CN115427391A - Asymmetric 1,2-bis (diarylamino) benzenes, method for producing same, and use thereof - Google Patents
Asymmetric 1,2-bis (diarylamino) benzenes, method for producing same, and use thereof Download PDFInfo
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- CN115427391A CN115427391A CN202180026647.XA CN202180026647A CN115427391A CN 115427391 A CN115427391 A CN 115427391A CN 202180026647 A CN202180026647 A CN 202180026647A CN 115427391 A CN115427391 A CN 115427391A
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- opda
- substituted
- unsubstituted
- bis
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- 125000004986 diarylamino group Chemical group 0.000 title claims abstract description 39
- 150000001555 benzenes Chemical class 0.000 title abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000000463 material Substances 0.000 claims abstract description 90
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 30
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 125000005843 halogen group Chemical group 0.000 claims description 25
- -1 dibenzofuranyl group Chemical group 0.000 claims description 22
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 19
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000001041 indolyl group Chemical group 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 57
- 238000000034 method Methods 0.000 abstract description 15
- 239000000543 intermediate Substances 0.000 abstract description 4
- 150000004987 o-phenylenediamines Chemical class 0.000 abstract description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 57
- 239000000047 product Substances 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 description 22
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 description 22
- 101100028078 Oryza sativa subsp. japonica OPR1 gene Proteins 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 17
- 229910052749 magnesium Inorganic materials 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 16
- 239000012043 crude product Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 13
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 13
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 125000005266 diarylamine group Chemical group 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012267 brine Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000004770 highest occupied molecular orbital Methods 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000006798 recombination Effects 0.000 description 9
- 238000005215 recombination Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000002366 halogen compounds Chemical class 0.000 description 8
- 238000000859 sublimation Methods 0.000 description 8
- 230000008022 sublimation Effects 0.000 description 8
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003623 transition metal compounds Chemical class 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 241000894007 species Species 0.000 description 5
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 4
- XYZWMVYYUIMRIZ-UHFFFAOYSA-N 4-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(Br)C=C1 XYZWMVYYUIMRIZ-UHFFFAOYSA-N 0.000 description 4
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 4
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- XESMNQMWRSEIET-UHFFFAOYSA-N 2,9-dinaphthalen-2-yl-4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC(C=2C=C3C=CC=CC3=CC=2)=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=C(C=3C=C4C=CC=CC4=CC=3)N=C21 XESMNQMWRSEIET-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 2
- 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 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- SLLDDDJWIRFAGU-UHFFFAOYSA-N 1,2-dichlorocycloocta-1,5-diene Chemical compound ClC1=C(Cl)CCC=CCC1 SLLDDDJWIRFAGU-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- DNBGKLNKPFOXLG-UHFFFAOYSA-N 2-bromo-9-phenylcarbazole Chemical compound BrC1=CC=2N(C3=CC=CC=C3C2C=C1)C1=CC=CC=C1.BrC1=CC=2N(C3=CC=CC=C3C2C=C1)C1=CC=CC=C1 DNBGKLNKPFOXLG-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 2
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- HKQCJJOXYWQRFN-UHFFFAOYSA-N 1-bromo-2-iodoethane Chemical compound BrCCI HKQCJJOXYWQRFN-UHFFFAOYSA-N 0.000 description 1
- JTWWWQGSFTWWDL-UHFFFAOYSA-N 1-chloro-2-iodoethane Chemical compound ClCCI JTWWWQGSFTWWDL-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- AZBMJICEQJIKIR-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical compound BrC=1C=CC=2N(C3=CC=CC=C3C2C1)C1=CC=CC=C1.BrC=1C=CC=2N(C3=CC=CC=C3C2C1)C1=CC=CC=C1 AZBMJICEQJIKIR-UHFFFAOYSA-N 0.000 description 1
- KUBSCXXKQGDPPD-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 1
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
- NSXJEEMTGWMJPY-UHFFFAOYSA-N 9-[3-(3-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 NSXJEEMTGWMJPY-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RJROSTOBLTZWNX-UHFFFAOYSA-N pentacene-5,13-diamine Chemical compound C1=CC=CC2=CC3=CC4=C(C5=CC=CC=C5C=C4C(=C3C=C12)N)N RJROSTOBLTZWNX-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000005182 potential energy surface Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
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Abstract
The present invention provides an asymmetric 1,2-bis (diaryl) useful as an organic EL element materialAmino) benzenes, processes for producing the same, uses thereof as hole-transporting materials and blue-emitting materials, and o-phenylenediamines which are useful intermediates for producing asymmetric 1,2-bis (diarylamino) benzenes. An asymmetric 1,2-bis (diarylamino) benzene represented by the following general formula (1) and use thereof.
Description
Technical Field
The present invention relates to asymmetric 1,2-bis (diarylamino) benzenes, a method for producing the same, and uses thereof such as hole transporting materials and blue light emitting materials, and the asymmetric 1,2-bis (diarylamino) benzenes are useful as organic EL element materials, particularly hole transporting materials and blue light emitting materials.
Background
Organic EL (organic electro-luminescence) has attracted attention as a next-generation flat panel display, and has high panel performance such as thin/light weight, high viewing angle, high-speed response, high luminance, and high energy efficiency. Therefore, practical developments are being carried out in domestic and foreign enterprises and research institutions, and the development is beginning to be applied to displays of mobile phones and thin televisions.
In general, an organic EL element has a structure in which a hole-transporting material, a light-emitting material (a host material and a dopant material), and an electron-transporting material are stacked between an anode and a cathode.
As a technical problem of the organic EL device, it is required to search for a material suitable for the above-mentioned high panel performance, particularly, blue light emission and hole transporting material, and to develop a material suitable for the industrial application.
For a material suitable for blue light emission, it is considered that the energy levels of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) have an influence on the wavelength of light emission, and that HOMO and LUMO have an influence on the injection barrier and efficiency from the electrode for holes and electrons, and therefore, it is considered to be an element to be considered in the compound design of the hole transporting material. Therefore, a material having an appropriate HOMO-LUMO energy level is required.
As a representative hole-transporting material, 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl shown by NPB below is generally known. However, an element using NPB for the hole transporting layer has insufficient driving voltage and low glass transition temperature (Tg), and thus has insufficient performance as a hole transporting material.
Documents of the prior art
Patent literature
Patent document 1: chinese patent application publication No. 108299282 specification
Patent document 2: japanese patent No. 3171755
Non-patent document
Non-patent document 1: nature Photonics,2019, pp678-682
Disclosure of Invention
Problems to be solved by the invention
In view of the above background, an object of the present invention is to provide asymmetric 1,2-bis (diarylamino) benzene which is useful as an organic EL element material such as a hole transporting material or a blue light emitting material, a method for producing the same, and use thereof as a hole transporting material or a blue light emitting material.
Further, an object of the present invention is to provide o-phenylenediamines which are intermediates for producing asymmetric 1,2-bis (diarylamino) benzenes.
Means for solving the problems
The present inventors have intensively studied the above-mentioned problems and found that a specific asymmetric bis (1,2-diarylamino) benzene shown below has an appropriate HOMO-LUMO level, particularly a preferable Eg value for use as an organic EL element material such as a hole transporting material or a blue light emitting material, and the present invention has been completed. Further, a highly efficient method for producing asymmetric 1,2-bis (diarylamino) benzenes, which has been difficult to produce so far, has been established by using diarylamines having various substituents as starting materials.
Namely, the present invention relates to the following aspects.
[1] An asymmetric 1,2-bis (diarylamino) benzenes represented by the following general formula (1).
[ in the formula (1),
R 1 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
R 2 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom,
R 3 and R 4 Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
a. b, c and d represent 0 or 1,
a represents an aryl group substituted by a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent directly bonded to a nitrogen atom only in the meta position or in the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A optionally forms a cyclic structure with the directly bonded nitrogen atom and the phenyl group directly bonded to the nitrogen atom. ]
In the present specification, the "asymmetric 1,2-bis (diarylamino) benzenes" also include structural analogs thereof, and as described above, the structure in which a is a substituted or unsubstituted furyl group or a substituted or unsubstituted phenylthio group is also included.
In the present specification, the "asymmetric 1,2-bis (diarylamino) benzene" may include a compound having a point-symmetric structure.
[2] An asymmetric 1,2-bis (diarylamino) benzenes wherein said a is an aryl group substituted with a substituent comprising a nitrogen atom.
[3] The asymmetric 1,2-bis (diarylamino) benzenes according to the above [2], wherein a nitrogen atom contained in the substituent is directly bonded to an aryl group.
[4] The asymmetric 1,2-bis (diarylamino) benzenes according to the above [3], wherein the substituent is a carbazolyl group having a nitrogen atom directly bonded to an aryl group.
[5] The asymmetric 1,2-bis (diarylamino) benzenes according to the above [3], wherein the substituent has an aryl group directly bonded to a nitrogen atom.
[6] The asymmetric 1,2-bis (diarylamino) benzene according to any one of [3] to [5], wherein a nitrogen atom is directly bonded to the para-position or meta-position of the aryl group.
[7] The asymmetric 1,2-bis (diarylamino) benzenes according to the above [2], wherein the substituent is a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group.
[8] The asymmetric 1,2-bis (diarylamino) benzenes according to [1], which are represented by any of the following formulae.
[9] A hole-transporting material or a blue light-emitting material, which comprises the asymmetric 1,2-bis (diarylamino) benzenes represented by the general formula (1) as described in any one of the above [1] to [8 ].
In this specification, the hole-transporting material includes a hole-transporting host material used in the light-emitting layer and a hole-transporting material used in the hole-transporting layer.
[10] An organic EL element comprising the hole-transporting material or the blue light-emitting material.
[11] A display includes the organic EL element.
In the present invention, an intermediate for producing the above-mentioned asymmetric 1,2-bis (diarylamino) benzene of the present invention, that is, an o-phenylenediamine represented by the following general formula (2), can be used.
