간체(18) 56.6 g(151.7 mmol)을 테트라하이드로퓨란 760 mL에 녹이고, -78℃에서 n-BuLi 63.7 mL(159.3 mmol)를 적가한 후, 1시간 동안 교반하였다. DMF 23.5 mL(303.5 mmol)를 적가한 후, 상온으로 온도를 올리고, 2시간 동안 반응시켰다. 반응물에 증류수를 넣고 에틸아세테이트로 추출하였다. 추출한 유기층을 무수 황산마그네슘으로 건조, 여과하고 감압 증류한 후 얻어진 고체 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:DCM)로 정제하여, 혼합용액(Hex/EA)으로 고체화하여, 흰색 고체의 화합물(중간체(19)) 69.0 g(수율: 76.4%)을 얻었다.In a 2-neck 2 L flask, 56.6 g (151.7 mmol) of Intermediate (18) was dissolved in 760 mL of tetrahydrofuran, and 63.7 mL (159.3 mmol) of n -BuLi was added dropwise at -78°C, followed by stirring for 1 hour. After adding DMF 23.5 mL (303.5 mmol) dropwise, the temperature was raised to room temperature, and the reaction was carried out for 2 hours. Distilled water was added to the reaction mixture, followed by extraction with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the resulting solid mixture was purified by silica gel column chromatography (Hex:DCM), and solidified with a mixed solution (Hex/EA), and a white solid compound (intermediate ( 19)) 69.0 g (yield: 76.4%) was obtained.
(중간체(20)의 합성)(Synthesis of Intermediate (20))
2구 3 L 플라스크에서 중간체(19) 69.0 g(250.8 mmol), 1,2-다이페닐에타논(1,2-diphenylethanone) 49.7 g(253.3 mmol), 피페리딘 4.9 mL(50.2 mmol), 아세틱에시드 14034 mL(250.8 mmol) 및 톨루엔 1 L를 혼합한 후, 140℃에서 16시간 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 정제수를 넣고 에틸아세테이트로 추출하였다. 추출한 유기층을 무수 황산마그네슘으로 건조, 여과 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용액(Hex/EA)으로 고체화하여, 흰색 고체의 화합물(중간체(20)) 77.9 g (수율: 68.5%)을 얻었다.In a 2-neck 3 L flask, 69.0 g (250.8 mmol) of intermediate (19), 49.7 g (253.3 mmol) of 1,2-diphenylethanone, 4.9 mL (50.2 mmol) of piperidine, acetic acid After mixing 14034 mL (250.8 mmol) of thiic acid and 1 L of toluene, the mixture was stirred at 140°C for 16 hours. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (Hex/EA) to obtain 77.9 g of a white solid compound (intermediate (20)) (yield: 68.5%).
(중간체(21)의 합성)(Synthesis of Intermediate (21))
2구 2 L 플라스크에서 중간체(20) 77.9 g(171.8 mmol), 벤즈아미딘 염산염(Benzamidine hydrochloride) 53.8 g(353.7 mmol), K2CO3 95.0 g(687.4 mmol) 및 1,4-다이옥세인 760 mL를 혼합한 후, 110℃에서 4일간 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 정제수를 넣고 에틸아세테이트로 추출하였다. 추출한 유기층을 무수 황산마그네슘으로 건조, 여과 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피 (CHCl3)로 정제하고 혼합용액(Hex/EA)으로 고체화하여, 흰색 고체의 화합물 (중간체(21)) 35.5 g (수율: 37.3%, 순도: 99.4%)을 얻었다.In a 2-neck 2 L flask, 77.9 g (171.8 mmol) of intermediate (20), 53.8 g (353.7 mmol) of benzamidine hydrochloride, 95.0 g (687.4 mmol) of K 2 CO 3 and 1,4-dioxane 760 After mixing mL, the mixture was stirred at 110° C. for 4 days. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (Hex/EA) to obtain 35.5 g of a white solid compound (intermediate (21)) (yield: 37.3%, purity: 99.4%) got it
중간체 intermediate
합성예Synthesis example
10: 중간체(24)의 합성 10: Synthesis of intermediate (24)
(중간체(22)의 합성)(Synthesis of Intermediate (22))
2구 2 L 플라스크에서 2-브로모다이벤조퓨란(2-bromodibenzo[b,d]furan) 50.0 g(202.4 mmol)을 THF 500 mL에 녹이고, -78℃에서 LDA 101.0 mL(2.0 M, 202.4 mmol)을 적가한 후, 2시간 동안 교반하였다. DMF 23.4 mL(303.5 mmol)를 적가한 후, 상온으로 온도를 올린 후 12시간 동안 반응시켰다. 2 N HCl 수용액으로 산성화시킨 후, 에틸아세테이트로 추출하였다. 추출한 유기층을 무수 황산마그네슘으로 건조, 여과하고 감압 증류한 후 얻어진 고체 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고, 혼합용액(DCM/Hex)으로 고체화하여, 흰색 고체의 화합물(중간체(22)) 27.5 g(수율: 49.4%)을 얻었다.Dissolve 50.0 g (202.4 mmol) of 2-bromodibenzofuran (2-bromodibenzo[b,d]furan) in 500 mL of THF in a 2-neck 2 L flask, and 101.0 mL of LDA at -78°C (2.0 M, 202.4 mmol) was added dropwise and stirred for 2 hours. After adding DMF 23.4 mL (303.5 mmol) dropwise, the temperature was raised to room temperature and the reaction was carried out for 12 hours. After acidification with 2N HCl aqueous solution, extraction was performed with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the resulting solid mixture was purified by silica gel column chromatography (CHCl 3 ), and solidified with a mixed solution (DCM/Hex), and a white solid compound (intermediate (22) )) 27.5 g (yield: 49.4%) was obtained.
(중간체(23)의 합성)(Synthesis of intermediate (23))
1구 1 L 플라스크에서 1,2-다이페닐에탄-1-온(1,2-diphenylethan-1-one) 19.6 g(100.0 mmol)과 중간체(22) 27.5 g(100.0 mmol)을 톨루엔 360 mL에 혼합한 후, AcOH 5.7 mL(100.0 mmol)와 피페리딘(Piperidine) 4.0 mL(40.0 mL)를 넣고 120℃에서 1일 동안 반응하였다. 반응이 종료되면 상온에서 물을 넣고 에틸아세테이트로 추출하고 유기층을 NaHCO3 수용액에 씻어서 감압 증류하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용액(CHCl3/EtOH)으로 고체화하여, 흰색 고체의 화합물(중간체(23)) 14.4 g(수율: 31.8%)을 얻었다. In a 1-neck 1 L flask, 19.6 g (100.0 mmol) of 1,2-diphenylethan-1-one and 27.5 g (100.0 mmol) of Intermediate (22) were added to 360 mL of toluene. After mixing, 5.7 mL (100.0 mmol) of AcOH and 4.0 mL (40.0 mL) of piperidine were added and reacted at 120° C. for 1 day. When the reaction was completed, water was added at room temperature, extracted with ethyl acetate, and the organic layer was washed with NaHCO 3 aqueous solution and distilled under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (CHCl 3 /EtOH) to obtain 14.4 g (yield: 31.8%) of the compound as a white solid (intermediate (23)).
(중간체(24)의 합성)(Synthesis of Intermediate 24)
1구 500 mL 플라스크에서 중간체(23) 10.0 g(22.1 mmol), 벤자미딘 염산염(Benzamidine hydrochloride) 4.2 g(26.5 mmol)을 다이옥산 110 mL에 혼합한 후, Cs2CO3 25.2 g(77.2 mmol)을 넣고 3일 동안 환류 교반하였다. K2CO3 6.1 g(44.1 mmol)을 넣고 2일 동안 환류 교반한 후, 상온으로 냉각하고 물을 넣고 교반하였다. 고체를 여과한 후, 물과 에탄올로 씻어서 건조하고, 건조한 고체를 클로로포름에 녹인 후, 실리카겔 컬럼 크로마토그래피(Hex:CHCl3) 정제하고 혼합용액(DCM/EtOH)으로 고체화하여, 흰색 고체의 화합물(중간체(24)) 4.3 g(수율: 35.2%)을 얻었다.In a 1-neck 500 mL flask, 10.0 g (22.1 mmol) of the intermediate (23) and 4.2 g (26.5 mmol) of benzamidine hydrochloride were mixed in 110 mL of dioxane, and then Cs 2 CO 3 25.2 g (77.2 mmol) was added and stirred under reflux for 3 days. K 2 CO 3 6.1 g (44.1 mmol) was added, and the mixture was stirred under reflux for 2 days, cooled to room temperature, water was added, and the mixture was stirred. The solid was filtered, washed with water and ethanol, dried, and the dried solid was dissolved in chloroform, purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with a mixed solution (DCM/EtOH), and a white solid compound ( 4.3 g (yield: 35.2%) of the intermediate (24)) was obtained.
중간체 intermediate
합성예Synthesis example
11: 중간체(25)의 합성 11: Synthesis of intermediate (25)
(중간체(25)의 합성)(Synthesis of Intermediate (25))
1구 2 L 플라스크에서 4'-브로모-[1,1'-바이페닐]-4-카보나이트릴(4'-bromo-[1,1'-biphenyl]-4-carbonitrile) 50.0 g(193.7 mmol), 피나콜디보론 (Bis(pinacolato)diboron) 73.8 g(290.6 mmol), Pd(dppf)Cl2 -CH2Cl2 3.2 g(3.9 mmol), KOAc 57.0 g(581.1 mmol) 및 1,4-디옥산 650 mL를 혼합한 후, 100℃에서 12시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용액(DCM/MeOH)으로 고체화하고 여과하여, 흰색 고체의 화합물(중간체(25)) 51.1 g(수율: 86.4%)을 얻었다.50.0 g (193.7 mmol) of 4'-bromo-[1,1'-biphenyl]-4-carbonitrile (4'-bromo-[1,1'-biphenyl]-4-carbonitrile) in a 1-neck 2 L flask ), pinacol diboron (Bis(pinacolato)diboron) 73.8 g (290.6 mmol), Pd(dppf ) Cl 2 -CH 2 Cl 2 3.2 g (3.9 mmol), KOAc 57.0 g (581.1 mmol) and 1,4- After mixing 650 mL of dioxane, the mixture was stirred at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 ), solidified with a mixed solution (DCM/MeOH), and filtered to obtain 51.1 g (yield: 86.4%) of the compound as a white solid (intermediate (25)).
중간체 intermediate
합성예Synthesis example
12: 중간체(27)의 합성 12: Synthesis of intermediate (27)
(중간체(26)의 합성)(Synthesis of Intermediate (26))
1구 2 L 플라스크에서 6-시아노-2-나프톨(6-Cyano-2-naphthol) 28.5 g(168.5 mmol)을 다이클로로메탄 800 mL에 녹이고 피리딘 68.0 mL(842.3 mmol)을 적가한 후 0℃로 온도를 낮췄다. Tf2O 56.0 mL(336.9 mmol)를 천천히 적가한 후, 상온으로 온도를 올린 후 12시간 동안 반응시켰다. 반응물을 증류수에 세척한 후, 분리한 유기층을 무수 황산나트륨으로 건조, 여과하고 농축한 후 컬럼 크로마토그래피로(CHCl3) 정제하고 에탄올로 고체화하여, 흰색 액체의 화합물(중간체(26)) 24.6 g(수율: 48.5%)을 얻었다.In a 1-neck 2 L flask, 28.5 g (168.5 mmol) of 6-cyano-2-naphthol (6-Cyano-2-naphthol) was dissolved in 800 mL of dichloromethane, and 68.0 mL (842.3 mmol) of pyridine was added dropwise at 0°C. lowered the temperature to 56.0 mL (336.9 mmol) of Tf 2 O was slowly added dropwise, and then the temperature was raised to room temperature, followed by reaction for 12 hours. After washing the reaction product with distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, purified by column chromatography (CHCl 3 ), and solidified with ethanol, 24.6 g of a white liquid compound (intermediate (26)) ( Yield: 48.5%) was obtained.
(중간체(27)의 합성)(Synthesis of intermediate (27))
1구 1 L 플라스크에서 중간체(26) 20.0 g(66.4 mmol), 피나콜디보론 (Bis(pinacolato)diboron) 25.3 g(99.6 mmol), Pd(dppf)Cl2 -CH2Cl2 1.1 g(1.3 mmol), KOAc 19.6 g(199.2 mmol) 및 1,4-디옥산 220 mL를 혼합한 후, 100℃에서 12시간 동안 교반하였다. 반응이 종결된 후, 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 에탄올로 고체화하여, 흰색 액체의 화합물 (중간체(27)) 14.6 g (수율: 78.8%)얻었다.In a 1-necked 1 L flask, 20.0 g (66.4 mmol) of intermediate (26), 25.3 g (99.6 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf ) Cl 2 -CH 2 Cl 2 1.1 g (1.3 mmol), KOAc 19.6 g (199.2 mmol) and 1,4-dioxane 220 mL were mixed, followed by stirring at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reactant was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with ethanol to obtain 14.6 g (yield: 78.8%) of the compound as a white liquid (Intermediate (27)).
중간체 intermediate
합성예Synthesis example
13: 중간체(29)의 합성 13: Synthesis of intermediate (29)
(중간체(28)의 합성)(Synthesis of Intermediate (28))
1구 250 mL 플라스크에서 중간체(26) 4.5 g(14.9 mmol), 4-클로로페닐보론산 ((4-chlorophenyl)boronic acid) 2.3 g(14.9 mmol), Pd(PPh3)4 863.0 mg(746.9 μmol), K3PO4 9.5 g(44.8 mmol), 톨루엔 50 mL 및 물 20 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(CHCl3) 정제하고 에탄올로 고체화하여, 흰색 고체의 화합물(중간체(28)) 3.0 g(수율: 76.2%)을 얻었다.Intermediate (26) 4.5 g (14.9 mmol), 4-chlorophenylboronic acid ((4-chlorophenyl) boronic acid) 2.3 g (14.9 mmol), Pd(PPh 3 ) 4 863.0 mg (746.9 μmol) in a 1-neck 250 mL flask ), K 3 PO 4 9.5 g (44.8 mmol), toluene 50 mL, and water 20 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with chloroform. The reaction mixture was purified by column chromatography (CHCl 3 ) and solidified with ethanol to obtain 3.0 g (yield: 76.2%) of the compound as a white solid (intermediate (28)).
(중간체(29)의 합성)(Synthesis of Intermediate (29))
1구 1 L 플라스크에서 중간체(28) 3.0 g(11.4 mmol), 피나콜디보론 (Bis(pinacolato)diboron) 4.3 g(17.1 mmol), Pd(dba)2 654 mg(1.1 mmol), X-phos 1.1 g(12.3 mmol), KOAc 3.3 g(34.1 mmol) 및 톨루엔 55 mL를 혼합한 후, 110℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 에탄올로 고체화하여, 흰색 액체의 화합물(중간체(29)) 2.9 g (수율: 72.5%)얻었다. Intermediate (28) 3.0 g (11.4 mmol), pinacol diboron (Bis(pinacolato)diboron) 4.3 g (17.1 mmol), Pd(dba) 2 654 mg (1.1 mmol), X-phos in a 1-neck 1 L flask After mixing 1.1 g (12.3 mmol), 3.3 g (34.1 mmol) of KOAc and 55 mL of toluene, the mixture was stirred at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with ethanol to obtain 2.9 g (yield: 72.5%) of the compound (intermediate (29)) as a white liquid.
중간체 intermediate
합성예Synthesis example
14: 중간체(30)의 합성 14: Synthesis of intermediate (30)
(중간체(30)의 합성)(Synthesis of intermediate (30))
1구 2 L 플라스크에서 5-브로모아이서프탈로나이트릴(5-bromoisophthalonitrile) 40.0 g(193.2 mmol), 피나콜디보론(Bis(pinacolato)diboron) 73.6 g(290.0 mmol), Pd(dppf)Cl2·CH2Cl2 7.9 g(9.7 mmol), KOAc 56.9 g(579.6 mmol) 및 1,4-디옥산 700 mL를 혼합한 후, 100℃에서 12시간 동안 교반하였다. 반응이 종결된 후, 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3:EA)로 정제하고 헥산으로 고체화하고 여과하여, 노란색 고체의 화합물(중간체(30)) 35.1 g(수율: 71.5%)을 얻었다.In a 1-neck 2 L flask, 5-bromoisophthalonitrile (5-bromoisophthalonitrile) 40.0 g (193.2 mmol), pinacol diboron (Bis (pinacolato) diboron) 73.6 g (290.0 mmol), Pd (dppf) Cl 2 After mixing 7.9 g (9.7 mmol) of CH 2 Cl 2 , 56.9 g (579.6 mmol) of KOAc and 700 mL of 1,4-dioxane, the mixture was stirred at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reactant was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 :EA), solidified with hexane, and filtered to obtain 35.1 g (yield: 71.5%) of the compound as a yellow solid (intermediate (30)).
