CN117777175A - Organic boron fused ring compound and preparation method and application thereof - Google Patents
Organic boron fused ring compound and preparation method and application thereof Download PDFInfo
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- CN117777175A CN117777175A CN202311802718.8A CN202311802718A CN117777175A CN 117777175 A CN117777175 A CN 117777175A CN 202311802718 A CN202311802718 A CN 202311802718A CN 117777175 A CN117777175 A CN 117777175A
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- compound
- unsubstituted
- substituted
- fused ring
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 410
- 238000002360 preparation method Methods 0.000 title claims abstract description 336
- 229910052796 boron Inorganic materials 0.000 title abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 90
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 229910052805 deuterium Inorganic materials 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 13
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001294 (C1-C30) cycloalkyl group Chemical group 0.000 claims description 3
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 3
- 229960003116 amyl nitrite Drugs 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 239000012414 tert-butyl nitrite Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000008282 halocarbons Chemical group 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 146
- 239000000463 material Substances 0.000 abstract description 24
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000005281 excited state Effects 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 2
- 230000005524 hole trap Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 339
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 288
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 217
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 213
- 239000012074 organic phase Substances 0.000 description 167
- 239000008367 deionised water Substances 0.000 description 155
- 229910021641 deionized water Inorganic materials 0.000 description 155
- 238000000921 elemental analysis Methods 0.000 description 128
- 239000010410 layer Substances 0.000 description 120
- 238000000605 extraction Methods 0.000 description 111
- 238000000926 separation method Methods 0.000 description 110
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 108
- 238000001816 cooling Methods 0.000 description 88
- 239000012300 argon atmosphere Substances 0.000 description 85
- 238000005406 washing Methods 0.000 description 77
- 239000000243 solution Substances 0.000 description 71
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 55
- 229910052786 argon Inorganic materials 0.000 description 54
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 44
- 238000004807 desolvation Methods 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 40
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 40
- 238000001914 filtration Methods 0.000 description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 34
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 26
- 239000012043 crude product Substances 0.000 description 26
- 239000003960 organic solvent Substances 0.000 description 24
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 24
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 22
- 238000001035 drying Methods 0.000 description 22
- 239000003446 ligand Substances 0.000 description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 description 22
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 22
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- -1 methoxy, methylthio, phenyl Chemical group 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 12
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 10
- 239000003637 basic solution Substances 0.000 description 10
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- OXVIUIAIVYDLDX-UHFFFAOYSA-N 1-bromo-3-chloro-5-phenoxybenzene Chemical compound ClC1=CC(Br)=CC(OC=2C=CC=CC=2)=C1 OXVIUIAIVYDLDX-UHFFFAOYSA-N 0.000 description 5
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 5
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- ROEOVWIEALGNLM-UHFFFAOYSA-N 5h-benzo[b]carbazole Chemical compound C1=CC=C2C=C3C4=CC=CC=C4NC3=CC2=C1 ROEOVWIEALGNLM-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- HYQUWYMJSAPGDY-UHFFFAOYSA-N 1,5-dibromo-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Br)C=C1Br HYQUWYMJSAPGDY-UHFFFAOYSA-N 0.000 description 3
- ZOPJIIGCXPBAKG-UHFFFAOYSA-N 3,5-dichloro-n,n-diphenylaniline Chemical compound ClC1=CC(Cl)=CC(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 ZOPJIIGCXPBAKG-UHFFFAOYSA-N 0.000 description 3
- MHYZYLQHHQNSPV-UHFFFAOYSA-N 4-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1C1=CC=CC=C1N2 MHYZYLQHHQNSPV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LHSCWNDROKEVMT-UHFFFAOYSA-N [3,5-di(carbazol-9-yl)phenyl]boronic acid Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC(B(O)O)=C1 LHSCWNDROKEVMT-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
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- PCMKGEAHIZDRFL-UHFFFAOYSA-N 3,6-diphenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=C(NC=2C3=CC(=CC=2)C=2C=CC=CC=2)C3=C1 PCMKGEAHIZDRFL-UHFFFAOYSA-N 0.000 description 2
- FHJJVSJWFYYPAC-UHFFFAOYSA-N 3-carbazol-9-yl-9h-carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C2NC3=CC=CC=C3C2=C1 FHJJVSJWFYYPAC-UHFFFAOYSA-N 0.000 description 2
- IAWRFMPNMXEJCK-UHFFFAOYSA-N 3-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=C(NC=2C3=CC=CC=2)C3=C1 IAWRFMPNMXEJCK-UHFFFAOYSA-N 0.000 description 2
- SJOKONNBSXFPSN-UHFFFAOYSA-N 9-(3-bromo-5-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC(Br)=C1 SJOKONNBSXFPSN-UHFFFAOYSA-N 0.000 description 2
- FFPUWZLVEGMKAR-UHFFFAOYSA-N 9-(4-bromo-3,5-dimethylphenyl)-3,6-ditert-butylcarbazole Chemical compound BrC1=C(C=C(C=C1C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)C FFPUWZLVEGMKAR-UHFFFAOYSA-N 0.000 description 2
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- KEWCSCZDKPGJSC-UHFFFAOYSA-N (2,6-dimethyl-4-phenylphenyl)boronic acid Chemical compound CC1=C(B(O)O)C(C)=CC(C=2C=CC=CC=2)=C1 KEWCSCZDKPGJSC-UHFFFAOYSA-N 0.000 description 1
- ZXDTWWZIHJEZOG-UHFFFAOYSA-N (2,6-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(C)=C1B(O)O ZXDTWWZIHJEZOG-UHFFFAOYSA-N 0.000 description 1
- GOXICVKOZJFRMB-UHFFFAOYSA-N (3-phenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=CC=CC=2)=C1 GOXICVKOZJFRMB-UHFFFAOYSA-N 0.000 description 1
- XSAOVBUSKVZIBE-UHFFFAOYSA-N (9-phenylcarbazol-2-yl)boronic acid Chemical compound C=1C(B(O)O)=CC=C(C2=CC=CC=C22)C=1N2C1=CC=CC=C1 XSAOVBUSKVZIBE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IWZNGNLJRXZVSV-UHFFFAOYSA-N 1,3-dibromo-2,5-dimethylbenzene Chemical group CC1=CC(Br)=C(C)C(Br)=C1 IWZNGNLJRXZVSV-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- AELBZZMQJAJEJW-UHFFFAOYSA-N 1-bromo-9-phenylcarbazole Chemical compound BrC1=CC=CC(C2=CC=CC=C22)=C1N2C1=CC=CC=C1 AELBZZMQJAJEJW-UHFFFAOYSA-N 0.000 description 1
- NWLCIOKUOGGKKK-UHFFFAOYSA-N 2,7-diphenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=C2C3=CC=C(C=4C=CC=CC=4)C=C3NC2=C1 NWLCIOKUOGGKKK-UHFFFAOYSA-N 0.000 description 1
- RRTLQRYOJOSPEA-UHFFFAOYSA-N 2-bromo-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(Br)C(C)=C1 RRTLQRYOJOSPEA-UHFFFAOYSA-N 0.000 description 1
- SFGFOJPGCOYQJK-UHFFFAOYSA-N 2-bromo-4-fluoro-1-methylbenzene Chemical compound CC1=CC=C(F)C=C1Br SFGFOJPGCOYQJK-UHFFFAOYSA-N 0.000 description 1
- SIZYXYRNXJSAON-UHFFFAOYSA-N 2-bromo-5-fluoro-1,3-dimethylbenzene Chemical group CC1=CC(F)=CC(C)=C1Br SIZYXYRNXJSAON-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- MOTSKOMBIKXMHG-UHFFFAOYSA-N 3,6-bis(trifluoromethyl)-9h-carbazole Chemical compound C1=C(C(F)(F)F)C=C2C3=CC(C(F)(F)F)=CC=C3NC2=C1 MOTSKOMBIKXMHG-UHFFFAOYSA-N 0.000 description 1
- NGEWHSNRTKEISQ-UHFFFAOYSA-N 3,6-ditert-butyl-1,8-diphenyl-9H-carbazole Chemical compound C=12NC3=C(C=4C=CC=CC=4)C=C(C(C)(C)C)C=C3C2=CC(C(C)(C)C)=CC=1C1=CC=CC=C1 NGEWHSNRTKEISQ-UHFFFAOYSA-N 0.000 description 1
- ZOIHCOOHDPEJNX-UHFFFAOYSA-N 3-carbazol-9-ylphenol Chemical compound OC1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 ZOIHCOOHDPEJNX-UHFFFAOYSA-N 0.000 description 1
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- IZEHZZZYZQTBGN-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C(C(=CC(=C1)C1=CC=CC=C1)C1=CC=CC=C1)B(O)O Chemical compound C1(=CC=CC=C1)C1=C(C(=CC(=C1)C1=CC=CC=C1)C1=CC=CC=C1)B(O)O IZEHZZZYZQTBGN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 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
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical group C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NPCBDQZLUSJKOW-UHFFFAOYSA-M sodium;4-[5-(4-chlorophenyl)-3,4-dihydropyrazol-2-yl]benzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1N1N=C(C=2C=CC(Cl)=CC=2)CC1 NPCBDQZLUSJKOW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention provides an organic boron fused ring compound, a preparation method and application thereof. The organic condensed-cyclic compound can be used in an organic electroluminescent device, on one hand, the relaxation degree of an excited state structure can be reduced by utilizing the rigid framework structure of the condensed-cyclic compound, so that the narrower half-peak width is realized; on the other hand, carbazole units are bonded to the rigid framework of the fused ring compound through two modes of carbon-nitrogen bond and carbon-carbon bond to form a symmetrical structure or an asymmetrical structure, and hole traps are formed between the main body material and the fluorescent material by reducing HOMO energy level, so that the luminous efficiency and stability of the device are improved. Meanwhile, the steric hindrance of carbazole moieties increases the dihedral angle with the planar molecular skeleton to inhibit self aggregation and promote solubility. The maximum external quantum efficiency of the device is 23.9-31.4% through test, and the device has a narrow electroluminescent spectrum, and the half-peak width is smaller than 20nm.
Description
Technical Field
The invention belongs to the technical field of organic light-emitting devices, and particularly relates to an organic boron fused ring compound, a preparation method and application thereof.
Background
Organic Light Emitting Devices (OLEDs) have the characteristics of rich color, thin thickness, wide viewing angle, rapid response, and the like, and can be manufactured into flexible devices, which are considered to be the next generation flat panel display and solid lighting technologies that have the most promising development. In general, an OLED is composed of an ITO anode, a hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1 to 2 organic layers may be omitted as needed, and excitons are formed by combining holes injected from the anode and the cathode on an organic thin film with electrons, and when the excitons return to a stable ground state from an excited state, energy is released in a light-emitting form to emit light. Thermally activated delayed fluorescence (thermally activated delayed fluorescence, TADF) materials are new generation organic luminescent materials following traditional fluorescent and phosphorescent materials, which generally have a small singlet-triplet energy level difference (Δe) ST ) The triplet state excitons are transferred to the singlet state excitons to emit fluorescence by utilizing a thermally activated reverse intersystem crossing (RISC) process, so that the full utilization of the singlet state excitons and the triplet state excitons is realized, and the internal quantum efficiency of 100% is realized. In 2019, the international telecommunications union radio communications sector (ITU-R) promulgates bt.2020 standards for new generation ultra-high definition video production and display systems, employing a wider color gamut space to meet richer color displays. To meet this requirement, researchers have found that improving the color purity of luminescent materials is one of the effective ways to achieve a wider color gamut display.
The multi-resonance heat-activated delayed fluorescence (MR-TADF) material has the characteristics of high efficiency and high color purity, and is suitable for the ultra-high definition display of a new generation of wide color gamut.
Disclosure of Invention
In view of the above, the present invention aims to provide an organoboron fused ring compound, a preparation method and an application thereof.
In a first aspect, the present invention provides an organoboron fused ring compound having the structure of formula I-A or formula I-B:
wherein m is 1 、m 2 Each independently is an integer of 1 to 4; n is n 1 、n 4 Each independently is an integer of 1 to 4; n is n 2 、n 3 Each independently is an integer of 1 to 4;
X 1 and X 2 Independently selected from N (R) a ) O, S, se or Te, said N (R a ) R in O a Independently selected from H, D, a substituted or unsubstituted C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group, wherein the heteroatoms in the heteroaryl groups are independently selected from Si, ge, N, P, O, S or Se;
R a and is connected to X 1 And X 2 Through carbon-carbon single bond, -O-, -S-, and, And->Any one or more of which are linked together;
L 1 and L 2 Each independently selected from the group consisting of a carbon-carbon single bond, an ether oxygen bond, a thioether bond, a seleno ether bond, a substituted or unsubstituted C1-C30 linear hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, and a substituted or unsubstituted C1 Alkylthio of C30;
or L 1 And L 2 Each independently selected from any one of U-1 to U-18:
a1 is selected from any one of the groups shown in formulas 1 to 56:
La-Lc are each independently selected from H, D, F, cl, br, I, -CN, -NO2,
A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
R 1 ～R 11 each independently selected from H, D, F, cl, br, I, -CN, Substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, substituted or unsubstituted C1-C30 haloalkyl groupSubstituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
R 1 、R 2 and R is 3 Each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
or (b)
R 1 、R 2 And R is 3 Through carbon-carbon single bond, -O-, -S-, any one or more of the connections;
q is independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; the hetero atom in the heteroaryl group is selected from one or more of Si, ge, N, P, O, S and Se;
or Q is selected from any one of Q-1 to Q-33:
in the present invention, "x" in the above chemical structure indicates a connection site.