[ in the formula (2),
R 1 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
R 2 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom,
R 3 and R 4 Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
a. b, c and d represent 0 or 1.]
In the present invention, a method for producing the asymmetric 1,2-bis (diarylamino) benzene (1) of the present invention, that is, a method for producing the asymmetric 1,2-bis (diarylamino) benzene of the present invention, which is a method for producing the asymmetric 1,2-bis (diarylamino) benzene represented by the following general formula (1), may be used, wherein diarylamines represented by the following general formula (3) and diarylamines represented by the following general formula (4) are reacted with a grignard reagent to obtain diarylamide magnesium species (5) represented by the following general formula (5) and diarylamide magnesium species (6) represented by the following general formula (6), and then the diarylamide magnesium species (5) and the diarylamide magnesium species (6) are reacted with a transition metal catalyst and an oxidizing agent to obtain orthophenylenediamines (2) represented by the following general formula (2), and further, the diarylamide magnesium species (7) is reacted with a halogen compound represented by the following general formula (7) in the presence of a transition metal catalyst and a base.
[ in the formula (1),
R 1 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
R 2 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom,
R 3 and R 4 Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
a. b, c and d represent 0 or 1,
a represents an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent directly bonded to a nitrogen atom only in the meta position or in the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A optionally forms a cyclic structure with the directly bonded nitrogen atom and the phenyl group directly bonded to the nitrogen atom. ]
[ in the formula (3), R 1 、R 2 A and b are the same as the formula (1).]
[ in the formula (4), R 3 、R 4 C and d are the same as those in the formula (1).]
[ in the formula (5), R 1 、R 2 A and b are the same as the formula (1), and X represents a halogen atom.]
[ in the formula (6), R 3 、R 4 C and d are the same as in the formula (1), and X represents a halogen atom.]
[ formula (2) wherein R 1 、R 2 、R 3 、R 4 A, b, c and d are the same as those in the formula (1).]
A-X n (7)
[ in the formula (7), A is the same as the formula (1), X represents a halogen atom, and n represents an integer of 1 to 3.]
In the asymmetric bis (1,2-diarylamino) benzene represented by the above general formula (1), R in the formula (1) 1 Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group, R 2 Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom, R 3 And R 4 Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, or a methoxy groupA group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group, or a phenyl group, a, b, c, and d each represent 0 or 1,A and represent an aryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, which is substituted or unsubstituted by a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent directly bonding a nitrogen atom only at the meta position or at the para position, and a optionally forms a cyclic structure with the directly bonded nitrogen atom and the phenyl group directly bonded to the nitrogen atom.
The compound is suitable for a hole transporting material or a blue light emitting material containing asymmetric 1,2-bis (diarylamino) benzene represented by the general formula (1).
Among them, examples of the linear, branched or cyclic alkyl group having 3 to 6 carbon atoms include: n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
Examples of the alkoxy group having 3 to 6 carbon atoms include: n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom or iodine atom.
The substituent containing a condensed polycyclic aromatic group is a substituent containing an aromatic condensed polycyclic group, and the aromatic condensed polycyclic group may contain no heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom, or may contain a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
Examples of the aromatic condensed polycyclic group include: fused carbocyclic groups such as naphthyl and fluorenyl; and condensed heterocyclic groups such as quinolyl, indolyl, benzimidazolyl, phenoxazinyl, phenothiazinyl, 9-dimethylazinyl, iminobisstillyl, 1, 12-iminoperylenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, oxanthrenyl and the like.
Furthermore, R 1 ～R 4 All may be the same substituent or hydrogen atom, or may be different substituents.
Examples of the asymmetric bis (1,2-diarylamino) benzenes represented by the above general formula (1) include, in part, the following compounds: (1-1) - (1-16), (2-1) - (2-18), (3-1) - (3-16), (4-1) - (4-7), (5-1) - (5-2), (6-1) - (6-6), (7-1) - (7-4), (8-1) - (8-4), (9-1) - (9-3), and (10-1) - (10-2).
(1-1)～(1-16)
(2-1)～(2-18)
(3-1)～(3-16)
(4-1)～(4-7)
(5-1)～(5-2)
(6-1)～(6-6)
(7-1)～(7-4)
(8-1)～(8-4)
(9-1)～(9-3)
(10-1)～(10-2)
OPDA-1 to OPDA-11 (same as OPDA-1 and (1-15), OPDA-2 and (2-1), OPDA-3 and (3-1), and OPDA-4 and (3-2))
F-1～F-18
As the following general formula (F), compounds F-1 to F-18 of compound No can be cited. They define a substituent R of the general formula (F) 1 ～R 3 。
(F-1 is the same as (3-1), (F-2 is the same as (3-2), and F-17 is the same as OPDA-7.)
Of the above compounds, OPDA-1 to OPDA-11 are preferably used as a hole transport material, a blue light emitting material, or a material for organic EL, as shown in examples described later. Further, materials having the structure of OPDA-1 to OPDA-11 as a skeleton are also preferably used as a hole transporting material, a blue light emitting material, or a material for organic EL.
Further, the HOMO-LUMO levels, that is, EHOMO, ELUMO, eg, ET, ETO, λ -, λ +, IP, EA, were calculated for the above-mentioned compounds (1-1) to (10-2), and are shown in tables 1 to 5 below.
The calculation method is as follows.
All calculations were performed by the Gaussian 16 program (Revision C01) using the B3LYP density functional method in combination with the 6-31G basis functions. The triplet energy is calculated as the difference (ET) between the electron energies of the optimized geometry (geometry) of the triplet state and the singlet state. It is understood that the triplet energy (ET 0) calculated by including the zero energy correction is better matched with the experimental value, and therefore, they are also calculated and compared. The recombination energy (reorganisation energy) is the difference in change of electron energy associated with a change in geometry of the molecular structure of the charge transfer state and the neutral state. The internal recombination energy (l) is the energy required to change the geometry of two molecules in order to facilitate electron/hole movement between the two molecules. The calculation was performed using the adiabatic potential energy surface using the following equation.
λ＝λ1+λ2＝(Echarged state in neutral geometry-Echarged state in charged geometry)+(Eneutral state in charged geometry-Eneutral state in neutral geometry)
(wherein Echarged state in neutral gel means the electron energy in a charged state determined for a neutral molecular structure, echarged state in charged gel means the electron energy in a charged state determined for a charged molecular structure, eneutral state in charged gel means the electron energy in a neutral state determined for a charged molecular structure, eneutral state in neutral gel means the electron energy in a charged state determined for a neutral molecular structure.)
In the case of internal recombination energy of hole transport (λ +) and electron transport (λ -), the charged states are cation and anion, respectively. The energy required to surround two molecules participating in charge movement and the structural change of the peripheral molecules is called external recombination energy, which is considered to be small and is not considered in the present calculation. Further, adiabatic Ionization Potential (IP) and Electron Affinity (EA) were also calculated. In this calculation, the energy of the optimized charged state is used, and the following equation is used for calculation.
IP＝Ecationic state geometry-Eneutral state geometry
EA＝Eanionic state geometry-Eneutral state geometry
(wherein IP represents ionization potential (adiabatic), EA represents electron affinity (adiabatic), electrochemical state geometry represents a molecular structure in a cationic state, eneutral state geometry represents a molecular structure in a neutral state, eanionic state geometry represents a molecular structure in an anionic state, and Eneutral state geometry represents a molecular structure in a neutral state.)
Further, citations are as follows.
(Revision C01)Gaussian 16,Revision C.01,Frisch,M.J.；Trucks,G.W.；Schlegel,H.B.；Scuseria,G.E.；Robb,M.A.；Cheeseman,J.R.；Scalmani,G.；Barone,V.；Petersson,G.A.；Nakatsuji,H.；Li,X.；Caricato,M.；Marenich,A.V.；Bloino,J.；Janesko,B.G.；Gomperts,R.；Mennucci,B.；Hratchian,H.P.；Ortiz,J.V.；Izmaylov,A.F.；Sonnenberg,J.L.；Williams-Young,D.；Ding,F.；Lipparini,F.；Egidi,F.；Goings,J.；Peng,B.；Petrone,A.；Henderson,T.；Ranasinghe,D.；Zakrzewski,V.G.；Gao,J.；Rega,N.；Zheng,G.；Liang,W.；Hada,M.；Ehara,M.；Toyota,K.；Fukuda,R.；Hasegawa,J.；Ishida,M.；Nakajima,T.；Honda,Y.；Kitao,O.；Nakai,H.；Vreven,T.；Throssell,K.；Montgomery,J.A.,Jr.；Peralta,J.E.；Ogliaro,F.；Bearpark,M.J.；Heyd,J.J.；Brothers,E.N.；Kudin,K.N.；Staroverov,V.N.；Keith,T.A.；Kobayashi,R.；Normand,J.；Raghavachari,K.；Rendell,A.P.；Burant,J.C.；Iyengar,S.S.；Tomasi,J.；Cossi,M.；Millam,J.M.；Klene,M.；Adamo,C.；Cammi,R.；Ochterski,J.W.；Martin,R.L.；Morokuma,K.；Farkas,O.；Foresman,J.B.；Fox,D.J.Gaussian,Inc.,Wallingford CT,2016.
(B3LYP functional)Becke,A.D.J.Chem.Phys.1993,98,5648-5652.
(6-31G*basis sets)(a)Ditchfie,R.；Hehre,W.J.；Pople,J.A.J.Chem.Phys.1971,54,724-728.(b)Hehre,W.J.；Ditchfie,R.；Pople,J.A.J.Chem.Phys.1972,56,2257-2261.(c)Hariharan,P.C.；Pople,J.A.Theor Chim Acta 1973,28,213-222.(d)Francl,M.M.；Pietro,W.J.；Hehre,W.J.；Binkley,J.S.；Gordon,M.S.；Defrees,D.J.；Pople,J.A.J.Chem.Phys.1982,77,3654-3665.
