WO2020220510A1 - Pyrene blue fluorescent dopant, and organic electroluminescent device comprising same - Google Patents
Pyrene blue fluorescent dopant, and organic electroluminescent device comprising same Download PDFInfo
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- WO2020220510A1 WO2020220510A1 PCT/CN2019/100146 CN2019100146W WO2020220510A1 WO 2020220510 A1 WO2020220510 A1 WO 2020220510A1 CN 2019100146 W CN2019100146 W CN 2019100146W WO 2020220510 A1 WO2020220510 A1 WO 2020220510A1
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- deuterated
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- organic electroluminescent
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- 239000002019 doping agent Substances 0.000 title abstract description 5
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 title abstract 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 23
- -1 3,5-diphenyl Phenyl Chemical group 0.000 claims description 65
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 29
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 28
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 26
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000004305 biphenyl Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000005401 electroluminescence Methods 0.000 claims description 10
- 125000003944 tolyl group Chemical group 0.000 claims description 10
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 8
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical group C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 6
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 4
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical group C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 46
- 238000004949 mass spectrometry Methods 0.000 description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 42
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- 239000000843 powder Substances 0.000 description 39
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 34
- 239000012043 crude product Substances 0.000 description 33
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- 238000004128 high performance liquid chromatography Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 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 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
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- 238000010992 reflux Methods 0.000 description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 23
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
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- 0 Cc1cc2c(C(O)(O)O)cc(*(c(cc3)ccc3[Zn])c3cccc4c3[n]c3ccccc43)c(c(C)c3)c2c2c3c(C(O)(O)O)cc(*(c(cc3)ccc3[Zn])c3cccc4c3[n]c3ccccc43)c12 Chemical compound Cc1cc2c(C(O)(O)O)cc(*(c(cc3)ccc3[Zn])c3cccc4c3[n]c3ccccc43)c(c(C)c3)c2c2c3c(C(O)(O)O)cc(*(c(cc3)ccc3[Zn])c3cccc4c3[n]c3ccccc43)c12 0.000 description 11
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
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- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
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- XLTFRTTTZWMJJQ-UHFFFAOYSA-N 4-methyldibenzofuran Chemical group O1C2=CC=CC=C2C2=C1C(C)=CC=C2 XLTFRTTTZWMJJQ-UHFFFAOYSA-N 0.000 description 1
- REOSPBZOZQJHPJ-UHFFFAOYSA-N CC(C)(C)c1cccc(c2ccc3)c1[o]c2c3N(c(cc1)ccc1F)c1c(c(C)cc(c2c3c(C)c4)c(C)cc3N(c(cc3)ccc3F)c3cccc5c3[o]c3c(C(C)(C)C)cccc53)c2c4c(C)c1 Chemical compound CC(C)(C)c1cccc(c2ccc3)c1[o]c2c3N(c(cc1)ccc1F)c1c(c(C)cc(c2c3c(C)c4)c(C)cc3N(c(cc3)ccc3F)c3cccc5c3[o]c3c(C(C)(C)C)cccc53)c2c4c(C)c1 REOSPBZOZQJHPJ-UHFFFAOYSA-N 0.000 description 1
- XHCBSWPIKFQXNG-UHFFFAOYSA-N CC(C)c(cccc1c2ccc3)c1[o]c2c3N(c(cc1)ccc1C#N)c1cc(C)c(cc2C)c3c1c(C)cc(c(C)c1)c3c2c1N(c(cc1)ccc1C#N)c1c2[o]c(c(C(C)C)ccc3)c3c2ccc1 Chemical compound CC(C)c(cccc1c2ccc3)c1[o]c2c3N(c(cc1)ccc1C#N)c1cc(C)c(cc2C)c3c1c(C)cc(c(C)c1)c3c2c1N(c(cc1)ccc1C#N)c1c2[o]c(c(C(C)C)ccc3)c3c2ccc1 XHCBSWPIKFQXNG-UHFFFAOYSA-N 0.000 description 1
- PBKKREINKVRZBI-UHFFFAOYSA-N CC(C)c1c2[o]c(c(N(c(cc3)ccc3F)c3cc(C)c(cc(C)c4c56)c5c3c(C)cc6c(C)cc4N(c(cc3)ccc3F)c3c4[o]c(c(C(C)C)ccc5)c5c4ccc3)ccc3)c3c2ccc1 Chemical compound CC(C)c1c2[o]c(c(N(c(cc3)ccc3F)c3cc(C)c(cc(C)c4c56)c5c3c(C)cc6c(C)cc4N(c(cc3)ccc3F)c3c4[o]c(c(C(C)C)ccc5)c5c4ccc3)ccc3)c3c2ccc1 PBKKREINKVRZBI-UHFFFAOYSA-N 0.000 description 1
- SHQOTCPDAIHVDG-UHFFFAOYSA-N COc1c(ccc(c2c3cc4)ccc3N)c2c4cc1 Chemical compound COc1c(ccc(c2c3cc4)ccc3N)c2c4cc1 SHQOTCPDAIHVDG-UHFFFAOYSA-N 0.000 description 1
- KRRVAYYVPBEGMQ-UHFFFAOYSA-N Cc(cccc1)c1Nc1cccc2c1[o]c1c2cccc1 Chemical compound Cc(cccc1)c1Nc1cccc2c1[o]c1c2cccc1 KRRVAYYVPBEGMQ-UHFFFAOYSA-N 0.000 description 1
- KBOHITDHAMSPKX-UHFFFAOYSA-N Cc1c(cc-2c(c3c(cc4C)c(C)c5)c5N(c5cccc6c5[o]c5ccccc65)c(cc5)c-2cc5C#N)c3c4c(N(c(cc2)ccc2C#N)c2cccc3c2[o]c2ccccc32)c1 Chemical compound Cc1c(cc-2c(c3c(cc4C)c(C)c5)c5N(c5cccc6c5[o]c5ccccc65)c(cc5)c-2cc5C#N)c3c4c(N(c(cc2)ccc2C#N)c2cccc3c2[o]c2ccccc32)c1 KBOHITDHAMSPKX-UHFFFAOYSA-N 0.000 description 1