중간체 intermediate
합성예Synthesis example
15: 중간체(31)의 합성 15: Synthesis of intermediate (31)
(중간체(31)의 합성)(Synthesis of intermediate (31))
2구 2 L 플라스크에서 4-브로모-1-나프토나이트릴(4-bromo-1-naphthonitrile) 30.0 g(129.3 mmol), 피나콜다이보론(Bis(pinacolato)diboron) 39.4 g(155.1 mmol), Pd(dppf)Cl2·CH2Cl2 5.3 g(6.5 mmol), KOAc 38.1 g(387.8 mmol) 및 1,4-다이옥세인 650 mL를 혼합한 후, 하루 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 정제수를 넣고 에틸아세테이트로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피 (Toluene)로 정제하고 혼합용액(Hex/EA)으로 고체화하여, 흰색 고체의 화합물 (중간체(31)) 23.4 g (수율: 64.9%)얻었다.In a 2-neck 2 L flask, 3-bromo-1-naphthonitrile (4-bromo-1-naphthonitrile) 30.0 g (129.3 mmol), pinacol diboron (Bis (pinacolato) diboron) 39.4 g (155.1 mmol) , Pd(dppf)Cl 2 .CH 2 Cl 2 5.3 g (6.5 mmol), KOAc 38.1 g (387.8 mmol) and 1,4-dioxane 650 mL were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Toluene) and solidified with a mixed solution (Hex/EA) to obtain 23.4 g (yield: 64.9%) of the compound as a white solid (intermediate (31)).
중간체 intermediate
합성예Synthesis example
16: 중간체(33)의 합성 16: Synthesis of intermediate (33)
(중간체(32)의 합성)(Synthesis of Intermediate (32))
2구 2000 mL 플라스크에서 1-브로모-2-니트로벤젠(1-bromo-2-nitrobenzene) 75.6 g(374.3 mmol), (4-시아노페닐)보론산((4-cyanophenyl)boronic acid) 50.0 g(340.2 mmol), Pd(PPh3)4 19.7 g(17.0 mmol), K2CO3 141.1 g(1020.8 mmol), 톨루엔 500 mL, 정제수 250 mL 및 에탄올 200 mL를 혼합한 후, 100℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 정제수를 넣고 에틸아세테이트로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하고 용매를 감압 농축하였다. 얻어진 반응 혼합물을 헥산으로 고체화하여, 흰색 고체의 화합물(중간체(32)) 76.0 g(수율: 99.6%)을 얻었다.In a 2-neck 2000 mL flask, 1-bromo-2-nitrobenzene 75.6 g (374.3 mmol), (4-cyanophenyl) boronic acid ((4-cyanophenyl) boronic acid) 50.0 g (340.2 mmol), Pd(PPh 3 ) 4 19.7 g (17.0 mmol), K 2 CO 3 141.1 g (1020.8 mmol), toluene 500 mL, purified water 250 mL, and ethanol 200 mL were mixed, reacted while Upon completion of the reaction, after cooling to room temperature, purified water was added, extraction was performed with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was dissolved in chloroform, filtered through silica gel, and the solvent was concentrated under reduced pressure. The obtained reaction mixture was solidified with hexane to obtain 76.0 g (yield: 99.6%) of a white solid compound (intermediate (32)).
(중간체(33)의 합성)(Synthesis of Intermediate (33))
2구 1000 mL 플라스크에서 중간체(32) 76.3 g(340.3 mmol), DPPE 162.7 g(408.4 mmol) 및 자일렌 210 mL를 혼합한 후, 135℃에서 하루 동안 반응하였다. 반응이 종료되면 100℃로 냉각한 후, 디클로로메탄 500 mL를 넣고 교반하였다. 생성된 고체를 여과하고 디클로로메탄으로 씻어준 후 용매를 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CH2Cl2)로 정제하여, 흰색 고체의 화합물(중간체(33)) 17.2 g(수율: 26.3%)을 얻었다.76.3 g (340.3 mmol) of the intermediate (32), 162.7 g (408.4 mmol) of DPPE and 210 mL of xylene were mixed in a two-necked 1000 mL flask, and then reacted at 135° C. for one day. After the reaction was completed, it was cooled to 100 °C, 500 mL of dichloromethane was added, and the mixture was stirred. The resulting solid was filtered, washed with dichloromethane, and the solvent was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CH 2 Cl 2 ) to obtain 17.2 g (yield: 26.3%) of the compound (intermediate (33)) as a white solid.
중간체 intermediate
합성예Synthesis example
17: 중간체(34)의 합성 17: Synthesis of intermediate (34)
(중간체(34)의 합성)(Synthesis of Intermediate (34))
1구 1 L 플라스크에서 3-브로모카바졸(3-bromocarbazole) 30.0 g(121.9 mmol), CuCN 16.3 g(182.2 mmol) 및 NMP 488 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 증류수와 에틸아세테이트를 첨가하여 교반한다. 셀라이트 여과하여 에틸아세테이트로 씻어주었다. 여과액에 혼합 수용액(암모니아수:탄산수소나트륨수용액)을 첨가하여 추출하였다. 유기층은 무수 황산 마그네슘으로 건조하여 감압 하에 용매를 제거하였다. 얻어진 반응물을 톨루엔으로 고체화하여 갈색 고체의 화합물(중간체(34)) 11.5 g(수율: 49.1%)을 얻었다.3-bromocarbazole in 1-neck 1 L flask After mixing 30.0 g (121.9 mmol), 16.3 g (182.2 mmol) of CuCN and 488 mL of NMP, the mixture was refluxed and stirred for 1 day. After completion of the reaction, the mixture is cooled to room temperature, distilled water and ethyl acetate are added thereto, and the mixture is stirred. It was filtered through Celite and washed with ethyl acetate. A mixed aqueous solution (ammonia: sodium bicarbonate aqueous solution) was added to the filtrate for extraction. The organic layer was dried over anhydrous magnesium sulfate to remove the solvent under reduced pressure. The obtained reaction product was solidified with toluene to obtain 11.5 g (yield: 49.1%) of a brown solid compound (intermediate (34)).
중간체 intermediate
합성예Synthesis example
18: 중간체(35)의 합성 18: Synthesis of intermediate (35)
(중간체(35)의 합성)(Synthesis of intermediate (35))
1구 1 L 플라스크에서 3,6-디브로모카바졸(3,6-Dibromocarbazole) 40.0 g(123.0 mmol), CuCN 27.6 g(307.5 mmol) 및 디메틸포름아미드(DMF) 320 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 암모니아수와 에틸아세테이트를 첨가하여 30분 교반한다. 에틸아세테이트 및 클로로포름으로 물층을 추출하였다. 추출 후 그대로 유기층을 여과하여 농축하였다. 얻어진 반응물을 디메틸포름아미드에 환류하여 녹이고, 실리카, 셀라이트 및 황산마그네슘 순으로 깔아준 후 여과하여 농축하였다. 얻어진 반응물을 디메틸포름아미드로 고체화하여 회색 고체의 화합물(중간체(35)) 8.8 g(수율: 32.9%)을 얻었다.3,6-Dibromocarbazole (3,6-Dibromocarbazole) in a 1-neck 1 L flask 40.0 g (123.0 mmol), 27.6 g (307.5 mmol) of CuCN and 320 mL of dimethylformamide (DMF) were mixed, followed by refluxing and stirring for 1 day. After the reaction was completed, it was cooled to room temperature, aqueous ammonia and ethyl acetate were added, and the mixture was stirred for 30 minutes. The aqueous layer was extracted with ethyl acetate and chloroform. After extraction, the organic layer was filtered and concentrated. The obtained reaction product was dissolved in dimethylformamide under reflux, and then laid over silica, celite and magnesium sulfate in that order, followed by filtration and concentration. The obtained reaction product was solidified with dimethylformamide to obtain 8.8 g (yield: 32.9%) of the compound (intermediate (35)) as a gray solid.
중간체 intermediate
합성예Synthesis example
19: 중간체(37)의 합성 19: Synthesis of intermediate (37)
(중간체(36)의 합성)(Synthesis of Intermediate (36))
1구 1 L 플라스크에서 2,5-디브로모피리딘(2,5-dibromopyridine) 15.0 g(63.3 mmol), 4-시아노페닐보론산(4-cyanophenylboronic acid) 9.8 g(66.5 mmol), Pd(PPh3)4 3.7 g(3.2 mmol), 2 M 수용액 K2CO3 64 mL(126.6 mmol), 톨루엔 211.3 mL 및 에탄올(EtOH) 105.7 mL를 혼합한 후, 3시간 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각하였다. 증류수와 메탄올을 넣고 교반 후, 생성된 고체를 여과하여 얻었다. 얻어진 반응물을 톨루엔에 환류하여 녹인 후, 셀라이트 여과하여 감압 하에 용매를 제거하여 흰색 고체의 화합물(중간체(36))을 7.8 g(수율: 47.3%)을 얻었다.In a 1-neck 1 L flask, 2,5-dibromopyridine 15.0 g (63.3 mmol), 4-cyanophenylboronic acid 9.8 g (66.5 mmol), Pd ( PPh 3 ) 4 3.7 g (3.2 mmol), 2 M aqueous K 2 CO 3 64 mL (126.6 mmol), toluene 211.3 mL and ethanol (EtOH) 105.7 mL were mixed, followed by refluxing and stirring for 3 hours. After the reaction was completed, it was cooled to room temperature. Distilled water and methanol were added and stirred, and the resulting solid was filtered and obtained. The obtained reactant was dissolved in toluene under reflux, filtered through celite, and the solvent was removed under reduced pressure to obtain 7.8 g (yield: 47.3%) of the compound as a white solid (intermediate (36)).
(중간체(37)의 합성)(Synthesis of intermediate (37))
1구 500 mL 플라스크에서 중간체(36) 7.8 g(29.9 mmol), PIN2B2 11.4 g(44.9 mmol), Pd(dppf)Cl2 ·CH2Cl2 1.2 g(1.5 mmol), KOAc 5.9 g(59.8 mmol) 및 디옥산(Dioxane) 150 mL를 혼합한 후, 3시간 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각한 뒤, 감압 하에 용매를 제거하였다. 반응물을 에틸아세테이트로 용해시키고 증류수를 넣고 추출하였다. 유기층은 무수 황산 마그네슘으로 건조하여 감압 하에 용매를 제거하였다. 얻어진 반응물을 실리카겔 컬럼크로마토 그래피(Hexanes:EtOAc)로 정제하여 갈색 고체의 화합물(중간체(37)) 7.4 g(수율: 80.8%)을 얻었다.Intermediate (36) 7.8 g (29.9 mmol), PIN 2 B 2 11.4 g (44.9 mmol) , Pd(dppf)Cl 2 CH 2 Cl 2 1.2 g (1.5 mmol), KOAc 5.9 g ( 59.8 mmol) and 150 mL of dioxane were mixed, followed by refluxing and stirring for 3 hours. After completion of the reaction, after cooling to room temperature, the solvent was removed under reduced pressure. The reaction product was dissolved with ethyl acetate, and distilled water was added thereto, followed by extraction. The organic layer was dried over anhydrous magnesium sulfate to remove the solvent under reduced pressure. The obtained reactant was purified by silica gel column chromatography (Hexanes: EtOAc) to obtain 7.4 g (yield: 80.8%) of the compound (intermediate (37)) as a brown solid.
중간체 intermediate
합성예Synthesis example
20: 중간체(39)의 합성 20: Synthesis of intermediate (39)
(중간체(38)의 합성)(Synthesis of Intermediate (38))
1구 1 L 플라스크에서 3,5-디브로모피리딘(3,5-dibromopyridine) 15.0 g(63.3 mmol), 4-시아노페닐보론산(4-cyanophenylboronic acid) 9.8 g(66.5 mmol), Pd(PPh3)4 3.7 g(3.2 mmol), 2 M 수용액 K2CO3 64 mL(126.6 mmol), 톨루엔 211.3 mL 및 에탄올(EtOH) 105.7 mL를 혼합한 후, 3시간 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각하였다. 증류수와 메탄올을 넣고 교반 후, 생성된 고체를 여과하여 얻었다. 얻어진 반응물을 톨루엔에 환류하여 녹인 후, 셀라이트 여과하여 감압 하에 용매를 제거하여 흰색 고체의 화합물(중간체(38)) 6.2 g(수율: 37.6%)을 얻었다.In a 1-neck 1 L flask, 15.0 g (63.3 mmol) of 3,5-dibromopyridine, 9.8 g (66.5 mmol) of 4-cyanophenylboronic acid, Pd ( PPh 3 ) 4 3.7 g (3.2 mmol), 2 M aqueous K 2 CO 3 64 mL (126.6 mmol), toluene 211.3 mL and ethanol (EtOH) 105.7 mL were mixed, followed by refluxing and stirring for 3 hours. After the reaction was completed, it was cooled to room temperature. Distilled water and methanol were added and stirred, and the resulting solid was filtered and obtained. The obtained reactant was dissolved in toluene under reflux, filtered through celite, and the solvent was removed under reduced pressure to obtain 6.2 g (yield: 37.6%) of the compound as a white solid (Intermediate (38)).
(중간체(39)의 합성)(Synthesis of Intermediate (39))
1구 500 mL 플라스크에서 중간체(38) 6.2 g(23.9 mmol), PIN2B2 9.1 g(35.9 mmol), Pd(dppf)Cl2 ·CH2Cl2 1.0 g(1.2 mmol), KOAc 4.7 g(47.9 mmol) 및 디옥산(Dioxane) 120 mL를 혼합한 후, 3시간 동안 환류, 교반하였다. 반응이 종결된 후, 상온으로 냉각한 뒤, 감압 하에 용매를 제거하였다. 반응물을 에틸아세테이트로 용해시키고 증류수를 넣고 추출하였다. 유기층은 무수 황산 마그네슘으로 건조하여 감압 하에 용매를 제거하였다. 얻어진 반응물을 실리카겔 컬럼크로마토 그래피(Hexanes:EtOAc)로 정제하여 갈색 고체의 화합물(중간체(39)) 5.2 g(수율: 71.0%)을 얻었다.Intermediate (38) 6.2 g (23.9 mmol), PIN 2 B 2 9.1 g (35.9 mmol) , Pd(dppf)Cl 2 CH 2 Cl 2 1.0 g (1.2 mmol), KOAc 4.7 g ( 47.9 mmol) and 120 mL of dioxane were mixed, followed by refluxing and stirring for 3 hours. After completion of the reaction, after cooling to room temperature, the solvent was removed under reduced pressure. The reaction product was dissolved with ethyl acetate, and distilled water was added thereto, followed by extraction. The organic layer was dried over anhydrous magnesium sulfate to remove the solvent under reduced pressure. The obtained reactant was purified by silica gel column chromatography (Hexanes: EtOAc) to obtain 5.2 g (yield: 71.0%) of the compound (intermediate (39)) as a brown solid.
중간체 intermediate
합성예Synthesis example
21: 중간체(41)의 합성 21: Synthesis of intermediate (41)
(중간체(40)의 합성)(Synthesis of intermediate (40))
1구 250 mL 플라스크에서 중간체(18) 10.0 g(26.8 mmol), 4-시아노페닐보론산 ((4-cyanophenyl)boronic acid) 4.7 g(32.2 mmol), Pd(PPh3)4 1.6 g(1.3 mmol), K2CO3 9.3 g(67.0 mmol), 1,4-다이옥산 80 mL 및 물 20 mL를 혼합한 후, 하루 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(40)) 6.8 g(수율: 73.0%)을 얻었다.In a one-necked 250 mL flask, 10.0 g (26.8 mmol) of Intermediate (18), 4.7 g (32.2 mmol) of 4-cyanophenyl boronic acid, and 1.6 g (1.3 of Pd(PPh 3 ) 4 ) mmol), K 2 CO 3 9.3 g (67.0 mmol), 80 mL of 1,4-dioxane and 20 mL of water were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. It was purified by column chromatography (Hex:CHCl 3 ) and solidified with a mixed solvent (DCM/EtOH) to obtain 6.8 g (yield: 73.0%) of the compound as a white solid (intermediate (40)).