(formula：l)(a)Yamada,T.；Sato,T.；Tanaka,K.；Kaji,H.Organic Electronics 2010,11,255-265.(b)Sakanoue,K.；Motoda,M.；Sugimoto,M.；Sakaki,S.J.Phys.Chem.A 1999,103,5551-5556.(c)Malagoli,M.；Bredas,J.L.Chem.Phys.Lett.2000,327,13-17.
In the above calculation, the parameters defined below were calculated and summarized in tables 1 to 5.
Procedure for calculating various photophysical characteristics (Procedure for calculation of differential photophysical properties)
Eg＝ELUMO-EHOMO
ET＝ETriplet-Esinglet
ET0＝ETriplet(with ZPE)-ESinglet(with ZPE)
λ＝(Echarged state in neutral geometry-Eneutral state geometry)+(Eneutral state in charged geometry-Echarged state geometry)
(in the formula, λ (Internal Reorganisation energy) is Internal recombination energy, and the definition of other various energies is the same as the above calculation method.)
Alternatively, in the case of λ = λ 1+ λ 2,
λ1＝Echarged state in neutral geometry-Echarged state in charged geometry
λ2＝Eneutral state in charged geometry-Eneutral state in neutral geometry
(wherein l1 (e) and l1 (h) are l1 values for electron transport and hole transport, respectively.)
λ + is Internal recombination energy for hole transport (Internal recombination energy for hole transport), and the charged state is a cation.
Lambda-is the Internal recombination energy for electron transport (Internal recombination energy) and the charged state is anionic.
IP is the ionization potential (adiabatic) and is calculated according to the electrochemical geometry-Eneutral state geometry.
EA is the electron affinity (adiabatic) calculated according to the Eanionic geometry-Eneutral state geometry.
From the calculation results, it was determined that the asymmetric 1,2-bis (diarylamino) benzene of the present invention of the above general formula (1) has an appropriate HOMO-LUMO level, that is, an appropriate EHOMO, ELUMO, eg, ET0, λ -, λ +, IP, and EA, and can be used as a hole-transporting material (a hole-transporting host material and/or a hole-transporting material) or a blue light-emitting material.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
In an organic EL device, for example, other factors such as compatibility with other layers may have a large influence. Therefore, it is impossible to determine which of the above-exemplified compounds is suitable for the hole-transporting material or the blue light-emitting material in a lump. However, in general, in the case of a hole-transporting host material, the compound is preferably a compound that satisfies one or more of the conditions of small HOMO, large Eg, large ET0, and small λ +.
From the viewpoint of easily satisfying the above conditions, in general, in the case of the hole transporting host material, in the general formula (1), a is preferably an aryl group substituted with a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group, and more preferably an aryl group substituted with a substituent containing a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group. Further, it is more preferable that a nitrogen atom of the substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group is directly bonded to the aryl group, and the substituent is still more preferably a carbazolyl group in which a nitrogen atom is directly bonded to the aryl group. In general, in the case of the hole transporting host material, a in the general formula (1) is preferably an aryl group to which a nitrogen atom is directly bonded at the para-position or meta-position.
In addition, from the viewpoint of easily satisfying the above conditions. In general, in the case of a hole transporting host material, R in the above general formula (1) 1 ～R 4 Preferably an electron withdrawing group. Furthermore, R 1 、R 3 、R 4 Preferably in the para position. Note that by appropriately changing the R 1 ～R 4 Kind of and/or R 1 ～R 4 The number of substituents (A) substituted by groups other than hydrogen atom(s) in (B) can be changed in the same manner as in (A) to give an asymmetric bis (1,2-diarylamino) benzene which easily satisfies the above-mentioned conditions.
The bis (1,2-diarylamino) benzenes represented by the above general formula (1) have an asymmetric structure, and therefore the crystallinity of the molecule is low and the amorphousness is high. Therefore, it is considered to have a high glass transition temperature (Tg). In particular, (1-1) to (1-15), (2-1) to (2-16), (2-18), (3-1) to (3-16), (4-1) to (4-7), (5-1) to (5-2), (6-1) to (6-6), (7-1) to (7-4), (8-1) to (8-4), and (9-1) to (9-3), OPDA-1 to OPDA-11, and F-1 to F-18 are considered to have particularly high amorphousness and particularly high glass transition temperatures (Tg).
Examples of the intermediate compound for producing the asymmetric bis (1,2-diarylamino) benzene represented by the above general formula (1) include orthophenylenediamines, and in the present invention, it is represented by the general formula (2).
Examples of the asymmetric bis (1,2-diarylamino) benzene represented by the above general formula (2) include, in part, the following compounds: (1-1 a) - (1-16 a), (2-1 a) - (2-18 a), (3-1 a) - (3-16 a), (4-1 a) - (4-7 a), (5-1 a) - (5-2 a), (6-1 a) - (6-6 a), (7-1 a) - (7-4 a), (8-1 a) - (8-4 a), (9-1 a) - (9-3 a), (10-1 a) - (10-2 a), OPDA-1 a) - (OPDA-11 a, and the like.
(1-1a)～(1-16a)
(2-1a)～(2-18a)
(3-1a)～(3-16a)
(4-1a)～(4-7a)
(5-1a)～(5-2a)
(6-1a)～(6-6a)
(7-1a)～(7-4a)
(8-1a)～(8-4a)
OPDA-1a～OPDA-11a
The diarylamine represented by the general formula (3) may be the same as or different from the diarylamine represented by the general formula (4).
In the magnesium diarylamide compounds represented by the above general formulae (5) and (6), X represents a halogen atom. Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom or iodine atom.
In the halogen compound represented by the above general formula (7), in the general formula (7), X represents a halogen atom. Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom or iodine atom. In addition, a part of the specific examples is illustrated, and the following configurations and the like are exemplified. X in the following formula represents a halogen atom. Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom or iodine atom. In the general formula (7), n (the number of substitution with X) represents an integer of 1 to 3, as shown in the following formula.
Examples of the halogen compound represented by the general formula (7) include, in part, the following compounds: (1-1 b) - (1-16 b), (2-1 b) - (2-18 b), (3-1 b) - (3-16 b), (4-1 b) - (4-7 b), (5-1 b) - (5-2 b), (6-1 b) - (6-6 b), (7-1 b) - (7-4 b), (8-1 b) - (8-4 b), (9-1 b) - (9-3 b), (10-1 b) - (10-2 b), and OPDA-1 b-OPDA-11 b.
(1-1b)～(1-16b)
(2-1b)～(2-18b)
(3-1b)～(3-16b)
(4-1b)～(4-7b)
(5-1b)～(5-2b)
(6-1b)～(6-6b)
(7-1b)～(7-4b)
(8-1b)～(8-4b)
OPDA-1b～OPDA-11b
In the formula (7), a is preferably an aryl group substituted with a substituent including a substituted or unsubstituted fused polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, more preferably an aryl group substituted with a substituent including a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, as in the case of the formula (1). Further, the nitrogen atom of the substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group is more preferably directly bonded to the aryl group, and the substituent is more preferably a carbazolyl group in which the nitrogen atom is directly bonded to the aryl group. Further, a in the general formula (7) is preferably an aryl group having a nitrogen atom directly bonded to X (halogen) at the para-position or meta-position.
< asymmetric 1,2-bis (diarylamino) benzenes >
The asymmetric 1,2-bis (diarylamino) benzenes represented by general formula (1) are not particularly limited, and can be produced by the following steps.
That is, the asymmetric 1,2-bis (diarylamino) benzenes of the present invention can be produced by step 1 (OPDA synthesis step) and step 2 (synthesis step of a target product such as a hole transporting material, a blue light emitting material, or the like).
(step 1
The magnesium diarylamides represented by the general formulae (5) and (6) can be produced by reacting diarylamines represented by the general formulae (3) and (4) with a grignard reagent.
The grignard reagent may be an aliphatic grignard reagent or an aromatic grignard reagent, and examples thereof include methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium bromide, isopropyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, phenyl magnesium bromide, and phenyl magnesium chloride, and the amount thereof to be used is preferably 1.0 to 100 molar equivalents, and more preferably 1.1 to 10.0 molar equivalents, with respect to the diarylamine (3) or diarylamine (4).
In addition, grignard reagents can also be prepared from alkyl lithium and magnesium salts.
Examples of the organic solvent used in the reaction include: ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, and the like. The solvent may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 1000 parts by weight based on the diarylamine (3) or diarylamine (4).
The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or under increased pressure. The reaction temperature is preferably in the range of-50 ℃ to 300 ℃, more preferably in the range of 0 ℃ to 150 ℃.
The reaction time is not particularly limited since it varies depending on the kind of substrate and the reaction temperature, and the reaction can be completed within a range of usually 1 to 48 hours.
After the reaction, the solvent may be removed under vacuum or under normal pressure, or may be used as it is in the next step 2.
The o-phenylenediamine represented by the general formula (2) can be produced by reacting a transition metal catalyst and an oxidizing agent with the magnesium diarylamide (5) represented by the general formula (5) and the magnesium diarylamide (6) represented by the general formula (6).
The amount of the magnesium diarylamide (5) represented by the general formula (5) to be used is preferably 1.0 to 10 molar equivalents, and more preferably 1.0 to 2.0 molar equivalents, relative to the magnesium diarylamide (6) represented by the general formula (6).
The transition metal catalyst may be any of iron compounds, palladium compounds, nickel compounds, cobalt compounds, and copper compounds, and examples thereof include: iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (II) fluoride, palladium chloride, palladium bromide, palladium acetate, palladium acetylacetonate, trichlorobis (triphenylphosphine) palladium, dichloro (cycloocta-1,5-diene) palladium, tris (dibenzylideneacetone) dipalladium chloroform complex, tetrakis (triphenylphosphine) palladium, nickel acetylacetonate, nickel (II) chloride, cobalt (II) chloride, copper acetylacetonate, copper (II) chloride, iron acetylacetonate, and the like. Among them, iron (II) chloride, iron (III) chloride, iron (II) acetate, and iron (II) fluoride are more preferable in order to further improve the reaction yield.