- MMVPTNFUMSRDHR-UHFFFAOYSA-N Cc1c2[o]c(c(N(c(cc3)ccc3C#N)c3cc(C)c(cc4C)c5c3c(C)cc(c(C)c3)c5c4c3N(c(cc3)ccc3C#N)c3c4[o]c(c(C)ccc5)c5c4ccc3)ccc3)c3c2ccc1 Chemical compound Cc1c2[o]c(c(N(c(cc3)ccc3C#N)c3cc(C)c(cc4C)c5c3c(C)cc(c(C)c3)c5c4c3N(c(cc3)ccc3C#N)c3c4[o]c(c(C)ccc5)c5c4ccc3)ccc3)c3c2ccc1 MMVPTNFUMSRDHR-UHFFFAOYSA-N 0.000 description 1
- BJMLYLSLLGXYKQ-UHFFFAOYSA-N Cc1cc(Br)c(c(Br)cc(c2c34)c(C)cc3Br)c2c1cc4Br Chemical compound Cc1cc(Br)c(c(Br)cc(c2c34)c(C)cc3Br)c2c1cc4Br BJMLYLSLLGXYKQ-UHFFFAOYSA-N 0.000 description 1
- WHMVNKMICDKELC-UHFFFAOYSA-N Cc1cc(N(c(cc2)ccc2F)c2cccc3c2[o]c2ccccc32)c(c(C)c2)c3c1cc-1c4c3c2c(C)cc4N(c2cccc3c2[o]c2ccccc32)c(cc2)c-1cc2F Chemical compound Cc1cc(N(c(cc2)ccc2F)c2cccc3c2[o]c2ccccc32)c(c(C)c2)c3c1cc-1c4c3c2c(C)cc4N(c2cccc3c2[o]c2ccccc32)c(cc2)c-1cc2F WHMVNKMICDKELC-UHFFFAOYSA-N 0.000 description 1
- IUIPUYJSJKXGDU-UHFFFAOYSA-N Cc1cccc2c1[o]c1c2cccc1N(c(cc1)ccc1F)c1cc(C)c(cc2C)c3c1c(C)cc(c(C)c1)c3c2c1N(c(cc1)ccc1F)c1c2[o]c(c(C)ccc3)c3c2ccc1 Chemical compound Cc1cccc2c1[o]c1c2cccc1N(c(cc1)ccc1F)c1cc(C)c(cc2C)c3c1c(C)cc(c(C)c1)c3c2c1N(c(cc1)ccc1F)c1c2[o]c(c(C)ccc3)c3c2ccc1 IUIPUYJSJKXGDU-UHFFFAOYSA-N 0.000 description 1
- ILSHRAVODWOCSZ-UHFFFAOYSA-N Cc1ccccc1N(c1c2[o]c(cccc3)c3c2ccc1)c1cc(C)c(cc2Br)c3c1c(Br)cc(c(C)c1)c3c2c1N(c1c2[o]c(cccc3)c3c2ccc1)c1ccccc1C Chemical compound Cc1ccccc1N(c1c2[o]c(cccc3)c3c2ccc1)c1cc(C)c(cc2Br)c3c1c(Br)cc(c(C)c1)c3c2c1N(c1c2[o]c(cccc3)c3c2ccc1)c1ccccc1C ILSHRAVODWOCSZ-UHFFFAOYSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- IJZNSWFRKKSGDM-UHFFFAOYSA-N [4-(2,2,2-trifluoroethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(CC(F)(F)F)C=C1 IJZNSWFRKKSGDM-UHFFFAOYSA-N 0.000 description 1
- GPIBKUJXKCEZOH-UHFFFAOYSA-M [Cl-].CC(C)[Mg+] Chemical class [Cl-].CC(C)[Mg+] GPIBKUJXKCEZOH-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Definitions
- the invention belongs to the technical field of organic electroluminescence materials, and specifically relates to an organic electroluminescence compound and a preparation method and application thereof.
- OLED Organic light-emitting devices
- fluorescent materials emit light through recombination of holes injected from the positive electrode and electrons injected from the negative electrode.
- This self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, fast response, and good temperature adaptability. It is also ultra-thin and can be fabricated on flexible panels. It is widely used in mobile phones, tablet computers, TVs, and lighting. And other fields.
- the organic electroluminescent device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers or self-recommended. Various functional materials are superimposed on each other according to the purpose to form an organic electroluminescent device.
- As a current device when a voltage is applied to the electrodes at both ends of the organic electroluminescence device, positive and negative charges are generated in the organic layer functional material film through the action of an electric field, and the positive and negative charges are further recombined in the light-emitting layer to generate light. For electroluminescence.
- the material designed in the present invention has higher efficiency, higher color purity, and longer service life.
- the blue doped material involved in the prior art 2015110294947 has a fluorescence emission wavelength between 468-490 nm, and its emission color is light blue to sky blue.
- the blue fluorescent compound designed by the present invention has a fluorescent emission wavelength between 440-460, and its color is deep blue, and its higher color purity is more conducive to improving the color saturation, luminous efficiency and service life of the light-emitting device.
- the molecular structure of the core structure is changed, the planarity of the core structure is reduced, thereby reducing the crystallinity of the product.
- the lower crystallinity can effectively prevent the material from being deposited during the evaporation process. Cracks are generated, thereby improving the yield of device preparation, and the changed core structure has better thermal stability, which increases the use range and purpose of the material.
- the present invention provides an organic electroluminescent compound and a preparation method and application thereof.
- the compound can be used as a blue dopant.
- Ar1, Ar2, Ar3, Ar4 are each independently a substituted or unsubstituted silyl group or silicon derivative group, a substituted or unsubstituted C1-C40 straight or branched alkyl group, a substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C6-C60 aromatic hydrocarbon group, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon group;
- R1, R2, R3, and R4 are each independently selected from cyano, CF3, substituted or unsubstituted silyl or silicon derivative groups, substituted or unsubstituted C1-C40 straight or branched alkyl, substituted Or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted Or unsubstituted C6-C60 aromatic hydrocarbon groups, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon groups.