(중간체(41)의 합성)(Synthesis of intermediate (41))
1구 250 mL 플라스크에서 중간체(40) 4.0 g(11.5 mmol), 피나콜디보론 (Bis(pinacolato)diboron) 4.4 g(17.2 mmol), Pd(dba)2 660.0 mg(1.2 mmol), X-phos 1.1 g(2.3 mmol), KOAc 2.8 g(28.7 mmol) 및 톨루엔 60 mL를 혼합한 후, 110℃에서 12시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(41)) 2.0 g (수율: 43.4%)얻었다. In a one-necked 250 mL flask, 4.0 g (11.5 mmol) of intermediate (40), 4.4 g (17.2 mmol) of pinacol diboron (Bis(pinacolato)diboron), 660.0 mg (1.2 mmol) of Pd(dba) 2 , X-phos After mixing 1.1 g (2.3 mmol), 2.8 g (28.7 mmol) of KOAc and 60 mL of toluene, the mixture was stirred at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) to obtain 2.0 g (yield: 43.4%) of the compound (intermediate (41)) as a white solid.
중간체 intermediate
합성예Synthesis example
22: 중간체(43)의 합성 22: Synthesis of intermediate (43)
(중간체(42)의 합성)(Synthesis of Intermediate (42))
1 구 1 L 플라스크에서 2,8-디브로모디벤조[b,d]사이오펜(2,8-dibromodibenzo [b,d]thiophene) 20.0 g(58.5 mmol), (4-시아노페닐)보론산((4-cyanophenyl) boronic acid) 12.8 g(70.2 mmol), Pd(PPh3)4 3.4 g(2.9 mmol), K2CO3 24.3 g(175.5 mmol), 테트라하이드로퓨란(THF) 233 mL 및 증류수 59 mL를 혼합한 후, 60℃에서 18시간 교반하였다. 반응이 종결된 후, 감압 증류하여 테트라하이드로퓨란을 제거하였다. 얻어진 반응물을 디클로로메탄을 이용하여 추출하고, 분리된 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에서 증류하였다. 얻어진 화합물을 실리카겔 컬럼크로마토그래피(Hexanes:CHCl3)로 정제하여 흰색 고체의 화합물(중간체(42)) 7.0 g(수율: 32.8%)을 얻었다.2,8-dibromodibenzo [b, d] thiophene (2,8-dibromodibenzo [b, d] thiophene) 20.0 g (58.5 mmol), (4-cyanophenyl) boronic acid in a 1-neck 1 L flask ((4-cyanophenyl) boronic acid) 12.8 g (70.2 mmol), Pd(PPh 3 ) 4 3.4 g (2.9 mmol), K 2 CO 3 24.3 g (175.5 mmol), tetrahydrofuran (THF) 233 mL and distilled water After mixing 59 mL, the mixture was stirred at 60° C. for 18 hours. After the reaction was completed, tetrahydrofuran was removed by distillation under reduced pressure. The obtained reaction product was extracted with dichloromethane, and the separated organic layer was dried over anhydrous sodium sulfate, and then distilled under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hexanes:CHCl 3 ) to obtain 7.0 g (yield: 32.8%) of the compound as a white solid (intermediate (42)).
(중간체(43)의 합성)(Synthesis of intermediate (43))
1구 250 mL 플라스크에서 중간체(42) 7.0 g(19.5 mmol), PIN2B2 7.3 g(28.8 mmol), Pd(dppf)Cl·DCM 0.8 g(1.0 mmol), KOAc 5.6 g(57.6 mmol) 및 디옥산(Dioxane) 96 mL를 혼합한 후, 18시간 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하고, 감압 하에서 용매를 제거하고, 증류수를 적가하였다. 반응물을 디클로로메탄으로 추출하고 분리한 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에 용매를 제거하였다. 얻어진 반응물을 실리카겔 컬럼크로마토그래피(Hexanes:DCM)로 정제하여 흰색 고체의 화합물(중간체(43)) 4.0 g(수율: 50.6%)을 얻었다.In a one-necked 250 mL flask, 7.0 g (19.5 mmol) of Intermediate (42), 7.3 g (28.8 mmol) of PIN 2 B 2 , 0.8 g (1.0 mmol) of Pd(dppf)Cl.DCM, 5.6 g (57.6 mmol) of KOAc, and After mixing 96 mL of dioxane, reflux and stirring for 18 hours. After the reaction was completed, it was cooled to room temperature, the solvent was removed under reduced pressure, and distilled water was added dropwise. The reaction product was extracted with dichloromethane, the separated organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained reactant was purified by silica gel column chromatography (Hexanes: DCM) to obtain 4.0 g (yield: 50.6%) of the compound as a white solid (intermediate (43)).
중간체 intermediate
합성예Synthesis example
23: 중간체(45)의 합성 23: Synthesis of intermediate (45)
(중간체(44)의 합성)(Synthesis of Intermediate 44)
1구 1 L 플라스크에서 2,8-디브로모디벤조[b,d]사이오펜(2,8-dibromodibenzo[b,d]thiophene) 12.2 g(35.8 mmol), 중간체(27) 10.0 g(35.8 mmol), Pd(PPh3)4 2.0 g(1.8 mmol), 2M 수용액 K2CO3 35.8 mL(71.6 mmol), 톨루엔 239 mL 및 에탄올 119 mL를 혼합한 후, 2시간 교반, 환류하였다. 반응이 종결된 후, 상온으로 냉각하고, 생성된 고체를 여과하였다. 톨루엔, 증류수 및 메탄올로 세척, 건조하였다. 얻어진 고체를 컬럼크로마토 그래피 (Hexanes:DCM)로 정제하여 흰색 고체의 화합물(중간체(44)) 4.5 g(수율: 30.6%)을 얻었다.In a 1-neck 1 L flask, 12.2 g (35.8 mmol) of 2,8-dibromodibenzo [b, d] thiophene, 10.0 g (35.8 mmol) of the intermediate (27) ), Pd(PPh 3 ) 4 2.0 g (1.8 mmol), 2M aqueous K 2 CO 3 35.8 mL (71.6 mmol), toluene 239 mL and ethanol 119 mL were mixed, stirred for 2 hours, and refluxed. After the reaction was completed, it was cooled to room temperature, and the resulting solid was filtered. Washed with toluene, distilled water and methanol, and dried. The obtained solid was purified by column chromatography (Hexanes:DCM) to obtain 4.5 g (yield: 30.6%) of the compound as a white solid (intermediate (44)).
(중간체(45)의 합성)(Synthesis of Intermediate (45))
1구 250 mL 플라스크에서 중간체(44) 4.5 g(10.9 mmol), PIN2B2 3.3 g(13.1 mmol), Pd(dppf)Cl·DCM 0.4 g(0.5 mmol), KOAc 3.2 g(32.7 mmol) 및 디옥산(Dioxane) 54 mL를 혼합한 후, 2시간 환류, 교반하였다. 반응이 종료된 후 상온으로 냉각하고, 감압 하에서 용매를 제거하고, 증류수를 적가하였다. 반응물을 디클로로메탄으로 추출하고 분리한 유기층을 무수 황산나트륨으로 건조한 후, 감압 하에 용매를 제거하였다. 얻어진 반응물을 실리카겔 컬럼크로마토그래피(Hexanes:DCM)로 정제하여 흰색 고체의 화합물(중간체(45)) 3.4 g(수율: 68.0%)을 얻었다.In a one-necked 250 mL flask, 4.5 g (10.9 mmol) of intermediate (44), 3.3 g (13.1 mmol) of PIN 2 B 2 , 0.4 g (0.5 mmol) of Pd(dppf)Cl.DCM, 3.2 g (32.7 mmol) of KOAc, and After mixing 54 mL of dioxane, refluxed for 2 hours and stirred. After the reaction was completed, it was cooled to room temperature, the solvent was removed under reduced pressure, and distilled water was added dropwise. The reaction product was extracted with dichloromethane, the separated organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained reactant was purified by silica gel column chromatography (Hexanes: DCM) to obtain 3.4 g (yield: 68.0%) of the compound as a white solid (intermediate (45)).
중간체 intermediate
합성예Synthesis example
24: 중간체(48)의 합성 24: Synthesis of intermediate (48)
(중간체(46)의 합성)(Synthesis of Intermediate (46))
1구 250 mL 플라스크에서 3-브로모-9-페닐-9H-카바졸(3-bromo-9-phenyl-9H-carbazole) 10.0 g(31.0 mmol), 4-시아노페닐보로닉엑시드((4-cyanophenyl)boronic acid) 5.0 g(34.1 mmol), Pd(PPh3)4 1.8 g(1.6 mmol), K3PO4 16.5 g(77.6 mmol), 톨루엔 100 mL, 에탄올 25 mL 및 물 25 mL를 혼합한 후, 하루 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 클로로포름으로 추출하여 용매를 감압 농축하였다. 반응 혼합물을 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(46)) 6.9 g(수율: 64.9%)을 얻었다.In a 1-neck 250 mL flask, 1-bromo-9-phenyl-9H-carbazole 10.0 g (31.0 mmol), 4-cyanophenylboronic acid (( 4-cyanophenyl)boronic acid) 5.0 g (34.1 mmol), Pd(PPh 3 ) 4 1.8 g (1.6 mmol), K 3 PO 4 16.5 g (77.6 mmol), toluene 100 mL, ethanol 25 mL and water 25 mL After mixing, the mixture was stirred under reflux for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with chloroform, and the solvent was concentrated under reduced pressure. The reaction mixture was purified by column chromatography (Hex:CHCl 3 ) and solidified with a mixed solvent (DCM/EtOH) to obtain 6.9 g (yield: 64.9%) of the compound (intermediate (46)) as a white solid.
(중간체(47)의 합성)(Synthesis of intermediate (47))
1구 500 mL 플라스크에서 중간체(46) 5.0 g(14.5 mmol)을 DMF 70 mL에 녹였다. NBS 2.6 g(14.5 mmol)을 천천히 넣어준 후, 상온에서 3시간 반응하였다. 반응이 종료 후, 증류수를 반응물에 넣고 교반하였다. 생성된 고체를 여과한 후 증류수와 에탄올로 씻어서 건조하여 흰색 고체의 화합물(중간체(47)) 6.1 g(수율: 98.8%)을 얻었다.In a one-necked 500 mL flask, 5.0 g (14.5 mmol) of the intermediate (46) was dissolved in 70 mL of DMF. After slowly adding 2.6 g (14.5 mmol) of NBS, the reaction was conducted at room temperature for 3 hours. After the reaction was completed, distilled water was added to the reaction product and stirred. The resulting solid was filtered, washed with distilled water and ethanol, and dried to obtain 6.1 g (yield: 98.8%) of the compound as a white solid (intermediate (47)).
(중간체(48)의 합성)(Synthesis of Intermediate (48))
1구 500 mL 플라스크에서 중간체(47) 6.0 g(14.2 mmol), 피나콜디보론(Bis(pinacolato)diboron) 5.4 g(21.3 mmol), Pd(dppf)Cl2 ·CH2Cl2 579 mg(708.7 μmol), KOAc 4.2 g(42.5 mmol) 및 1,4-디옥산 70 mL를 혼합한 후, 100℃에서 12시간 동안 교반하였다. 반응이 종결된 후, 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후, 감압 농축하였다. 혼합용매(DCM/MeOH)로 고체화하고 여과하여, 흰색 고체의 화합물(중간체(48)) 5.9 g(수율: 87.7%)을 얻었다.Intermediate (47) 6.0 g (14.2 mmol), pinacol diboron (Bis(pinacolato)diboron) 5.4 g (21.3 mmol) , Pd(dppf)Cl 2 CH 2 Cl 2 579 mg (708.7) in a 1-neck 500 mL flask μmol), KOAc 4.2 g (42.5 mmol) and 1,4-dioxane 70 mL were mixed, followed by stirring at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reactant was passed through a celite pad, and then concentrated under reduced pressure. It was solidified with a mixed solvent (DCM/MeOH) and filtered to obtain 5.9 g (yield: 87.7%) of the compound as a white solid (intermediate (48)).
상기와 같이 합성된 중간체 화합물을 이용하여 이하와 같이 다양한 유기 화합물를 합성하였다. Various organic compounds were synthesized as follows using the intermediate compound synthesized as described above.
합성예Synthesis example
1: 화합물 3-1(LT20-30-183)의 합성 1: Synthesis of compound 3-1 (LT20-30-183)
1구 250 mL 플라스크에서 중간체(2) 4.0 g(8.6 mmol), 페닐보론산(phenylboronic acid) 1.6 g(12.9 mmol), Pd(PPh3)4 498.0 mg(430.7 μmol), K3PO4 5.5 g(25.8 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피(CHCl3:EA)로 정제하고 에틸아세테이트로 고체화하여, 흰색 고체의 화합물 3-1(LT20-30-183) 2.0 g(수율: 50.1%)을 얻었다.In a 1-neck 250 mL flask, 4.0 g (8.6 mmol) of intermediate (2), 1.6 g (12.9 mmol) of phenylboronic acid, Pd(PPh 3 ) 4 498.0 mg (430.7 μmol), K 3 PO 4 5.5 g (25.8 mmol), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 :EA), and solidified with ethyl acetate to obtain 2.0 g (yield: 50.1%) of compound 3-1 (LT20-30-183) as a white solid.
합성예Synthesis example
2: 화합물 3-2(LT20-30-150)의 합성 2: Synthesis of compound 3-2 (LT20-30-150)
1구 250 mL 플라스크에서 중간체(2) 3.5 g(7.5 mmol), 4-시아노페닐보론산((4-cyanophenyl)boronic acid) 1.2 g(8.3 mmol), Pd(PPh3)4 435.5 mg(376.9 μmol), K3PO4 4.8 g(22.6 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카패드에(CHCl3:EA) 여과하고 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 3-2(LT20-30-150) 1.8 g(수율: 49.9%)을 얻었다.Intermediate (2) 3.5 g (7.5 mmol), 4-cyanophenyl boronic acid ((4-cyanophenyl) boronic acid) 1.2 g (8.3 mmol), Pd (PPh 3 ) 4 435.5 mg (376.9) in a 1-neck 250 mL flask μmol), K 3 PO 4 4.8 g (22.6 mmol), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 :EA), and solidified with a mixed solution (DCM/MeOH), 1.8 g of compound 3-2 (LT20-30-150) as a white solid (yield: 49.9%) ) was obtained.
합성예Synthesis example
3: 화합물 3-3(LT20-35-197)의 합성 3: Synthesis of compound 3-3 (LT20-35-197)
1구 250 mL 플라스크에서 중간체(12) 6.0 g(16.3 mmol), 중간체(39) 6.5 g(21.2 mmol), Pd(PPh3)4 0.9 g(0.8 mmol), 2 M 수용액 K2CO3 25 mL(48.9 mmol), 톨루엔 60 mL 및 에탄올 30 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 반응온도에서 생성된 고체를 여과하였다. 얻어진 고체 화합물을 실리카겔 컬럼크로마토그래피(Hexanes:Chloroform)로 정제 후, 메탄올로 고체화하여 흰색 고체의 화합물 3-3(LT20-35-197) 2.5 g(수율: 30.0%)을 얻었다.In a 1-neck 250 mL flask, intermediate (12) 6.0 g (16.3 mmol), intermediate (39) 6.5 g (21.2 mmol), Pd(PPh 3 ) 4 0.9 g (0.8 mmol), 2 M aqueous K 2 CO 3 25 mL (48.9 mmol), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for 1 day. After the reaction was completed, the solid produced at the reaction temperature was filtered. The obtained solid compound was purified by silica gel column chromatography (Hexanes:Chloroform), and then solidified with methanol to obtain 2.5 g (yield: 30.0%) of compound 3-3 (LT20-35-197) as a white solid.
합성예Synthesis example
4: 화합물 3-5(LT20-30-207)의 합성 4: Synthesis of compound 3-5 (LT20-30-207)
1구 250 mL 플라스크에서 중간체(2) 4.0 g(8.6 mmol), 중간체(30) 2.6 g(10.3 mmol), Pd(PPh3)4 497.7 mg(430.7 μmol), K3PO4 5.5 g(25.8 mmol), 톨루엔 30 mL, 에탄올10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3:EA) 여과하고 클로로포름으로 고체화하여, 흰색 고체의 화합물 3-5(LT20-30-207) 3.1 g(수율: 69.7%)을 얻었다.In a 1-neck 250 mL flask, intermediate (2) 4.0 g (8.6 mmol), intermediate (30) 2.6 g (10.3 mmol), Pd(PPh 3 ) 4 497.7 mg (430.7 μmol), K 3 PO 4 5.5 g (25.8 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 :EA), and solidified with chloroform to obtain 3.1 g (yield: 69.7%) of compound 3-5 (LT20-30-207) as a white solid.