The amount of the transition metal catalyst to be added is preferably in the range of 0.01 to 100 mol% based on the magnesium diarylamide (5) or magnesium diarylamide (6). More preferably, the content is in the range of 0.05 to 5.0 mol%.
Examples of the oxidizing agent include: 1,2-diiodoethane, 1,2-dibromoethane, 1,2-dichloroethane, 1-chloro-2-iodoethane, 1-bromo-2-chloroethane, 1-iodo-2-bromoethane, and the like. Among them, 1,2-dichloroethane and 1,2-dibromoethane are more preferable.
The amount of the oxidizing agent to be added is preferably in the range of 0.5 to 10 molar equivalents relative to the magnesium diarylamide (5) or magnesium diarylamide (6). More preferably, the molar equivalent is in the range of 1 to 5 molar equivalents.
The organic solvent used in the reaction may be any of a polar solvent and a nonpolar solvent, and examples thereof include: aromatic hydrocarbons such as benzene, toluene, and xylene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, and the like. The solvent may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 1000 parts by weight based on the magnesium diarylamide (5) or magnesium diarylamide (6).
The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or under increased pressure. The reaction temperature is preferably in the range of 0 ℃ to 300 ℃, more preferably in the range of 50 ℃ to 150 ℃.
The reaction time is not particularly limited since it varies depending on the kind of substrate and the reaction temperature, and the reaction can be completed within a range of usually 1 to 48 hours.
After the reaction is completed, a generally known purification method may be used, and for example, the organic layer may be separated by a liquid separation operation, and the obtained organic layer may be washed with water, a saline solution, an aqueous alkali solution, or the like, and then separated and purified by a general method such as column chromatography, crystallization, or the like.
Step 2 (step of synthesizing the target product)
The bis (1,2-diarylamino) benzenes represented by the general formula (1) can be produced by reacting an orthophenylenediamine represented by the general formula (2) with a halogen compound represented by the general formula (7) in the presence of a transition metal catalyst.
The transition metal compound constituting the transition metal catalyst may be any compound as long as it is a palladium compound, a nickel compound, a copper compound or an iron compound, and examples thereof include: sodium hexachloropalladate tetrahydrate, potassium hexachloropalladate, palladium chloride, palladium bromide, palladium acetate, palladium acetylacetonate, dichlorobis (benzonitrile) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (triphenylphosphine) palladium, tetraaminopalladium dichloride, dichloro (cycloocta-1,5-diene) palladium, trifluoroacetylpalladium, tris (dibenzylideneacetone) dipalladium chloroform complex, tetrakis (triphenylphosphine) palladium, nickel acetylacetonate, nickel chloride, copper acetylacetonate, copper chloride, iron acetylacetonate, iron chloride and the like. The transition metal compound may be used in combination with various ligands, and the ligand may be added by a method in which the transition metal compound and the ligand are reacted in advance outside the system and then added, or a method in which the transition metal compound and the ligand are added to the reaction system and the reaction system is prepared inside the system.
The amount of the transition metal compound added is preferably in the range of 0.01 to 100 mol% relative to 1 mol of the o-phenylenediamine represented by the general formula (2). In order to further improve the reaction selectivity, the range of 0.1 to 5 mol% is more preferable.
The ligand may be any ligand that coordinates to the transition metal compound, and examples thereof include phosphine compounds, nitrogen compounds, olefin compounds, and the like. Examples thereof include: alkyl phosphines such as triethylphosphine, tricyclohexylphosphine, and tri (t-butyl) phosphine, aryl phosphines such as triphenylphosphine, 1,1 '-bis (diphenylphosphino) ferrocene [ dppf ], 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene [ XANTphos ], 1,5-cyclooctadiene [ COD ], 2,2' -bipyridine, and the like. Among them, tricyclohexylphosphine or tri (tert-butyl) phosphine is preferable in order to increase the reaction selectivity.
The amount of the ligand to be added is preferably in the range of 0.1 to 100 mol per mol of the transition metal compound. In order to further improve the reaction selectivity, the range of 1-fold mol to 10-fold mol is more preferable.
The organic solvent used in the reaction may be any of polar solvents and nonpolar solvents, and examples thereof include: aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, and the like; hydrocarbon solvents such as hexane, heptane, pentane, octane, nonane, decane, etc.; acetonitrile, N-Dimethylformamide (DMF), 1-methyl-2-pyrrolidone (NMP), N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), triethyl phosphate (TEP), trimethyl phosphate (TMP), acetic acid, and the like. The solvent may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 10000 parts by weight per 100 parts by weight of the o-phenylenediamine represented by the general formula (2).
The base used in the reaction may be exemplified by: metal hydroxides, metal carbonates, metal phosphates, metal sulfates, and metal alkoxides. Examples thereof include: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tripotassium phosphate, sodium sulfate, sodium hydrogen sulfate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, and the like. Among them, potassium hydroxide, potassium carbonate, tripotassium phosphate, and sodium tert-butoxide are preferable. The amount of these compounds to be used is preferably in the range of 1 to 50 mol based on 1 mol of the halogen compound represented by the general formula (7). In order to further improve the reaction selectivity, the molar ratio is more preferably in the range of 1.5 to 5 times, and two or more bases may be used alone or in combination.
The amount of the halogen compound (7) used is preferably in the range of 0.1 to 10 mol per 1 mol of the o-phenylenediamine represented by the general formula (2). In order to further improve the reaction selectivity, the range of 0.3 to 5 times by mole is more preferable.
The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or under increased pressure. The reaction temperature is preferably in the range of 0 to 300 ℃ and more preferably in the range of 50 to 150 ℃.
The reaction time is not particularly limited since it varies depending on the kind of substrate and the reaction temperature, and the reaction can be completed within a range of usually 1 to 48 hours.
After the reaction is completed, a generally known purification method may be used, and for example, the organic layer may be separated by a liquid separation operation, and the obtained organic layer may be washed with water, a saline solution, an aqueous alkali solution, or the like, and then separated and purified by a general method such as column chromatography, crystallization, or the like.
Effects of the invention
According to the present invention, the asymmetric bis (1,2-diarylamino) benzene represented by the general formula (1) has an appropriate HOMO-LUMO level, and thus can be used as an organic EL element material such as a hole transporting material and a blue light emitting material.
According to the present invention, it is possible to efficiently produce an asymmetric bis (1,2-diarylamino) benzene which has been difficult to produce. Further, according to this production method, various substituents can be easily introduced into a position selectively, and molecular design having an energy level suitable for an organic EL element material such as a hole transporting material or a blue light emitting material can be performed.
Drawings
Fig. 1 is a graph showing the energy level of HOMO-LUMO calculated from the absorption edge and oxidation potential of a solution for a material used in the present invention and a conventional material, the horizontal axis (X axis) is the material used for the calculation of the energy level, and the vertical axis (Y axis) is the energy level (in eV).
FIG. 2 is a view showing a laminated structure for evaluating an element in which m-CBP as a control and OPDA-3 and OPDA-4 of the present invention were evaluated in an OPDA layer. For reference, a comparison was also made with the data shown in the paper.
FIG. 3 is data obtained by evaluating the device, and is a graph showing Voltage-Current characteristics, wherein the horizontal axis (X axis) represents Voltage (Voltage in V (volt)), and the vertical axis (Y axis) represents Current Density (Current Density in mA/cm) 2 ). In the figure, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 of the present invention.
Fig. 4 is data obtained by evaluating the device, and is a graph showing an EL (Electroluminescence) spectrum, in which the horizontal axis (X axis) is a Wavelength (Wavelength, unit is nm) and the vertical axis (Y axis) is an EL intensity (normalized). In the figure, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 of the present invention.
Detailed Description
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples, since these examples show the outline of the present invention.
Identification of the Compound of interest by 1 H NMR( 1 H nuclear magnetic resonance spectrum), 13 C NMR( 13 C nuclear magnetic resonance spectrum) of, 19 F NMR( 19 F nuclear magnetic resonance spectroscopy), MS (mass spectrometry), IR analysis, HRMS analysis, melting point analysis, and elemental analysis. Purity and isomer ratio were determined by GC analysis and yield was determined by NMR analysis using dibromoethane as an internal standard. In addition, for purification of the target product, a recovery preparative GPC is used as necessary. The apparatus used is as follows.
Nuclear magnetic resonance spectroscopy: JEOL ECS-400NR, bruker AVANCE III US Plus.
IR device: perkinelmer Spectrum One FT-IR Spectrometer.
HR-MS device: JEOL JMS-700 massspecrometer.
Melting point measuring apparatus: yanaco MP-500D.
A GC device: shimadzu GC-2010 (FID).
Column: ZB-1MS (10 m.times.0.10 mm I.D.df.) (manufactured by Phenomenex K.K..
A detector: a hydrogen flame ionization detector.
Recovery of preparative GPC: japan Analytical Industry LC-9204Instrument.
Column: JAIGEL-1H-40/JAIGEL-2H-40.
EXAMPLE 1 Synthesis of OPDA (1-1 a)
Diphenylamine (18.0 g, 110mmol) and Et were mixed under an argon atmosphere 2 O (108 mL) was placed in a 500mL flask, and EtMgBr (39.0 mL,3.0M in Et) was added under ice-cooling 2 O,121 mmol) was added, and the mixture was stirred with heating at 40 ℃ for 2 hours.
Thereafter, et was removed under reduced pressure 2 O, addition of FeCl 2 (0.67g, 5.5 mmol) and dibromoethane (18.0mL, 220mmol), bu 2 O108 mL, heated and stirred at 80 ℃ for 24 hours, then at room temperature, 1N HCl 108mL was added, extraction was performed with AcOEt 108mL x3, and washing was performed with 108mL of brine (brine).