Preferably, the method comprises the steps of,any one selected from the formulas H-1 to H-47:
preferably, the method comprises the steps of,any one selected from the formulas H-48 to H-72:
preferably, the organoboron fused ring compound is selected from any one of formulas I-1 to I-192:
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in a second aspect, the present invention provides a method for preparing an organic fused ring compound, comprising the steps of:
reacting a compound shown in a formula II with a compound shown in a formula III in a solvent to obtain a fused ring compound shown in a formula I-A or a formula I-B;
wherein, the compound structure shown in formula II:
wherein the compound shown in the formula III comprises a structure shown in a formula III-1, a formula III-2 or a formula III-3:
wherein Lu 1 、Lu 2 、Lu 3 Each independently selected from halogen,
Preferably, the compound shown in the formula II is prepared by the following method:
s1: compound Ar 1 ' with compound Ar, respectively 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 4 ′；
S2: compound Ar 4 ' and BI 3 Reacting to form a compound shown in a formula II;
preferably, the reaction in step S1 is carried out in the presence of a catalyst selected from Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Any one or more of NaH, naOH, or KOH.
Preferably, the catalyst is combined with a compound AT 1 ' Compound Ar 2 ' sum Compound Ar 3 The mol ratio of' is (0.5-8): 1:1.05-3): 1.05-3.
Preferably, the BI 3 With compound Ar 4 The mol ratio of' is (1-5) to 1.
Preferably, the compound shown in the formula II is prepared by the following method:
s1: compound Ar 5 ' with Compound Ar 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 6 ′；
S2: compound Ar 6 ' formation of Compound Ar by nitroreduction reaction 7 ′；
S3: compound Ar 7 ' formation of Compound Ar by diazotisation reaction 8 ′；
S4: compound Ar 8 ' and BBr 3 Reacting to form a compound shown in a formula II;
preferably, the reaction in step S1 is performed in the presence of a reducing agent selected from one or more of iron powder, hydrogen, sodium sulphide or sodium disulphide.
Preferably, the reducing agent is combined with a compound Ar 6 ' molar ratio of(2～20)∶1。
Preferably, the reaction in step S2 is carried out in the presence of a diazotising agent selected from one or more of sodium nitrite, amyl nitrite, butyl nitrite or tert-butyl nitrite;
preferably, the diazotising agent is combined with a compound Ar 7 The mol ratio of' is (0.5-5) to 1.
Preferably, the reaction in step S3 is carried out under the action of butyllithium selected from n-butyllithium) and/or tert-butyllithium.
Preferably, the butyllithium is combined with compound Ar 8 The mol ratio of' is (1-5) to 1.
Preferably, the reaction in step S4 is carried out in the presence of an organic amine base, preferably N, N-diisopropylethylamine and/or triethylamine.
Preferably, the BBr 3 (i.e., boron tribromide), organic amine base compound Ar 8 The mol ratio of' is (1-10): 1.
In a third aspect, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode;
the organic thin film layer comprises the organic fused ring compound.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an organic condensed-cyclic compound with a structure shown in a formula I-A or a formula I-B, which can be used as a luminescent material in an organic electroluminescent device, on one hand, the relaxation degree of an excited state structure can be reduced by means of a rigid framework structure of the condensed-cyclic compound, so that the narrower half-peak width of the organic electroluminescent device is realized; on the other hand, carbazole units are bonded to the rigid framework of the fused ring compound through two modes of carbon-nitrogen bond and carbon-carbon bond to form a symmetrical structure or an asymmetrical structure, and hole traps are formed between the main body material and the fluorescent material by reducing HOMO energy level, so that the luminous efficiency and stability of the device are improved. Meanwhile, the steric hindrance of carbazole moieties increases the dihedral angle with the planar molecular skeleton to inhibit self aggregation and promote solubility. Experimental results show that the organic fused ring compound can be used for assembling an OLED device by an evaporation process and can also be used for preparing a luminescent layer of the OLED device by a solution processing process, so that the OLED device with high efficiency and long service life is prepared.
The organic electroluminescent device is used as a luminescent material and has high luminous efficiency, the maximum external quantum efficiency is 23.9-31.4%, the device efficiency is obviously higher than that of the contrast compounds v-DABA, cz-DABA and t-Bucz-DABA, and the device has narrower electroluminescent spectrums, and the half-peak width is less than 20nm.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with the preparation examples of the present invention, and it is apparent that the preparation examples described are only some of the preparation examples of the present invention, but not all of the preparation examples. All other examples of preparation, which a person of ordinary skill in the art would obtain without undue effort based on the examples of preparation in the present invention, are within the scope of the present invention.
The invention provides an organoboron fused ring compound, which is shown as a formula I-A or a formula I-B:
wherein m is 1 And m 2 Each independently is an integer of 1 to 4, and may be 1, 2, 3, 4; n is n 1 、n 4 Each independently is an integer of 1 to 4, and may be 1, 2, 3, 4; n is n 2 、n 3 Each independently is an integer of 1 to 5, and may be 1, 2, 3, 4, 5;
wherein X is 1 And X 2 Independently selected from N (R) a ) O, S, se or Te, said N (R a ) R in O a Independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbon groups, substituted or unsubstituted C1-C30 branched hydrocarbon groups, substituted or unsubstituted C1-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aryl groups, or substituted or unsubstitutedUnsubstituted C5-C60 heteroaryl, wherein the heteroatoms in the heteroaryl are independently selected from Si, ge, N, P, O, S or Se;
R a and is connected to X 1 ～X 4 The benzene rings of (C) may be linked by a single bond, -O-, -S-, or, And->Any one or more of which are linked together.
Wherein L is 1 And L 2 Independently selected from the group consisting of a carbon-carbon single bond, an ether oxygen bond, a thioether bond, a seleno ether bond, a substituted or unsubstituted C1-C30 linear hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, and a substituted or unsubstituted C1-C30 alkylthio group;
or L 1 And L 2 Each independently selected from any one of U-1 to U-18:
A 1 any one selected from the groups shown in formulas 1 to 56:
La-Lc are each independently selected from H, D, F, cl, br, I, -CN, -NO 2 、 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se. / >
R 1 ～R 11 Are each independently selected from H, D, F, cl, br, I, -CN, A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group;
R 1 、R 2 and R is 3 Each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se;
or said R 1 、R 2 And R is 3 Can be mutually connected by a single bond of carbon-carbon, O-, -S-, and, And->One or more of the connections in (a).
Wherein Q is independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; the hetero atom in the heteroaryl group is selected from one or more of Si, ge, N, P, O, S and Se;
Or Q is selected from any one of Q-1 to Q-33:
the substituted or unsubstituted group may be any one or more selected from the group consisting of D, methyl, isopropyl, t-butyl, n-butyl, cyclohexyl, methoxy, methylthio, phenyl, xylyl, t-butylphenyl, 2,4, 6-trimethylphenyl, phenylene ether, phenylthio, phenylselenoether, furyl and pyridyl.
In some preferred embodiments of the present invention, the organoboron fused ring compound has a structure represented by formula I-A or formula I-B, wherein theSelected from the following structures: />
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In some preferred embodiments of the present invention, the organoboron fused ring compound has a structure represented by formula I-A or formula I-B, wherein theSelected from the following structures: />
In some embodiments of the invention, the organoboron fused ring compound containing a carbazole moiety has a structure represented by any one of formulas I-1 to 192;
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the invention also provides a preparation method of the boron-containing organic condensed-cyclic compound in the technical scheme, which comprises the following steps:
reacting a compound shown in a formula II with a compound shown in a formula III in a solvent to obtain a fused ring compound shown in a formula I-A or a formula I-B;
Wherein, the compound structure shown in formula II:
wherein the compound shown in the formula III comprises a structure shown in a formula III-1, a formula III-2 or a formula III-3:
wherein Lu 1 、Lu 2 、Lu 3 Each independently selected from halogen,
The compounds of formula II and formula III are the same as those described in the previous technical schemes, and are not described in detail herein.
In the present invention, the compound represented by the formula II is preferably produced by the following two production methods:
first kind:
s1, compound Ar 1 ' with Compound Ar 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 4 ′；
S2, compound Ar 4 ' and BI 3 Reacting to form a compound shown in a formula II;
second kind:
s3, compound Ar 5 ' with Compound Ar 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 6 ′；
S4, compound Ar 6 ' formation of Compound Ar by nitroreduction reaction 7 ′；
S5, compound Ar 7 ' formation of Compound Ar by diazotisation reaction 8 ′；
S6, compound Ar 8 ' and BBr 3 Reacting to form a compound shown in a formula II;
the compound Ar' is a compound Ar 2 ' and/or Compound Ar 3 ′；
Wherein:
ar (Ar) 1 ′～Ar 8 X, R and n in' are the same as those in the previous technical scheme, and are not described in detail herein.
Regarding step S1:
the reaction is preferably carried out under the action of a catalyst. The catalyst is preferably Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 One or more of NaH, naOH and KOH. The catalyst and the compound Ar 1 ' Compound Ar 2 ' sum Compound Ar 3 The molar ratio of' is (0.5-8) to 1:1.05:1.05.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of N-methylpyrrolidone (NMP), N-Dimethylethylenediamine (DMF), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The ratio of the organic solvent to the compound Ar1' is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 25-180 ℃, preferably 50-120 ℃; the reaction time is preferably 4 to 48 hours, preferably 8 to 24 hours. After the reaction, a compound Ar is generated in the system 4 ′。
Regarding step S2:
the reaction is preferably carried out under the action of boron triiodide. The molar ratio of the boron triiodide to the compound C is preferably (1-5) to 1, and is preferably (2-4) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of chlorobenzene, o-dichlorobenzene, 1,2, 4-trichlorobenzene and tert-butylbenzene. The organic solvent and the compound Ar 4 The ratio of the amount of the catalyst to be used is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol. The organic solvent is preferably a dry organic solvent.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 90-200 ℃, preferably 120-150 ℃; the reaction time is preferably 8 to 48 hours, preferably 12 to 24 hours. After the above reaction, a condensed ring intermediate represented by formula (II) is formed in the system.
Specifically, in the above process, the mixing sequence of each material is preferably: first, compound Ar 4 Mixing' with boron triiodide, introducing organic solvent, adding all materials, and heating to the reaction temperature to react. After the reaction, a condensed ring intermediate represented by formula (II) is produced in the system.
Regarding step S3:
the reaction is preferably carried out under the action of a base. The base is preferably Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 One or more of NaH, naOH and KOH. The base is combined with a compound Ar 5 The molar ratio of' is preferably (0.5About 8) to 1, preferably (1 to 5) to 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of N-methyl pyrrolidone (NMP), N-dimethyl ethylenediamine (DMF), dimethyl sulfoxide (DMSO), 1, 4-dioxane and tetrahydrofuran. The organic solvent and the compound Ar 5 The ratio of the amount of the catalyst to be used is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 25 to 180 ℃, more preferably 50 to 100 ℃; the reaction time is preferably 4 to 48 hours, more preferably 8 to 24 hours. After the reaction, a compound Ar is generated in the system 6 ′。
Regarding step S4:
the reaction is preferably performed as a nitroreduction reaction. The reducing agent is preferably one of iron powder, hydrogen, sodium sulfide and sodium disulfide. The reducing agent and the compound Ar 6 The molar ratio of `' is preferably (2 to 20): 1, more preferably (5 to 10): 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of glacial acetic acid, benzene, toluene, acetonitrile, dichloromethane and tetrahydrofuran. The organic solvent and the compound Ar 6 The ratio of the amount of the catalyst to be used is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol.
The temperature of the reaction is preferably-20 to 150 ℃, more preferably 20 to 100 ℃; the reaction time is preferably 4 to 48 hours, more preferably 8 to 24 hours. After the reaction, a compound Ar is generated in the system 7 ′。
Regarding step S5:
the reaction is preferably carried out as a diazotisation reaction. The diazotizing agent is preferably one of sodium nitrite, amyl nitrite, butyl nitrite and tert-butyl nitrite. The saidDiazotizing agent and compound Ar 7 The molar ratio of `' is preferably (0.5 to 5): 1, more preferably (1 to 3): 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of glacial acetic acid, acetonitrile, dimethylformamide and tetrahydrofuran. The organic solvent and the compound Ar 7 The ratio of the amount of the catalyst to be used is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol.
The temperature of the reaction is preferably-20 to 80 ℃, more preferably 20 to 50 ℃; the reaction time is preferably 4 to 48 hours, more preferably 8 to 24 hours. After the reaction, a compound Ar is generated in the system 8 ′。
Regarding step S6:
the reaction is preferably carried out under the action of butyllithium. The butyllithium is preferably n-BuLi (i.e., n-butyllithium) and tert-BuLi (i.e., tert-butyllithium). The butyl lithium and the compound Ar 8 The molar ratio of `' is preferably (1 to 5): 1, more preferably (2 to 3): 1.
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of o-xylene, m-xylene, p-xylene, isopropyl benzene and tert-butylbenzene. The organic solvent and the compound Ar 8 The ratio of the amount of the catalyst to be used is preferably (50-500) mL to (0.1-10) mol, more preferably (100-200) mL to (1-5) mol. The organic solvent is preferably a dry organic solvent.
Said BBr 3 (i.e., boron tribromide) with Compound Ar 8 The molar ratio of `' is preferably (1 to 10): 1, more preferably (2 to 5): 1.