합성예Synthesis example
5: 화합물 3-8(LT20-30-169)의 합성 5: Synthesis of compound 3-8 (LT20-30-169)
1구 250 mL 플라스크에서 중간체(2) 3.5 g(7.5 mmol), 중간체(25) 2.5 g(8.3 mmol), Pd(PPh3)4 435.5 mg(376.9 μmol), K3PO4 4.8 g(22.6 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3:EA) 여과하고 혼합용액(DCM/Acetone)으로 고체화하여, 흰색 고체의 화합물 3-8(LT20-30-169) 2.2 g(수율: 50.7%)을 얻었다.In a one-necked 250 mL flask, intermediate (2) 3.5 g (7.5 mmol), intermediate (25) 2.5 g (8.3 mmol), Pd(PPh 3 ) 4 435.5 mg (376.9 μmol), K 3 PO 4 4.8 g (22.6 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 :EA), and solidified with a mixed solution (DCM/Acetone), 2.2 g of compound 3-8 (LT20-30-169) as a white solid (yield: 50.7%) ) was obtained.
합성예Synthesis example
6: 화합물 3-12(LT20-30-243)의 합성 6: Synthesis of compound 3-12 (LT20-30-243)
1구 250 mL 플라스크에서 중간체(2) 3.5 g(7.5 mmol), 중간체(31) 2.5 g(9.0 mmol), Pd(PPh3)4 435.5 mg(376.9 μmol), K3PO4 4.8 g(22.6 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피로(CHCl3:EA) 정제하고 혼합용액(DCM/EtOH)으로 고체화하여, 흰색 고체의 화합물 3-12(LT20-30-243) 1.1 g(수율: 27.0%)을 얻었다.In a one-necked 250 mL flask, intermediate (2) 3.5 g (7.5 mmol), intermediate (31) 2.5 g (9.0 mmol), Pd(PPh 3 ) 4 435.5 mg (376.9 μmol), K 3 PO 4 4.8 g (22.6 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was purified by column chromatography (CHCl 3 :EA) and solidified with a mixed solution (DCM/EtOH) to obtain 1.1 g (yield: 27.0%) of compound 3-12 (LT20-30-243) as a white solid. .
합성예Synthesis example
7: 화합물 3-13(LT20-30-185)의 합성 7: Synthesis of compound 3-13 (LT20-30-185)
1구 250 mL 플라스크에서 중간체(2) 3.5 g(7.5 mmol), 중간체(27) 2.5 g(9.0 mmol), Pd(PPh3)4 435.5 mg(376.9 μmol), K3PO4 4.8 g(22.6 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피로(CHCl3:EA) 정제하고 에틸아세테이트로 고체화하여, 흰색 고체의 화합물 3-13(LT20-30-185) 2.2 g(수율: 55.1%)을 얻었다.In a one-necked 250 mL flask, intermediate (2) 3.5 g (7.5 mmol), intermediate (27) 2.5 g (9.0 mmol), Pd(PPh 3 ) 4 435.5 mg (376.9 μmol), K 3 PO 4 4.8 g (22.6 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was purified by column chromatography (CHCl 3 :EA) and solidified with ethyl acetate to obtain 2.2 g (yield: 55.1%) of compound 3-13 (LT20-30-185) as a white solid.
합성예Synthesis example
8: 화합물 3-16(LT20-30-201)의 합성 8: Synthesis of compound 3-16 (LT20-30-201)
1구 250 mL 플라스크에서 중간체(2) 3.0 g(6.5 mmol), 중간체(29) 2.7 g(7.8 mmol), Pd(PPh3)4 373.3 mg(323.0 μmol), K3PO4 4.1 g(19.4 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피로(CHCl3:EA) 정제하고 에틸아세테이트로 고체화하여, 흰색 고체의 화합물 3-16(LT20-30-201) 2.7 g(수율: 68.5%)을 얻었다.In a one-necked 250 mL flask, intermediate (2) 3.0 g (6.5 mmol), intermediate (29) 2.7 g (7.8 mmol), Pd(PPh 3 ) 4 373.3 mg (323.0 μmol), K 3 PO 4 4.1 g (19.4 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was purified by column chromatography (CHCl 3 :EA) and solidified with ethyl acetate to obtain 2.7 g (yield: 68.5%) of compound 3-16 (LT20-30-201) as a white solid.
합성예Synthesis example
9: 화합물 3-19(LT20-30-167)의 합성 9: Synthesis of compound 3-19 (LT20-30-167)
1구 250 mL 플라스크에서 중간체(2) 4.0 g(8.6 mmol), 카바졸(9H-carbazole) 1.7 g(10.3 mmol), Pd(dba)2 495.0 mg(861.4 μmol), S-phos 707.0 mg(1.7 mmol), NaOtBu 2.5 g(25.8 mmol) 및 자일렌 40 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 노란색 고체의 화합물 3-19(LT20-30-167) 1.9 g(수율: 40.5%)을 얻었다.In a one-necked 250 mL flask, 4.0 g (8.6 mmol) of intermediate (2), 1.7 g (10.3 mmol) of carbazole (9H-carbazole), 495.0 mg (861.4 μmol) of Pd(dba) 2 , 707.0 mg (1.7 of S-phos) mmol), NaOtBu 2.5 g (25.8 mmol) and xylene 40 mL were mixed, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and distilled under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 1.9 g (yield: 40.5%) of compound 3-19 (LT20-30-167) as a yellow solid.
합성예Synthesis example
10: 화합물 3-20(LT20-30-195)의 합성 10: Synthesis of compound 3-20 (LT20-30-195)
1구 250 mL 플라스크에서 중간체(2) 4.0 g(8.6 mmol), 중간체(33) 2.0 g(10.3 mmol), Pd2(dba)3 788.8 mg(861.4 μmol), S-phos 707.0 mg(1.7 mmol), NaOtBu 2.5 g(25.8 mmol) 및 자일렌 45 mL를 혼합한 후, 2일 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(DCM에서 CHCl3:EA)로 정제하여, 흰색 고체의 화합물 3-20(LT20-30-195) 1.1 g(수율: 21.4%)을 얻었다. In a 1-neck 250 mL flask, Intermediate (2) 4.0 g (8.6 mmol), Intermediate (33) 2.0 g (10.3 mmol), Pd 2 (dba) 3 788.8 mg (861.4 μmol), S-phos 707.0 mg (1.7 mmol) , NaOtBu 2.5 g (25.8 mmol) and xylene 45 mL were mixed, and the mixture was stirred under reflux for 2 days. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and distilled under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 :EA in DCM) to obtain 1.1 g (yield: 21.4%) of compound 3-20 (LT20-30-195) as a white solid.
합성예Synthesis example
11: 화합물 3-28(LT20-30-262)의 합성 11: Synthesis of compound 3-28 (LT20-30-262)
1구 250 mL 플라스크에서 중간체(10) 6.2 g(18.1 mmol), 중간체(37) 7.4 g(24.2 mmol), Pd(PPh3)4 1.1 g(0.9 mmol), 2 M 수용액 K2CO3 27 mL(54.3 mmol), 톨루엔 60 mL 및 에탄올 30 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 반응온도에서 생성된 고체를 여과하였다. 얻어진 고체 화합물을 실리카겔 컬럼크로마토그래피(Hexanes:Chloroform)로 정제 후, 메탄올로 고체화하여 흰색 고체의 화합물 3-28(LT20-30-262) 3.5 g(수율: 39.8%)을 얻었다.In a one-necked 250 mL flask, intermediate (10) 6.2 g (18.1 mmol), intermediate (37) 7.4 g (24.2 mmol), Pd(PPh 3 ) 4 1.1 g (0.9 mmol), 2 M aqueous K 2 CO 3 27 mL (54.3 mmol), 60 mL of toluene, and 30 mL of ethanol were mixed, followed by stirring under reflux for 1 day. After the reaction was completed, the solid produced at the reaction temperature was filtered. The obtained solid compound was purified by silica gel column chromatography (Hexanes:Chloroform) and then solidified with methanol to obtain 3.5 g (yield: 39.8%) of compound 3-28 (LT20-30-262) as a white solid.
합성예Synthesis example
12: 화합물 3-29(LT20-35-210)의 합성 12: Synthesis of compound 3-29 (LT20-35-210)
1구 250 mL 플라스크에서 중간체(14) 6.0 g(17.5 mmol), 중간체(37) 7.0 g(22.7 mmol), Pd(PPh3)4 1.0 g(0.9 mmol), 2 M 수용액 K2CO3 26 mL(52.4 mmol), 톨루엔 60 mL 및 에탄올 30 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 반응온도에서 생성된 고체를 여과하였다. 얻어진 고체 화합물을 실리카겔 컬럼크로마토그래피(Hexanes:Chloroform)로 정제 후, 메탄올로 고체화하여 흰색 고체의 화합물 3-29(LT20-35-210) 2.1 g(수율: 24.7%)을 얻었다.In a 1-neck 250 mL flask, Intermediate (14) 6.0 g (17.5 mmol), Intermediate (37) 7.0 g (22.7 mmol), Pd(PPh 3 ) 4 1.0 g (0.9 mmol), 2 M aqueous K 2 CO 3 26 mL (52.4 mmol), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for 1 day. After the reaction was completed, the solid produced at the reaction temperature was filtered. The obtained solid compound was purified by silica gel column chromatography (Hexanes:Chloroform), and then solidified with methanol to obtain 2.1 g (yield: 24.7%) of compound 3-29 (LT20-35-210) as a white solid.
합성예Synthesis example
13: 화합물 3-47(LT20-30-168)의 합성 13: Synthesis of compound 3-47 (LT20-30-168)
1구 100 mL 플라스크에서 중간체(4) 4.3 g(9.3 mmol), 4-시아노페닐보론산((4-cyanophenyl)boronic acid) 2.1 g(14 mmol), Pd(PPh3)4 0.5 g(0.5 mmol), K3PO4 5.9 g(27.9 mmol), 디옥산 50 mL 및 증류수 10 mL를 혼합한 후, 1시간 동안 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하였다. 생성된 고체를 모노클로로벤젠에 환류하여 녹인 후, 셀라이트 여과하여 모노클로로벤젠으로 세척하였다. 상온으로 냉각하여 교반하였고, 생성된 고체를 여과, 건조하여 흰색 고체의 화합물 3-47(LT20-30-168) 3.4 g(수율: 74.6%)을 얻었다.In a 1-neck 100 mL flask, intermediate (4) 4.3 g (9.3 mmol), 4-cyanophenyl boronic acid ((4-cyanophenyl) boronic acid) 2.1 g (14 mmol), Pd (PPh 3 ) 4 0.5 g (0.5 mmol), K 3 PO 4 5.9 g (27.9 mmol), 50 mL of dioxane and 10 mL of distilled water were mixed, followed by refluxing and stirring for 1 hour. After the reaction was completed, it was cooled to room temperature. The resulting solid was dissolved under reflux in monochlorobenzene, filtered through celite, and washed with monochlorobenzene. It was cooled to room temperature and stirred, and the resulting solid was filtered and dried to obtain 3.4 g (yield: 74.6%) of compound 3-47 (LT20-30-168) as a white solid.
합성예Synthesis example
14: 화합물 3-51(LT20-30-193)의 합성 14: Synthesis of compound 3-51 (LT20-30-193)
2구 250mL 플라스크에서 중간체(4) 10.0 g(21.5 mmol), 중간체(25) 6.84 g(23.6 mmol), Pd(PPh3)4 1.24 g(1.0 mmol), K3PO4 13.6 g(64.5 mmol), 톨루엔 100 mL, 에탄올 50 mL 및 증류수 50 mL를 혼합한 후, 1시간 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 증류수 30 mL 추가투입 후 생성된 고체를 감압여과하고, 증류수와 메탄올로 세척, 건조하였다. 얻어진 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피(Hexane:EA)로 정제하였다. 농축 후 에틸 아세테이트 100 mL로 결정화하였다. 감압여과 및 건조하였다. 건조 후 흰색의 고체의 화합물 3-51(LT20-30-193) 4.6 g(수율: 83.3%)을 얻었다.In a 2-neck 250mL flask, 10.0 g (21.5 mmol) of intermediate (4), 6.84 g (23.6 mmol) of intermediate (25), 1.24 g (1.0 mmol) of Pd(PPh 3 ) 4 , 13.6 g (64.5 mmol) of K 3 PO 4 , 100 mL of toluene, 50 mL of ethanol, and 50 mL of distilled water were mixed, followed by stirring under reflux for 1 hour. After completion of the reaction, the reaction was cooled to room temperature, and after 30 mL of distilled water was added, the resulting solid was filtered under reduced pressure, washed with distilled water and methanol, and dried. The obtained solid was dissolved in chloroform and purified by column chromatography (Hexane:EA). After concentration, crystallized with 100 mL of ethyl acetate. It was filtered under reduced pressure and dried. After drying, 4.6 g (yield: 83.3%) of compound 3-51 (LT20-30-193) as a white solid was obtained.
합성예Synthesis example
15: 화합물 3-53(LT20-30-216)의 합성 15: Synthesis of compound 3-53 (LT20-30-216)
2구 500mL 플라스크에서 중간체(4) 10.0 g(21.5 mmol), 중간체(31) 7.2 g(25.8 mmol), Pd(PPh3)4 1.1 g(1.0 mmol), K2CO3 8.9 g(64.5 mmol), 톨루엔 100 mL, 에탄올(EtOH) 50 mL 및 증류수 50 mL를 혼합한 후, 3시간 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트 50 mL 및 증류수 50 mL 추가투입 후 층분리하여 물 층은 제거하였다. 유기층에 MgSO4 20g 투입 및 교반 후 셀라이트 여과하였다. 여액을 감압 농축하였다. 농축잔사를 에틸아세테이트로 용해시킨 후 실리카겔 여과하였다. 여액을 농축 후 에틸아세테이트 30ml 사용하여 환류상태에서 완전히 용해시킨다. 상온까지 냉각 후, 헥산을 적가하고, 생성된 고체를 감압 여과하였다. 건조 후 흰색의 고체의 화합물 3-53(LT20-30-216) 2.0 g(수율: 17.4%)을 얻었다.10.0 g (21.5 mmol) of intermediate (4), 7.2 g (25.8 mmol) of intermediate (31), 1.1 g (1.0 mmol) of Pd(PPh 3 ) 4 , 8.9 g (64.5 mmol) of K 2 CO 3 in a two-necked 500 mL flask , 100 mL of toluene, 50 mL of ethanol (EtOH), and 50 mL of distilled water were mixed, followed by stirring under reflux for 3 hours. After completion of the reaction, the reaction was cooled to room temperature, and after addition of 50 mL of ethyl acetate and 50 mL of distilled water, the layers were separated, and the water layer was removed. 20 g of MgSO 4 was added to the organic layer, stirred, and filtered through Celite. The filtrate was concentrated under reduced pressure. The concentrated residue was dissolved with ethyl acetate and filtered through silica gel. After concentration of the filtrate, it was completely dissolved under reflux using 30 ml of ethyl acetate. After cooling to room temperature, hexane was added dropwise, and the resulting solid was filtered under reduced pressure. After drying, 2.0 g (yield: 17.4%) of compound 3-53 (LT20-30-216) as a white solid was obtained.
합성예Synthesis example
16: 화합물 3-58(LT20-30-253)의 합성 16: Synthesis of compound 3-58 (LT20-30-253)
1구 100 mL 플라스크에서 중간체(4) 5.0 g(10.8 mmol), 카바졸(Carbazole) 1.4 g(8.3 mmol), Cu 0.3 g(34.5 mmol), K2CO3 1.5 g(10.8 mmol) 및 디메틸포름아미드(DMF) 54 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하였다. 반응액에 증류수를 첨가하여 교반하였다. 얻어진 고체를 실리카겔 컬럼 크로마토그래피(Hexanes:EtOAc)로 정제하였다. 얻어진 고체를 톨루엔으로 고체화하여 흰색 고체의 화합물 3-58(LT20-30-253) 0.6 g(수율: 12.3%)을 얻었다.In a 1-neck 100 mL flask, 5.0 g (10.8 mmol) of intermediate (4), 1.4 g (8.3 mmol) of carbazole, 0.3 g (34.5 mmol) of Cu, 1.5 g (10.8 mmol) of K 2 CO 3 and dimethylform After mixing 54 mL of amide (DMF), the mixture was refluxed and stirred for 1 day. After the reaction was completed, it was cooled to room temperature. Distilled water was added to the reaction solution and stirred. The obtained solid was purified by silica gel column chromatography (Hexanes:EtOAc). The obtained solid was solidified with toluene to obtain 0.6 g (yield: 12.3%) of compound 3-58 (LT20-30-253) as a white solid.