MgSO (MgSO) 4 The resulting organic layer was added, filtered through Florisil (90 g), and concentrated by an evaporator. To 22g of the crude product obtained, 53mL of EtOH was added and dissolved by heating, and after stirring at room temperature for 1 hour, the precipitate was filtered, whereby a beige powder was obtained.
Since this powder contained a small amount of impurities, etOH 48mL was added again and dissolved by heating, and after stirring at room temperature for 1 hour, filtration and drying were carried out to obtain 14.8g of OPDA as a white powder in 83% yield.
The analysis results are as follows.
1 H NMR(DMSO-d 6 392MHz)δ6.76-6.79(m，1H)，6.91-6.97(m，9H)，7.08-7.29(m，10H)
Example 2 Synthesis of OPDA (2-8 a)
Diarylamine (14.0g, 70.8mmol) and Bu were added under an argon atmosphere 2 O (94 mL) was added to a 500mL flask, and BuMgBr (100mL, 0.779M in Bu was added at room temperature (25 deg.C) 2 O,77.9 mmol) was added thereto, and the mixture was stirred with heating at 100 ℃ for 1 hour.
Thereafter, feCl was added at room temperature (25 ℃ C.) 2 (0.45g, 3.54mmol) and dibromoethane (26.6g, 142mmol) were stirred at 80 ℃ for 24 hours. After 1N HCl (200 mL) was added to the reaction solution, the mixture was filtered through Celite and extracted with AcOEt 100mL x 3.
The resulting organic layer was filtered with filter paper and concentrated with an evaporator to obtain 15.6g of a crude product. Silica gel column purification was carried out using 500g of silica gel and hexane as developing solvents to obtain 8.97g of OPDA having a GC purity of > 99% in 64% yield and 4.80g of OPDA having a GC purity of 92% in 34% yield.
The analysis results are as follows.
1 H NMR(CDCl 3 ，392MHz)δ2.20(s，3H)，2.24(s，3H)，2.26(s，6H)，5.66(s，1H)，6.78(d，2H，J＝8.2Hz)，6.89-6.94(m，6H)，6.97-7.06(m，6H)，7.16(d，1H，J＝8.6Hz)
EXAMPLE 3 Synthesis of OPDA-Biphenyl
Diarylamine (5.00g, 15.6 mmol) and Et were added under argon atmosphere 2 O (50 mL) was added to a 300mL flask, and EtMgBr (5.73mL, 3.0M in Et) was added at room temperature 2 O,17.2 mmol) was added, and the mixture was stirred with heating at 40 ℃ for 2 hours. Thereafter, et was removed under reduced pressure 2 O, addition of FeCl 2 (98.8mg, 0.78mmol), dibromoethane (5.8g, 31.2mmol), bu 2 O (50 mL) was heated and stirred at 80 ℃ for 12 hours, and then further heated and stirred at 140 ℃ for 24 hours. At room temperature, 1N HCl (50 mL) was added, extraction was performed with AcOEt (30mL. Times.3), and MgSO was added to the resulting organic layer 4 After filtration using filter paper, the filtrate was concentrated by an evaporator. Relative to 4.21g of the crude product obtained, 0.78g of OPDA-biphenyl was obtained in < 16% yield by purification on silica gel column.
The analysis results are as follows.
1 HNMR(CDCl 3 ，392MHz)δ5.99(s，1H)，7.01-7.03(m，2H)，7.21-7.31(m，7H)，7.36-7.56(m，26H)
EXAMPLE 4 Synthesis of 4-Br-N, N-dimethylaniline-substituted Compound
Under an argon atmosphere, OPDA (4.68g, 13.9mmol) obtained in example 1 and 4-bromo-N, N-dimethylaniline (4.12g, 20.6 mmol), pd (OAc) 2 (62.9mg，0.28mmol)、tBu 3 P (228mg, 1.12mmol), naOtBu (2.67g, 27.8mmol) and toluene (70 mL) were placed in a 300mL flask, dissolved at room temperature (25 ℃) and then stirred at 120 ℃ for 4 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25 ℃ C.), extracted with AcOEt (20mL. Times.3), and concentrated with an evaporator. Reprecipitation by using a toluene/hexane solvent system gave 5.63g of the target product in < 89% yield.
The analysis results are as follows.
1 H NMR(CDCl 3 ，392MHz)δ3.02(s，6H)，6.70(d，4H，J＝7.8Hz)，6.76(t，4H，J＝9.6Hz)，6.86(t，2H，J＝7.4Hz)，6.94-7.01(m，1H)，7.08(t，4H，J＝7.8Hz)，7.14-7.15(m，6H)，7.32-7.44(m，2H)
GC purity 100.0%
EXAMPLE 5 Synthesis of 4-Br-N, N-dimethylaniline-substituted Compound
Under argon atmosphere, OPDA _ Tol (4.55g, 11.6 mmol) and 4-bromo-N, N-dimethylaniline (4.64g, 23.2mmol), pd (OAc) 2 (51.6mg，0.230mmol)、tBu 3 P (186mg, 0.92mmol), naOtBu (2.23g, 23.2mmol) and toluene (58 mL) were charged into a 300mL flask, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 120 ℃ C. For 6 hours. After 1N HCl (50 mL) was added to the reaction solution at room temperature (25 ℃), it was extracted with AcOEt (50mL. Times.3). Using MgSO 4 The obtained organic layer was dried, filtered through florisil, and concentrated by an evaporator to obtain 6.71g of a crude product. Using GPC (toluene) pPurification was attempted at 3.00g of crude product, but it was considered that tailing (tailing) occurred in the peak to cause oxidation. Reprecipitation of the remaining 3.71g of crude product by using a toluene/hexane solvent system gave 2.88g of the desired product in 49% yield with a GC purity > 99%.
The analysis results are as follows.
1 H NMR(CDCl 3 ，392MHz)δ2.22(s，6H)，2.25(s，3H)，2.26(s，3H)，3.05(s，6H)，6.56-6.58(m，4H)，6.67(d，2H，J＝8.8Hz)，6.73(d，2H，J＝9.0Hz)，6.87-6.98(m，9H)，7.32(d，2H，J＝8.6Hz)
GC purity is 100.0%
EXAMPLE 6 Synthesis of 4-Br-N, N-dimethylaniline substituted Compound
Under argon atmosphere, OPDA _ Biphenyl (0.78g, 1.22mmol) and 4-bromo-N, N-dimethylaniline (366mg, 1.83mmol), pd (OAc) 2 (5.5mg，0.024mmol)、tBu 3 P (19.6 mg,0.096 mmol), naOtBu (177mg, 1.83mmol) and toluene (12 mL) were put in a 100mL flask, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 120 ℃ for 4 hours. After 1N HCl (30 mL) was added to the reaction solution at room temperature (25 ℃), CHCl was used 3 (20mL. Times.3), and extraction was performed using MgSO 4 Dried, filtered through filter paper, and concentrated by an evaporator. Crude 885mg was obtained in < 95% yield by reprecipitation using a toluene/hexane solvent system.
The analysis results are as follows.
1 H NMR(CDCl 3 ，392MHz)δ3.00(s，6H)，6.91-6.96(m，4H)，7.16-7.46(m，18H)，7.48-7.55(m，8H)
EXAMPLE 7 Synthesis of 3-Br-9-phenyl-9H-carbazole-substituted Compound
Under argon atmosphere, OPDA _ Ph (2.91g, 8.66mmol) and 3-bromo-9-phenyl-9H-carbazole (4.19g, 12.99mmol), pd (OAc) 2 (38.7mg，0.17mmol)、tBu 3 P (140mg, 0.692mmol), naOtBu (1.25g, 12.99mmol) and xylene (43 mL) were put in a 100mL flask, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 130 ℃ C. For 14 hours. Further Pd (OAc) was added at room temperature (25 ℃ C.) 2 (141mg, 0.63mmol) and tBu 3 P (141mg, 0.70mmol) was stirred at 130 ℃ for 5 hours. After 1N HCl (50 mL) was added to the reaction solution at room temperature (25 ℃), it was extracted with AcOEt (30 mLx 3), and concentrated with an evaporator. By reprecipitation using a toluene/hexane solvent system, 3.67g was obtained in < 73% yield.
The analysis results are as follows.
1 H NMR(CDCl 3 ，392MHz)δ6.77-6.90(m，5H)，7.07-7.61(m，25H)，7.91(d，1H,J＝7.6Hz)
GC purity is 94.3%
Example 8 Synthesis of OPDA-1
Under an inert atmosphere, OPDA (336mg, 1mmol), 2-bromo-9-phenylcarbazole (2-bromo-9-phenylcarbazole) (322mg, 1mmol), pd (OAc) were reacted at 150 deg.C 2 (4.5mg、0.02mmol)、tBu 3 P (16.2mg, 0.08 mmol) and NaOtBu (144mg, 1.5 mmol) in mesitylene (2.7 mL) were stirred for 4 hours. The reaction was quenched (quenched) with 1M HCl at room temperature (reaction stopped) and extracted with ethyl acetate. The organic layer was washed with brine (brine) and MgSO 4 Dried and filtered through a pad of Florisil. The solvent was removed under reduced pressure to give the crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-1 as a white solid (0.43g, 74% yield).