- Ar1, Ar2, Ar3, Ar4 are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted 3,5-diphenyl Phenyl, substituted or unsubstituted 1,2-diphenylphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted carbazole Group, substituted or unsubstituted 9,9-spirobifluorene group, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted carbazole and its derivative group, substituted or unsubstituted Substituted furans and their derivative groups, substituted or unsubstituted thiophenes and their derivative groups, substituted substituted
- R1, R2, R3, and R4 are each independently selected from methyl, one or more hydrogens of which are substituted or unsubstituted by deuterium hydrogen (D), methyl, ethyl, and one or more of hydrogens are deuterated hydrogen (D) Substituted or unsubstituted hexyl, isopropyl, isopropyl, tert-butyl in which one or more hydrogens are replaced by deuterium hydrogen (D) or unsubstituted, in which one or more hydrogens are replaced by deuterium hydrogen (D) Or unsubstituted tert-butyl, substituted or unsubstituted silyl or silicon derivative groups, substituted or substituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Substituted terphenyl, substituted or unsubstituted various fluorene derivative groups, substituted or
- Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, o-fluorophenyl, m-fluorophenyl Phenyl, 4-fluorophenyl, 4-cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyl Dibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyl dibenzofuranyl, carbazolyl, 3-phenylcarbazolyl, 3-biphenylcarbazolyl, 9 -Benzocarbazolyl, dibenzothienyl;
- R1, R2, R3, R4 are each independently selected from methyl, mono-deuterated methyl, di-deuterated methyl, tri-deuterated methyl, ethyl, mono-deuterated ethyl, double-deuterated ethyl, tri-deuterated Ethyl, tetra-deuterated ethyl, penta-deuterated ethyl, isopropyl, single deuterated isopropyl, double deuterated isopropyl, tri-deuterated isopropyl, tetra-deuterated isopropyl, pentadeuterium Isopropyl, six-deuterated isopropyl, seven-deuterated isopropyl, tert-butyl, single-deuterated tert-butyl, double-deuterated tert-butyl, tri-deuterated tert-butyl, tetradeuterated tert-butyl , Five
- Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4 -Cyanophenyl, biphenyl (o-biphenyl, m-biphenyl, p-biphenyl,), 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuran Group, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl, dibenzothienyl, carbazolyl;
- R1, R2, R3, and R4 are each independently selected from methyl, tri-deuterated methyl, ethyl, double deuterated ethyl, pentadeuterated ethyl, isopropyl, single deuterated isopropyl, seven deuterated Isopropyl, tert-butyl, non-deuterated tert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, tert-phenyl, 4-tris Fluoromethylphenyl, 3,5-diphenylphenyl, 1,2-diphenylphenyl, hexadeuterated 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group Group, 9,9-spirobifluorene group, carbazolyl, 9-phenylcarbazolyl, 3-phenylcarbazolyl, 3-b
- the organic electroluminescent compound of the present invention is specifically any one of compounds G1 to G228:
- An organic electroluminescent device containing the above-mentioned organic electroluminescent compound.
- the organic electroluminescent device includes:
- an electron barrier layer is also provided between the anode and the light-emitting layer
- a hole blocking layer is also arranged between the cathode and the light-emitting layer
- the surface of the cathode is also provided with a covering layer.
- At least one of the above-mentioned hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, light-emitting layer material, or covering layer contains the above-mentioned organic electroluminescent compound.
- An organic electroluminescence display device comprising the above organic electroluminescence device.
- the blue doped material involved in the prior art 2015110294947 has a fluorescence emission wavelength between 468-490 nm, and its emission color is light blue to sky blue.
- the blue fluorescent compound invented and designed by our company has a fluorescence emission wavelength between 440-460, and its color is deep blue. Its higher color purity is more conducive to improving the color saturation, luminous efficiency and Service life.
- the planarity of the core structure is reduced, thereby reducing the crystallinity of the product.
- the lower crystallinity can effectively prevent the material from being deposited during the evaporation process. Cracks are generated, and the yield of the device is improved (using this technology, the yield of the device is increased from 10% to 80%), and the changed core structure has better thermal stability, which increases the use range of materials and use.
- the material designed and invented by this technology has a great improvement and enhancement in luminous efficiency, life span, color purity, thermal stability of the material and application range. It effectively solves the problems of short life, low efficiency and low yield in the prior art.
- the present invention provides a new type of organic electroluminescent compound, as well as devices and devices containing the same.
- the lifetime of the device, the luminous efficiency of the device, and the color saturation of the device can be effectively improved.
- the yield of the device is prepared to solve the problems of low yield and short life in the prior art.
- Rx and Rr are C1-C6 alkyl or cycloalkyl or heterocycloalkyl
- the preparation scheme is as follows:
- the organic phase was extracted after separation.
- the organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate.
- the structure was confirmed using mass spectrometry (MS).
- the intermediate C is obtained after passing through the column, and the intermediate C is purified by preparative chromatography to obtain the high-purity intermediate C.
- MS mass spectrometry
- the organic phase is extracted after separation and separation.
- the organic phase is dried with anhydrous magnesium sulfate and filtered.
- the filtrate, the filtrate was spin-dried, and 5-10 times the silica gel powder of Intermediate C was added for mixing and passing through the column.
- MS mass spectrometry
- Rx and Rr are substituted or unsubstituted C5-C30 heterocyclic aryl groups or substituted or substituted C6-C30 aryl groups, the preparation scheme is as follows:
- the filter cake was heated to dissolve the filter cake with toluene of 50 times the weight of the filter cake and passed through the activated carbon funnel while hot to obtain a filtrate.
- the crude product was recrystallized three times with toluene to obtain compound I.
- MS mass spectrometry
- HAT-CN 10 nanometers thick HAT-CN on the hole injection layer (HIL)
- HTL hole transport layer
- NPD hole transport layer
- ADN blue EML 9,10-Bis (2-naphthyl) anthraces
- the chemical formula G1 of the present invention is selected as the dopant material, and the light-emitting layer is formed by doping about 5% with a thickness of 25 nanometers, and a mixture of ETM and LiQ with a thickness of 35 nanometers is deposited on the electron transport layer at a ratio of 1:1. (ETL), then on the electron injection layer (EIL) with a thickness of 2 nanometers of LiQ vapor deposition. After that, magnesium (Mg) and silver (Ag) are mixed in a ratio of 9:1 on the cathode and the thickness is 15 nanometers.
- the surface of the cathode is sealed with a UV curable adhesive and a seal cap containing a desiccant to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere.
- the organic electroluminescent device is thus prepared.
- the compounds G2-G228 were used as blue light doping (BD) materials, and the other parts were the same as those in Application Example 1. Accordingly, organic electroluminescent devices of Application Examples 2 to 228 were fabricated.
- BD blue light doping
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Abstract
A pyrene blue fluorescent dopant, and an organic electroluminescent device comprising same. The structural formula of the compound is shown in formula (I). The compound can be applied as an organic electroluminescent material, has the light emitting efficiency, service life, colorimetric purity, material thermal stability, and use scope thereof greatly improved and increased, and effectively solve the problems in the prior art such as short service life, low efficiency, and low yield.
Description
本发明属于有机电致发光材料技术领域，具体涉及一种有机电致发光化合物及其制备方法和应用。The invention belongs to the technical field of organic electroluminescence materials, and specifically relates to an organic electroluminescence compound and a preparation method and application thereof.
有机电致发光器件(Organic Light-emitting Devices,OLED)是利用如下原理的自发性发光器件：当施加电场时，荧光物质通过正极注入的空穴和负极注入的电子的重新结合而发光。这种自发光器件，具有电压低、亮度高、视角宽、响应快、温度适应性好等特性，并且超薄，能制作在柔性面板上等优点，广泛应用于手机、平板电脑、电视、照明等领域。Organic light-emitting devices (OLED) are spontaneous light-emitting devices that use the following principle: when an electric field is applied, fluorescent materials emit light through recombination of holes injected from the positive electrode and electrons injected from the negative electrode. This self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, fast response, and good temperature adaptability. It is also ultra-thin and can be fabricated on flexible panels. It is widely used in mobile phones, tablet computers, TVs, and lighting. And other fields.