합성예Synthesis example
17: 화합물 3-59(LT20-30-198)의 합성 17: Synthesis of compound 3-59 (LT20-30-198)
1구 250 mL 플라스크에서 중간체(4) 4.0 g(8.6 mmol), 중간체(33) 1.3 g(6.6 mmol), Cu 0.2 g(3.6 mmol), K2CO3 1.2 g(8.6 mmol) 및 디메틸포름아미드(DMF) 43 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하였다. 반응액에 증류수를 첨가하여 교반하였다. 생성된 고체를 메탄올로 고체화한 후 실리카겔 컬럼 크로마토그래피(Hexanes:EtOAc)로 정제하였다. 얻어진 고체를 메탄올로 고체화하여 흰색 고체의 화합물 3-59(LT20-30-198) 2.9 g(수율: 38.2%)을 얻었다.In a one-necked 250 mL flask, 4.0 g (8.6 mmol) of intermediate (4), 1.3 g (6.6 mmol) of intermediate (33), 0.2 g (3.6 mmol) of Cu, 1.2 g (8.6 mmol) of K 2 CO 3 and dimethylformamide (DMF) was mixed with 43 mL, refluxed for 1 day, and stirred. After the reaction was completed, it was cooled to room temperature. Distilled water was added to the reaction solution and stirred. The resulting solid was solidified with methanol and purified by silica gel column chromatography (Hexanes:EtOAc). The obtained solid was solidified with methanol to obtain 2.9 g (yield: 38.2%) of compound 3-59 (LT20-30-198) as a white solid.
합성예Synthesis example
18: 화합물 3-60(LT20-30-179)의 합성 18: Synthesis of compound 3-60 (LT20-30-179)
1구 100 mL 플라스크에서 중간체(4) 4.0 g(8.6 mmol), 중간체(34) 1.3 g(6.6 mmol), Cu 0.2 g(3.6 mmol), K2CO3 1.2 g(8.6 mmol) 및 디메틸포름아마이드(Dimethylformamide) 43 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하였다. 반응액에 증류수를 첨가하여 교반하였다. 생성된 고체를 모노클로로벤젠에 환류하여 녹인 후, 셀라이트 여과하여 모노클로로벤젠으로 세척 후 감압 하에 용매를 제거하였다. 반응액을 아세톤으로 고체화하여 흰색 고체의 화합물 3-60(LT20-30-179) 1.6 g(수율: 43.2%)을 얻었다.In a one-necked 100 mL flask, 4.0 g (8.6 mmol) of intermediate (4), 1.3 g (6.6 mmol) of intermediate (34), 0.2 g (3.6 mmol) of Cu, 1.2 g (8.6 mmol) of K 2 CO 3 and dimethylformamide (Dimethylformamide) 43 mL was mixed, refluxed for 1 day, and stirred. After the reaction was completed, it was cooled to room temperature. Distilled water was added to the reaction solution and stirred. The resulting solid was dissolved under reflux in monochlorobenzene, filtered through Celite, washed with monochlorobenzene, and the solvent was removed under reduced pressure. The reaction solution was solidified with acetone to obtain 1.6 g (yield: 43.2%) of compound 3-60 (LT20-30-179) as a white solid.
합성예Synthesis example
19: 화합물 3-62(LT20-30-244)의 합성 19: Synthesis of compound 3-62 (LT20-30-244)
1구 250 mL 플라스크에서 중간체(4) 8.9 g(19.2 mmol), 중간체(35) 3.2 g(14.8 mmol), Cu 0.5 g(8.0 mmol), K2CO3 2.7 g(19.2 mmol) 및 디메틸포름아미드(DMF) 94 mL를 혼합한 후, 1일 동안 환류, 교반하였다. 반응이 종료된 후, 상온으로 냉각하였다. 반응액에 증류수를 첨가하여 교반하였다. 얻어진 반응물을 클로로포름과 에틸아세테이트 혼합용액으로 녹여 실리카 여과하여 감압 하에 용매를 제거하였다. 얻어진 농축액을 디클로로메탄에 환류하여 녹인 후, 상온으로 냉각하여 생성된 고체를 여과하였다. 반응물은 실리카겔 컬럼 크로마토그래피(Hexanes:EtOAc)로 정제하였다. 얻어진 고체를 혼합용액(Hexanes:Chloroform)에서 고체화하여 갈색 고체의 화합물 3-62(LT20-30-244) 2.3 g(수율: 26.0%)을 얻었다.In a one-necked 250 mL flask, 8.9 g (19.2 mmol) of intermediate (4), 3.2 g (14.8 mmol) of intermediate (35), 0.5 g (8.0 mmol) of Cu, 2.7 g (19.2 mmol) of K 2 CO 3 and dimethylformamide (DMF) was mixed with 94 mL, refluxed for 1 day, and stirred. After the reaction was completed, it was cooled to room temperature. Distilled water was added to the reaction solution and stirred. The obtained reactant was dissolved in a mixed solution of chloroform and ethyl acetate, filtered through silica, and the solvent was removed under reduced pressure. The resulting concentrate was dissolved in dichloromethane under reflux, cooled to room temperature, and the resulting solid was filtered. The reaction was purified by silica gel column chromatography (Hexanes:EtOAc). The obtained solid was solidified in a mixed solution (Hexanes:Chloroform) to obtain 2.3 g (yield: 26.0%) of compound 3-62 (LT20-30-244) as a brown solid.
합성예Synthesis example
20: 화합물 3-65(LT20-30-147)의 합성 20: Synthesis of compound 3-65 (LT20-30-147)
2구 250 mL 플라스크에서 중간체(6) 5.0 g(10.7 mmol), (4-시아노페닐)보론산((4-cyanophenyl)boronic acid) 1.6 g(10.7 mmol), Pd(PPh3)4 0.6 g(0.5 mmol), K2CO3 2.9 g(21.5 mmol), 톨루엔 60 mL, 정제수 30 mL 및 에탄올 20 mL를 혼합한 후, 100℃에서 4시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 여과하여 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하였다. 얻어진 반응 혼합물을 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 3-65(LT20-30-147) 3.8 g(수율: 73.2%)을 얻었다.In a 2-neck 250 mL flask, 5.0 g (10.7 mmol) of intermediate (6), 1.6 g (10.7 mmol) of (4-cyanophenyl) boronic acid, Pd (PPh 3 ) 4 0.6 g (0.5 mmol), K 2 CO 3 2.9 g (21.5 mmol), toluene 60 mL, purified water 30 mL, and ethanol 20 mL were mixed, followed by reaction at 100° C. for 4 hours. Upon completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and the obtained reaction mixture was dissolved in chloroform and filtered through silica gel. The obtained reaction mixture was solidified with chloroform/methanol to obtain 3.8 g (yield: 73.2%) of compound 3-65 (LT20-30-147) as a white solid.
합성예Synthesis example
21: 화합물 3-71(LT20-30-285)의 합성 21: Synthesis of compound 3-71 (LT20-30-285)
2구 250 mL 플라스크에서 중간체(6) 4.0 g(8.6 mmol), 중간체(25) 2.7 g(8.7 mmol), Pd(PPh3)4 0.5 g(0.4 mmol), K2CO3 2.4 g(17.2 mmol), 톨루엔 40 mL, 정제수 20 mL 및 에탄올 12 mL를 혼합한 후, 92℃에서 하루 동안 반응하였다. 반응이 종료 후, 실온으로 냉각하고, 정제수를 넣어 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하여 용매를 제거한 후 뜨거운 클로로포름으로 고체화하여, 흰색 고체의 화합물 3-71(LT20-30-285) 1.3 g(수율: 27.2%)을 얻었다.In a two-necked 250 mL flask, 4.0 g (8.6 mmol) of intermediate (6), 2.7 g (8.7 mmol) of intermediate (25), 0.5 g (0.4 mmol) of Pd(PPh 3 ) 4 , 2.4 g (17.2 mmol) of K 2 CO 3 ), 40 mL of toluene, 20 mL of purified water, and 12 mL of ethanol were mixed, followed by reaction at 92°C for one day. After the reaction was completed, the mixture was cooled to room temperature, purified water was added, and the resulting solid was filtered. The obtained reaction mixture was dissolved in chloroform, filtered through silica gel to remove the solvent, and then solidified with hot chloroform to obtain 1.3 g (yield: 27.2%) of compound 3-71 (LT20-30-285) as a white solid.
합성예Synthesis example
22: 화합물 3-75(LT20-30-263)의 합성 22: Synthesis of compound 3-75 (LT20-30-263)
2구 100 mL 플라스크에서 중간체(6) 3.5 g(7.5 mmol), 중간체(31) 2.5 g(9.0 mmol), Pd(PPh3)4 261.3 mg(226.1 μmol), K2CO3 3.1 g (22.6 mmol), 톨루엔 40 mL, 에탄올 10 ml 및 증류수 10 ml를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료 후, 실온으로 냉각하고, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올, 에틸아세테이트로 씻어 주었다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 톨루엔으로 고체화하여, 흰색 고체의 화합물 3-75(LT20-30-263) 2.08 g(수율: 51.4%)을 얻었다.In a two-necked 100 mL flask, intermediate (6) 3.5 g (7.5 mmol), intermediate (31) 2.5 g (9.0 mmol), Pd(PPh 3 ) 4 261.3 mg (226.1 μmol), K 2 CO 3 3.1 g (22.6 mmol) ), 40 mL of toluene, 10 mL of ethanol, and 10 mL of distilled water were mixed, followed by reaction at 90° C. for one day. After the reaction was completed, it was cooled to room temperature, and 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water, methanol, and ethyl acetate. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and solidified with toluene to obtain 2.08 g (yield: 51.4%) of compound 3-75 (LT20-30-263) as a white solid.
합성예Synthesis example
23: 화합물 3-76(LT20-30-218)의 합성 23: Synthesis of compound 3-76 (LT20-30-218)
2구 250 mL 플라스크에서 중간체(6) 3.1 g(6.6 mmol), 중간체(27) 1.8 g(6.6 mmol), Pd(PPh3)4 0.4 g(0.3 mmol), K2CO3 1.8 g(13.4 mmol), 톨루엔 37 mL, 정제수 15 mL 및 에탄올 10 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 여과하여 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하여 감압 농축 후 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 3-76(LT20-30-218) 2.3 g(수율: 65.4%)을 얻었다.In a two-necked 250 mL flask, 3.1 g (6.6 mmol) of intermediate (6), 1.8 g (6.6 mmol) of intermediate (27), Pd(PPh 3 ) 4 0.4 g (0.3 mmol), K 2 CO 3 After mixing 1.8 g (13.4 mmol), 37 mL of toluene, 15 mL of purified water and 10 mL of ethanol, the reaction was conducted at 90° C. for one day. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and the obtained reaction mixture was dissolved in chloroform, filtered through silica gel, concentrated under reduced pressure, and solidified with chloroform/methanol, 2.3 g of compound 3-76 (LT20-30-218) as a white solid ( Yield: 65.4%) was obtained.
합성예Synthesis example
24: 화합물 3-79(LT20-30-217)의 합성 24: Synthesis of compound 3-79 (LT20-30-217)
2구 250 mL 플라스크에서 중간체(6) 3.1 g(6.7 mmol), 중간체(29) 2.4 g(6.7 mmol), Pd(PPh3)4 0.4 g(0.3 mmol), K2CO3 1.8 g(13.4 mmol), 톨루엔 37 mL, 정제수 15 mL 및 에탄올 10 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료 후, 실온으로 냉각한 후, 여과하여 얻어진 반응 혼합물을 클로로포름에 녹여 실리카겔에 여과하여 감압 농축 후, 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 3-79(LT20-30-217) 1.5 g(수율: 36.7%)을 얻었다.In a two-necked 250 mL flask, 3.1 g (6.7 mmol) of intermediate (6), 2.4 g (6.7 mmol) of intermediate (29), Pd(PPh 3 ) 4 0.4 g (0.3 mmol), K 2 CO 3 After mixing 1.8 g (13.4 mmol), 37 mL of toluene, 15 mL of purified water and 10 mL of ethanol, the reaction was conducted at 90° C. for one day. After completion of the reaction, after cooling to room temperature, the reaction mixture obtained by filtration was dissolved in chloroform, filtered through silica gel, concentrated under reduced pressure, and solidified with chloroform/methanol, as a white solid Compound 3-79 (LT20-30-217) 1.5 g (yield: 36.7%) was obtained.
합성예Synthesis example
25: 화합물 3-82(LT20-30-169)의 합성 25: Synthesis of compound 3-82 (LT20-30-169)
2구 100 mL 플라스크에서 중간체(6) 3.0 g(6.5 mmol), 9H-카바졸(9H-carbazole) 1.3 g(7.8 mmol), Pd2(dba)3 1.2 g(1.3 mmol), S-Phos 1.1 mg(2.6 mmol), NaOtBu 931.3 mg (9.7 mmol) 및 자일렌 60 mL를 혼합한 후, 130℃에서 하루 동안 교반하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올, 헥세인으로 씻어 주었다. 얻어진 고체 혼합물을 뜨거운 톨루엔에 녹여 셀라이트 패드 여과를 하고, 혼합용매(Tol/IPA)로 재결정 정제 후, 흰색 고체의 화합물 3-82(LT20-30-169) 2.39 g(수율: 67.2%)을 얻었다.In a 2-neck 100 mL flask, 3.0 g (6.5 mmol) of intermediate (6), 1.3 g (7.8 mmol) of 9H-carbazole, 1.2 g (1.3 mmol) of Pd 2 (dba) 3 , S-Phos 1.1 mg (2.6 mmol), NaO t Bu 931.3 mg (9.7 mmol) and xylene 60 mL were mixed, followed by stirring at 130° C. for one day. After the reaction was completed, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water, methanol, and hexane. The obtained solid mixture was dissolved in hot toluene, filtered through a celite pad, and after recrystallization purification with a mixed solvent (Tol/IPA), 2.39 g (yield: 67.2%) of compound 3-82 (LT20-30-169) as a white solid got it
합성예Synthesis example
26: 화합물 3-83(LT20-30-204)의 합성 26: Synthesis of compound 3-83 (LT20-30-204)
2구 250 mL 플라스크에서 중간체(6) 4.1 g(9.0 mmol), 중간체(33) 1.8 g(9.4 mmol), Pd(dba)2 1.0 g(0.2 mmol), S-Phos 1.5 g(0.4 mmol), NaOtBu 2.6 g(27.0 mmol) 및 자일렌 50 mL를 혼합한 후, 120℃에서 18시간 동안 반응하였다. 반응이 종료 후, 실온으로 냉각하고, 여과하여 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올/헥산으로 고체화하여, 흰색 고체의 화합물 3-83(LT20-30-204) 2.7 g(수율: 87.3%)을 얻었다.In a two-necked 250 mL flask, 4.1 g (9.0 mmol) of intermediate (6), 1.8 g (9.4 mmol) of intermediate (33), Pd (dba) 2 1.0 g (0.2 mmol), S-Phos 1.5 g (0.4 mmol), NaOtBu After mixing 2.6 g (27.0 mmol) and 50 mL of xylene, the reaction was conducted at 120° C. for 18 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered, and the obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol/hexane, and compound 3-83 as a white solid (LT20-30- 204) 2.7 g (yield: 87.3%) was obtained.