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 392MHz)δ6.56-6.59(m，5H)，6.64-6.68(m，3H)，6.79-6.86(m，3H)，7.00-7.04(m，5H)，7.07-7.12(m，3H)，7.15-7.17(m，2H)，7.20-7.23(m，2H)，7.31-7.35(m，1H)，7.42(d，J＝7.2Hz，2H)，7.50(t，J＝7.4Hz，1H)，7.63(t，J＝7.9Hz，2H)，8.00(d，J＝8.5Hz，1H)，8.47(d，J＝8.5Hz，1H)；Anal.Calcd for C 42 H 31 N 3 C，87.32；H，5.41；N，7.27.Found C，87.42；H，5.52；N，7.16。
Example 9 Synthesis of OPDA-2
Under an inert atmosphere, OPDA (336mg, 1mmol), 3-bromo-9-phenylcarbazole (3-bromo-9-phenylcarbazole) (322mg, 1mmol), pd (OAc) were reacted at 150 deg.C 2 (4.5mg、0.02mmol)、tBu 3 P (16.2mg, 0.08 mmol) and NaOtBu (144mg, 1.5 mmol) in mesitylene (5 mL) were stirred for 4 hours. The reaction was quenched with 1M HCl at room temperature (reaction stopped) and extracted with 4ml of ethyl acetate. Filtration was performed through a pad of 1.5g of Florisil (fluorisil). The solvent was removed under reduced pressure (hexane: ethyl acetate = 30: 1) to give the crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-2 as a white solid (0.50772g, 88% yield).
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(CDCl 3 ，392MHz)δ6.83-6.97(m，10H)，7.12-7.17(m，9H)，7.22-7.27(m，8H)，7.33(dd，2H，J＝1.3，1.3Hz)，8.1(d，2H，J＝7.6Hz)；Anal.Calcd for C 42 H 31 N 3 C，87.32；H，5.41；N，7.27.Found C，87.09；H，5.57；N，7.09。
EXAMPLE 10 Synthesis of OPDA-3
Under an inert atmosphere, OPDA (336mg, 1mmol), 2-bromo-9-phenylcarbazole (2-bromo-9-phenylcarbazole) (322mg, 1mmol), pd (OAc) were reacted at 150 deg.C 2 (4.5mg，0.02mmol)、tBu 3 P (16.2mg, 0.08 mmol) and NaOtBu (144mg, 1.5 mmol) in mesitylene (2.5 mL) were stirred for 5.5 h. The reaction was quenched (quenched) with 1.5ml of 1M HCl at room temperature and extracted with 10ml of ethyl acetate. Filtration was carried out through a pad of 1.5g of Florisil (fluorinil). The solvent was removed under reduced pressure to give the crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-3 (0.51068g, 88% yield) as a white solid.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.59(s，1H)，6.63(d，4H，J＝8.0Hz)，6.82(m，5H)，6.92(dd，1H，J＝7.6，7.6Hz)，6.99-7.09(m，6H)，7.16-7.26(m，9H)，7.35-7.43(m，3H)，8.19(d，2H，J＝7.6Hz)；Anal.Calcd for C 42 H 31 N 3 C，87.32；H，5.41；N，7.27.Found C，87.53；H，5.48；N，7.48.
Example 11 Synthesis of Me-OPDA-4 (methyl substituted Compound)
Me-OPDA-4a (393 mg), mesitylene (2.7 ml), me-OPDA-4b (Br derivative) (487 mg), pd (OAc) were added under an argon atmosphere 2 (4.5mg，0.02mmol)、tBu 3 P (16.2 mg) and NaOtBu (144 mg) were added to the reaction vessel, and dissolved at room temperature (25 ℃ C.), followed by stirring and heating at 150 ℃ for 4 hours. After 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25 ℃), extraction was performed with AcOEt (2 mLx 2), and 1.34g of Florisil (60-100 mesh) was passed through, washing was performed with AcOEt (2 mL), and the reaction solution was evaporated. Is brownIs oil-like. Purifying by silica gel column chromatography, and filtering. 0.48g of the expected product (Me-OPDA-4) is obtained. The target product was a white powder.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ2.02(s，6H)，2.14(s，3H)，2.19(s，3H)，6.46(d，J＝8.5Hz，4H)，6.64(d，J＝8.1Hz，4H)，6.74-6.77(m，3H)，6.95-7.02(m，3H)，7.1(d，J＝8.5Hz，2H)，7.27-7.31(m，6H)，7.39-7.47(m，8H)，8.23(d，J＝8.1Hz，4H)；Anal.Calcd for C 58 H 46 N 4 C，87.19；H，5.80；N，7.01.Found C，87.25；H，5.88；N，6.75。
Example 12 Synthesis of F-OPDA-4 (fluoro substituted Compound)
Under argon atmosphere, F-OPDA-4a (408.40mg, 1.00mmol) was mixed with F-OPDA-4b (Br derivative) (487.40mg, 1.00mmol), pd (OAc) 2 (4.5mg，0.02mmol)、tBu 3 P (144.2mg, 1.50mmol), naOtBu (144mg, 1.5mmol) and mesitylene (5.0 ml) were put into a reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ C. For 8 hours. The reaction was stopped at room temperature (25 ℃ C.), extracted with AcOEt (20mL. Times.3), and then with MgSO 4 And (5) drying. Purification by column chromatography gave 467mg of the desired product (F-OPDA-4). The yield was 57.3%. The target product was a light brown solid.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.64-6.68(m，3H)，6.71-6.78(m，5H)，7.09(td，1H，J＝8.2，2.7Hz)，7.11(d，3H，J＝2.7Hz)，7.15-7.30(m，7H)，7.40-7.56(m，10H)，8.21-8.26(m，5H)；Anal.Calcd for C 54 H 34 F 4 N 4 C，79.59；H，4.21；N，6.88.Found C，80.97；H，4.39；N，6.63.
EXAMPLE 13 Synthesis of OPDA-5
Under argon atmosphere, OPDA (OPDA-5 a) (336.44mg, 1.00mmol) and OPDA-5b (Br derivative) (322.21mg, 1.00mmol), pd (OAc) 2 (4.5mg，0.02mmol)、tBu 3 P (16.2mg, 0.08mmol), naOtBu (144mg, 1.5 mmol) and mesitylene (5.0 ml) were put into a reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ C. For 8 hours. The reaction was stopped by adding 1N-HCl at room temperature (25 ℃ C.), and the reaction mixture was introduced into 1.5g of Florisil and purified by using 20g of silica gel (solvent: hexane: acOEt = 30: 1) to obtain 507.72mg of the objective product (OPDA-5). The yield was 88%. The target product was a white solid.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.68-6.77(m，8H)，6.86-6.93(m，3H)，7.10-7.22(m，12H)，7.29(dd，1H，J＝7.3，7.3Hz)，7.37-7.44(m，2H)，7.55-7.71(m，7H)，8.30(d，1H，J＝7.6)，8.45(s，1H)；Anal.Calcd for C 48 H 35 N 3 C，88.18；H，5.39；N，6.43.Found C，88.33；H，5.44；N，6.23.
EXAMPLE 14 Synthesis of OPDA-6
Under argon atmosphere, OPDA (OPDA-6 a) (336.44mg, 1.00mmol) and OPDA-6b (Br derivative) (372.27mg, 1.00mmol), pd (OAc) 2 (4.5mg，0.02mmol)、tBu 3 P (16.2mg, 0.08mmol), naOtBu (144mg, 1.5 mmol) and mesitylene (5.0 ml) were put into a reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ C. For 7 hours. 1N-HCl is added at room temperature (25 ℃) to stop the reaction,extraction with AcOEt (20mL. Times.3), extraction with MgSO 4 And (5) drying. The solution was introduced into 1.5g of Florisil and recrystallized after solvent extraction, to obtain 566.91mg of the objective product (OPDA-6). The yield was 90.3%. The target product was a white solid.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.66(d，6H，J＝7.6Hz)，6.76(s，3H)，6.84-6.88(m，4H)，7.08(dd，7H，J＝14.7，7.6Hz)，7.18-7.24(m，4H)，7.31(dd，2H，J＝14.1，7.4Hz)，7.44(s，1H)，7.59(dd，1H，J＝7.6，7.6Hz)，7,70-7.79(m，2H)，8.07(d，1H，J＝7.6Hz)，8.16(dd，2H，J＝18.1，8.2Hz)；Anal.Calcd for C 46 H 33 N 3 C，88.01；H，5.30；N，6.69.Found C，87.77；H，5.36；N，6.55。
EXAMPLE 15 Synthesis of OPDA-7
Under argon atmosphere, OPDA (OPDA-7 a) (670mg, 2.0mmol), mesitylene (4 ml), OPDA-7b (Br derivative, 1,3-dibromobenzene) (240mg, 1.0mmol), pd (OAc) 2 (9mg，0.04mmol)、tBu 3 P (32.4 mg) and NaOtBu (290 mg) were added to the reaction vessel, dissolved at room temperature (25 ℃ C.), and stirred at 150 ℃ C. For 6 hours. 1N HCl (3 mL) was added to the reaction solution at room temperature (25 ℃ C.), followed by extraction with AcOEt (5 mL,3 mL), washing with Brine (Brine), and then introducing 3.5g of silica gel to evaporate it. It is dark brown. This was solidified, filtered and dried to obtain 0.65g of the aimed product (OPDA-7). The target product was a light beige powder.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.23(dd，J＝8.1，2.2Hz，2H)，6.27-6.28(m，1H)，6.43(d，J＝7.6Hz，4H)，6.57-6.59(m，8H)，6.76-6.89(m，8H)，6.93-7.17(m，19H)；Anal.Calcd for C 54 H 42 N 4 C，86.83；H，5.67；N，7.50.Found C，86.62；H，5.67；N，7.39.