The reaction is preferably carried out in the presence of an organic amine base for neutralizing the acid during the reaction. The organic amine base is preferably N, N-diisopropylethylamine and/or triethylamine. The organic amine base and the compound Ar 8 The molar ratio of `' is preferably (1 to 10): 1, more preferably (2 to 5): 1.
The reaction is preferably carried out under a protective atmosphere. The protective gas for providing the protective atmosphere is not particularly limited, and the protective gas is conventional protective gas in the field, such as nitrogen, helium or argon.
The temperature of the reaction is preferably 90 to 200 ℃, more preferably 120 to 150 ℃; the reaction time is preferably 8 to 48 hours, more preferably 12 to 24 hours. After the above reaction, a condensed ring intermediate represented by formula (II) is formed in the system.
Specifically, in the above process, the mixing sequence of each material is preferably: first, compound Ar 8 ' mixing with an organic solvent, then dropwise adding butyl lithium at a first temperature, dropwise adding BBr3 at a second temperature after the dropwise adding is finished, and stirring and mixing at a third temperature after the dropwise adding is finished; then, at a fourth temperature, an organic amine base is added dropwise. After the dripping is finished, the temperature is raised to the reaction temperature to react, and the compound E is generated. Wherein the first temperature is a low temperature of below 0 ℃, specifically-5 to-78 ℃. The second temperature is also a low temperature below 0 ℃, and can be specifically between-5 ℃ and-78 ℃; preferably the same as the first temperature. The third temperature is preferably room temperature, and may specifically be 20 to 40 ℃. The stirring and mixing time is preferably 0.5 to 6 hours. The fourth temperature <The third temperature, namely, after stirring and mixing, cooling and then dropwise adding organic amine alkali; specifically, the fourth temperature is-78-0 ℃. After all materials are added, the temperature is raised to the reaction temperature for reaction. After the reaction, a condensed ring intermediate shown in the formula II is generated in the system.
The invention also provides application of the condensed-ring compound shown in the formula I-A and the formula I-B in electroluminescent devices.
The invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic film layer positioned between the anode and the cathode; the organic film layer comprises a fused ring compound shown in the formula I-A and the formula I-B.
The structure of the organic electroluminescent device is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the application situation, quality requirements and product requirements by using a conventional organic electroluminescent device well known to the person skilled in the art, and the structure of the organic electroluminescent device preferably comprises: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.
The thickness of the substrate is preferably 0.3 to 0.7mm, more preferably 0.4 to 0.6mm; the choice of the substrate is not particularly limited and may be any substrate known to those skilled in the art for conventional organic electroluminescent devices, and may be chosen and adjusted by those skilled in the art according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.
According to the present invention, the anode is preferably a material that facilitates hole injection, more preferably a conductive metal or conductive metal oxide, and still more preferably indium tin oxide.
The organic film layer can be one layer or a plurality of layers, and at least one layer is a light-emitting layer; the light-emitting layer comprises dendritic organic condensed ring compounds shown in the formula I-A and the formula I-B; preferably, the light-emitting layer is directly composed of the condensed ring compound shown in the formulas I-A and I-B.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light emitting layer and the cathode preferably further includes one or more of a hole blocking layer and an electron injection layer and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the process for preparing the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron injection layer and the electron transport layer, and preferably, the present invention is prepared by using a process of vacuum evaporation, solution spin coating, solution doctor blading, ink-jet printing, offset printing and three-dimensional printing. The present invention is not particularly limited in the process for preparing the organic electroluminescent layer, and is preferably prepared using processes of solution spin coating, solution blade coating, inkjet printing, offset printing and three-dimensional printing.
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, including a light emitting layer; forming a cathode on the organic thin film layer;
the light-emitting layer includes one or more compounds represented by the formula (I-1) and the formula (I-2).
The structure and the materials of the organic electroluminescent device and the corresponding preferred principles of the preparation method of the invention can correspond to the corresponding materials and structures of the organic electroluminescent device and the corresponding preferred principles, and are not described in detail herein.
The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. And then forming an organic thin film layer below the light emitting layer, and an organic thin film layer above the light emitting layer on the anode. The method of forming the organic thin film layer below and above the light-emitting layer is not particularly limited, and the organic thin film layer may be formed by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. The formation mode of the light emitting layer is not particularly limited, and may be formed by solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited as to the manner of forming the cathode after the formation of the above-mentioned organic layer, and is preferably a method known to those skilled in the art, including but not limited to vacuum deposition, for preparing the cathode on the surface thereof.
The test shows that the organic fused ring compound provided by the invention is used as a luminescent material in an organic electroluminescent device, has very high luminous efficiency, the maximum external quantum efficiency is 23.9-31.4%, the device efficiency is obviously higher than that of the contrast compounds v-DABA, cz-DABA and t-BuCz-DABA, and the electroluminescent device has narrower electroluminescent spectrum, and the half-peak width is less than 20nm.
In order to further illustrate the present invention, the following preparation examples and preparation examples are described in detail. The experimental materials used in the following preparation examples and preparation examples of the present invention are all generally commercially available.
Preparation example 1
The preparation example provides a fused ring compound shown as a formula I-1, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 was prepared according to the synthetic route described in the document Angew.chem.int.ed.2023, e 202313084.
1-1 (8.3 g,10 mmol), 3, 6-di-tert-butylcarbazole (2.8 g,10 mmol), pd in a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (0.46g，0.5mmol)，t-Bu 3 PHBF 4 (0.58 g,2 mmol), t-Buona (1.92 g,20 mmol) and then 50mL toluene were injected and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 1-2 (5.9 g, yield: 55%). Elemental analysis: theoretical value C,82.73; h,5.44; n,6.52; test value C,83.11; h,5.50; n,6.57. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1073.4; experimental value 1073.4 (m+).
1-2 (1.1 g,1 mmol), 2, 6-dimethylbenzeneboronic acid (0.18 g,1.2 mmol) and the catalyst Pd were placed in a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. Adding anhydrous sodium sulfate, drying, and removing the organic phaseThe solvent was removed and the crude product was isolated by column to give fused ring compound I-1 (0.74 g, yield: 65%). Elemental analysis: theoretical value C,86.09; h,5.90; n,6.12; test value C,86.14; h,5.88; n,6.22.MALDI-TOF (m/z): theoretical value 1143.5; experimental values 1143.5 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 1 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 2
The preparation example provides a fused ring compound shown as a formula I-7, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-2 (1.1 g,1 mmol), 4-phenyl-9H-carbazole (0.29 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-7 (0.77 g, yield: 60%). Elemental analysis: theoretical value C,86.25; h,5.51; n,6.56; test value C,86.30; h,5.46; n,6.61. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1280.5; experimental value 1280.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 2 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 3
The preparation example provides a fused ring compound shown as a formula I-9, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-2 (1.1 g,1 mmol), 9H-pyridine [3,4-b ] was added to a 50mL Schlenk flask under argon atmosphere]Indole (0.2 g,1.2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-9 (0.74 g, yield: 61%). Elemental analysis: theoretical value C,84.65; h,5.43; n,8.13; test value C,84.67; h,5.42; n,8.16. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1205.5; experimental value 1205.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 3 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 4
The preparation example provides a fused ring compound shown as a formula I-10, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-2 (1.1 g,1 mmol) of benzimidazole was added to a 50mL Schlenk flask under an argon atmosphere<1，2-A>Benzimidazole (0.25 g,1.2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating the organic phase, separating by column, and desolventizing to obtain condensed ringCompound I-10 (0.62 g, yield: 50%). Elemental analysis: theoretical value C,83.92; h,5.34; n,9.00; test value C,83.93; h,5.29; n,9.07. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1244.5; experimental value 1244.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 4 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 5
The preparation example provides a fused ring compound shown as a formula I-14, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-2 (1.1 g,1 mmol), 3- (2-dibenzofuran) -9H-carbazole (0.4 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-14 (0.62 g, yield: 50%). Elemental analysis: theoretical value C,85.84; h,5.29; n,6.13; test value C,85.81; h,5.22; n,6.16. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1370.6; experimental value 1370.6 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 5 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 6
The preparation example provides a fused ring compound shown as a formula I-23, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 3, 6-di-tert-butyl-1, 8-diphenyl-9H-carbazole (1.08 g,2.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-23 (0.65 g, yield: 41%). Elemental analysis: theoretical value C,87.39; h,6.09; n,5.18; test value C,87.33; h,6.04; n,5.21. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1620.8; experimental value 1620.8 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 6 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 7
The preparation example provides a fused ring compound shown as a formula I-25, and the synthetic route is as follows:
/>
the preparation method comprises the following specific steps:
7-1 (6.33 g,30 mmol), m-dibromobenzene (1.08 g,10 mmol), pd were added to a 250mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol), BINAP (124 mg,0.2 mmol), t-Buona (3.9 g,40 mmol), and then 100mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and 200mL of dichloromethane for extraction, and washing with deionized water for multiple times. Separating the organic phase, separating with column, and removing solvent to obtain compound 7-2 (2.78) g, yield: 56%). Elemental analysis: theoretical value C,87.05; h,7.31; n,5.64; test value C,87.01; h,7.29; n,5.70. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 496.3; experimental 496.3 (m+).
7-2 (2.48 g,5 mmol), (3, 5-dichlorophenyl) -diphenylamine (3.78 g,12 mmol), pd in a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 7-3 (2.78 g, yield: 53%). Elemental analysis: theoretical value C,82.19; h,5.75; n,5.32; test value C,82.12; h,5.71; n,5.38. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1050.4; experimental value 1050.4 (m+).
7-3 (1 g,1 mmol), boron triiodide (1.57 g,4 mmol) and dried o-dichlorobenzene (20 mL) were weighed out in a 100mL two-necked flask under argon atmosphere, and heated to 90℃for reaction for 10 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (0.52 g,4 mmol) was added dropwise to the reaction system, after the completion of the addition, methylene chloride and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 7-4 (0.22 g, yield: 21%) was obtained by column separation. Elemental analysis: theoretical value C,80.99; h,5.10; n,5.25; test value C,80.93; h,5.12; n,5.23.MALDI-TOF (m/z): theoretical value 1066.4; experimental value 1066.4 (m+).
7-4 (0.21 g,0.2 mmol), 3, 6-di-tert-butylcarbazole (0.14 g,0.5 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (9.2mg，0.01mmol)，t-Bu 3 PHBF 4 (11.6 mg,0.04 mmol), t-Buona (39 mg,0.4 mmol), then 10mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating organic phase, separating by column, and desolventizingThe reagent gave fused ring compound I-25 (0.15 g, yield: 48%). Elemental analysis: theoretical value C,86.58; h,6.62; n,5.41; test value C,86.54; h,6.65; n,5.43. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1552.8; experimental value 1552.8 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 7 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 8
The preparation example provides a fused ring compound shown as a formula I-26, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
aniline (2.8 g,30 mmol), 1, 3-dibromo-2, 5-xylene (2.6 g,10 mmol), pd were added to a 250mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol), BINAP (124 mg,0.2 mmol), t-Buona (3.9 g,40 mmol), then 50mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and 200mL of dichloromethane for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give Compound 8-1 (1.9 g, yield: 66%). Elemental analysis: theoretical value C,83.30; h,6.99; n,9.71; test value C,83.35; h,6.93; n,9.72. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 288.1; experimental value 288.1 (m+).
In a 100mL Schlenk flask under argon was added 8-1 (1.44 g,5 mmol), (3, 5-dichlorophenyl) -diphenylamine (3.78 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating the organic phase, separating by columnThe solvent was removed to give Compound 8-2 (2.1 g, yield: 50%). Elemental analysis: theoretical value C,79.70; h,5.26; n,6.64; test value C,79.71; h,5.23; n,6.68. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 842.3; experimental value 842.3 (m+).
8-2 (1.7 g,2 mmol), boron triiodide (3.14 g,8 mmol) and dried o-dichlorobenzene (20 mL) were weighed out in a 100mL two-necked flask under argon atmosphere, and heated to 90℃for reaction for 10 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (1.04 g,8 mmol) was added dropwise to the reaction system, after the completion of the addition, methylene chloride and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent and separated by column to give the product 8-3 (0.26 g, yield: 15%). Elemental analysis: theoretical value C,78.26; h,4.46; n,6.52; test value C,78.22; h,4.47; n,6.55.MALDI-TOF (m/z): theoretical value 858.2; experimental value 858.2 (m+).
In a 50mL Schlenk flask under argon was added 8-3 (0.17 g,0.2 mmol), 3, 6-di-tert-butylcarbazole (0.14 g,0.5 mmol), pd 2 (dba) 3 (9.2mg，0.01mmol)，t-Bu 3 PHBF 4 (11.6 mg,0.04 mmol), t-Buona (39 mg,0.4 mmol), then 10mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-26 (0.13 g, yield: 50%). Elemental analysis: theoretical value C,85.70; h,6.44; n,6.25; test value C,85.74; h,6.48; n,6.29. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1344.7; experimental value 1344.7 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 8 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 9
The preparation example provides a fused ring compound shown as a formula I-29, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 6H-dibenzo [ B, H ] was placed in a 50mL Schlenk flask under argon atmosphere]Carbazole (0.67 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-29 (0.52 g, yield: 40%). Elemental analysis: theoretical value C,87.31; h,4.52; n,6.50; test value C,87.35; h,4.52; n,6.53. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1292.5; experimental value 1292.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 9 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 10
The preparation example provides a fused ring compound shown as a formula I-30, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 5, 7-dihydro-7, 7-dimethyl-indeno [2,1-B ] was introduced into a 50mL Schlenk flask under an argon atmosphere]Carbazole (0.71 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating outThe organic phase was separated by column and desolvated to give the fused ring compound I-30 (0.50 g, yield: 38%). Elemental analysis: theoretical value C,87.01; h,5.02; n,6.34; test value C,87.06; h,5.01; n,6.36. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1324.5; experimental value 1324.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 10 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 11
The preparation example provides a fused ring compound shown as a formula I-31, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol) 7H-benzofuran [2,3-B ] was charged in a 50mL Schlenk flask under argon atmosphere]Carbazole (0.64 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-31 (0.56 g, yield: 44%). Elemental analysis: theoretical value C,84.91; h,4.28; n,6.60; test value C,84.95; h,4.26; n,6.62. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1272.4; experimental value 1272.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 11 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 12
The preparation example provides a fused ring compound shown as a formula I-32, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 11H-benzo [4,5 ] in a 50mL Schlenk flask under argon ]Thieno [3,2-B]Carbazole (0.68 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-32 (0.56 g, yield: 43%). Elemental analysis: theoretical value C,82.82; h,4.17; n,6.44; test value C,82.85; h,4.11; n,6.43. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1304.4; experimental value 1304.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 12 of the present invention were examined.