합성예Synthesis example
27: 화합물 3-142(LT20-30-293)의 합성 27: Synthesis of compound 3-142 (LT20-30-293)
2구 250 mL 플라스크에서 중간체(10) 5.0 g(14.6 mmol), 디벤조퓨란-2-닐보론산 (dibenzofuran-2-ylboronic acid) 3.2 g(15.3 mmol), Pd(PPh3)4 0.8 g(0.7 mmol), K2CO3 4.1 g(29.2 mmol), 1,4-디옥세인 50 mL, 정제수 25 mL 및 에탄올 15 mL를 혼합한 후, 90℃에서 3시간 동안 반응하였다. 반응이 종료 후, 실온으로 냉각하고, 정제수로 생성된 고체를 여과하여 얻어진 반응 혼합물을 메틸렌클로라이드에 녹여 실리카겔에 여과하고 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 3-142(LT20-30-293) 2.4 g(수율: 34.6%)을 얻었다.In a 2-neck 250 mL flask, 5.0 g (14.6 mmol) of intermediate (10), 3.2 g (15.3 mmol) of dibenzofuran-2-ylboronic acid, Pd (PPh 3 ) 4 0.8 g (0.7 mmol), K 2 CO 3 After mixing 4.1 g (29.2 mmol), 50 mL of 1,4-dioxane, 25 mL of purified water and 15 mL of ethanol, the reaction was conducted at 90° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered with purified water, and the resulting reaction mixture was dissolved in methylene chloride, filtered through silica gel, and solidified with chloroform/methanol, and compound 3-142 as a white solid (LT20-30-293) ) to obtain 2.4 g (yield: 34.6%).
합성예Synthesis example
28: 화합물 3-146(LT20-30-199)의 합성 28: Synthesis of compound 3-146 (LT20-30-199)
1구 250 mL 플라스크에서 중간체(17) 4.3 g (7.8 mmol), (4-시아노페닐)보론산((4-cyanophenyl)boronic acid) 1.4 g (9.4 mmol), Pd(PPh3)4 0.3 g (0.2 mmol), K3PO4 4.2 g (19.6 mmol), 톨루엔 40 mL, 에탄올 20 mL 및 물 20 mL을 혼합한 후, 72 시간 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후, 실리카 패드에 여과하고 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 3-146(LT20-30-199) 3.5 g(수율: 77.4%)을 얻었다.In a one-necked 250 mL flask, 4.3 g (7.8 mmol) of intermediate (17), 1.4 g (9.4 mmol) of (4-cyanophenyl)boronic acid, 0.3 g of Pd(PPh 3 ) 4 (0.2 mmol), K 3 PO 4 4.2 g (19.6 mmol), toluene 40 mL, ethanol 20 mL, and water 20 mL were mixed and stirred under reflux for 72 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad, and solidified with a mixed solution (DCM/MeOH) to obtain 3.5 g (yield: 77.4%) of compound 3-146 (LT20-30-199) as a white solid.
합성예Synthesis example
29: 화합물 3-162(LT20-30-287)의 합성 29: Synthesis of compound 3-162 (LT20-30-287)
1구 250 mL 플라스크에서 중간체(17) 5.8 g (10.4 mmol), 중간체(33) 2.4 g (12.5 mmol), Pd2(dba)3 0.5 g (0.5 mmol), S-phos 0.4 g (1.0 mmol), NaOtBu 3.0 g (31.2 mmol) 및 자일렌 90 mL를 혼합한 후, 48시간 동안 환류 교반하였다. 반응이 종결된 후, 상온으로 냉각하고, 물과 CHCl3로 씻었다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(n-hex:CHCl3)로 정제한 후, toluene/MeOH로 재결정하여 흰색 고체의 화합물 3-162(LT20-30-287) 1.7 g(수율: 24.3%)을 얻었다. In a one-necked 250 mL flask, intermediate (17) 5.8 g (10.4 mmol), intermediate (33) 2.4 g (12.5 mmol), Pd 2 (dba) 3 0.5 g (0.5 mmol), S-phos 0.4 g (1.0 mmol) , NaO t Bu 3.0 g (31.2 mmol) and xylene 90 mL were mixed, and the mixture was stirred under reflux for 48 hours. After the reaction was completed, it was cooled to room temperature, and washed with water and CHCl 3 . The resulting mixture was purified by silica gel column chromatography (n-hex:CHCl 3 ), and then recrystallized from toluene/MeOH to obtain 1.7 g (yield: 24.3%) of compound 3-162 (LT20-30-287) as a white solid. .
합성예Synthesis example
30: 화합물 3-169(LT20-30-289)의 합성 30: Synthesis of compound 3-169 (LT20-30-289)
1구 250 mL 플라스크에서 중간체(10) 3.5 g(10.2 mmol), 다이벤조퓨란-4-일보로닉엑시드 (dibenzo[b,d]furan-4-ylboronic acid) 2.2 g(10.2 mmol), Pd(PPh3)4 590.0 mg(510.5 μmol), K3PO4 6.5 g(30.6 mmol) 톨루엔 30 mL, 에탄올10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3) 여과하고 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물 3-169(LT20-30-289) 3.4 g(수율: 70.4%)을 얻었다.In a 1-neck 250 mL flask, 3.5 g (10.2 mmol) of intermediate (10), 2.2 g (10.2 mmol) of dibenzofuran-4-ylboronic acid (dibenzo[b,d]furan-4-ylboronic acid), Pd ( PPh 3 ) 4 590.0 mg (510.5 μmol), K 3 PO 4 6.5 g (30.6 mmol) 30 mL of toluene, 10 mL of ethanol and 10 mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 ), and solidified with dichloromethane to obtain 3.4 g (yield: 70.4%) of compound 3-169 (LT20-30-289) as a white solid.
합성예Synthesis example
31: 화합물 3-170(LT20-30-305)의 합성 31: Synthesis of compound 3-170 (LT20-30-305)
2구 100 mL 플라스크에서 중간체(21) 4.0 g(7.2 mmol), 페닐보론산 (phenylboronic acid) 1.1 g(8.7 mmol), Pd(PPh3)4 250.6 mg(216.8 μmol), K2CO3 3.0 g (21.7 mmol), 톨루엔 36 mL, 에탄올 9 mL 및 증류수 9 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올, 헥세인으로 씻어 주었다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 에틸아세테이트로 고체화하여, 흰색 고체의 화합물 3-170(LT20-30-305) 1.6 g(수율: 40.7%)을 얻었다.In a 2-neck 100 mL flask, 4.0 g (7.2 mmol) of intermediate (21), 1.1 g (8.7 mmol) of phenylboronic acid, Pd(PPh 3 ) 4 250.6 mg (216.8 μmol), K 2 CO 3 3.0 g (21.7 mmol), 36 mL of toluene, 9 mL of ethanol, and 9 mL of distilled water were mixed, followed by reaction at 90° C. for one day. After the reaction was completed, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water, methanol, and hexane. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and solidified with ethyl acetate to obtain 1.6 g (yield: 40.7%) of compound 3-170 (LT20-30-305) as a white solid.
합성예Synthesis example
32: 화합물 3-171(LT20-30-215)의 합성 32: Synthesis of compound 3-171 (LT20-30-215)
2구 100 mL 플라스크에서 중간체(21) 3.0 g(5.4 mmol), (4-시아노페닐)보론산((4-cyanophenyl)boronic acid) 955.8 mg(6.5 mmol), Pd(PPh3)4 187.9 mg(162.6 μmol), K2CO3 2.2 g (16.3 mmol), 톨루엔 27 mL, 에탄올 7 mL 및 증류수 7 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 정제수를 넣고 에틸아세테이트로 추출하였다. 추출한 유기층을 무수 황산마그네슘으로 건조, 여과 후 감압 하에 용매를 제거하였다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 혼합용액(MC/MeOH)으로 고체화하여, 흰색 고체의 화합물 3-171(LT20-30-215) 2.8 g(수율: 89.7%)을 얻었다.In a 2-neck 100 mL flask, 3.0 g (5.4 mmol) of intermediate (21), (4-cyanophenyl) boronic acid ((4-cyanophenyl) boronic acid) 955.8 mg (6.5 mmol), Pd (PPh 3 ) 4 187.9 mg (162.6 μmol), K 2 CO 3 2.2 g (16.3 mmol), toluene 27 mL, ethanol 7 mL, and distilled water 7 mL were mixed, followed by reaction at 90° C. for one day. Upon completion of the reaction, after cooling to room temperature, purified water was added to the reaction mixture, and extraction was performed with ethyl acetate. The extracted organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and solidified with a mixed solution (MC/MeOH) to obtain 2.8 g (yield: 89.7%) of compound 3-171 (LT20-30-215) as a white solid.
합성예Synthesis example
33: 화합물 3-173(LT20-30-304)의 합성 33: Synthesis of compound 3-173 (LT20-30-304)
2구 100 mL 플라스크에서 중간체(21) 3.0 g(5.4 mmol), 중간체(30) 1.7 g(6.5 mmol), Pd(PPh3)4 187.9 mg(162.6 μmol), K2CO3 2.2 g (16.3 mmol), 톨루엔 27 mL, 에탄올 7 mL 및 증류수 7 mL를 혼합한 후, 90℃에서 2시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 에틸아세세이트로 추출하여 무수황산마그네슘으로 건조한 후 여과하고, 농축하였다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 혼합용액(Tol/IPA/Hex)으로 고체화하여, 흰색 고체의 화합물 3-173(LT20-30-304) 2.13 g(수율: 65.4%)을 얻었다.In a two-necked 100 mL flask, 3.0 g (5.4 mmol) of intermediate (21), 1.7 g (6.5 mmol) of intermediate (30), 187.9 mg (162.6 μmol) of Pd(PPh 3 ) 4 , K 2 CO 3 2.2 g (16.3 mmol) ), toluene 27 mL, ethanol 7 mL, and distilled water 7 mL were mixed, and then reacted at 90° C. for 2 hours. Upon completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and solidified with a mixed solution (Tol/IPA/Hex) to obtain 2.13 g (yield: 65.4%) of compound 3-173 (LT20-30-304) as a white solid. .
합성예Synthesis example
34: 화합물 3-175(LT20-30-298)의 합성 34: Synthesis of compound 3-175 (LT20-30-298)
2구 100 mL 플라스크에서 중간체(21) 3.0 g(5.4 mmol), 중간체(25) 2.0 g(6.5 mmol), Pd(PPh3)4 187.9 mg(162.6 μmol), K2CO3 2.2 g (16.3 mmol), 톨루엔 27 mL, 에탄올 7 mL 및 증류수 7 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올 및 헥세인으로 씻어 주었다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 에틸아세테이트로 재결정하여 흰색 고체의 화합물 3-175(LT20-30-298) 2.2 g(수율: 62.6%)을 얻었다.In a two-necked 100 mL flask, intermediate (21) 3.0 g (5.4 mmol), intermediate (25) 2.0 g (6.5 mmol), Pd(PPh 3 ) 4 187.9 mg (162.6 μmol), K 2 CO 3 2.2 g (16.3 mmol) ), toluene 27 mL, ethanol 7 mL, and distilled water 7 mL were mixed, and then reacted at 90° C. for one day. After completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction mixture, filtered, and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and recrystallized from ethyl acetate to obtain 2.2 g (yield: 62.6%) of compound 3-175 (LT20-30-298) as a white solid.
합성예Synthesis example
35: 화합물 3-179(LT20-30-309)의 합성 35: Synthesis of compound 3-179 (LT20-30-309)
2구 100 mL 플라스크에서 중간체(21) 3.5 g(6.3 mmol), 중간체(27) 2.12 g(7.6 mmol), Pd(PPh3)4 219.2 mg(189.7 μmol), K2CO3 2.6 g (19.0 mmol), 톨루엔 32 mL, 에탄올 8 mL 및 증류수 7 mL를 혼합한 후, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올 및 헥세인으로 씻어 주었다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 에틸아세테이트로 재결정하고, 아세톤으로 여과하여 흰색 고체의 화합물 3-179(LT20-30-309) 1.53 g(수율: 38.7%)을 얻었다.In a 2-neck 100 mL flask, intermediate (21) 3.5 g (6.3 mmol), intermediate (27) 2.12 g (7.6 mmol), Pd(PPh 3 ) 4 219.2 mg (189.7 μmol), K 2 CO 3 2.6 g (19.0 mmol) ), toluene 32 mL, ethanol 8 mL and distilled water 7 mL were mixed, and then reacted at 90° C. for one day. After completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction mixture, filtered, and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, recrystallized from ethyl acetate, and filtered with acetone to obtain 1.53 g of compound 3-179 (LT20-30-309) as a white solid (yield: 38.7%).
합성예Synthesis example
36: 화합물 3-184(LT20-30-303)의 합성 36: Synthesis of compound 3-184 (LT20-30-303)
2구 100 mL 플라스크에서 중간체(21) 3.0 g(5.4 mmol), 중간체(33) 1.3 g(6.5 mmol), Pd2(dba)3 496.4 mg(542.1 μmol), S-Phos 890.1 mg(2.2 mmol), K3PO4 3.5 g (16.3 mmol) 및 자일렌 27 mL를 혼합한 후, 130℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올 및 헥세인으로 씻어 주었다. 얻어진 고체 혼합물을 톨루엔에 녹여 실리카 패드 여과를 하고, 혼합용매(Hex/EA)로 고체화하여, 흰색 고체의 화합물 3-184(LT20-30-303) 2.4 g(수율: 65.5%)을 얻었다.In a 2-neck 100 mL flask, Intermediate (21) 3.0 g (5.4 mmol), Intermediate (33) 1.3 g (6.5 mmol), Pd 2 (dba) 3 496.4 mg (542.1 μmol), S-Phos 890.1 mg (2.2 mmol) , K 3 PO 4 3.5 g (16.3 mmol) and xylene 27 mL were mixed, and then reacted at 130° C. for one day. After completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction mixture, filtered, and washed with distilled water, methanol and hexane. The obtained solid mixture was dissolved in toluene, filtered through a silica pad, and solidified with a mixed solvent (Hex/EA) to obtain 2.4 g (yield: 65.5%) of compound 3-184 (LT20-30-303) as a white solid.
합성예Synthesis example
37: 화합물 3-193(LT20-30-290)의 합성 37: Synthesis of compound 3-193 (LT20-30-290)
1구 250 mL 플라스크에서 중간체(10) 1.7 g(5.0 mmol), 중간체(41) 2.0 g(5.0 mmol), Pd(PPh3)4 288.0 mg(249.2 μmol), K3PO4 2.3 g(11.0 mmol), 다이옥산 20 mL 및 물 5 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 클로로포름으로 추출하여 용매를 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 에틸아세테이트로 고체화하여, 흰색 고체의 화합물 3-193(LT20-30-290) 1.6 g(수율: 56.5%)을 얻었다.In a one-necked 250 mL flask, intermediate (10) 1.7 g (5.0 mmol), intermediate (41) 2.0 g (5.0 mmol), Pd(PPh 3 ) 4 288.0 mg (249.2 μmol), K 3 PO 4 2.3 g (11.0 mmol) ), 20 mL of dioxane and 5 mL of water were mixed, and then stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with chloroform, and the solvent was concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with ethyl acetate to obtain 1.6 g (yield: 56.5%) of compound 3-193 (LT20-30-290) as a white solid.
합성예Synthesis example
38: 화합물 3-255(LT20-30-258)의 합성 38: Synthesis of compound 3-255 (LT20-30-258)
1구 250 mL 플라스크에서 중간체(24) 4.0 g(7.2 mmol), 4-시아노페닐보론산 ((4-cyanophenyl)boronic acid) 1.3 g(8.7 mmol), Pd(PPh3)4 417.0 mg(361.4 μmol), K3PO4 4.6 g(21.7 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후, 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3) 여과하고 혼합용액(EA/EtOH)으로 고체화하여, 흰색 고체의 화합물 3-255(LT20-30-258) 1.1 g(수율: 26.4)을 얻었다.Intermediate (24) 4.0 g (7.2 mmol), 4-cyanophenyl boronic acid ((4-cyanophenyl) boronic acid) 1.3 g (8.7 mmol), Pd (PPh 3 ) 4 417.0 mg (361.4) in a 1-neck 250 mL flask μmol), K 3 PO 4 4.6 g (21.7 mmol), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 ), and solidified with a mixed solution (EA/EtOH) to obtain 1.1 g (yield: 26.4) of compound 3-255 (LT20-30-258) as a white solid. .