有机电致发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层或者自荐的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成有机电致发光器件。作为电流器件，当对有机电致发光器件的两端电极施加电压，并通过电场作用在有机层功能材料膜层中产生正负电荷，正负电荷进一步在发光层中复合，产生光，此过程为电致发光。The organic electroluminescent device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers or self-recommended. Various functional materials are superimposed on each other according to the purpose to form an organic electroluminescent device. As a current device, when a voltage is applied to the electrodes at both ends of the organic electroluminescence device, positive and negative charges are generated in the organic layer functional material film through the action of an electric field, and the positive and negative charges are further recombined in the light-emitting layer to generate light. For electroluminescence.
对于有机电致发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现有机电致发光器件性能的不断提升，不但需要有机电致发光器件的结构和制作工艺的创新，更需要有机电致光电功能材料的不断研究和创新，创制出更高性能的有机电致功能材料。Research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. In order to achieve the continuous improvement of the performance of organic electroluminescent devices, not only the innovation of the structure and manufacturing process of organic electroluminescent devices, but also the continuous research and innovation of organic electroluminescent functional materials are needed to create higher performance organic electroluminescent devices. Functional Materials.
就当前有机电致发光产业的实际需求而言，目前有机电致发光材料的发展还远远不够，落后于面板制造企业的要求。As far as the actual needs of the current organic electroluminescence industry are concerned, the current development of organic electroluminescence materials is far from enough and lags behind the requirements of panel manufacturers.
就目前现有技术2015110294947对比而言，本发明设计的材料具有更高的效率、更高的色纯度、且更长的使用寿命。现有技术2015110294947中涉及的蓝光掺杂材料，其荧光发射波长在468-490nm之间，其发射色彩为淡蓝色至天蓝色。本发明设计的蓝色荧光化合物，其荧光发射波长为440-460之间，其色彩为深蓝色，其较高的色纯度更有利于提高发光器件的色彩饱和度、发光效率及使用寿命。与现有技术2015110294947对比而言，由于改变了核心结构的分子构造，降低了该核心结构的平面性，进而降低了该产品的结晶性，较低的结晶性能够有效阻止材料在蒸镀过程中产生裂缝，进而提高器件制备的良率，改变后的核心结构有更好的热稳定性，增加了材料的使用范围及用途。In comparison with the current prior art 2015110294947, the material designed in the present invention has higher efficiency, higher color purity, and longer service life. The blue doped material involved in the prior art 2015110294947 has a fluorescence emission wavelength between 468-490 nm, and its emission color is light blue to sky blue. The blue fluorescent compound designed by the present invention has a fluorescent emission wavelength between 440-460, and its color is deep blue, and its higher color purity is more conducive to improving the color saturation, luminous efficiency and service life of the light-emitting device. Compared with the prior art 2015110294947, because the molecular structure of the core structure is changed, the planarity of the core structure is reduced, thereby reducing the crystallinity of the product. The lower crystallinity can effectively prevent the material from being deposited during the evaporation process. Cracks are generated, thereby improving the yield of device preparation, and the changed core structure has better thermal stability, which increases the use range and purpose of the material.
发明内容Summary of the invention
发明目的：针对上述技术问题，本发明提供了一种有机电致发光化合物及其制备方法和应用，该化合物可以作为蓝光掺杂物质(Blue dopant)。Objective of the invention: In view of the above technical problems, the present invention provides an organic electroluminescent compound and a preparation method and application thereof. The compound can be used as a blue dopant.
为了达到上述发明目的，本发明所采用的技术方案如下：In order to achieve the above-mentioned purpose of the invention, the technical solutions adopted by the invention are as follows:
一种有机电致发光化合物，其结构式如式(I)所示：An organic electroluminescent compound whose structural formula is shown in formula (I):
其中，Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的硅烷基或硅类衍生物基团、取代或未取代的C1-C40的直连或支链烷基、取代或未取代的C3-C40的环烷基、取代或未取代的C1-C40的杂烷基、取代或未取代的C2-C40的烯基、取代或未取代的C2-C40的炔基、取代或未取代的C6-C60的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基；Wherein, Ar1, Ar2, Ar3, Ar4 are each independently a substituted or unsubstituted silyl group or silicon derivative group, a substituted or unsubstituted C1-C40 straight or branched alkyl group, a substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C6-C60 aromatic hydrocarbon group, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon group;
R1、R2、R3、R4各自独立的选自氰基、CF3、取代或未取代的硅烷基或硅类衍生物基团、取代或未取代的C1-C40的直连或支链烷基、取代或未取代的C3-C40的环烷基、取代或未取代的C1-C40的杂烷基、取代或未取代的C2-C40的烯基、取代或未取代的C2-C40的炔基、取代或未取代的C6-C60的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基。R1, R2, R3, and R4 are each independently selected from cyano, CF3, substituted or unsubstituted silyl or silicon derivative groups, substituted or unsubstituted C1-C40 straight or branched alkyl, substituted Or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted Or unsubstituted C6-C60 aromatic hydrocarbon groups, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon groups.
本发明进一步的优选技术方案为：Further preferred technical solutions of the present invention are:
其中，Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的3,5-二苯基苯基、取代或未取代的1,2-二苯基苯基、取代或未取代的萘基、取代或未取代的菲基、取代或未取代的蒽基、取代或未取代的咔唑基、取代或未取代9,9-螺二芴基团、取代或未取代的9,9-二甲基芴基团、取代或未取代的咔唑类及其衍生物基团、取代或未取代的呋喃类及其衍生物基团、取代或未取代的噻吩类及其衍生物基团、取代或未取代的萘类及其衍生物基团；Wherein, Ar1, Ar2, Ar3, Ar4 are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted 3,5-diphenyl Phenyl, substituted or unsubstituted 1,2-diphenylphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted carbazole Group, substituted or unsubstituted 9,9-spirobifluorene group, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted carbazole and its derivative group, substituted or unsubstituted Substituted furans and their derivative groups, substituted or unsubstituted thiophenes and their derivative groups, substituted or unsubstituted naphthalenes and their derivative groups;
R1、R2、R3、R4各自独立的选自甲基、其中一个或多个氢被氘氢(D)取代或未取代的甲基、乙基、其中一个或多个氢被氘氢(D)取代或未取代的已基、异丙基、其中一个或多个氢被氘氢(D)取代或未取代的异丙基、叔丁基、其中一个或多个氢被氘氢(D)取代或未取代的叔丁基、取代或未取代的硅烷基或硅类衍生物基团、取代或为取代的苯基、取代或未 取代甲苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的各种芴类衍生物基团、取代或未取代的咔唑类及其衍生物基团、取代或未取代的呋喃类及其衍生物基团、取代或未取代的噻吩类及其衍生物基团。R1, R2, R3, and R4 are each independently selected from methyl, one or more hydrogens of which are substituted or unsubstituted by deuterium hydrogen (D), methyl, ethyl, and one or more of hydrogens are deuterated hydrogen (D) Substituted or unsubstituted hexyl, isopropyl, isopropyl, tert-butyl in which one or more hydrogens are replaced by deuterium hydrogen (D) or unsubstituted, in which one or more hydrogens are replaced by deuterium hydrogen (D) Or unsubstituted tert-butyl, substituted or unsubstituted silyl or silicon derivative groups, substituted or substituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Substituted terphenyl, substituted or unsubstituted various fluorene derivative groups, substituted or unsubstituted carbazoles and their derivative groups, substituted or unsubstituted furans and their derivative groups, substituted Or unsubstituted thiophenes and their derivative groups.