Referring to Table 1, table 1 shows the photophysical properties of the fused ring compounds prepared according to the preparation examples of the present invention
Preparation example 13
The preparation example provides a fused ring compound shown as a formula I-33, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 5, 7-dihydro-5-phenylindolo [2,3-B ] was added to a 50mL Schlenk flask under an argon atmosphere]Carbazole (0.83 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane 100mL extraction and washing with deionized water multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-33 (0.57 g, yield: 40%). Elemental analysis: theoretical value C,86.08; h,4.53; n,7.87; test value C,86.02; h,4.56; n,7.88. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1422.5; experimental value 1422.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 13 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 14
The preparation example provides a fused ring compound shown as a formula I-34, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 3,9' -dicarbazole (0.83 g,2.5 mmol), pd were added to a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the fused ring compound I-34 (0.60 g, yield: 42%). Elemental analysis: theoretical value C,86.08; h,4.53; n,7.87; test value C,86.10; h,4.54; n,7.85. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1422.5; experimental value 1422.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 14 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 15
The preparation example provides a fused ring compound shown as a formula I-35, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 9' -phenyl-9H, 9H ' -3,3' -carbazole (1.02 g,2.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol), t-Bu3PHBF4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) and then 20mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-35 (0.64 g, yield: 41%). Elemental analysis: theoretical value C,86.91; h,4.61; n,7.11; test value C,86.95; h,4.60; n,7.12. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1574.6; experimental value 1574.6 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 15 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 16
The preparation example provides a fused ring compound shown as a formula I-36, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 5, 10-diphenyl-10, 15-dihydro-5H-diindolo [3,2-A ] was added to a 50mL Schlenk flask under an argon atmosphere: 3',2' -C]Carbazole (1.24 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol), then 20mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-36 (0.52 g, yield: 30%). Elemental analysis: theoretical value C,86.30; h,4.48; n,7.99; test value C,86.33; h,4.50; n,7.92. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1752.6; experimental value 1752.6 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 16 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 17
The preparation example provides a fused ring compound shown as a formula I-37, and the synthetic route is as follows:
The preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol) of N-phenyl-3-carbazoleboronic acid (0.72 g,2.5 mmol), pd, was added to a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-37 (0.75 g, yield: 60%). Elemental analysis: theoretical value C,86.82; h,4.70; n,6.75; test value C,86.81; h,4.69; n,6.77.MALDI-TOF (m/z): theoretical value 1244.5; experimental values 1244.5 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 17 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 18
The preparation example provides a fused ring compound shown as a formula I-44, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (2.5 g,3 mmol) and a boronate ester (1.5 g,6 mmol) were weighed out in a 100mL two-necked flask under argon atmosphere, pdCl 2 (dppf) (0.11 g,0.15 mmol), potassium acetate (0.6 g,6 mmol), 40mL of DMF was taken and added to the flask, and the temperature was raised to 85℃and the reaction was stirred for 10 hours. Then cooled to room temperature, the reaction solution was washed with deionized water, extracted with methylene chloride solution to give an organic phase which was concentrated and dried, and the crude product was separated by column to give the product 18-1 (1.4 g, yield: 46%). Elemental analysis: theoretical value C,78.14; h,5.76; n,5.52; test value C,78.12; h,5.71; n,5.54.MALDI-TOF (m/z): theoretical 1014.5; experimental value 1014.5 (M+)
9- (4-bromo-3, 5-dimethyl-phenyl) -3, 6-di-tert-butylcarbazole (0.51 g,1.1 mmol), 18-1 (0.51 g,0.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give fused ring compound I-44 (0.34 g, yield: 45%). Elemental analysis: theoretical value C,86.60; h,6.47; n,5.51; test value C,86.61; h,6.43; n,5.52.MALDI-TOF (m/z): theoretical value 1524.8; experimental values 1524.8 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 18 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 19
The preparation example provides a fused ring compound shown as a formula I-47, and the synthetic route is as follows:
3,9' -Bicarbazole (7.3 g,22 mol), 2-bromo-4-fluorotoluene (3.78 g,20 mol) and Cs were weighed in a 250mL three-necked flask under an argon atmosphere 2 CO 3 (13.0 g,40 mol) 80mL of DMF was taken in a bottle, warmed to 90℃and stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 19-1 (7.1 g, yield: 71%). Elemental analysis: theoretical value C,74.26; h,4.22; n,5.59; test value C,74.22; h,4.24; n,5.57.MALDI-TOF (m/z): theoretical 500.0; experimental 500.0 (m+).
19-1 (0.55 g,1.1 mmol), 18-1 (0.51 g,0.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-47 (0.40 g, yield: 50%). Elemental analysis: theoretical value C,86.89; h,4.78; n,6.99; test value C,86.83; h,4.74; n,7.02.MALDI-TOF (m/z): theoretical value 1602.6; experimental values 1602.6 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 19 of the present invention were examined.
Referring to Table 1, table 1 shows the photophysical properties of the fused ring compounds prepared according to the preparation examples of the present invention
Preparation example 20
The preparation example provides a fused ring compound shown as a formula I-48, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
3,9' -Bicarbazole (7.3 g,22 mol), 2-bromo-5-fluoro-1, 3-xylene (4.06 g,20 mol) and Cs were weighed in a 250mL three-necked flask under argon atmosphere 2 CO 3 (13.0 g,40 mol) 80mL of DMF was taken in a bottle, warmed to 90℃and stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated off, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give the product 20-1 (7.2 g, yield: 70%). Elemental analysis: theoretical value C,74.57; h,4.50; n,5.43; test value C,74.54; h,4.52; n,5.42.MALDI-TOF (m/z): theoretical 514.1; experimental 514.1 (m+).
20-1 (0.56 g,1.1 mmol), 18-1 (0.51 g,0.5 mmol), pd were added to a 50mL Schlenk flask under argon 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-48 (0.33 g, yield: 40%). Elemental analysis: theoretical value C,86.89; h,4.78; n,6.99; test value C,86.83; h,4.74; n,7.02.MALDI-TOF (m/z): theoretical value 1630.6; experimental values 1630.6 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 20 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 21
The preparation example provides a fused ring compound shown as a formula I-56, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
9,9' - (5-bromo-1, 3-phenylene) bis (9H-carbazole) (0.54 g,1.1 mmol), 18-1 (0.51 g,0.5 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol) and ligand S-phos (164 mg,0.4 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.54 g,4 mmol) was dissolved in 2mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-56 (0.27 g, yield: 35%). Elemental analysis: theoretical value C,86.91; h,4.61; n,7.11; test value C,86.95; h,4.60; n,7.06.MALDI-TOF (m/z): theoretical value 1574.6; experimental value 1574.6 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 21 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 22
The preparation example provides a fused ring compound shown as a formula I-57, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
3- (9H-carbazol-9-yl) phenol (0.73 g,2.2 mmol) was weighed in a 50mL three-necked flask under argon atmosphere,18-1 (1.0 g,1 mmol), and Cs 2 CO 3 (1.3 g,4 mmol) 20mL of DMF was taken and added to a bottle, the temperature was raised to 120℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a thick ring compound I-57 (0.65 g, yield: 51%). Elemental analysis: theoretical value C,84.64; h,4.58; n,6.58; test value C,84.68; h,4.55; n,6.53.MALDI-TOF (m/z): theoretical value 1276.4; experimental value 1276.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 22 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 23
The preparation example provides a fused ring compound shown as a formula I-65, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 3-phenyl-9H carbazole (0.61 g,2.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-65 (0.75 g, yield: 60%). Elemental analysis: theoretical value C,86.82; h,4.70; n,6.75; test value C,86.81; h,4.68; n,6.77. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1244.5; experimental value 1244.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 23 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 24
The preparation example provides a fused ring compound shown as a formula I-102, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 3-phenyl-9H carbazole (0.24 g,1 mmol), pd were added to a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol), t-Bu3PHBF4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 24-1 (0.5 g, yield: 48%). Elemental analysis: theoretical value C,83.29; h,4.47; n,6.75; test value C,83.33; h,4.46; n,6.69. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1037.3; experimental value 1037.3 (m+).
Triphenylene-2-boronic acid (0.16 g,0.6 mmol), 24-1 (0.51 g,0.5 mmol), pd were placed in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-102 (0.4 g, yield: 65%). Elemental analysis: theoretical value C,87.88; h,4.67; n,5.69; test value C,87.85; h,4.66; n,5.67.MALDI-TOF (m/z): theoretical 1229..5; experimental value 1229..5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 24 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 25
The preparation example provides a fused ring compound shown as a formula I-133, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (1.66 g,2 mmol), 11H-benzofuro [3,2-B ] was placed in a 50mL Schlenk flask under argon]Carbazole (0.52 g,2 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 25-1 (1.06 g, yield: 51%). Elemental analysis: theoretical value C,82.18; h,4.21; n,6.66; test value C,82.14; h,4.19; n,6.69; . Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 1051.3; experimental value 1051.3 (m+).
25-1 (1.0 g,1 mmol), 5-phenyl-5, 11-indolino [3,2-B ] carbazole (0.4 g,1.2 mmol), pd2 (dba) 3 (46 mg,0.05 mmol), t-Bu3PHBF4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) were added to a 50mL Schlenk flask under argon, followed by 20mL toluene and reaction at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-133 (0.60 g, yield: 45%). Elemental analysis: theoretical value C,85.53; h,4.41; n,7.27; test value C,85.56; h,4.36; n,7.29. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1347.5; experimental value 1347.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 25 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 26
The preparation example provides a fused ring compound shown as a formula I-134, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (1.66 g,2 mmol), 7H-benzofuran [2,3-B ] was prepared in a 50mL Schlenk flask under argon]Carbazole (0.52 g,2 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 26-1 (0.95 g, yield: 45%). Elemental analysis: theoretical value C,82.18; h,4.21; n,6.66; test value C,82.15; h,4.22; n,6.63; . Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 1051.3; experimental value 1051.3 (m+).
26-1 (1.0 g,1 mmol), 2, 3-benzocarbazole (0.26 g,1.2 mmol), pd2 (dba) 3 (46 mg,0.05 mmol), t-Bu3PHBF4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, followed by injection of 20mL toluene and reaction at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-134 (0.67 g, yield: 55%). Elemental analysis: theoretical value C,85.72; h,4.41; n,6.82; test value C,85.69; h,4.41; n,6.83. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1232.4; experimental value 1232.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 26 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 27
The preparation example provides a fused ring compound shown as a formula I-135, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (1.66 g,2 mmol), 3, 6-diphenyl-9H-carbazole (0.64 g,2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92 mg,0.1 mmol), t-Bu3PHBF4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) and then 20mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 27-1 (1.22 g, yield: 55%). Elemental analysis: theoretical value C,84.07; h,4.52; n,6.28; test value C,84.10; h,4.51; n,6.24. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1113.4; experimental value 1113.4 (m+).
27-1 (1.1 g,1 mmol), 2, 7-diphenyl-9H-carbazole (0.38 g,1.2 mmol), pd was added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-135 (0.64 g, yield: 46%). Elemental analysis: theoretical value C,87.68; h,4.76; n,6.01; test value C,87.64; h,4.73; n,6.02. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1396.5; experimental value 1396.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 27 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 28
The preparation example provides a fused ring compound shown in the formula I-138, and the synthetic route is as follows:
27-1 (1.0 g,1 mmol), 9' -phenyl-9H, 9H ' -3,3' -carbazole (0.49 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-138 (0.61 g, yield: 41%). Elemental analysis: theoretical value C,87.27; h,4.68; n,6.60; test value C,87.23; h,4.65; n,6.62. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1485.5; experimental value 1485.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 28 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 29
The preparation example provides a fused ring compound shown as a formula I-139, and the synthetic route is as follows:
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the preparation method comprises the following specific steps:
1-bromo-N-phenylcarbazole (0.39 g,1.1 mmol), 18 in a 50mL Schlenk flask under argon atmosphere-1(0.51g，1mmol)，Pd 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column chromatography to give compound 29-1 (0.59 g, yield: 52%). Elemental analysis: theoretical value C,82.92; h,5.17; n,6.20; test value C,82.97; h,5.15; n,6.18.MALDI-TOF (m/z): theoretical value 1129.5; experimental values 1129.5 (M+)
9- (4-bromo-3, 5-dimethyl-phenyl) -3, 6-di-tert-butylcarbazole (0.21 g,0.6 mmol), 29-1 (0.56 g,0.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-139 (0.22 g, yield: 35%). Elemental analysis: theoretical value C,86.79; h,4.91; n,6.60; test value C,86.76; h,4.89; n,6.64.MALDI-TOF (m/z): theoretical value 1272.5; experimental values 1272.5 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 29 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 30
The preparation example provides a fused ring compound shown as the formula I-140, and the synthetic route is as follows:
9,9' - (5-bromo-1, 3-phenylene) bis (9H-carbazole) (0.54 g,1.1 mmol), 18-1 (0.51 g,1 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give compound 30-1 (0.66 g, yield: 51%). Elemental analysis: theoretical value C,83.48; h,5.06; n,6.49; test value C,83.46; h,5.10; n,6.45.MALDI-TOF (m/z): theoretical value 1294.5; experimental value 1294.5 (m+).