합성예Synthesis example
39: 화합물 3-269(LT20-30-200)의 합성 39: Synthesis of compound 3-269 (LT20-30-200)
1구 250mL 플라스크에서 중간체(10) 3.0 g(8.7 mmol), 중간체(43) 3.9 g(9.6 mmol), Pd(PPh3)4 0.5 g(0.4 mmol), 2 M 수용액 K2CO3 13.0 mL (26.1 mmol), 톨루엔 29 mL 및 에탄올 15 mL를 혼합한 후, 2시간 환류, 교반하였다. 반응이 종결된 후, 생성된 고체를 여과한 후, 톨루엔, 증류수 및 메탄올로 세척하였다. 얻어진 고체를 모노클로로벤젠에 환류하고, 셀라이트 여과하였다. 모노클로로벤젠으로 세척하여 생성된 고체를 여과, 건조하여 흰색의 고체의 화합물 3-269(LT20-30-200) 3.8 g(수율: 73.1%)을 얻었다.In a 1-neck 250mL flask, intermediate (10) 3.0 g (8.7 mmol), intermediate (43) 3.9 g (9.6 mmol), Pd(PPh 3 ) 4 0.5 g (0.4 mmol), 2 M aqueous K 2 CO 3 13.0 mL ( 26.1 mmol), 29 mL of toluene and 15 mL of ethanol were mixed, followed by refluxing and stirring for 2 hours. After the reaction was completed, the resulting solid was filtered and washed with toluene, distilled water and methanol. The obtained solid was refluxed in monochlorobenzene, and filtered through Celite. The solid produced by washing with monochlorobenzene was filtered and dried to obtain 3.8 g (yield: 73.1%) of compound 3-269 (LT20-30-200) as a white solid.
합성예Synthesis example
40: 화합물 3-277(LT20-30-286)의 합성 40: Synthesis of compound 3-277 (LT20-30-286)
1구 250mL 플라스크에서 중간체(10) 2.5 g(7.4 mmol), 중간체(45) 3.4 g(7.4 mmol), Pd(PPh3)4 0.4 g(0.4 mmol), 2 M 수용액 K2CO3 11.1 mL (22.2 mmol), 톨루엔 24 mL 및 에탄올 12 mL를 혼합한 후, 3시간 환류, 교반하였다. 반응이 종결된 후, 생성된 고체를 여과한 후, 톨루엔, 증류수 및 메탄올로 세척하였다. 얻어진 고체를 디클로로벤젠에 환류하고, 셀라이트 여과하였다. 디클로로벤젠으로 세척하고 상온으로 냉각하여 생성된 고체를 여과, 건조하여 흰색의 고체의 화합물 3-277(LT20-30-286) 2.0 g(수율: 42.6%)을 얻었다.Intermediate (10) 2.5 g (7.4 mmol), Intermediate (45) 3.4 g (7.4 mmol), Pd(PPh 3 ) 4 0.4 g (0.4 mmol), 2 M aqueous solution K 2 CO 3 11.1 mL ( 22.2 mmol), toluene 24 mL and ethanol 12 mL were mixed, refluxed for 3 hours and stirred. After the reaction was completed, the resulting solid was filtered and washed with toluene, distilled water and methanol. The obtained solid was refluxed in dichlorobenzene and filtered through Celite. After washing with dichlorobenzene and cooling to room temperature, the resulting solid was filtered and dried to obtain 2.0 g (yield: 42.6%) of compound 3-277 (LT20-30-286) as a white solid.
합성예Synthesis example
41: 화합물 3-278(LT20-35-283)의 합성 41: Synthesis of compound 3-278 (LT20-35-283)
1구 250 mL 플라스크에서 중간체(12) 6.0 g(16.3 mmol), 중간체(45) 9.8 g(21.2 mmol), Pd(PPh3)4 0.9 g(0.8 mmol), 2 M 수용액 K2CO3 24 mL(48.9 mmol), 톨루엔 60 mL 및 에탄올 30 mL를 혼합한 후, 1일 동안 환류 교반하였다. 반응이 종결된 후, 반응온도에서 생성된 고체를 여과하였다. 얻어진 고체 화합물을 실리카겔 컬럼 크로마토그래피(Hexanes:Chloroform)로 정제 후, 메탄올로 고체화하여 흰색 고체의 화합물 3-278(LT20-35-283) 2.3 g(수율: 21.2%)을 얻었다.In a 1-neck 250 mL flask, Intermediate (12) 6.0 g (16.3 mmol), Intermediate (45) 9.8 g (21.2 mmol), Pd(PPh 3 ) 4 0.9 g (0.8 mmol), 2 M aqueous K 2 CO 3 24 mL (48.9 mmol), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for 1 day. After the reaction was completed, the solid produced at the reaction temperature was filtered. The obtained solid compound was purified by silica gel column chromatography (Hexanes:Chloroform), and then solidified with methanol to obtain 2.3 g (yield: 21.2%) of compound 3-278 (LT20-35-283) as a white solid.
합성예Synthesis example
42: 화합물 3-292(LT20-30-296)의 합성 42: Synthesis of compound 3-292 (LT20-30-296)
1구 250 mL 플라스크에서 중간체(10) 3.0 g(8.8 mmol), 다이벤조싸이오펜-4-일보론산(dibenzo[b,d]thiophen-4-ylboronic acid) 2.0 g(8.8 mmol), Pd(PPh3)4 505.0 mg(437.5 μmol), K3PO4 5.6 g(26.3 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후, 실리카 패드에(CHCl3) 여과하고 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물 3-292(LT20-30-296) 2.3 g(수율: 52.4%)을 얻었다.In a 1-neck 250 mL flask, 3.0 g (8.8 mmol) of intermediate (10), 2.0 g (8.8 mmol) of dibenzo[b,d]thiophen-4-ylboronic acid, Pd (PPh) 3 ) 4 505.0 mg (437.5 μmol), K 3 PO 4 5.6 g (26.3 mmol), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After completion of the reaction, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad (CHCl 3 ), and solidified with dichloromethane to obtain 2.3 g (yield: 52.4%) of compound 3-292 (LT20-30-296) as a white solid.
합성예Synthesis example
43: 화합물 3-376(LT20-30-288)의 합성 43: Synthesis of compound 3-376 (LT20-30-288)
1구 250 mL 플라스크에서 중간체(10) 3.0 g(8.8 mmol), 9-페닐-9-카바졸-3-일 보로닉엑시드 ((9-phenyl-9H-carbazol-3-yl)boronic acid) 2.5 g(8.8 mmol), Pd(PPh3)4 505.0 mg(437.5 μmol), K3PO4 5.6 g(26.3 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카 패드에(CHCl3) 여과하고 혼합용매(DCM/EA)로 고체화하여, 흰색 고체의 화합물 3-376(LT20-30-288) 2.3 g(수율: 48.0%)을 얻었다.In a 1-neck 250 mL flask, 3.0 g (8.8 mmol) of intermediate (10), 9-phenyl-9-carbazol-3-yl boronic acid ((9-phenyl-9H-carbazol-3-yl)boronic acid) 2.5 g (8.8 mmol), Pd(PPh 3 ) 4 505.0 mg (437.5 μmol), K 3 PO 4 5.6 g (26.3 mmol), toluene 30 mL, ethanol 10 mL and water 10 mL were mixed and refluxed for 12 hours. stirred. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, filtered through a silica pad (CHCl 3 ), and solidified with a mixed solvent (DCM/EA), 2.3 g (yield: 48.0%) of compound 3-376 (LT20-30-288) as a white solid got it
합성예Synthesis example
44: 화합물 3-380(LT20-30-306)의 합성 44: Synthesis of compound 3-380 (LT20-30-306)
1구 250 mL 플라스크에서 중간체(10) 3.0 g(8.8 mmol), 중간체(48) 4.1 g(8.8 mmol), Pd(PPh3)4 505.6 mg(437.5 μmol), K3PO4 4.6 g(21.9 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카겔 컬럼 크로마토그래피 (Hex:CHCl3) 정제하고 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물 3-380(LT20-30-306) 1.8 g(수율: 32.0%)을 얻었다.In a one-necked 250 mL flask, intermediate (10) 3.0 g (8.8 mmol), intermediate (48) 4.1 g (8.8 mmol), Pd(PPh 3 ) 4 505.6 mg (437.5 μmol), K 3 PO 4 4.6 g (21.9 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by silica gel column chromatography (Hex:CHCl 3 ), and solidified with dichloromethane to obtain 1.8 g (yield: 32.0%) of compound 3-380 (LT20-30-306) as a white solid. .
합성예Synthesis example
45: 화합물 3-381(LT20-35-313)의 합성 45: Synthesis of compound 3-381 (LT20-35-313)
1구 250 mL 플라스크에서 중간체(14) 3.0 g(8.7 mmol), 중간체(48) 5.3 g(10.5 mmol), Pd(PPh3)4 504.2 mg(436.3 μmol), K3PO4 3.6 g(26.2 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 후, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 실리카겔 컬럼 크로마토그래피 (Hex:CHCl3) 정제하고 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물 3-381(LT20-35-313) 1.2 g(수율: 21.1%)을 얻었다.In a one-necked 250 mL flask, 3.0 g (8.7 mmol) of intermediate (14), 5.3 g (10.5 mmol) of intermediate (48), 504.2 mg (436.3 μmol) of Pd(PPh 3 ) 4 , 3.6 g (26.2 mmol) of K 3 PO 4 ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by silica gel column chromatography (Hex:CHCl 3 ), and solidified with dichloromethane to obtain 1.2 g (yield: 21.1%) of compound 3-381 (LT20-35-313) as a white solid. .
소자 제작device fabrication
소자 제작을 위해 투명 전극인 ITO는 양극 층으로 사용하였고, 2-TNATA는 정공 주입층, NPB는 정공 수송층, αβ-ADN은 발광층의 호스트, Pyrene-CN은 청색 형광 도판트, Liq는 전자 주입층, Al은 음극으로 사용하였다. 이 화합물들의 구조는 하기의 화학식과 같다.For device fabrication, ITO, a transparent electrode, was used as the anode layer, 2-TNATA is a hole injection layer, NPB is a hole transport layer, αβ-ADN is a host of the light emitting layer, Pyrene-CN is a blue fluorescent dopant, and Liq is an electron injection layer. , Al was used as the cathode. The structures of these compounds are as follows.
비교실시예 1: ITO / 2-TNATA(60 nm) / NPB(20 nm) / αβ-ADN:10% Pyrene-CN(30 nm) / Alq3(30 nm) / Liq(2 nm) / Al(100 nm)Comparative Example 1: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Al ( 100 nm)
비교실시예 2: ITO / 2-TNATA(60 nm) / NPB(20 nm) / αβ-ADN:10% Pyrene-CN(30 nm) / REF02(30 nm) / Liq(2 nm) / Al(100 nm)Comparative Example 2: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / REF02 (30 nm) / Liq (2 nm) / Al (100 nm)
청색 형광 유기발광소자는 ITO(180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN:Pyrene-CN 10% (30 nm) / 전자수송층 (30 nm) / Liq (2 nm) / Al(100 nm)순으로 증착하여 소자를 제작하였다. Blue fluorescent organic light emitting diode ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN:Pyrene-CN 10% (30 nm) / electron transport layer (30 nm) / Liq (2 nm) / Al (100 nm) was deposited in the order to fabricate a device.
유기물을 증착하기 전에 ITO 전극은 2 × 10- 2Torr에서 125W로 2분간 산소 플라즈마 처리를 하였다. 유기물은 9 × 10- 7Torr의 진공도에서 증착하였으며, Liq는 0.1 Å/sec, αβ-ADN은 0.18 Å/sec의 기준으로 Pyrene-CN는 0.02 Å/sec으로 동시 증착하였고, 나머지 유기물들은 모두 1 Å/sec의 속도로 증착하였다. Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 2 × 10 - 2 Torr at 125 W for 2 minutes. Organic materials were deposited at a vacuum degree of 9 × 10 - 7 Torr, Liq was 0.1 Å/sec, αβ-ADN was 0.18 Å/sec, and Pyrene-CN was simultaneously deposited at 0.02 Å/sec, and the remaining organic materials were all 1 Deposited at a rate of Å/sec.
소자 제작이 끝난 후 소자의 공기 및 수분의 접촉을 막기 위하여 질소 기체로 채워져 있는 글러브 박스 안에서 봉지를 하였다. 3M사의 접착용 테이프로 격벽을 형성 후 수분 등을 제거할 수 있는 흡습제인 바륨산화물(Barium Oxide)을 넣고 유리판을 붙였다.After the device was manufactured, it was encapsulated in a glove box filled with nitrogen gas to prevent the device from contacting air and moisture. After forming the barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.
REF01(Alq3) REF02 3-71(LT20-30-285)REF01 (Alq 3 ) REF02 3-71 (LT20-30-285)
< 실시예 1 내지 45 >< Examples 1 to 45 >
상기 비교실시예 1에서, REF01(Alq3)을 이용하는 대신에 하기 표 1에 나타낸 각각의 화합물을 사용한 것을 제외하고는 상기 비교실시예와 동일한 방법으로 소자를 제작하였다.In Comparative Example 1, a device was manufactured in the same manner as in Comparative Example, except that each compound shown in Table 1 was used instead of using REF01 (Alq 3 ).
상기 비교실시예 1, 비교실시예 2 및 실시예 1 내지 45에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 표 1에 나타냈다.Table 1 shows the electroluminescence characteristics of the organic light emitting devices prepared in Comparative Example 1, Comparative Example 2, and Examples 1-45.