EXAMPLE 16 Synthesis of OPDA-8
Under argon atmosphere, OPDA (OPDA-8 a) (670mg, 2.0mmol), mesitylene (4 ml), OPDA-8b (Br derivative, 1,3-dibromobenzene) (240mg, 1.0mmol), pd (OAc) 2 (9mg，0.04mmol)、tBu 3 P (32.4 mg) and NaOtBu (290 mg) were put into a reaction vessel, dissolved at room temperature (25 ℃ C.), and then stirred at 150 ℃ C. For 6 hours under heating. After 1N HCl (3 mL) was added to the reaction solution at room temperature (25 ℃), it was extracted with AcOEt (5 mL,3 mL) and washed with brine (bromine) to give a crude product (0.8 g) as a gray powder. Dissolving it in CHCl 3 After that, 7.5g of silica gel was passed through and evaporated. In the form of a green bubble. This was dissolved, filtered and dried to obtain 0.69g of the objective product (OPDA-8). The target product was a light grey white powder.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.50-6.60(m，4H)，6.76-6.78(m，10H)，6.87-6.99(m，5H)，7.00-7.11(m，20H)，7.25-7.26(m，3H)；Anal.Calcd for C 54 H 42 N 4 C，86.83；H，5.67；N，7.50.Found C，86.64；H，5.72；N，7.46.
Example 17 Synthesis of OPDA-9
Under argon atmosphere, OPDA (OPDA-9 a) (472.88mg, 1.50mmol) and OPDA-9b (Br derivative) (401.1mg, 1.00mmol), pd (OAc) 2 (9mg，0.04mmol)、tBu 3 P(32.4mg，0.16mmol)、NaOtBu(288.3mg,3 mmol) and mesitylene (5.0 ml) were charged into the reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ C. For 6 hours. The reaction was stopped by adding 1N-HCl at room temperature (25 ℃ C.), extracted with AcOEt (20mL. Times.3), and extracted with MgSO 4 And (5) drying. After passing through silica gel 25g and extraction with a solvent (hexane: etOAc =25: 1), recrystallization was performed to obtain 782.62mg of the objective product (OPDA-9). The yield was 85.8%. The target product was a white solid.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ5.92(s，2H)，6.56-6.63(m，13H)，6.74(dd，3H，J＝7.4，7.4Hz)，6.83-7.20(m，27H)，7.31(dd，2H，J＝7.4，7.4Hz)，8.12(d，2H，J＝7.6Hz)；Anal.Calcd for C 66 H 49 N 5 C，86.91；H，5.41；N，7.68.Found C，86.91；H，5.56；N，7.72。
EXAMPLE 18 Synthesis of OPDA-10
Under argon atmosphere, OPDA-10a (640mg, 1.0mmol), mesitylene (2.7 ml), OPDA-10b (Br derivative, 1,3-dibromobenzene) (230mg, 1.0mmol), pd (OAc) 2 (4.5mg，0.02mmol)、tBu 3 P (16.2mg, 0.08mmol) and NaOtBu (144mg, 1.5 mmol) were charged into a reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ for 4 hours. After 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25 ℃), it was extracted with AcOEt (5 mL,3 mL) and washed with Brine (Brine) to obtain a crude product (0.83 g) as a beige powder. Purifying by column chromatography and dissolving in CHCl 3 After that, 8g of silica gel was passed through and evaporated. 0.93g of a crude target product in the form of a reddish purple foam was obtained. This was dissolved in a solvent, and the solution was filtered and dried to obtain 0.67g of the desired product (OPDA-10). The target product was a white powder.
By passing 1 H-NMR on the target productThe analysis was carried out, and the following results were obtained.
1 H NMR(CDCl 3 ，392MHz)δ6.95-6.99(m，8H)，7.27-7.34(m，5H)，7.36-7.42(m，19H)，7.49-7.54(m，12H)；Anal.Calcd for C 60 H 44 N 2 C，90.87；H，5.59；N，3.53.Found C，91.06；H，5.69；N，3.25。
EXAMPLE 19 Synthesis of OPDA-11
Under argon atmosphere, OPDA-11a (640mg, 1.0mmol), mesitylene (2.7 ml), OPDA-11b (Br derivative) (320mg, 1.0mmol), pd (OAc) 2 (4.5mg，0.02mmol)、tBu 3 P (16.2mg, 0.08mmol) and NaOtBu (144mg, 1.5 mmol) were added to a reaction vessel, dissolved at room temperature (25 ℃ C.), and then heated and stirred at 150 ℃ for 4 hours. 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25 ℃ C.), followed by extraction with AcOEt (5 mL,3 mL) and washing with brine (bromine) to obtain a crude product (0.97 g) in the form of a brown bubble. It was purified by column chromatography on silica gel (9 g) and CHCl was added 3 When it is used, it is in the form of purple bubbles. When 10ml of IpA was added thereto, the mixture became clay-like and was pulverized. After filtration, a pale brown white powder (0.76 g) was obtained. Further, purification was performed by column chromatography on silica gel (11 g), and extraction was performed with a solvent (hexane: etOAc = 10: 1 → 4: 1) to obtain a bubble of orange yellow color (0.72 g). To this solution, 5mL of ethanol was added, followed by filtration and drying to obtain 0.64g of the aimed product (OPDA-11) as a pale brown white powder.
By passing 1 The target product was analyzed by H-NMR, and the following results were obtained.
1 H NMR(DMSO-d 6 ，392MHz)δ6.72(t，J＝2.0Hz，1H)，6.90(d，J＝8.5Hz，4H)，7.04(d，J＝9.0Hz，3H)，7.70-7.45(m，29H)，7.49-7.63(m，8H)，8.22(d，J＝7.2，1.3Hz，2H)；Anal.Calcd for C 66 H 47 N 3 C，89.87；H，5.37；N，4.76.Found C，89.66；H，5.48；N，4.61。
Example 20 Synthesis of OPDA-7-X, OPDA-7-cbz and OPDA-8-X
In the same manner as above, OPDA-7-X, OPDA-7-cbz and OPDA-8-X were synthesized under the following reaction formulae and used for evaluation.
Example 21 measurement of basic Properties
The results of measuring the glass transition temperature, absorption maximum wavelength, log ε, absorption edge (absorption edge), fluorescence maximum wavelength, fluorescence quantum yield, and oxidation potential vsAg/Ag + of OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, me-OPDA-4, F-OPDA-4, OPDA-7, and OPDA-9 are shown in Table 6.
Each measurement was performed under the following conditions.
Glass transition temperature
By differential scanning calorimetry (apparatus: hitachi High-Tech Science DSC/TG-DTA 6200). The measurement conditions were carried out at a sample amount of 5mg, a temperature rise of 10 ℃/min, a temperature drop rate of 20 ℃/min between 1st run and 2nd run, and a glass transition temperature of 2nd run.
Absorption maximum wavelength
The measurement was carried out by a spectrometer SEC2020 (manufactured by BAS corporation) as a measuring apparatus. The measurement conditions were adjusted so that the material was dissolved in about 10-5mol/l tetrahydrofuran, and the wavelength of the maximum point of the absorption band on the longest wavelength side in the absorption spectrum observed by the measurement apparatus was determined as the absorption maximum wavelength.
log epsilon is the logarithm of the molar absorption coefficient at the wavelength of maximum absorption.
The absorption edge is a wavelength at a point where a curve is linearly approximated to intersect the x axis (absorbance 0) on the long-wavelength edge side of the absorption spectrum.
Maximum wavelength of fluorescence
By fluorescence chromatography (apparatus: japanese Spectroscopy F8200). The measurement conditions were carried out at an excitation wavelength of 310nm, an excitation band of 2.5nm, and a fluorescence band of 2.5 nm.
Fluorescence quantum yield
The relative method of 9, 10-diphenyl anthracene to cyclohexane solution is used for determination.
Oxidation potential vsAg/Ag +
By cyclic voltammetry. The determination conditions were as follows: dichloromethane, compound concentration: 10-3mol/l, supporting electrolyte: TBAP 0.1M, working electrode: platinum disk, counter electrode: platinum wire, reference electrode: ag/AgNO 3 0.01M CH 3 CN solution, scanning speed: at 50 mV/sec.
[ Table 6]
One of basic physical properties
Example 22 measurement of basic Properties
The optical energy gap, HOMO and LUMO levels were calculated for OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, me-OPDA-4, F-OPDA-4, OPDA-7 and OPDA-9, and the results are shown in Table 7.
[ Table 7]
Basic physical properties of the second
In table 7 above, the HOMO energy level was obtained from cyclic voltammetry. The assay conditions were NPD oxidation potential 477mVvsAg/Ag +, HOMO5.43eV reference.
The optical bandgap is calculated from the long wavelength edge of the absorption spectrum.
The LUMO level is calculated from the difference between the optical energy gap and the HOMO level.
Example 23 HOMO-LUMO map calculated from absorption edge and oxidation potential of solution
The energy levels of OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7 and OPDA-9 were calculated, and the results are shown in FIG. 1.
NPD and TPD were calculated as existing materials and added to fig. 1. Note that NPD used in this specification is abbreviated as N, N '-bis (1-naphthyl) -N, N' -diphenyl- (1,1 '-diphenyl) -4,4' -diamine (N, N '-bis (1-naphthyl) -N, N' -diphenyl- (1,1 '-biphenyl) -4,4' -diamine), and TPD is N, N '-diphenyl-N, N' -bis (3-methylphenyl) - (1,1 '-diphenyl) -4,4' -diamine.
From these results, it is understood that the materials of OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7 and OPDA-9 of the present invention have appropriate intensity as the difference of HOMO-LUMO energy levels and energy levels, and are suitable as light emitting materials.
Example 24 measurement of basic Properties
The energy levels of OPDA-3 and OPDA-9, and NPD, CBP and m-CBP to be compared were calculated, and the results are shown in Table 8.
[ Table 8]
Third of the basic Properties (calculated value)
| OPDA-3 | Comparative 1) NPD | Comparison 2) CBP | OPDA-9 | Comparison) m-CBP | |
| S1 energy level (eV) | 3.63 | 3.14 | 3.59 | 3.52 | 3.69 |
| T1 level (eV) | 3.01 | 2.33 | 2.82 | 3.00 | 3.05 |
| ΔE ST (eV) | 0.62 | 0.70 | 0.78 | 0.52 | 0.64 |
In table 8, the S1 level is calculated from the short wavelength edge of the fluorescence spectrum, and the T1 level is calculated from the short wavelength edge of the phosphorescence spectrum.