本发明更进一步的优选技术方案为：A further preferred technical solution of the present invention is:
其中，Ar1、Ar2、Ar3、Ar4各自独立的为苯基、甲基苯基、乙基苯基、异丙基苯基、叔丁基苯基、五氟苯基、邻氟苯基、间氟苯基、4-氟苯基、4-氰基苯基、联苯基、1-萘基、2-萘基、二苯并呋喃基、4-甲基二苯并呋喃基、4-乙基二苯并呋喃基、4-异丙基二苯并呋喃基、4-叔丁基二苯并呋喃基、咔唑基、3-苯基咔唑基、3-联苯基咔唑基、9-苯咔唑基、二苯并噻吩基；Among them, Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, o-fluorophenyl, m-fluorophenyl Phenyl, 4-fluorophenyl, 4-cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyl Dibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyl dibenzofuranyl, carbazolyl, 3-phenylcarbazolyl, 3-biphenylcarbazolyl, 9 -Benzocarbazolyl, dibenzothienyl;
R1、R2、R3、R4各自独立的选自甲基、单氘代甲基、二氘代甲基、三氘代甲基、乙基、单氘代乙基、双氘代乙基、三氘代乙基、四氘代乙基、五氘代乙基、异丙基、单氘代异丙基、双氘代异丙基、三氘代异丙基、四氘代异丙基、五氘代异丙基、六氘代异丙基、七氘代异丙基、叔丁基、单氘代叔丁基、双氘代叔丁基、三氘代叔丁基、四氘代叔丁基、五氘代叔丁基、六氘代叔丁基、七氘代叔丁基、八氘代叔丁基、九氘代叔丁基、苯基、甲苯基、4-氟苯基、4-氰基苯基、五氟苯基、联苯基、三联苯基、4-三氟甲基苯基、3,5-二苯基苯基、1,2-二苯基苯基等基团、六氘代的9,9-二甲基芴基团、9,9-二苯基芴基团、9,9-螺二芴基团。R1, R2, R3, R4 are each independently selected from methyl, mono-deuterated methyl, di-deuterated methyl, tri-deuterated methyl, ethyl, mono-deuterated ethyl, double-deuterated ethyl, tri-deuterated Ethyl, tetra-deuterated ethyl, penta-deuterated ethyl, isopropyl, single deuterated isopropyl, double deuterated isopropyl, tri-deuterated isopropyl, tetra-deuterated isopropyl, pentadeuterium Isopropyl, six-deuterated isopropyl, seven-deuterated isopropyl, tert-butyl, single-deuterated tert-butyl, double-deuterated tert-butyl, tri-deuterated tert-butyl, tetradeuterated tert-butyl , Five deuterated tert-butyl, six deuterated tert-butyl, seven deuterated tert-butyl, eight deuterated tert-butyl, nine deuterated tert-butyl, phenyl, tolyl, 4-fluorophenyl, 4- Cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3,5-diphenylphenyl, 1,2-diphenylphenyl and other groups, Six-deuterated 9,9-dimethylfluorene group, 9,9-diphenylfluorene group, 9,9-spirobifluorene group.
本发明更进一步的优选技术方案为：A further preferred technical solution of the present invention is:
其中，Ar1、Ar2、Ar3、Ar4各自独立的为苯基、甲基苯基、乙基苯基、异丙基苯基、叔丁基苯基、五氟苯基、4-氟苯基、4-氰基苯基、联苯基(邻联苯基、间联苯基、对联苯基、)、1-萘基、2-萘基、二苯并呋喃基、4-甲基二苯并呋喃基、4-乙基二苯并呋喃基、4-异丙基二苯并呋喃基、4-叔丁基二苯并呋喃基、二苯并噻吩基、咔唑基；Among them, Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4 -Cyanophenyl, biphenyl (o-biphenyl, m-biphenyl, p-biphenyl,), 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuran Group, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl, dibenzothienyl, carbazolyl;
R1、R2、R3、R4各自独立的选自甲基、三氘代甲基、乙基、双氘代乙基、五氘代乙基、异丙基、单氘代异丙基、七氘代异丙基、叔丁基、九氘代叔丁基、苯基、甲苯基、4-氟苯基、4-氰基苯基、五氟苯基、联苯基、三联苯基、4-三氟甲基苯基、3,5-二苯基苯基、1,2-二苯基苯基、六氘代的9,9-二甲基芴基团、9,9-二苯基芴基团、9,9-螺二芴基团、咔唑基、9-苯基咔唑基、3-苯基咔唑基、3-联苯基咔唑基、3,6-二苯基咔唑基。R1, R2, R3, and R4 are each independently selected from methyl, tri-deuterated methyl, ethyl, double deuterated ethyl, pentadeuterated ethyl, isopropyl, single deuterated isopropyl, seven deuterated Isopropyl, tert-butyl, non-deuterated tert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, tert-phenyl, 4-tris Fluoromethylphenyl, 3,5-diphenylphenyl, 1,2-diphenylphenyl, hexadeuterated 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group Group, 9,9-spirobifluorene group, carbazolyl, 9-phenylcarbazolyl, 3-phenylcarbazolyl, 3-biphenylcarbazolyl, 3,6-diphenylcarbazole base.
本发明的有机电致发光化合物具体为化合物G1至G228中任意一个：The organic electroluminescent compound of the present invention is specifically any one of compounds G1 to G228:
一种包含上述的有机电致发光化合物的有机电致发光器件。An organic electroluminescent device containing the above-mentioned organic electroluminescent compound.
优选的，所述有机电致发光器件包括：Preferably, the organic electroluminescent device includes:
阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层以及阴极顺次堆积 的构造；A structure in which anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer, electron injection layer and cathode are sequentially stacked;
其中，阳极和发光层之间还设置有电子阻隔层；Wherein, an electron barrier layer is also provided between the anode and the light-emitting layer;
阴极和发光层之间还设置有空穴阻隔层；A hole blocking layer is also arranged between the cathode and the light-emitting layer;
阴极表面还设置有覆盖层。The surface of the cathode is also provided with a covering layer.