| 구분division | 화합물compound | 구동전압[V]Driving voltage [V] | 효율[cd/A]Efficiency [cd/A] | 수명(%)life span(%) |
| 비교실시예 1Comparative Example 1 | REF01(Alq3)REF01(Alq 3 ) | 6.606.60 | 5.105.10 | 91.7891.78 |
| 비교실시예 2Comparative Example 2 | REF02REF02 | 5.115.11 | 6.186.18 | 94.1594.15 |
| 실시예 1Example 1 | 3-1(LT20-30-183)3-1 (LT20-30-183) | 3.563.56 | 8.438.43 | 99.2999.29 |
| 실시예 2Example 2 | 3-2(LT20-30-150)3-2 (LT20-30-150) | 3.973.97 | 6.766.76 | 98.6498.64 |
| 실시예 3Example 3 | 3-3(LT20-35-197)3-3 (LT20-35-197) | 4.004.00 | 6.826.82 | 98.6198.61 |
| 실시예 4Example 4 | 3-5(LT20-30-207)3-5 (LT20-30-207) | 3.733.73 | 6.676.67 | 99.5299.52 |
| 실시예 5Example 5 | 3-8(LT20-30-169)3-8 (LT20-30-169) | 3.433.43 | 7.897.89 | 99.6599.65 |
| 실시예 6Example 6 | 3-12(LT20-30-243)3-12 (LT20-30-243) | 4.154.15 | 6.686.68 | 98.4798.47 |
| 실시예 7Example 7 | 3-13(LT20-30-185)3-13 (LT20-30-185) | 3.403.40 | 7.287.28 | 98.9598.95 |
| 실시예 8Example 8 | 3-16(LT20-30-201)3-16 (LT20-30-201) | 3.333.33 | 7.747.74 | 99.7799.77 |
| 실시예 9Example 9 | 3-19(LT20-30-167)3-19 (LT20-30-167) | 3.503.50 | 8.308.30 | 99.0699.06 |
| 실시예 10Example 10 | 3-20(LT20-30-195)3-20 (LT20-30-195) | 3.323.32 | 8.048.04 | 99.5699.56 |
| 실시예 11Example 11 | 3-28(LT20-30-262)3-28 (LT20-30-262) | 3.853.85 | 7.277.27 | 100.62100.62 |
| 실시예 12Example 12 | 3-29(LT20-35-210)3-29 (LT20-35-210) | 3.393.39 | 8.758.75 | 98.8598.85 |
| 실시예 13Example 13 | 3-47(LT20-30-168)3-47 (LT20-30-168) | 3.433.43 | 8.818.81 | 98.7998.79 |
| 실시예 14Example 14 | 3-51(LT20-30-193)3-51 (LT20-30-193) | 4.134.13 | 6.276.27 | 98.5698.56 |
| 실시예 15Example 15 | 3-53(LT20-30-216)3-53 (LT20-30-216) | 3.463.46 | 7.967.96 | 98.6798.67 |
| 실시예 16Example 16 | 3-58(LT20-30-253)3-58 (LT20-30-253) | 3.673.67 | 8.518.51 | 98.8998.89 |
| 실시예 17Example 17 | 3-59(LT20-30-198)3-59 (LT20-30-198) | 3.733.73 | 7.867.86 | 98.2198.21 |
| 실시예 18Example 18 | 3-60(LT20-30-179)3-60 (LT20-30-179) | 4.324.32 | 7.337.33 | 98.1598.15 |
| 실시예 19Example 19 | 3-62(LT20-30-244)3-62 (LT20-30-244) | 3.493.49 | 6.766.76 | 98.2998.29 |
| 실시예 20Example 20 | 3-65(LT20-30-147)3-65 (LT20-30-147) | 3.323.32 | 8.328.32 | 97.5897.58 |
| 실시예 21Example 21 | 3-71(LT20-30-285)3-71 (LT20-30-285) | 3.323.32 | 8.878.87 | 101.68101.68 |
| 실시예 22Example 22 | 3-75(LT20-30-263)3-75 (LT20-30-263) | 3.463.46 | 7.967.96 | 98.6798.67 |
| 실시예 23Example 23 | 3-76(LT20-30-218)3-76 (LT20-30-218) | 3.563.56 | 8.818.81 | 98.4198.41 |
| 실시예 24Example 24 | 3-79(LT20-30-217)3-79 (LT20-30-217) | 3.403.40 | 7.287.28 | 99.9599.95 |
| 실시예 25Example 25 | 3-82(LT20-30-169)3-82 (LT20-30-169) | 3.333.33 | 7.747.74 | 99.7799.77 |
| 실시예 26Example 26 | 3-83(LT20-30-204)3-83 (LT20-30-204) | 3.503.50 | 8.308.30 | 99.0699.06 |
| 실시예 27Example 27 | 3-142(LT20-30-293)3-142 (LT20-30-293) | 3.703.70 | 8.908.90 | 99.6199.61 |
| 실시예 28Example 28 | 3-146(LT20-30-199)3-146 (LT20-30-199) | 4.034.03 | 8.318.31 | 98.9898.98 |
| 실시예 29Example 29 | 3-162(LT20-30-287)3-162 (LT20-30-287) | 3.933.93 | 7.577.57 | 98.6498.64 |
| 실시예 30Example 30 | 3-169(LT20-30-289)3-169 (LT20-30-289) | 3.303.30 | 8.548.54 | 99.1999.19 |
| 실시예 31Example 31 | 3-170(LT20-30-305)3-170 (LT20-30-305) | 3.703.70 | 8.828.82 | 98.4998.49 |
| 실시예 32Example 32 | 3-171(LT20-30-215)3-171 (LT20-30-215) | 3.383.38 | 9.029.02 | 98.5798.57 |
| 실시예 33Example 33 | 3-173(LT20-30-304)3-173 (LT20-30-304) | 3.573.57 | 7.997.99 | 104.67104.67 |
| 실시예 34Example 34 | 3-175(LT20-30-298)3-175 (LT20-30-298) | 3.333.33 | 9.299.29 | 100.44100.44 |
| 실시예 35Example 35 | 3-179(LT20-30-309)3-179 (LT20-30-309) | 3.633.63 | 7.937.93 | 116.70116.70 |
| 실시예 36Example 36 | 3-184(LT20-30-303)3-184 (LT20-30-303) | 3.403.40 | 8.038.03 | 102.94102.94 |
| 실시예 37Example 37 | 3-193(LT20-30-290)3-193 (LT20-30-290) | 3.373.37 | 9.479.47 | 100.43100.43 |
| 실시예 38Example 38 | 3-255(LT20-30-258)3-255 (LT20-30-258) | 3.523.52 | 7.627.62 | 108.33108.33 |
| 실시예 39Example 39 | 3-269(LT20-30-200)3-269 (LT20-30-200) | 3.483.48 | 9.349.34 | 104.39104.39 |
| 실시예 40Example 40 | 3-277(LT20-30-286)3-277 (LT20-30-286) | 3.573.57 | 7.767.76 | 113.00113.00 |
| 실시예 41Example 41 | 3-278(LT20-35-283)3-278 (LT20-35-283) | 3.833.83 | 8.368.36 | 98.0798.07 |
| 실시예 42Example 42 | 3-292(LT20-30-296)3-292 (LT20-30-296) | 3.263.26 | 8.758.75 | 100.46100.46 |
| 실시예 43Example 43 | 3-376(LT20-30-288)3-376 (LT20-30-288) | 3.213.21 | 8.388.38 | 101.04101.04 |
| 실시예 44Example 44 | 3-380(LT20-30-306)3-380 (LT20-30-306) | 3.703.70 | 8.648.64 | 99.6299.62 |
| 실시예 45Example 45 | 3-381(LT20-30-313)3-381 (LT20-30-313) | 3.833.83 | 8.368.36 | 98.0798.07 |
상기 표 1로부터 비교실시예 2(REF02)와 실시예 21(화합물 3-71)을 비교할 경우에, 두 화합물의 화학적 구조는 유사하지만, 실시예 21의 화합물은 피리미딘에 헤테로아릴렌(피리딘) 및 시아노기의 도입에 따라 전자 주입 및 전자 이동도를 향상시키고 정공과 전자의 밸런스(Balance)를 맞추는 것에 의해, 저전압(5.11 대비 3.32(V)), 고효율(6.18 대비 8.87(cd/A)) 및 장수명(94.15 대비 101.68(%))의 특성을 나타내는 것을 확인할 수 있다. When comparing Comparative Example 2 (REF02) and Example 21 (Compound 3-71) from Table 1 above, the chemical structures of the two compounds are similar, but the compound of Example 21 is pyrimidine to heteroarylene (pyridine) and by improving electron injection and electron mobility according to the introduction of a cyano group and balancing holes and electrons, low voltage (3.32 compared to 5.11 (V)), high efficiency (6.87 compared to 6.18 (cd/A)) and long life (101.68 (%) compared to 94.15).
본 발명에 따른 헤테로알릴렌기가 치환된 피리미딘 유도체 화합물은 전반적으로 유기 발광 소자를 비롯한 유기 전자 소자의 유기물층의 재료로서 사용될 수 있고, 이를 이용한 유기 발광 소자를 비롯한 유기 전자 소자는 효율, 구동전압, 안정성 등에서 우수한 특성을 나타냄을 알 수 있다. 특히, 본 발명에 따른 화합물은 정공전자 균형 능력 및 전자전달 능력이 우수하여 높은 효율 특성을 나타낸다.The pyrimidine derivative compound substituted with a heteroallylene group according to the present invention can be generally used as a material for an organic material layer of an organic electronic device including an organic light emitting device, and an organic electronic device including an organic light emitting device using the same can have efficiency, driving voltage, It can be seen that excellent characteristics such as stability are exhibited. In particular, the compound according to the present invention exhibits high efficiency characteristics due to excellent hole-electron balancing ability and electron transport ability.
본 발명에 따른 피리미딘 유도체 화합물은 유기 전계 발광 소자의 유기물층에 사용되는 것에 의해 유기 전계 발광 소자의 품질 향상에 이용될 수 있다. The pyrimidine derivative compound according to the present invention can be used to improve the quality of an organic electroluminescent device by being used in the organic layer of the organic electroluminescent device.
상기 화합물을 유기물층에 사용할 경우에, 유기 전계 발광 소자가 본래의 특성을 발현하면서 동시에 상기 화합물의 특성에 의해 수명 향상이 가능해진다.When the compound is used in the organic material layer, the organic electroluminescent device exhibits the original characteristics and at the same time, the lifespan can be improved by the characteristics of the compound.
Claims (6)
- 하기 화학식 1로 표시되는 유기전계발광소자 용 피리미딘 유도체. A pyrimidine derivative for an organic electroluminescent device represented by the following formula (1).[화학식 1][Formula 1]
상기 화학식 1에 있어서, In Formula 1,Ar1, Ar2 및 Ar3는 각각 독립적으로 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 1 , Ar 2 and Ar 3 are each independently a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,L 은 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴렌기이고,L is substituted or unsubstituted It is a heteroarylene group having 5 or more and 20 or less carbon atoms,Ar4 는 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기이거나, 치환 또는 비치환된 탄소수 5 이상 20 이하의 헤테로아릴기이고,Ar 4 is a substituted or unsubstituted aryl group having 6 or more and 20 or less carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 or more and 20 or less carbon atoms,p는 0 내지 2의 정수이고, p is an integer from 0 to 2,p가 2일 경우 복수의 Ar4는 같거나 상이하다.When p is 2, a plurality of Ar 4 are the same or different. - 제 1항에 있어서, The method of claim 1,상기 화학식 1은 하기 화학식 2로 표시되는 유기전계발광소자 용 피리미딘 유도체.Formula 1 is a pyrimidine derivative for an organic light emitting device represented by Formula 2 below.[화학식 2][Formula 2]
상기 화학식 2에 있어서,In Formula 2,L 은 치환 또는 비치환된, 피리딘기; 디벤조퓨란기; 디벤조티오펜기; 카바졸기; 퀴놀린기; 및 아이소퀴놀린기; 중 어느 하나이며,L is a substituted or unsubstituted, pyridine group; dibenzofuran group; dibenzothiophene group; a carbazole group; quinoline group; and an isoquinoline group; is any one ofAr4 은 치환 또는 비치환된 탄소수 6 이상 20 이하의 아릴기; 또는 치환 또는 비치환된 카바졸기;이고,Ar 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted carbazole group;Ar3 및 p는 상기 화학식 1에서 정의된 것과 같다.Ar 3 and p are as defined in Formula 1 above. - 상기 화학식 1에 있어서,In Formula 1,Ar3 은 시아노가 치환된 페닐기; 페닐기; 및 피리딜기; 중에서 선택되는 어느 하나인 것을 특징으로 하는 유기전계발광소자 용 피리미딘 유도체. Ar 3 is a phenyl group substituted with cyano; phenyl group; and a pyridyl group; A pyrimidine derivative for an organic light emitting device, characterized in that it is any one selected from among.
- 제 1항에 있어서,The method of claim 1,상기 화학식 1은 하기 화학식 3의 화합물 중에서 선택되는 유기전계 발광소자 용 피리미딘 유도체.Formula 1 is a pyrimidine derivative for an organic light emitting device selected from the compounds of Formula 3 below.[화학식 3][Formula 3]
- 양극;anode;상기 양극 상에 배치된, 복수의 유기물층으로 구성된 유기물층; 및an organic material layer comprising a plurality of organic material layers disposed on the anode; and상기 유기물층 상에 배치된 음극;을 포함하고,a cathode disposed on the organic material layer; and상기 유기물층은 상기 제 1항 내지 제 4항 중 어느 한 항에 따른 피리미딘 유도체를 포함하는 유기전계발광소자.The organic material layer is an organic electroluminescent device comprising the pyrimidine derivative according to any one of claims 1 to 4.
- 제 5항에 있어서, 6. The method of claim 5,상기 피리미딘 유도체가 상기 유기물층의 전자수송층 재료로 사용되는 것을 특징으로 하는 유기전계발광소자.The organic electroluminescent device, characterized in that the pyrimidine derivative is used as a material for the electron transport layer of the organic layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202180070243.0A CN116323591A (en) | 2020-10-30 | 2021-10-14 | Pyrimidine derivative and organic electroluminescent element comprising same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200142721A KR102563234B1 (en) | 2020-10-30 | 2020-10-30 | Pyrimidine derivatives and organic electroluminescent device including the same |
| KR10-2020-0142721 | 2020-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022092638A1 true WO2022092638A1 (en) | 2022-05-05 |
Family
ID=81382676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2021/014275 WO2022092638A1 (en) | 2020-10-30 | 2021-10-14 | Pyrimidin derivative and organic electroluminescent device comprising same |
Country Status (3)
| Country | Link |
|---|---|
| KR (2) | KR102563234B1 (en) |
| CN (1) | CN116323591A (en) |
| WO (1) | WO2022092638A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120072787A (en) * | 2010-12-24 | 2012-07-04 | 에스에프씨 주식회사 | Pyridine derivative compound and organic electroluminescent devices comprising the same |
| KR20160082067A (en) * | 2014-12-30 | 2016-07-08 | 희성소재 (주) | Compound and organic light emitting device using the same |
| CN106967052A (en) * | 2017-05-11 | 2017-07-21 | 江苏三月光电科技有限公司 | A kind of organic compound and its application based on pyridine and benzimidazole |
| CN107629011A (en) * | 2017-09-29 | 2018-01-26 | 江苏三月光电科技有限公司 | A kind of organic compound and its application based on pyridine and quinoline beautiful jade |
| CN110229145A (en) * | 2019-03-28 | 2019-09-13 | 江苏三月光电科技有限公司 | A kind of organic compound based on pyridine and its application on OLED |
| KR20190111824A (en) * | 2018-03-22 | 2019-10-02 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553606B (en) * | 2017-09-25 | 2021-02-19 | 北京鼎材科技有限公司 | General formula compound and organic light-emitting device |
| KR20200140968A (en) * | 2019-06-07 | 2020-12-17 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
-
2020
- 2020-10-30 KR KR1020200142721A patent/KR102563234B1/en active IP Right Grant
-
2021
- 2021-10-14 CN CN202180070243.0A patent/CN116323591A/en active Pending
- 2021-10-14 WO PCT/KR2021/014275 patent/WO2022092638A1/en active Application Filing
-
2023
- 2023-03-07 KR KR1020230029686A patent/KR102580437B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120072787A (en) * | 2010-12-24 | 2012-07-04 | 에스에프씨 주식회사 | Pyridine derivative compound and organic electroluminescent devices comprising the same |
| KR20160082067A (en) * | 2014-12-30 | 2016-07-08 | 희성소재 (주) | Compound and organic light emitting device using the same |
| CN106967052A (en) * | 2017-05-11 | 2017-07-21 | 江苏三月光电科技有限公司 | A kind of organic compound and its application based on pyridine and benzimidazole |
| CN107629011A (en) * | 2017-09-29 | 2018-01-26 | 江苏三月光电科技有限公司 | A kind of organic compound and its application based on pyridine and quinoline beautiful jade |
| KR20190111824A (en) * | 2018-03-22 | 2019-10-02 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| CN110229145A (en) * | 2019-03-28 | 2019-09-13 | 江苏三月光电科技有限公司 | A kind of organic compound based on pyridine and its application on OLED |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230038675A (en) | 2023-03-21 |
| KR102580437B1 (en) | 2023-09-20 |
| CN116323591A (en) | 2023-06-23 |
| KR20220058724A (en) | 2022-05-10 |
| KR102563234B1 (en) | 2023-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018066830A1 (en) | Organic light-emitting device having long life, low voltage and high efficiency | |
| WO2020022751A1 (en) | Organic electroluminescent device | |
| WO2013105747A1 (en) | Compound for organic electronic element, organic electronic element using same and electronic device thereof | |
| WO2017082556A1 (en) | Novel organic light-emitting compound and organic light-emitting device comprising same | |
| WO2013081315A1 (en) | Compound for organic electronic device, organic electronic device comprising same and electronic device comprising the organic electronic device | |
| WO2012077902A9 (en) | Compound for an organic optoelectronic device, organic light-emitting diode including the compound, and display device including the organic light-emitting diode | |
| WO2021112403A1 (en) | Organic electronic element comprising organic compound, and electronic device comprising same | |
| WO2022015084A1 (en) | Organic light-emitting element | |
| WO2019240464A1 (en) | Organic light-emitting device | |
| WO2020251183A1 (en) | Compound for organic light-emitting element and organic light-emitting element comprising same | |
| WO2013069939A1 (en) | Compound for organic electronic element, organic electronic element including the same, electronic device thereof | |
| WO2017082574A1 (en) | Novel heterocyclic compound and organic light-emitting device comprising same | |
| WO2014025209A1 (en) | Novel compound and organic electroluminescence device comprising same | |
| WO2018182300A1 (en) | Heterocyclic compound and organic light-emitting device comprising same | |
| WO2021210911A1 (en) | Novel compound and organic light-emitting element comprising same | |
| WO2022039520A1 (en) | Novel compound and organic light-emitting device comprising same | |
| WO2014046392A1 (en) | Organic compound and electroluminescent element having same | |
| WO2014027822A1 (en) | Novel compound and organic electroluminescent device comprising same | |
| WO2020141949A1 (en) | Novel compound and organic light emitting device using same | |
| WO2023008895A1 (en) | Organic compound and organic light-emitting device comprising same | |
| WO2018147638A1 (en) | Organic compound and organic electroluminescent element using same | |
| WO2022086149A1 (en) | Compound for organic electronic device, organic electronic device including same, and display apparatus including organic electronic device | |
| WO2020159333A1 (en) | Compound and organic light emitting device comprising same | |
| WO2018212463A1 (en) | Organic light-emitting compound, and organic electroluminescent element using same | |
| WO2022203276A1 (en) | Nucleation inhibition forming material, and organic electroluminescent device comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21886632 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21886632 Country of ref document: EP Kind code of ref document: A1 |