As is clear from Table 8, the T1 levels of OPDA-3 and OPDA-9 are higher in energy than NPD and CBP, and the Δ EST of OPDA-3 and OPDA-9 is smaller than that of NPD, CBP, or m-CBP. OPDA-3 and OPDA-9 hold favorable energy levels as hosts for triplet Blue and as exciton diffusion blocking layers.
Note that m-CBP used in this specification is an abbreviation of 3,3 '-bis (9H-carbazol-9-yl) -1,1' -diphenyl (3,3 '-bis (9H-carbazol-9-yl) -1,1' -biphenyl).
Example 25 study of purification method of product by sublimation
The results of the sublimation method-based purification of OPDA-1, OPDA-2, OPDA-5, OPDA-6, me-OPDA-4 and F-OPDA-4 are shown in Table 9.
[ Table 9]
One study of biological purification method by sublimation
Example 26 study of purification method of product by sublimation
The results of the purification method by sublimation of OPDA-3, OPDA-4, OPDA-7, OPDA-9, OPDA-10 and OPDA-11 are shown in Table 10.
[ Table 10]
Second study on method for purifying product by sublimation
OPDA-10: purity after sublimation: 99.1 percent
Temperature after sublimation of OPDA-11: 97.1 percent
As is clear from tables 9 and 10 above, the material of the present invention can be purified by sublimation and is useful as a purification method.
Example 27 evaluation of refractive index (ease of Total reflection)
The refractive indices of F-OPDA-4 and OPDA-4, and NPD as a comparative sample were measured, and the results are shown in Table 11.
[ Table 11]
Evaluation of refractive index (ease of Total reflection)
| 400nm | 450nm | 500nm | 600nm | 700nm | |
| F-OPDA-4 | 1.79 | 1.74 | 1.72 | 1.69 | 1.67 |
| OPDA-4 | 1.84 | 1.78 | 1.75 | 1.72 | 1.70 |
| NPD | 2.12 | 1.89 | 1.83 | 1.78 | 1.76 |
In table 11, the measurement was performed by the ellipsometry.
The measurement is performed in a general manner, and a change in the polarization state of the incident light with respect to the polarization state of the incident light is observed, and Ψ (tan Ψ = | rp |/| rs |) and Δ (= δ rp- δ rs) are obtained by the measurement. Then, an optical model was created, and the model and the measured values were combined by fitting to determine the refractive index.
As is clear from table 11, the material of the present invention is less susceptible to total reflection than the NPD of the conventional material, and is particularly low on the low wavelength side of 400nm, as well as on the high wavelength side.
Example 28 evaluation of the elements
The structures of the elements (laminated structures composed of organic layers) used for evaluation in fig. 2 were prepared for OPDA-3 and OPDA-4 and m-CBP as a comparative control, and the driving voltage, luminance, luminous efficiency and chromaticity CIE1931 were measured, and the results are shown in table 12.
The laminated structure is constituted as follows.
The organoborane used as the light-emitting material is a material described below, and can be produced by nat. Photon.8, 326-332 (2014).
Organoborane: n7, N7, N13, N13,5,9, 11, 15-octaphenyl-5,9, 11, 15-tetrahydroo-5,9, 11, 15-tetraaza-19b, 20b-diboraraptho [3,2,1-de:1',2',3' -jk ] pentacene-7, 13-diamine.
Composition of m-CBP:
ITO/HAT-CN (5 nm)/NPD (40 nm)/TCTA (15 nm)/m-CBP (15 nm)/m-CBP +1wt% organoborane (20 nm)/NBPhen (40 nm)/Al.
OPDA-3 constitution:
ITO/HAT-CN (5 nm)/NPD (50 nm)/TCTA (20 nm)/OPDA-3 +1wt% organoborane (20 nm)/NBPhen (40 nm)/Al.
Composition of OPDA-4:
ITO/HAT-CN (5 nm)/NPD (50 nm)/TCTA (20 nm)/OPDA-4 +1wt% organoborane (20 nm)/NBPhen (40 nm)/Al.
[ Table 12]
Evaluation of components
| Driving voltage | Brightness of light | Luminous efficiency | Chromaticity CIE1931 | |
| rn-CBP | 8.2V | 258cd/m2 | 2.6cd/A | (0.136，0.107) |
| OPDA-3 | 5.7V | 196cd/m2 | 2.0cd/A | (0.138，0.115) |
| OPDA-4 | 6.1V | 128cd/m2 | 1.3cd/A | (0.138，0.085) |
In table 12, the drive voltage measurement was performed by I-V measurement, and the luminance measurement was performed by a color luminance meter. Further, the light emission efficiency is luminance current efficiency.
As is clear from Table 12, the driving voltages of the layered structure using OPDA-3 and the layered structure using OPDA-4 of the present invention are lower than those of the layered structure using m-CBP, which is a conventional material, and are not inferior in terms of luminance, luminous efficiency and chromaticity, and thus, they are suitable as a material for light emission.
Example 29 Voltage-Current characteristics
The voltage-current characteristics of the stacked structures of m-CBP as a comparative control using OPDA-3 and OPDA-4, respectively, were measured and the results are shown in FIG. 3. The laminated structure has the same configuration as that of fig. 2.
As can be seen from fig. 3, the OPDA device having the stacked structure using the OPDA-3 and the OPDA-4 of the present invention can lower the driving voltage as compared with the m-CBP device having the stacked structure using the m-CBP.
Example 30EL Spectroscopy
The EL spectra of the layered structure using OPDA-3, the layered structure using OPDA-4, and the layered structure using m-CBP as a comparative control were measured and shown in fig. 4. The laminated structure has the same configuration as that of fig. 2.
As can be seen from fig. 4, the OPDA device having the stacked structure using the OPDA-3 and the stacked structure using the OPDA-4 of the present invention has a spectrum having a maximum value almost the same as that of the m-CBP device, and the OPDA device having the stacked structure using the OPDA-4 has a shoulder (shoulder) on the low wavelength side.
Example 31 Cyclic voltammetry of dichloromethane solution
The results of cyclic voltammetry in a methylene chloride solution were measured for OPDA-1, OPDA-2, OPDA-5, OPDA-6, me-OPDA-4, F-OPDA-4, OPDA-7, OPDA-9, OPDA-10 and OPDA-11, and are shown in tables 13 and 14.
The determination conditions were as follows: dichloromethane, compound concentration: 10-3mol/l, supporting electrolyte: TBAP 0.1M, working electrode: platinum disk, counter electrode: platinum wire, reference electrode: ag/AgNO 3 0.01M CH 3 CN solution, scanning speed: 50mV/sec, where the NPD oxidation potential is 477mV vs Ag/Ag +, HOMO 5.43eV.
[ Table 13]
Cyclic voltammetry of dichloromethane solutions
| OPDA-1 | OPDA-2 | OPDA-5 | OPDA-6 | Me-OPDA-4 | F-OPDA | |
| Oxidation potential vsAg/Ag + | 519mV | 605mV | 500mV | 392mV | 521mV | 821mV |
| HOMO energy level of | 5.47eV | 5.56eV | 5.45eV | 5.35eV | 5.47eV | 5.77eV |
[ Table 14]
Cyclic voltammetry of dichloromethane solutions
| OPDA-7 | OPDA-9 | |
| Oxidation potential vsAg/Ag + | 597mV (irreversible) | 651mV |
| HOMO energy level of | 5.51eV | 5.60eV |
OPDA-10: the redox potential was 590mV, HOMO5.52eV
OPDA-11: the redox potential was 650mV, HOMO5.58eV
Industrial applicability
The organic EL element is industrially useful as a hole transporting material, a blue light emitting material, or the like.
Claims (11)
1. An asymmetric 1,2-bis (diarylamino) benzenes represented by the following general formula (1),
in the formula (1), the reaction mixture is,
R 1 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, a carbon atomAlkoxy groups having a number of 3 to 6, halogen atoms, substituted or unsubstituted carbazolyl groups or phenyl groups,
R 2 represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom,
R 3 and R 4 Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazolyl group or a phenyl group,
a. b, c and d represent 0 or 1,
a represents an aryl group substituted by a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent directly bonded to a nitrogen atom only in the meta position or in the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A optionally forms a cyclic structure with the directly bonded nitrogen atom and the phenyl group directly bonded to the nitrogen atom.
2. An asymmetric 1,2-bis (diarylamino) benzenes, wherein,
in the general formula (1) according to claim 1, A is an aryl group substituted with a substituent containing a nitrogen atom.
3. The asymmetric 1,2-bis (diarylamino) benzenes of claim 2 wherein,
the nitrogen atom contained in the substituent is directly bonded to the aryl group.
4. The asymmetric 1,2-bis (diarylamino) benzenes of claim 3 wherein,
the substituent is carbazolyl which is directly bonded with nitrogen atoms on aryl.
5. The asymmetric 1,2-bis (diarylamino) benzenes of claim 3 wherein,
the substituent has an aryl group directly bonded to a nitrogen atom.
6. The asymmetric 1,2-bis (diarylamino) benzenes of any of claims 3-5 wherein,
the nitrogen atom is directly bonded to the para or meta position of the aryl group.
7. The asymmetric 1,2-bis (diarylamino) benzenes of claim 2 wherein,
the substituent is a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group.
8. The asymmetric 1,2-bis (diarylamino) benzenes of claim 1 which are any of the following formulas,
9. a hole transporting material or a blue light emitting material, which is composed of the asymmetric 1,2-bis (diarylamino) benzenes represented by the general formula (1) according to any one of claims 1 to 8.
10. An organic EL element comprising the hole transporting material or the blue light emitting material according to claim 9.
11. A display comprising the organic EL element as claimed in claim 10.
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