2-bromo-1, 3, 5-trimethylbenzene (0.12 g,0.6 mmol), 30-1 (0.65 g,0.5 mmol), pd in a 50mL Schlenk flask under argon 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-140 (0.28 g, yield: 44%). Elemental analysis: theoretical value C,86.78; h,5.01; n,6.53; test value C,86.75; h,5.02; n,6.53.MALDI-TOF (m/z): theoretical 1286.5; experimental 1286.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 30 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 31
The preparation example provides a fused ring compound shown as a formula I-141, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (1.66 g,2 mmol), 9H-pyridine [3,4-b ] was added to a 50mL Schlenk flask under argon atmosphere ]Indole (0.34 g,2 mmol), pd 2 (dba) 3 (92 mg,0.1 mmol), t-Bu3PHBF4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) and then 20mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 31-1 (1.08 g, yield: 56%). Elemental analysis: theoretical value C,81.06; h,4.29; n,8.73; test value C,81.03; h,4.26; n,8.74. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 962.3; experimental value 962.3 (m+).
3, 5-bis (9H-carbazol-9-yl) phenylboronic acid (0.5 g,1.1 mmol), 31-1 (0.96 g,1 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give fused ring compound I-141 (0.64 g, yield: 48%). Elemental analysis: theoretical value C,85.46; h,4.53; n,8.39; test value C,85.43; h,4.55; n,8.36.MALDI-TOF (m/z): theoretical value 1334.5; experimental value 1334.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 31 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 32
The preparation example provides a fused ring compound shown as a formula I-142, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (1.0 g,1 mmol), 9' -phenyl-9H, 9H ' -3,3' -carbazole (0.49 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 32-1 (0.64 g, yield: 53%). Elemental analysis: theoretical value C,83.83; h,4.44; n,6.98; test value C,83.81; h,4.46; n,6.95. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1202.4; experimental value 1202.4 (m+).
In a 50mL Schlenk flask under argon was added 3-biphenylboronic acid (0.12 g,0.6 mmol), 32-1 (0.6 g,0.5 mmol), pd 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-142 (0.4 g, yield: 60%). Elemental analysis: theoretical value C,87.27; h,4.73; n,6.36; test value C,87.24; h,4.75; n,6.38.MALDI-TOF (m/z): theoretical value 1320.5; experimental value 1320.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 32 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 33
The preparation example provides a fused ring compound shown as a formula I-151, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
aniline (27.9 g,0.3 mol), 1, 5-dibromo-2, 4-dinitrobenzene (32.6 g,0.1 mol), pd were added to a 500mL Schlenk flask under an argon atmosphere 2 (dba) 3 (0.92 g,1 mmol), BINAP (1.24 g,2 mmol), t-Buona (39.6 g,0.4 mol), and then 200mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and 300mL of dichloromethane for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 33-1 (25.2 g, yield: 72%). Elemental analysis: theoretical value C,61.71; h,4.03; n,15.99; test value C,61.73; h,4.05; n,15.95. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 350.1; experimental value 350.1 (m+).
In a 100mL Schlenk flask under argon was added 33-1 (3.5 g,10 mmol), (3, 5-dichlorophenyl) -diphenylamine (3.78 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 33-2 (3.45 g, yield: 55%). Elemental analysis: theoretical value C,68.84; h,4.17; n,11.15; test value C,68.82; h,4.12; n,11.13. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 627.1; experimental value 627.1 (m+).
In a 100mL Schlenk flask under argon was added 33-2 (6.3 g,10 mmol), 1-bromo-3-chloro-5-phenoxybenzene (3.4 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 33-3 (5.3 g, yield: 64%). Elemental analysis: theoretical C,69.40; h,4.00; n,8.43; test value C,69.38; h,4.01; n,8.42. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 829.2; experimental value 829.2 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 33-3 (8.3 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 33-4 (4.6 g, yield: 60%). Elemental analysis: theoretical value C,74.80; h,4.84; n,9.09; test value C,74.81; h,4.82; n,9.10. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 769.2; experimental 769.2 (m+).
In a 100mL three-port reaction flask, 33-4 (3.84 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 33-5 (2.5 g, yield: 56%). Elemental analysis: theoretical value C,64.16; h,3.70; n,4.68; test value C,64.14; h,3.72; n,4.65. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 895.0; experimental value 895.0 (m+).
33-5 (1.8 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 33-6 (0.5 g, yield: 33%) was obtained by column separation. Elemental analysis: theoretical value C,76.23; h,3.86; n,5.56; test value C,76.21; h,3.87; n,5.59.MALDI-TOF (m/z): theoretical value 755.2; experimental 755.2 (m+).
In a 50mL Schlenk flask under argon was added 33-6 (0.38 g,0.5 mmol), 4-phenyl-9H-carbazole (0.48 g,2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-151 (0.33 g, yield: 56%). Elemental analysis: theoretical value C,86.23; h,4.57; n,5.99; test value C,86.27; h,4.56; n,5.95. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1169.4; experimental value 1169.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 33 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 34
The preparation example provides a fused ring compound shown as a formula I-154, and the synthetic route is as follows:
33-6 (0.75 g,1 mmol), 3, 6-di-tert-butylcarbazole (0.33 g,1.2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 34-1 (0.54 g, yield: 54%). Elemental analysis: theoretical value C,81.73; h,5.35; n,5.61; test value C,81.75; h,5.34; n,5.63. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 998.4; experimental value 998.4 (m+).
N-phenylcarbazole-2-boronic acid (0.17 g,0.6 mmol), 34-1 (0.5 g,0.5 mmol), pd were placed in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give fused ring compound I-154 (0.37 g, yield: 61%). Elemental analysis: theoretical value C,85.64; h,5.43; n,5.81; test value C,85.65; h,5.42; n,5.83.MALDI-TOF (m/z): theoretical value 1205.5; experimental value 1205.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 34 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 35
The preparation example provides a fused ring compound shown as the formula I-163, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-2 (6.3 g,10 mmol), 1-bromo-3-chloro-5-phenylsulfanylbenzene (3.6 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolventization to give compound 35-1 (5.2 g, yield: 62%). Elemental analysis: theoretical value C,68.08; h,3.93; n,8.27; test value C,68.03; h,3.94; n,8.26. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 845.1; experimental value 845.1 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 35-1 (8.4 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 35-2 (4.7 g, yield: 60%). Elemental analysis: theoretical C,73.27; h,4.74; n,8.90; test value C,73.25; h,4.71; n,8.92. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 785.2; experimental values: 785.2 (M+).
In a 100mL three-port reaction flask, 35-2 (3.9 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 35-3 (2.45 g, yield: 54%). Elemental analysis: theoretical value C,63.04; h,3.64; n,4.59; test value C,63.01; h,3.66; n,4.57. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 911.0; experimental value 911.0 (m+).
35-3 (1.8 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 35-4 (0.46 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical value C,76.23; h,3.86; n,5.56; test value C,76.21; h,3.87; n,5.59.MALDI-TOF (m/z): theoretical value 771.1; experimental value 771.1 (m+).
3, 5-bis (9H-carbazol-9-yl) phenylboronic acid (0.5 g,1.1 mmol), 35-4 (0.77 g,1 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as compound 35-5 (0.55 g, yield: 48%). Elemental analysis: theoretical value C,81.86; h,4.23; n,6.12; test value C,81.88; h,4.20; n,6.11.MALDI-TOF (m/z): theoretical value 1143.3; experimental value 1143.3 (m+).
In a 50mL Schlenk flask under argon atmosphere was added 3, 5-dimethyl-4-biphenylboronic acid (0.14 g,0.6 mmol), 35-5 (0.57 g,0.5 mmol), pd 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol), 20mL of toluene was taken and added to a bottle, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, and an aqueous potassium carbonate solution was introduced into the bottle, and the temperature was raised to 100℃under argon The reaction was stirred under gas for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with dichloromethane. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-163 (0.3 g, yield: 46%). Elemental analysis: theoretical value C,85.65; h,4.77; n,5.43; test value C,85.61; h,4.74; n,5.45.MALDI-TOF (m/z): theoretical value 1289.4; experimental value 1289.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 35 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 36
The preparation example provides a fused ring compound shown as a formula I-164, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 50mL Schlenk flask under argon atmosphere was added 35-4 (1.54 g,2 mmol), 3, 6-di-tert-butylcarbazole (0.64 g,2 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 36-1 (1.15 g, yield: 55%). Elemental analysis: theoretical value C,80.44; h,5.26; n,5.52; test value C,80.41; h,5.24; n,5.54. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1014.4; experimental value 1014.4 (m+).
36-1 (1.0 g,1 mmol) 9H-pyridine [3,4-b ] was added to a 50mL Schlenk flask under argon atmosphere]Indole (0.2 g,1.2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58mg，0.2mmol)，t-BuONa(0.19g,2 mmol) and then 20mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-164 (0.54 g, yield: 47%). Elemental analysis: theoretical value C,82.72; h,5.27; n,7.33; test value C,82.70; h,5.24; n,7.35. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1146.4; experimental value 1146.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 36 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 37
The preparation example provides a fused ring compound shown as a formula I-165, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
2, 6-dimethylboronic acid (0.16 g,1.1 mmol), 35-4 (0.77 g,1 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as compound 37-1 (0.46 g, yield: 51%). Elemental analysis: theoretical value C,79.88; h,4.55; n,4.99; test value C,79.87; h,4.52; n,5.01.MALDI-TOF (m/z): theoretical value 841.2; experimental values 841.2 (M+)
N-phenylcarbazole-3-boronic acid (0.17 g,0.6 mmol), 37-1 (0.65 g,0.5 mmol), pd were placed in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give fused ring compound I-165 (0.23 g, yield: 45%). Elemental analysis: theoretical C,84.74; h,4.80; n,5.34; test value C,84.73; h,4.81; n,5.35.MALDI-TOF (m/z): theoretical value 1048.4; experimental values 1048.4 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 37 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 38
The preparation example provides a fused ring compound shown as a formula I-166, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 50mL Schlenk flask under argon atmosphere was added 35-5 (1.14 g,1 mmol), carbazole (0.2 g,1.2 mmol), pd 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-166 (0.59 g, yield: 46%). Elemental analysis: theoretical C,84.77; h,4.43; n,6.59; test value C,84.74; h,4.41; n,6.61. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1274.4; experimental value 1274.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 38 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 39
The preparation example provides a fused ring compound shown as a formula I-171, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-2 (6.3 g,10 mmol), 1-bromo-3-chloro-5-phenylselenophene (4.2 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolventization to give compound 39-1 (5.4 g, yield: 60%). Elemental analysis: theoretical value C,64.51; h,3.72; n,7.84; test value C,64.49; h,3.71; n,7.86. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 893.1; experimental value 893.1 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 39-1 (8.9 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolventization to give compound 39-2 (5.0 g, yield: 60%). Elemental analysis: theoretical C,69.15; h,4.47; n,8.40; test value C,69.14; h,4.45; n,8.43. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 833.1; experimental values: 833.1 (M+).
In a 100mL three-port reaction flask, 39-2 (4.2 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 39-3 (2.4 g, yield: 50%). Elemental analysis: theoretical value C,59.96; h,3.46; n,4.37; test value C,59.94; h,3.46; n,4.39. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 958.9; experimental value 958.9 (m+).
39-3 (1.9 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 39-4 (0.5 g, yield: 32%) was obtained by column separation. Elemental analysis: theoretical value C,70.37; h,3.57; n,5.13; test value C,70.35; h,3.53; n,5.17.MALDI-TOF (m/z): theoretical value 819.1; experimental value 819.1 (m+).
39-4 (1.64 g,2 mmol), 3, 6-di-tert-butylcarbazole (0.64 g,2 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolventization to give compound 39-5 (0.95 g, yield: 45%). Elemental analysis: theoretical value C,76.89; h,5.03; n,5.27; test value C,76.88; h,5.01; N,5.29. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1062.3; experimental value 1062.3 (m+).