上述空穴传输层、电子阻隔层、空穴阻隔层、电子传输层、发光层材料，或者覆盖层中的至少一层包含上述的有机电致发光化合物。At least one of the above-mentioned hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, light-emitting layer material, or covering layer contains the above-mentioned organic electroluminescent compound.
一种包含上述的有机电致发光器件的有机电致发光显示设备。An organic electroluminescence display device comprising the above organic electroluminescence device.
上述化合物在作为有机电致发光材料中的应用。Application of the above-mentioned compounds as organic electroluminescent materials.
本发明的有益效果：The beneficial effects of the present invention:
就目前现有技术2015110294947对比而言，我司设计发明的材料具有更高的效率、更高的色纯度、且更长的使用寿命。现有技术2015110294947中涉及的蓝光掺杂材料，其荧光发射波长在468-490nm之间，其发射色彩为淡蓝色至天蓝色。而我司该技术发明设计的蓝色荧光化合物，其荧光发射波长为440-460之间，其色彩为深蓝色，其较高的色纯度更有利于提高发光器件的色彩饱和度、发光效率及使用寿命。与现有技术2015110294947对比而言，由于改变了核心结构的分子构造，降低了该核心结构的平面性，进而降低了该产品的结晶性，较低的结晶性能够有效阻止材料在蒸镀过程中产生裂缝，进而提高器件制备的良率(使用该技术，器件的良率由之前的10％提高至80％)，改变后的核心结构有更好的热稳定性，增加了材料的使用范围及用途。与对比技术相比，该技术设计发明的材料在发光效率、寿命、色纯度、材料的热稳定性及使用范围上有极大的改善及提高。有效的解决了现有技术中寿命短，效率低、良率低等问题。In comparison with the current existing technology 2015110294947, the material designed and invented by our company has higher efficiency, higher color purity, and longer service life. The blue doped material involved in the prior art 2015110294947 has a fluorescence emission wavelength between 468-490 nm, and its emission color is light blue to sky blue. The blue fluorescent compound invented and designed by our company has a fluorescence emission wavelength between 440-460, and its color is deep blue. Its higher color purity is more conducive to improving the color saturation, luminous efficiency and Service life. Compared with the prior art 2015110294947, because the molecular structure of the core structure is changed, the planarity of the core structure is reduced, thereby reducing the crystallinity of the product. The lower crystallinity can effectively prevent the material from being deposited during the evaporation process. Cracks are generated, and the yield of the device is improved (using this technology, the yield of the device is increased from 10% to 80%), and the changed core structure has better thermal stability, which increases the use range of materials and use. Compared with the comparative technology, the material designed and invented by this technology has a great improvement and enhancement in luminous efficiency, life span, color purity, thermal stability of the material and application range. It effectively solves the problems of short life, low efficiency and low yield in the prior art.
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。If specific conditions are not indicated in the examples, it shall be carried out in accordance with the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used without the manufacturer's indication are all conventional products that can be purchased commercially.
本发明特提供了一种新型有机电致发光化合物，以及包含其的器件和装置，通过使用本发明有机电致发光化合物，可以有效提高器件的寿命、器件的发光效率、器件的色彩饱和度、器件制备的良率，以解决现有技术中良率低，寿命短的问题。The present invention provides a new type of organic electroluminescent compound, as well as devices and devices containing the same. By using the organic electroluminescent compound of the present invention, the lifetime of the device, the luminous efficiency of the device, and the color saturation of the device can be effectively improved. The yield of the device is prepared to solve the problems of low yield and short life in the prior art.
化合物G1-G228的制备方案如下：The preparation scheme of compound G1-G228 is as follows:
当Rx、Rr为C1-C6的烷基或环烷基或杂环烷基时，制备方案如下：When Rx and Rr are C1-C6 alkyl or cycloalkyl or heterocycloalkyl, the preparation scheme is as follows:
中间体A的制备：Preparation of Intermediate A:
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘(1eq)、Pd(dppf)Cl
2(0.05eq)，ZnCl
2(2.5eq)溶于20倍1,6-二溴芘的无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L的烷基氯化镁(烷基为Rxr)(2.5eq)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入适量稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入5-10倍1,6-二溴芘质量的硅胶粉进行拌样并过柱层析，淋洗液使用Hex：EA＝9:1进行洗脱后得中间体A。使用质谱(MS)对结构进行确认。
Under the protection of nitrogen, add 1,6-dibromopyrene (1eq), Pd(dppf)Cl 2 (0.05eq), and ZnCl 2 (2.5eq) dissolved in 20 times the amount of 1,6-dibromopyrene in a 2000ml three-necked flask. In anhydrous tetrahydrofuran, lower the reaction solution to -25°C, slowly add 2.0M/L of alkyl magnesium chloride (alkyl group Rxr) (2.5eq) in the flask, and slowly raise the temperature to 80°C and stir 4 hour. After the reaction, the reaction solution was cooled to room temperature, and then an appropriate amount of dilute hydrochloric acid (5%) was slowly added. The organic phase was extracted after separation. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was spin-dried and added 5 Silica gel powder with -10 times the mass of 1,6-dibromopyrene was mixed and passed through column chromatography, and the eluent was eluted with Hex:EA=9:1 to obtain Intermediate A. The structure was confirmed using mass spectrometry (MS).
中间体B的制备：Preparation of Intermediate B:
于1000ml三口烧瓶中加入中间体A(1eq)，20倍中间体A重量比的硝基苯后开启搅拌，室温下将溴素(5eq)、20倍溴素重量比的硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后使用高效液相制备色谱制备得中间体B。使用质谱(MS)对结构进行确认。Add Intermediate A (1eq) and 20 times the weight ratio of Intermediate A to nitrobenzene in a 1000ml three-necked flask and start stirring. Mix bromine (5eq) and 20 times the weight ratio of Bromine nitrobenzene at room temperature. Slowly add dropwise to the reaction solution, and pass nitrogen gas to remove the HBr produced. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat to 80°C to continue the reaction for 5 hours. After the reaction is completed, stop the reaction. After the reaction liquid is cooled to room temperature, a solid is obtained by filtration. The solid is recrystallized with 5 times toluene and then used HPLC Intermediate B was prepared. The structure was confirmed using mass spectrometry (MS).