39-5 (1.0 g,1 mmol), 3, 6-diphenylcarbazole (0.38 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-171 (0.6 g, yield: 45%). Elemental analysis: theoretical value C,82.15; h,5.17; n,5.21; test value C,82.15; h,5.13; n,5.25. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1345.5; experimental value 1345.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 39 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 40
The preparation example provides a fused ring compound shown as the formula I-172, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
(3, 5-Diphenyl) boronic acid (0.16 g,0.6 mmol), 39-5 (0.53 g,0.5 mmol), pd were placed in a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. Drying with anhydrous sodium sulfate, removing solvent from the organic phase, and coarseThe product was isolated in a column to give fused ring compound I-172 (0.31 g, yield: 50%). Elemental analysis: theoretical value C,82.24; h,5.30; n,4.46; test value C,82.23; h,5.30; n,4.49.MALDI-TOF (m/z): theoretical 1256.4; experimental value 1256.4 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 40 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 41
The preparation example provides a fused ring compound shown as a formula I-177, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-1 (3.5 g,10 mmol), 1-bromo-3-chloro-5-phenoxybenzene (7.1 g,25 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (3.9 g,40 mmol) was then added 40mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 41-1 (4.9 g, yield: 65%). Elemental analysis: theoretical value C,66.76; h,3.74; n,7.41; test value C,66.73; h,3.72; n,7.44. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 754.1; experimental value 754.1 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 41-1 (7.5 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 41-2 (4.2 g, yield: 60%). Elemental analysis: theoretical value C,72.52; h,4.64; n,8.05; test value C,72.51; h,4.62; n,8.07. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 694.2; experimental values: 694.2 (M+).
In a 100mL three-port reaction flask, 41-2 (3.5 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 41-3 (2.1 g, yield: 51%). Elemental analysis: theoretical value C,61.26; h,3.43; n,3.40; test value C,61.24; h,3.42; n,3.43. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 820.0; experimental value 820.0 (m+).
41-3 (1.6 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 41-4 (0.41 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical value C,74.06; h,3.55; n,4.11; test value C,74.03; h,3.53; n,4.15.MALDI-TOF (m/z): theoretical value 680.1; experimental value 680.1 (m+).
In a 50mL Schlenk flask under argon was added 41-4 (1.76 g,2 mmol), 3, 6-di-tert-butylcarbazole (0.56 g,2 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol), then 20mL of nail were injectedBenzene was reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 41-5 (1.0 g, yield: 55%). Elemental analysis: theoretical value C,80.58; h,5.24; n,4.55; test value C,80.55; h,5.23; n,4.57. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 923.3; experimental value 923.3 (m+).
41-5 (0.9 g,1 mmol), 3,9' -dicarbazole (0.4 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-177 (0.55 g, yield: 45%). Elemental analysis: theoretical C,84.66; h,5.20; n,5.74; test value C,84.64; h,5.20; n,5.76. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1219.5; experimental value 1219.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 41 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 42
The preparation example provides a fused ring compound shown as a formula I-180, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-amino-3, 5-dimethylbenzene (27.9 g,0.3 mol), 1, 5-dibromo-2, 4-dinitrobenzene (32.6 g,0.1 mol), pd, were charged into a 500mL Schlenk flask under an argon atmosphere 2 (dba) 3 (0.92g，1mmol)，BINAP(1.24g，2mmol)，t-BuONa(39.6g，04 mol) and then 200mL of toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and 300mL of dichloromethane for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 42-1 (29.2 g, yield: 72%). Elemental analysis: theoretical value C,65.01; h,5.46; n,13.78; test value C,65.03; h,5.44; n,13.79. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 406.1; experimental 406.1 (m+).
42-1 (4.1 g,10 mmol), 1-bromo-3-chloro-5-phenylsulfanylbenzene (7.5 g,25 mmol), pd were added to a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (3.9 g,40 mmol) was then added 40mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 42-2 (5.3 g, yield: 63%). Elemental analysis: theoretical value C,65.47; h,4.30; n,6.64; test value C,65.45; h,4.28; n,6.67. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 842.1; experimental value 842.1 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 42-2 (8.4 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and the solvent was removed by column separation to give compound 42-3 (4.8 g, yield: 61%). Elemental analysis: theoretical value C,70.48; h,5.14; n,7.15; test value C,70.47; h,5.11; n,7.18. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 782.2; experimental values: 782.2 (M+).
In a 100mL three-port reaction flask, 42-3 (3.9 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 42-4 (2.3 g, yield: 50%). Elemental analysis: theoretical value C,60.60; h,3.98; n,3.07; test value C,60.60; h,3.96; n,3.09. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 908.0; experimental value 908.0 (m+).
42-4 (1.8 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 42-5 (0.46 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical value C,71.81; h,4.19; n,3.64; test value C,71.80; h,4.15; n,3.66.MALDI-TOF (m/z): theoretical value 768.1; experimental value 768.1 (m+).
In a 50mL Schlenk flask under argon atmosphere was 42-5 (0.77 g,1 mmol), 3, 6-di-tert-butylcarbazole (0.7 g,2.5 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 100℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-180 (0.50 g, yield: 40%). Elemental analysis: theoretical value C,82.28; h,6.42; n,4.46; test value C,82.24; h,6.40; n,4.48. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1254.6; experimental value 1254.6 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 42 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 43
The preparation example provides a fused ring compound shown as a formula I-182, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 50mL Schlenk flask under argon atmosphere was 42-5 (1.54 g,2 mmol), 2, 3-benzocarbazole (0.43 g,2 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give compound 43-1 (1.04 g, yield: 55%). Elemental analysis: theoretical value C,78.37; h,4.46; n,4.42; test value C,78.36; h,4.43; n,4.45. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 949.2; experimental value 949.2 (m+).
(3, 5-Diphenyl) boronic acid (0.16 g,0.6 mmol), 43-1 (0.47 g,0.5 mmol), pd were placed in a 50mL Schlenk flask under an argon atmosphere 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-182 (0.29 g, yield: 51%). Elemental analysis: theoretical value C,83.99; h,4.85; n,3.67; testing Values C,83.97; h,4.82; n,3.68.MALDI-TOF (m/z): theoretical value 1143.4; experimental values 1143.4 (M+)
Photophysical properties of the fused ring compound prepared in preparation example 43 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 44
The preparation example provides a fused ring compound shown as the formula I-183, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-1 (3.5 g,10 mmol), 1-bromo-3-chloro-5-phenoxybenzene (3.4 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 44-1 (3.59 g, yield: 65%). Elemental analysis: theoretical value C,65.16; h,3.83; n,10.13; test value C,65.14; h,3.82; n,10.16. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 552.1; experimental value 552.1 (m+).
44-1 (6.3 g,10 mmol), 1-bromo-3-chloro-5-phenylsulfanylbenzene (3.6 g,12 mmol), pd, were added to a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 44-2 (4.6 g, yield: 60%). Elemental analysis: theoretical value C,65.37; h,3.66; n,7.26; test value C,65.35; h,362; n,7.29. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 770.1; experimental value 770.1 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 44-2 (7.7 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 44-3 (4.1 g, yield: 58%). Elemental analysis: theoretical value C,70.88; h,4.53; n,7.87; test value C,70.85; h,4.52; n,7.89. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 710.1; experimental 710.1 (m+).
In a 100mL three-port reaction flask, 44-3 (3.55 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 44-4 (2.1 g, yield: 50%). Elemental analysis: theoretical value C,60.09; h,3.36; n,3.34; test value C,60.08; h,3.32; n,3.37. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 835.9; experimental value 835.9 (m+).
44-4 (1.7 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 44-5 (0.42 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical value C,72.35; h,3.47; n,4.02; test value C,72.37; h,3.43; n,4.05.MALDI-TOF (m/z): theoretical value: 696.1; experimental values: 696.1 (M+).
In a 50mL Schlenk flask under argon was added 3, 5-bis (9H-carbazol-9-yl) phenylboronic acid (0.5 g,1.1 mmol), 44-5 (0.7 g,1 mmol), pd 2 (dba) 3 (46 mg,0.05 mmol) and ligand S-phos (82 mg,0.2 mmol) were added to a bottle, 20mL of toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL of water, an aqueous potassium carbonate solution was introduced into the bottle, the temperature was raised to 100℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as compound 44-6 (0.52 g, yield: 49%). Elemental analysis: theoretical value C,80.87; h,4.05; n,5.24; test value C,80.86; h,4.03; n,5.26.MALDI-TOF (m/z): theoretical value 1068.3; experimental values 1068.3 (M+)
2,4, 6-triphenylphenylboronic acid (0.21 g,0.6 mmol), 44-6 (0.54 g,0.5 mmol), pd2 (dba) 3 (46 mg,0.05 mmol) and the ligand S-phos (82 mg,0.2 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, 20mL toluene was taken up in the flask, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL water, an aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 100℃under argon, the reaction was stirred for 8 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give the fused ring compound I-183 (0.27 g, yield: 40%). Elemental analysis: theoretical value C,86.10; h,4.52; n,4.18; test value C,86.11; h,4.50; n,4.19.MALDI-TOF (m/z): theoretical value 1338.4; experimental value 1338.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 44 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 45
The preparation example provides a fused ring compound shown as a formula I-184, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 500mL Schlenk flask under argon was added 4-tert-butylaniline (44.7 g,0.3 mol), 1, 5-dibromo-2, 4-dinitrobenzene (32.6 g,0.1 mol), pd 2 (dba) 3 (0.92 g,1 mmol), BINAP (1.24 g,2 mmol), t-Buona (39.6 g,0.4 mol), and then 200mL of toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and 300mL of dichloromethane for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 45-1 (32.3 g, yield: 70%). Elemental analysis: theoretical value C,67.51; h,6.54; n,12.11; test value C,67.52; h,6.53; n,12.15. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 462.2; experimental 462.2 (m+).
45-1 (4.6 g,10 mmol), 1-bromo-3-chloro-5-phenoxybenzene (3.4 g,12 mmol), pd in a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 45-2 (4.1 g, yield: 60%). Elemental analysis: theoretical value C,68.76; h,6.07; n,8.22; test value C,68.74; h,6.05; n,8.27. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 680.2; experimental value 680.2 (m+).
45-2 (6.8 g,10 mmol), 1-bromo-3-chloro-5-phenylsulfanylbenzene (3.6 g,12 mmol), pd were placed in a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (3.9 g,40 mmol) was then added 40mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 45-3 (5.6 g, yield: 63%). Elemental analysis: theoretical value C,67.94; h,5.02; n,6.34; test value C,67.93; h,5.00; n,6.37. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 882.2; experimental value 882.2 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred 45-3 (8.8 g,10 mmol) solution in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 45-4 (4.9 g, yield: 60%). Elemental analysis: theoretical value C,72.89; h,5.87; n,6.80; test value C,72.88; h,5.85; n,6.83. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 822.2; experimental values: 822.2 (M+).
In a 100mL three-port reaction flask, 45-4 (4.1 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 45-5 (2.4 g, yield: 50%). Elemental analysis: theoretical value C,63.10; h,4.66; n,2.94; test value C,63.11; h,4.65; n,2.97. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 948.0; experimental value 948.0 (m+).
45-5 (1.9 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 45-6 (0.48 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical value C,74.19; h,4.98; n,3.46; test value C,74.17; h,4.95; n,3.48.MALDI-TOF (m/z): theoretical value 808.2; experimental 808.2 (m+).
45-6 (1.6 g,2 mmol), 4-phenylcarbazole (0.49 g,2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolventization to obtain compound 45-7 (1.1 g, yield: 55%). Elemental analysis: theoretical value C,80.36; h,5.16; n,4.13; test value C,80.35; h,5.14; n,4.15; . Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1015.3; experimental value 1015.3 (m+).
45-7 (1.0 g,1 mmol), 7H-benzofuran [2,3-B ] carbazole (0.28 g,1.2 mmol), pd2 (dba) 3 (46 mg,0.05 mmol), t-Bu3PHBF4 (58 mg,0.2 mmol), t-BuONa (0.19 g,2 mmol) were added to a 50mL Schlenk flask under argon atmosphere, and then 20mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-184 (0.53 g, yield: 43%). Elemental analysis: theoretical value C,83.49; h,5.05; n,4.53; test value C,83.46; h,5.03; n,4.55. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1236.4; experimental value 1236.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 45 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 46
The preparation example provides a fused ring compound shown as a formula I-185, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-1 (3.5 g,10 mmol), 1-bromo-3-chloro-5-phenylselenophene (8.6 g,25 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (3.9 g,40 mmol) was then added 40mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolventization to give compound 46-1 (5.3 g, yield: 60%). Elemental analysis: theoretical value C,57.22; h,3.20; n,6.36; test value C,57.21; h,3.18; n,6.39. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 881.2; experimental value 881.2 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 46-1 (8.8 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolventization to give compound 46-2 (4.9 g, yield: 60%). Elemental analysis: theoretical value C,61.40; h,3.93; n,6.82; test value C,61.42; h,3.91; n,6.85. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 822.0; experimental values: 822.0 (M+).
In a 100mL three-port reaction flask, 46-2 (4.1 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 46-3 (2.3 g, yield: 50%). Elemental analysis: theoretical value C,53.14; h,2.97; n,2.95; test value C,53.12; h,2.94; n,2.98. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 947.8; experimental value 947.8 (m+).
46-3 (1.9 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 46-4 (0.38 g, yield: 24%) was obtained by column separation. Elemental analysis: theoretical value C,62.50; h,3.00; n,3.47; test value C,62.48; h,3.00; n,3.49.MALDI-TOF (m/z): theoretical value 807.9; experimental value 807.9 (m+).
46-4 (0.8 g,1 mmol), 3, 6-di-tert-butylcarbazole (0.7 g,2.5 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating the organic phase, separating by column, and desolventizing to obtain condensed ringCompound I-185 (0.51 g, yield: 40%). Elemental analysis: theoretical value C,76.17; h,5.61; n,4.33; test value C,76.14; h,5.60; n,4.36. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1294.4; experimental value 1294.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 46 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 47
The preparation example provides a fused ring compound shown as a formula I-187, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
in a 100mL Schlenk flask under argon was added 33-1 (3.5 g,10 mmol), 1-bromo-3-chloro-5-phenylselenophene (4.1 g,12 mmol), pd 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 47-1 (3.7 g, yield: 60%). Elemental analysis: theoretical value C,58.50; h,3.44; n,9.10; test value C,58.51; h,3.43; n,9.14. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 616.0; experimental value 616.0 (m+).
47-1 (6.2 g,10 mmol), 1-bromo-3-chloro-5-phenoxybenzene (3.4 g,12 mmol), pd were added to a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. Separating the organic phase byColumn separation and desolvation gave compound 47-2 (5.0 g, yield: 61%). Elemental analysis: theoretical value C,61.63; h,3.45; n,6.84; test value C,61.62; h,3.43; n,6.87. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 818.0; experimental value 818.0 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 47-2 (8.2 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 47-3 (4.5 g, yield: 60%). Elemental analysis: theoretical value C,66.50; h,4.25; n,7.39; test value C,66.51; h,4.23; n,7.40. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: 758.1; experimental values: 758.1 (M+).
In a 100mL three-port reaction flask, 47-3 (3.8 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to obtain compound 47-4 (2.2 g, yield: 50%). Elemental analysis: theoretical value C,56.91; h,3.18; n,3.16; test value C,56.90; h,3.16; n,3.18. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 883.9; experimental value 883.9 (m+).
47-4 (1.7 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 47-5 (0.36 g, yield: 24%) was obtained by column separation. Elemental analysis: theoretical value C,67.79; h,3.25; n,3.76; test value C,67.79; h,3.25; n,3.76.MALDI-TOF (m/z): theoretical value 744.0; experimental value 744.0 (m+).
47-5 (1.6 g,2 mmol), 3, 6-di-tert-butylcarbazole (0.56 g,2 mmol), pd2 (dba) 3 (92 mg,0.1 mmol), t-Bu3PHBF4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) were placed in a 50mL Schlenk flask under an argon atmosphere, and then 20mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to obtain compound 47-6 (1.0 g, yield: 50%). Elemental analysis: theoretical value C,75.44; h,4.90; n,4.26; test value C,75.42; h,4.90; n,4.28. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 987.2; experimental value 987.2 (m+).
47-6 (1.0 g,1 mmol), 9' -phenyl-9H, 9H ' -3,3' -carbazole (0.49 g,1.2 mmol), pd were added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-187 (0.58 g, yield: 43%). Elemental analysis: theoretical value C,81.30; h,4.97; n,5.15; test value C,81.32; h,4.95; n,5.18. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1359.4; experimental value 1359.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 47 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 48
The preparation example provides a fused ring compound shown as a formula I-188, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
47-1 (6.2 g,10 mmol), 1-bromo-3-chloro-5-phenylsulfanylbenzene (3.6 g,12 mmol), pd in a 100mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (1.92 g,20 mmol), then 40mL toluene was injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 48-2 (5.0 g, yield: 61%). Elemental analysis: theoretical value C,60.44; h,3.38; n,6.71; test value C,60.42; h,3.36; n,6.73. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 834.0; experimental value 834.0 (m+).
In a 250mL three-port reaction flask, iron powder (0.56 g,10 mmol) and acetic acid 10mL were added sequentially to a stirred solution of 48-2 (8.3 g,10 mmol) in ethanol (50 mL). The color of the reaction mixture became black. The mixture was refluxed for 5.5 hours and then cooled to give a grey precipitate. The mixture was filtered through celite and washed with ethanol. Sodium hydroxide solution (25%) was added to the filtrate until pH 12 was reached. The basic solution was filtered through celite and the solvent was removed to give a brown residue which was extracted with diethyl ether. The organic phase was separated, and subjected to column separation and desolvation to give compound 48-3 (4.6 g, yield: 60%). Elemental analysis: theoretical value C,65.12; h,4.16; n,7.23; test value C,65.13; h,4.13; n,7.25. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value: :774.0; experimental values: 774.0 (M+).
In a 100mL three-port reaction flask, 48-3 (3.9 g,5 mmol), cuprous bromide (1.43 g,10 mmol), t-butyl nitrite (1.0 g,10 mmol) and 40mL anhydrous acetonitrile were added and reacted at 65℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 48-4 (2.2 g, yield: 50%). Elemental analysis: theoretical value C,55.90; h,3.13; n,3.10; test value C,55.91; h,3.13; n,3.15. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical 899.8; experimental 899.8 (m+).
48-4 (1.8 g,2 mmol) and dried tert-butylbenzene (20 mL) were weighed into a 250mL double-neck reaction flask under argon atmosphere, butyllithium solution (1.6 mL,2.5M,4 mmol) was added dropwise at-30℃and stirred at room temperature for 2 hours, and boron tribromide (1.12 g,4.4 mmol) was added dropwise to the system at-30℃and stirred at room temperature for 1 hour after the addition. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (1.0 g,8 mmol) into the reaction system, and heating to 160 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 48-5 (0.35 g, yield: 23%) was obtained by column separation. Elemental analysis: theoretical value C,66.36; h,3.18; n,3.68; test value C,66.33; h,3.17; n,3.69.MALDI-TOF (m/z): theoretical value 760.0; experimental value 760.0 (m+).
48-5 (1.5 g,2 mmol), 3, 6-di-tert-butylcarbazole (0.56 g,2 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and subjected to column separation and desolvation to give compound 48-6 (0.9 g, yield: 45%). Elemental analysis: theoretical value C,74.23; h,4.82; n,4.19; test value C,74.21; h,4.80; n,4.21. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1003.2; experimental value 1003.2 (m+).
48-6 (1.0 g,1 mmol), 3,9' -dicarbazole ((0.4 g,1.2 mmol), pd) was added to a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (46mg，0.05mmol)，t-Bu 3 PHBF 4 (58 mg,0.2 mmol), t-Buona (0.19 g,2 mmol) and then 20mL toluene were injected and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-188 (0.52 g, yield: 40%). Elemental analysis: theory C,79.51; h,4.89; n,5.39; test value C,79.50; h,4.86; n,5.42. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1299.4; experimental value 1299.4 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 48 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 49
The preparation example provides a fused ring compound shown as a formula I-189, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), 3, 6-bis (trifluoromethyl) -9H-carbazole (0.76 g,2.5 mmol), pd in a 50mL Schlenk flask under argon atmosphere 2 (dba) 3 (92mg，0.1mmol)，t-Bu 3 PHBF 4 (116 mg,0.4 mmol), t-Buona (0.39 g,4 mmol) was then added 20mL of toluene and reacted at 110℃for 12 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-189 (0.70 g, yield: 51%). Elemental analysis: theoretical value C,72.16; h,3.40; n,6.16; test value C,72.12; h,3.40; n,6.19. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 1364.3; experimental value 1364.3 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 49 of the present invention were examined.
Referring to Table 1, table 1 shows the photophysical properties of the fused ring compounds prepared according to the preparation examples of the present invention
PREPARATION EXAMPLE 50
The preparation example provides a fused ring compound shown as a formula I-190, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-1 (0.83 g,1 mmol), di-p-tert-butylphenyl diselenide (0.21 g,0.5 mmol) and sodium borohydride (38 mg,1 mmol) were weighed into a 50mL three-neck flask under argon atmosphere, 20mL DMF was slowly added dropwise into the flask, the temperature was raised to 90℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated off, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and fused ring compound I-190 (0.47 g, yield: 40%) was obtained by column separation and desolvation. Elemental analysis: theoretical value C,75.01; h,5.10; n,4.73; test value C,75.02; h,5.04; n,4.75.ESI-MS: theoretical value 1186.3; experimental value 1186.3 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 50 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
PREPARATION EXAMPLE 51
The preparation example provides a fused ring compound shown as a formula I-191, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
1-2 (1.07 g,1 mmol), di-p-tert-butylphenyl diselenide (0.21 g,0.5 mmol) and sodium borohydride (38 mg,1 mmol) were weighed into a 50mL three-neck flask under argon atmosphere, 20mL DMF was slowly added dropwise into the flask, the temperature was raised to 90℃and the reaction was stirred under argon for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and fused ring compound I-191 (0.56 g, yield: 45%) was obtained by column separation and desolvation. Elemental analysis: theoretical value C,80.64; h,5.72; n,5.60; test value C,80.62; h,5.70; n,5.63.ESI-MS: theoretical value 1251.5; experimental value 1251.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 51 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
Preparation example 52
The preparation example provides a fused ring compound shown as the formula I-192, and the synthetic route is as follows:
the preparation method comprises the following specific steps:
parafiltybenzylthiophenol (0.2 g,1.2 mmol), 1-2 (1.07 g,1 mmol), and Cs were weighed out in a 50mL three-necked flask under an argon atmosphere 2 CO 3 (0.65 g,2 mmol) of DMF (20 mL) was taken and added to a bottle, the temperature was raised to 120℃and the reaction was stirred under argon protection for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was separated by column to give fused ring compound I-192 (0.53 g, yield: 44%). Elemental analysis: theoretical value C,83.78; h,5.94; n,5.82; test value C,83.76; h,5.91; n,5.83.MALDI-TOF (m/z): theoretical value 1203.5; experimental value 1203.5 (m+).
Photophysical properties of the fused ring compound prepared in preparation example 52 of the present invention were examined.
Referring to Table 1, table 1 shows photophysical properties of the fused ring compounds prepared in the preparation examples of the present invention.
TABLE 1 photophysical Properties of fused Ring Compounds prepared in accordance with the preparation examples of the present invention
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Note that: ΔE in table ST As a difference between the singlet energy level and the triplet energy level, a sample film to be measured was prepared by doping the condensed-cyclic compound obtained in the above preparation example in mCP at a concentration of 1.5wt.%, and a difference between the measured fluorescence spectrum and the initial (onset) value of the phosphorescence spectrum was measured, with a test instrument of HORIBA FluoroMax spectrofluorometer (japan); the delayed fluorescence lifetime was obtained by preparing a sample to be tested by doping the fused ring compound obtained in the preparation example into polystyrene at a concentration of 1wt%, and testing the sample with a time-resolved fluorescence spectrometer, wherein the testing instrument is Edinburgh fluorescence spectrometer (FLS-980, UK).
As can be seen from Table 1, the condensed-cyclic compound in the preparation example provided by the invention has smaller ΔE ST And (less than 0.1 eV), the thermal activation delayed fluorescence effect is shown, and the delayed fluorescence lifetime is 4.3-9.6 mu s, so that the triplet exciton is utilized, and the device efficiency is improved.
Device embodiment
As an embodiment of the device, the present invention provides a device structure including: ITO/PEDOT: PSS (40 nm)/PVK (15 nm)/EML (30 nm)/mSiTRZ (12 nm)/TmPPPyTz (55 nm)/LiF (1 nm)/Al (150 nm). The organic film layer is laminated in turn and is arranged to include: a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer, wherein the light emitting layer (EML) comprises a host material selected from any one of mCP, mCBP, siCzCz and SiCzTrz, a sensitizer 5CzTRZ and the condensed cyclic compound according to the present invention.
The preparation method of the device comprises the following steps: spin-coating poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) on indium tin oxide supported on a glass substrate, annealing at 120 ℃ for 30 minutes; a 1, 2-dichlorobenzene solution of PVK was then spin-coated onto PEDOT: on the PSS layer, and annealing at 100℃for 10 minutes; spin-coating toluene solution containing the fused ring compound to PVK layer, and annealing at 100 ℃ for 10 minutes; finally at 6x10 -7 And depositing mSiTRZ, tmPPPPyTz and LiF/Al cathodes in sequence under the vacuum degree of Torr to obtain the organic electroluminescent device.
The structure of part of materials in the preparation example of the device is as follows:
example 1
The organic electroluminescent device was prepared by doping I-1 into an organic light emitting layer using the device structure using I-1 of preparation example 1 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-1 provided herein.
Example 2
The device structure was used to prepare an organic electroluminescent device by doping I-7 into an organic light-emitting layer using I-7 in preparation example 2 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-7 provided herein.
Example 3
The device structure was used to prepare an organic electroluminescent device by doping I-9 into an organic light-emitting layer using I-9 in preparation example 3 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-9 provided herein.
Example 4
The organic electroluminescent device was prepared by doping the I-10 into an organic light emitting layer using the device structure using the I-10 of preparation example 4 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-10 provided herein.
Example 5
The organic electroluminescent device was prepared by doping the I-14 into an organic light emitting layer using the device structure using the I-14 of preparation example 5 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-14 provided herein.
Example 6
The organic electroluminescent device was prepared by doping the I-23 into an organic light emitting layer using the device structure using the I-23 of preparation example 6 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-23 provided herein.
Example 7
The organic electroluminescent device was prepared by doping the I-25 into an organic light emitting layer using the device structure using the I-25 of preparation example 7 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-25 provided herein.
Example 8 an organic electroluminescent device was prepared by doping the I-26 into an organic light emitting layer using the device structure, taking the I-26 of preparation example 8 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-26 provided herein.
Example 9
The organic electroluminescent device was prepared by doping the I-29 into an organic light emitting layer using the device structure using the I-29 of preparation example 9 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-29 provided herein.
Example 10
The organic electroluminescent device was prepared by doping the I-30 into an organic light emitting layer using the I-30 of preparation example 10 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-30 provided herein.
Example 11
The organic electroluminescent device was prepared by doping the I-31 into an organic light emitting layer using the device structure using the I-31 of preparation example 11 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-31 provided herein.
Example 12
The organic electroluminescent device was prepared by doping the I-32 into an organic light emitting layer using the device structure using the I-32 of preparation example 12 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-32 provided herein.