中间体C的制备：Preparation of Intermediate C:
氮气保护下，于1000ml三口烧瓶中加入中间体B(1eq)、化合物X(2.5eq)、叔丁醇钠(2.5eq)、Pd
2(dba)
3(5％eq)、30倍中间体B质量的甲苯，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入足量二氯甲烷、5-10倍中间体B质量的硅胶粉拌样后过柱后得到纯度较低的中间体C，将中间体C使用制备色谱进行提纯后得高纯度的中间体C。使用质谱(MS)对产品结构进行确认。
Under nitrogen protection, add Intermediate B (1eq), Compound X (2.5eq), Sodium tert-butoxide (2.5eq), Pd 2 (dba) 3 (5% eq), 30 times Intermediate B to a 1000ml three-necked flask After the addition of toluene of quality, the temperature is raised to reflux for 5 hours. After the reaction is completed, the temperature is lowered to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 5-10 times the quality of intermediate B silica gel powder, the intermediate C is obtained after passing through the column, and the intermediate C is purified by preparative chromatography to obtain the high-purity intermediate C. Use mass spectrometry (MS) to confirm the product structure.
化合物D的制备：Preparation of compound D:
氮气保护下，于1000ml三口烧瓶中加入中间体C(1eq)、Pd(dppf)Cl
2(5％eq)，ZnCl
2(2.5eq)溶于20倍中间体C质量的无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M烷基基氯化镁(烷基为Rr)(2.5eq)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入适量稀盐酸(5％)(PH值调至中性)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入5-10倍中间体C的硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得化合物D粗品，将化合物D粗品使用甲苯重结晶3次后得纯度较高的化合物D。使用质谱(MS)对产品结构进行确认。
Under the protection of nitrogen, add Intermediate C (1eq), Pd(dppf)Cl 2 (5% eq), and ZnCl 2 (2.5eq) in a 1000ml three-necked flask dissolved in 20 times the mass of Intermediate C in anhydrous tetrahydrofuran. The reaction solution was reduced to -25°C, and 2.0M alkyl magnesium chloride (alkyl group is Rr) (2.5eq) was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction is over, the reaction solution is cooled to room temperature, and then an appropriate amount of dilute hydrochloric acid (5%) (pH adjusted to neutral) is slowly added. The organic phase is extracted after separation and separation. The organic phase is dried with anhydrous magnesium sulfate and filtered. The filtrate, the filtrate was spin-dried, and 5-10 times the silica gel powder of Intermediate C was added for mixing and passing through the column. The eluent was eluted with Hex:EA=10:1 to obtain the crude compound D, and the crude compound D was toluene After three recrystallizations, compound D with higher purity was obtained. Use mass spectrometry (MS) to confirm the product structure.
当Rx、Rr为取代或未取代的C5-C30杂环芳基或取代或为取代的C6-C30的芳基时，制备方案如下：When Rx and Rr are substituted or unsubstituted C5-C30 heterocyclic aryl groups or substituted or substituted C6-C30 aryl groups, the preparation scheme is as follows:
中间体F的制备：Preparation of intermediate F:
氮气保护下，于3000ml三口烧瓶中加入1,6-二溴芘(1eq)、芳基硼酸(芳基为Rx)或芳基硼酸酯(芳基为Rx)(2.5eq)、四三苯基膦钯(0.05eq)、碳酸钾(5eq)、甲苯(1,6-二溴芘质量的20倍)、乙醇(芳基硼酸质量的5倍)、水(碳酸钾质量的3倍)，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应，降温至室温后过滤得滤饼，滤饼使用滤饼质量50倍的甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体F。使用质谱(MS)对产品结构进行确认。Under the protection of nitrogen, add 1,6-dibromopyrene (1eq), aryl boronic acid (aryl is Rx) or aryl boronic acid ester (aryl is Rx) (2.5eq), tetrakistribenzene in a 3000ml three-necked flask Phosphine palladium (0.05eq), potassium carbonate (5eq), toluene (20 times the mass of 1,6-dibromopyrene), ethanol (5 times the mass of arylboronic acid), water (3 times the mass of potassium carbonate), After the addition, the temperature was raised to reflux for 5 hours. After the reaction was completed by HPLC, the reaction was stopped, and the filter cake was filtered after cooling to room temperature. The filter cake was heated and dissolved in toluene with 50 times the weight of the filter cake and passed through the activated carbon funnel to obtain the filtrate. Intermediate F was obtained by crystallization. Use mass spectrometry (MS) to confirm the product structure.
中间体G的制备：Preparation of Intermediate G:
于3000ml三口烧瓶中加入中间体F(1eq)，20倍中间体F重量比的硝基苯后开启搅拌，室温下将溴素(5eq)及20倍溴素重量比的硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后，将得到的产品使用高效液相制备色谱制备得中间体G。使用质谱(MS)对结构进行确认。Add Intermediate F (1eq) to a 3000ml three-necked flask, 20 times the weight ratio of Intermediate F nitrobenzene and start stirring. Mix bromine (5eq) and 20 times the weight ratio of Bromine nitrobenzene at room temperature. Slowly add dropwise to the reaction solution, and pass nitrogen gas to remove the HBr produced. After the addition is complete, stir at room temperature for 2 hours and then heat to 80°C to continue the reaction for 5 hours. After the reaction is completed, stop the reaction. After the reaction solution is cooled to room temperature, a solid is obtained by filtration. After the solid is recrystallized with 5 times toluene, the obtained product Intermediate G was prepared by high performance liquid chromatography. The structure was confirmed using mass spectrometry (MS).
中间体H的制备Preparation of Intermediate H
氮气保护下，于1000ml三口烧瓶中加入中间体G(1eq)、化合物Y(2.5eq)、叔丁醇钠(2.5eq)、Pd
2(dba)
3(5％eq)、30倍中间体G质量的甲苯，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后过硅胶短柱得滤液，滤液旋干后得到纯度较低的中间体H，将中间体H使用制备色谱进行提纯后得高纯度的中间体H。使用质谱(MS)对产品结构进行确认。
Under nitrogen protection, add Intermediate G (1eq), Compound Y (2.5eq), Sodium tert-butoxide (2.5eq), Pd 2 (dba) 3 (5% eq), 30 times Intermediate G to a 1000ml three-necked flask After the addition of toluene of quality, the temperature is raised to reflux for 5 hours. After the reaction is completed, the temperature is lowered to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after the filtrate is separated. The organic phase is dried with anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. The filtrate is spin-dried to obtain a lower purity The intermediate H is purified by preparative chromatography to obtain high-purity intermediate H. Use mass spectrometry (MS) to confirm the product structure.