Example 13
The organic electroluminescent device was prepared by doping the I-33 into an organic light emitting layer using the device structure using the I-33 of preparation example 13 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-33 provided herein.
Example 14
The organic electroluminescent device was prepared by doping the I-34 into an organic light emitting layer using the device structure using the I-34 of preparation example 14 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-34 provided herein.
Example 15
The organic electroluminescent device was prepared by doping the I-35 into the organic light emitting layer using the device structure using the I-35 of preparation example 15 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-35 provided herein.
Example 16
The organic electroluminescent device was prepared by doping the I-36 into an organic light emitting layer using the device structure using the I-36 of preparation example 16 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-36 provided herein.
Example 17
The organic electroluminescent device was prepared by doping the I-37 in preparation example 17 into an organic light emitting layer, using the device structure, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-37 provided herein.
Example 18
The device structure was used to prepare an organic electroluminescent device by doping the I-44 into an organic light-emitting layer using the I-44 in preparation example 18 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-44 provided herein.
Example 19
The organic electroluminescent device was prepared by doping the I-47 into an organic light emitting layer using the device structure with the I-47 of preparation example 19 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-47 provided herein.
Example 20
The organic electroluminescent device was prepared by doping the I-48 into the organic light emitting layer using the device structure using the I-48 of preparation example 20 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-48 provided herein.
Example 21
The organic electroluminescent device was prepared by doping the I-56 in preparation example 21 into an organic light emitting layer, using the device structure, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-56 provided herein.
Example 22
The organic electroluminescent device was prepared by doping the I-57 into an organic light emitting layer using the device structure with the I-57 of preparation example 22 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-57 provided herein.
Example 23
The organic electroluminescent device was prepared by doping the I-65 into the organic light emitting layer using the device structure using the I-65 of preparation example 23 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-65 provided herein.
Example 24
Taking the I-102 in the preparation example 24 as an implementation object, doping the I-102 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-102 provided herein.
Example 25
The organic electroluminescent device was prepared by doping the I-133 into an organic light emitting layer using the device structure using the I-133 of preparation example 25 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-133 provided herein.
Example 26
The device structure was used to prepare an organic electroluminescent device by doping the I-134 into an organic light-emitting layer using the I-134 of preparation example 26 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-134 provided herein.
Example 27
The organic electroluminescent device was prepared by doping the I-135 of preparation example 27 into an organic light emitting layer, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-135 provided herein.
Example 28
The device structure was used to prepare an organic electroluminescent device by doping the I-138 into an organic light-emitting layer, taking the I-138 in preparation example 28 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-138 provided herein.
Example 29
Taking I-139 in preparation example 29 as an implementation object, doping the I-139 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-139 provided herein.
Example 30
The organic electroluminescent device was prepared by doping the I-140 into the organic light emitting layer using the I-140 of preparation example 30 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-140 provided herein.
Example 31
The organic electroluminescent device was prepared by doping the I-141 of preparation example 31 into an organic light emitting layer, and testing the resulting device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-141 provided herein.
Example 32
The organic electroluminescent device was prepared by doping the I-142 into an organic light emitting layer using the device structure using the I-142 of preparation example 32 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-142 provided herein.
Example 33
The organic electroluminescent device was prepared by doping the I-151 of preparation example 33 into an organic light emitting layer, using the device structure, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-151 provided herein.
Example 34
The organic electroluminescent device was fabricated by doping the I-154 into the organic light emitting layer using the device structure using the I-154 of preparation example 34 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-154 provided herein.
Example 35
The organic electroluminescent device was prepared by doping the I-163 into an organic light emitting layer using the device structure using the I-163 of preparation example 35 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-163 provided herein.
Example 36
The organic electroluminescent device was fabricated by doping the I-164 into the organic light emitting layer using the device structure using the I-164 of fabrication example 36 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-164 provided by the present invention.
Example 37
The device structure was used to prepare an organic electroluminescent device by doping the I-165 into an organic light emitting layer with the I-165 of preparation example 37 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-165 provided herein.
Example 38
The device structure was used to prepare an organic electroluminescent device by doping the I-166 into an organic light emitting layer with the I-166 of preparation example 38 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-166 provided herein.
Example 39
The organic electroluminescent device was prepared by doping the I-171 into an organic light emitting layer using the device structure using the I-171 of preparation example 39 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-171 provided herein.
Example 40
Taking the I-172 in the preparation example 40 as an implementation object, doping the I-172 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-172 provided by the present invention.
Example 41
Taking I-177 in preparation example 41 as an implementation object, doping the I-177 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-177 provided by the present invention.
Example 42
Taking the I-180 in the preparation example 42 as an implementation object, doping the I-180 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-180 provided herein.
Example 43
The organic electroluminescent device was fabricated by doping the I-182 into the organic light emitting layer using the device structure with the I-182 of preparation example 43 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-182 provided by the present invention.
Example 44
Taking I-183 in preparation example 44 as an implementation object, doping the I-183 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-183 provided herein.
Example 45
The organic electroluminescent device was prepared by doping the I-184 into an organic light emitting layer using the device structure with the I-184 of preparation example 45 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-184 provided herein.
Example 46
The organic electroluminescent device was fabricated by doping the I-185 into the organic light emitting layer using the device structure using the I-185 of preparation example 46 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-185 provided herein.
Example 47
The organic electroluminescent device was prepared by doping the I-187 into an organic light emitting layer using the device structure, taking the I-187 in preparation example 47 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-187 provided herein.
Example 48
The organic electroluminescent device was prepared by doping the I-188 into an organic light emitting layer using the device structure using the I-188 of preparation example 48 as an implementation object, and the obtained device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-188 provided herein.
Example 49
The organic electroluminescent device was fabricated by doping the I-189 into an organic light emitting layer using the device structure, taking the I-189 of preparation example 49 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-189 provided by the present invention.
Example 50
The organic electroluminescent device was fabricated by doping the I-190 into an organic light emitting layer using the device structure using the I-190 of preparation example 50 as an implementation object, and the resulting device was tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-190 provided herein.
Example 51
The organic electroluminescent device was prepared by doping the I-191 of preparation example 51 into an organic light emitting layer, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-191 provided by the present invention.
Example 52
Taking the I-192 in the preparation example 52 as an implementation object, doping the I-192 into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with I-192 provided herein.
Comparative example 1
And taking the v-DABA as an implementation object, doping the v-DABA into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to table 2, table 2 provides the performance parameters of the electroluminescent device prepared in comparative example 1.
Comparative example 2
And taking Cz-DABA as an implementation object, doping the Cz-DABA into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
Referring to table 2, table 2 provides the performance parameters of the electroluminescent device prepared in comparative example 2.
Comparative example 3
And taking t-BuCz-DABA as an implementation object, doping the t-BuCz-DABA into an organic light-emitting layer, preparing an organic electroluminescent device by using the device structure, and testing the obtained device.
The chemical structure of the v-DABA, cz-DABA and t-BuCz-DABA is as follows:
TABLE 2 Performance parameters of electroluminescent devices prepared from the fused Ring Compounds provided by the invention
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Note that: the starting voltage in the table is the driving voltage of the device when the brightness is 1cd m-2; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device and the calculation method described in the literature (Jpn.J.appl.Phys.2001, 40, L783); the half-width is the width of the peak at half the peak height of the electroluminescent spectrum, i.e. the distance between the point where the line intersects the two sides of the peak, passing through the midpoint of the peak height and making a line parallel to the bottom of the peak.
As can be seen from Table 2, the solution processing organic electroluminescent device prepared from the dendritic fused ring compound provided by the invention has very high luminous efficiency, the maximum external quantum efficiency is 23.9-31.4%, the device efficiency is obviously higher than that of the comparative compounds v-DABA, cz-DABA and t-BuCz-DABA, and the device efficiency has narrower electroluminescent spectrums, and the half-peak width is smaller than 20nm.
The previous description of the disclosed preparation is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these examples will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other examples without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the examples of preparation shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An organoboron fused ring compound characterized by having a structure represented by formula I-a or formula I-B:
wherein m is 1 、m 2 Each independently is an integer of 1 to 4; n is n 1 、n 4 Each independently is an integer of 1 to 4; n is n 2 、n 3 Each independently is an integer of 1 to 5;
X 1 And X 2 Independently selected from N (R) a ) O, S, se or Te, said N (R a ) R in (a) a Independently selected from H, D, a substituted or unsubstituted C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group, wherein the heteroatoms in the heteroaryl groups are independently selected from Si, ge, N, P, O, S or Se;
R a and is connected to X 1 And X 2 Through carbon-carbon single bond, -O-, -S-, and, And->Any one or more of which are linked together;
L 1 and L 2 Each independently selected from the group consisting of a carbon-carbon single bond, an ether oxygen bond, a thioether bond, a seleno ether bond, a substituted or unsubstituted C1-C30 linear hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, and a substituted or unsubstituted C1-C30 alkylthio group;
or L 1 And L 2 Each independently selected from any one of U-1 to U-18The meaning is as follows:
a1 is selected from any one of the groups shown in formulas 1 to 56:
La-Lc are each independently selected from H, D, F, cl, br, I, -CN, -No 2 、 -O-R 1 、-S-R 1 、/>-Se-R 1 、/>-Te-R 1 、 A linear hydrocarbon group of substituted or unsubstituted C1 to C30, a branched hydrocarbon group of substituted or unsubstituted C1 to C30, a halogenated hydrocarbon group of substituted or unsubstituted C1 to C30, a cycloalkyl group of substituted or unsubstituted C3 to C30, an aryl group of substituted or unsubstituted C6 to C60, a heteroaryl group of substituted or unsubstituted C5 to C60; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
R 1 ～R 11 each independently selected from H, D, F, Cl、Br、I、-CN、-O-R 1 、-S-R 1 、/>A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
R 1 、R 2 and R is 3 Each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH 2 A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group; the hetero atom in the heteroaryl is selected from any one or more of Si, ge, N, P, O, S or Se;
Or (b)
R 1 、R 2 And R is 3 Through carbon-carbon single bond, -O-, -S-, any one or more of the connections;
q is independently selected from H, D, substituted or unsubstituted C1-C30 straight chain hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; the hetero atom in the heteroaryl group is selected from one or more of Si, ge, N, P, O, S and Se;
or Q is selected from any one of Q-1 to Q-33:
2. the organoboron fused ring compound according to claim 1, wherein,any one selected from the formulas H-1 to H-47:
3. the organoboron fused ring compound according to claim 1, wherein,any one selected from the formulas H-48 to H-72:
4. the organoboron fused ring compound according to any one of claims 1 to 3, wherein the organoboron fused ring compound is selected from any one of formulas I-1 to I-192:
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5. the method for producing an organic fused ring compound according to any one of claims 1 to 4, comprising the steps of:
Reacting a compound shown in a formula II with a compound shown in a formula III in a solvent to obtain a fused ring compound shown in a formula I-A or a formula I-B;
wherein, the compound structure shown in formula II:
wherein the compound shown in the formula III comprises a structure shown in a formula III-1, a formula III-2 or a formula III-3:
wherein Lu 1 、Lu 2 、Lu 3 Each independently selected from halogen,
6. The preparation method according to claim 5, wherein the compound represented by formula II is prepared by:
s1: compound Ar 1 ' with compound Ar, respectively 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 4 ′；
S2: compound Ar 4 ' and BI 3 Reacting to form a compound shown in a formula II;
7. the process according to claim 6, wherein the reaction in step S1 is carried out in the presence of a catalyst selected from the group consisting of Na 2 CO 3 、K 2 CO 3 、Cs 2 CO 3 Any one or more of NaH, naOH or KOH;
the catalyst and the compound Ar 1 ' Compound Ar 2 ' sum Compound Ar 3 ' the molar ratio is (0.5-8))∶1∶(1.05～3)∶(1.05～3)；
The BI 3 With compound Ar 4 The mol ratio of' is (1-5) to 1.
8. The preparation method according to claim 5, wherein the compound represented by formula II is prepared by:
S1: compound Ar 5 ' with Compound Ar 2 ' sum Compound Ar 3 ' reaction to form Compound Ar 6 ′；
S2: compound Ar 6 ' formation of Compound Ar by nitroreduction reaction 7 ′；
S3: compound Ar 7 ' formation of Compound Ar by diazotisation reaction 8 ′；
S4: compound Ar 8 ' and BBr 3 Reacting to form a compound shown in a formula II;
9. the preparation method according to claim 8, wherein the reaction in step S1 is performed in the presence of a reducing agent selected from one or more of iron powder, hydrogen gas, sodium sulfide or sodium disulfide;
the reducing agent and the compound Ar 6 The mol ratio of' is (2-20) to 1;
the reaction in step S2 is carried out in the presence of a diazotizing agent selected from one or more of sodium nitrite, amyl nitrite, butyl nitrite or tert-butyl nitrite;
the diazotizing agent and the compound Ar 7 The mol ratio of' is (0.5-5) to 1;
the reaction in step S3 is carried out under the action of butyllithium, wherein the butyllithium is selected from n-butyllithium and/or tert-butyllithium;
the butyl lithium and the compound Ar 8 The mol ratio of' is (1-5) to 1;
the reaction in step S4 is carried out in the presence of an organic amine base, preferably N, N-diisopropylethylamine and/or triethylamine;
Said BBr 3 Organic amine base compound, ar 8 The mol ratio of' is (1-10): 1.
10. An organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode;
the organic thin film layer comprises the organic condensed-cyclic compound according to any one of claims 1 to 4 or the organic condensed-cyclic compound produced according to the production method according to any one of claims 5 to 9.
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