化合物I的制备：Preparation of Compound I:
氮气保护下，于1000ml三口烧瓶中加入中间体H(1eq)、芳基硼酸(芳基为Rr)或芳基硼酸酯(芳基为Rr)(2.5eq)、四三苯基膦钯(0.05eq)、碳酸钾(5eq)、甲苯(中间体H质量的30倍)、乙醇(芳基硼酸质量的5倍)、水(碳酸钾质量的3倍)，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应，降温至室温后过滤得滤饼，使用滤饼质量50倍的甲苯将滤饼加热溶解后趁热过活性炭漏斗得滤液，滤液旋蒸除去甲苯后得化合物I粗品，将粗品使用甲苯重结晶三次后得化合物I。使用质谱(MS)对产品结构进行确认。Under nitrogen protection, add intermediate H (1eq), aryl boronic acid (aryl is Rr) or aryl borate (aryl is Rr) (2.5eq), tetrakistriphenylphosphine palladium ( 0.05eq), potassium carbonate (5eq), toluene (30 times the mass of intermediate H), ethanol (5 times the mass of arylboronic acid), water (3 times the mass of potassium carbonate), after the addition, the temperature is raised to reflux reaction 5 hour. After the reaction was completed by HPLC, the reaction was stopped, the temperature was lowered to room temperature and then filtered to obtain a filter cake. The filter cake was heated to dissolve the filter cake with toluene of 50 times the weight of the filter cake and passed through the activated carbon funnel while hot to obtain a filtrate. , The crude product was recrystallized three times with toluene to obtain compound I. Use mass spectrometry (MS) to confirm the product structure.
具体制备实施例：Specific preparation examples:
实施例1：化合物G18的合成Example 1: Synthesis of compound G18
1)中间体1的合成：1) Synthesis of Intermediate 1:
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
2 13.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-1 18.6g(65％)。MS(EI)：230(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was lowered to -25°C, and 125ml (250mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 18.6g (65%) of white solid intermediate-1. MS(EI): 230(M + )
2)中间体-2的合成：2) Synthesis of Intermediate-2:
于1000ml三口烧瓶中加入中间体-1 18g(78mmol)，硝基苯150ml后开启搅拌，室温下将62.4g(390mmol)溴素(Br
2)、1200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-2 26.4g(62％)。MS(EI)：545(M
+)
Add 18g (78mmol) of Intermediate-1 to a 1000ml three-necked flask and 150ml of nitrobenzene, then start stirring. Mix 62.4g (390mmol) of bromine (Br 2 ) and 1200ml of nitrobenzene at room temperature and then slowly add dropwise to the reaction. In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 26.4 g (62%) of Intermediate-2. MS(EI): 545(M + )
3)中间体-4的合成：3) Synthesis of Intermediate-4:
氮气保护下，于1000ml三口烧瓶中加入26g(28mmol)中间体-2、17g(62mmol)化合物-1、叔丁醇钠6.5g(67mmol)、5.4g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、220g硅胶粉拌样后过柱得到纯度较低的中间体-4，将中间体-4使用制备色谱进行提纯后得高纯度的中间体-4白色固体15.6g(60％)。MS(EI)：930(M
+)
Under the protection of nitrogen, add 26g (28mmol) of Intermediate-2, 17g (62mmol) of Compound-1, 6.5g (67mmol) of sodium tert-butoxide, 5.4g (0.56mmol) of Pd 2 (dba) 3 into a 1000ml three-necked flask. 350ml of toluene, the temperature was raised to reflux for 5 hours after the addition was completed. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 220 g of silica gel powder were mixed and passed through the column to obtain Intermediate-4 with lower purity. Intermediate-4 was purified by preparative chromatography to obtain 15.6g (60%) of white solid with high purity Intermediate-4. MS(EI): 930(M + )
4)化合物G18的合成：4) Synthesis of compound G18:
氮气保护下，于1000ml三口烧瓶中加入15g(16.1mmol)中间体-4、Pd(dppf)Cl
20.6g(0.8mmol)，ZnCl
2 5.5g(40.3mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁20.3ml(40.5mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入150g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固8.4g，使用20倍甲苯进行重结晶三次后得黄绿色固体4.8g(45％)。MS(EI)：800(M
+)。
Under nitrogen protection, add 15g (16.1mmol) Intermediate-4, Pd(dppf)Cl 2 0.6g (0.8mmol), ZnCl 2 5.5g (40.3mmol) in 400ml dry tetrahydrofuran into a 1000ml three-necked flask, and The reaction solution was reduced to -25°C, and 20.3ml (40.5mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 150g The silica gel powder was mixed and passed through the column. The eluent was eluted with Hex: EA=10:1 to obtain a yellow-green solid 8.4g. After recrystallization with 20 times toluene three times, a yellow-green solid 4.8g (45%) was obtained. . MS (EI): 800 (M + ).
实施例2：化合物G28Example 2: Compound G28
1)中间体-5的合成：1) Synthesis of Intermediate-5:
氮气保护下，于100ml三口烧瓶中加入26g(28mmol)中间体-2、21g(70mmol)化合物-2、叔丁醇钠6.73g(70mmol)、0.5g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤 液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、250g硅胶粉拌样后过柱得纯度较低的中间体-5，将中间体-5使用制备色谱进行提纯后得高纯度的中间体-5 13.8g(50％)。MS(EI)：986(M
+)
Under the protection of nitrogen, add 26g (28mmol) Intermediate-2, 21g (70mmol) Compound-2, Sodium tert-butoxide 6.73g (70mmol), 0.5g (0.56mmol) Pd 2 (dba) 3 , into a 100ml three-necked flask. 350ml of toluene, the temperature was raised to reflux for 5 hours after the addition was completed. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 250 g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-5 with lower purity. Intermediate-5 was purified by preparative chromatography to obtain 13.8g (50%) of Intermediate-5 with high purity. MS(EI): 986(M + )
2)化合物G28的合成：2) Synthesis of compound G28:
氮气保护下，于1000ml三口烧瓶中加入13g(13.2mmol)中间体-5、Pd(dppf)Cl
20.5g(0.66mmol)，ZnCl
2 4.5g(33mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁18ml(33mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固7.6g，使用20倍甲苯进行重结晶三次后得黄绿色固体4.5g(40％)。MS(EI)：857(M
+)。
Under the protection of nitrogen, add 13g (13.2mmol) Intermediate-5, Pd(dppf)Cl 2 0.5g (0.66mmol), ZnCl 2 4.5g (33mmol) in 400ml dry tetrahydrofuran into a 1000ml three-necked flask. The solution was lowered to -25°C, and 18ml (33mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=10:1 to obtain a yellow-green solid 7.6g. After recrystallization with 20 times toluene for three times, a yellow-green solid 4.5g (40%) was obtained. . MS (EI): 857 (M + ).
实施例3：化合物G90Example 3: Compound G90
1)中间体-6的合成：1) Synthesis of Intermediate-6:
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
2 13.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至- 25℃，在烧瓶内缓慢滴加2.0M异丙基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-6 17.2g(60％)。MS(EI)：286(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was reduced to -25°C, and 125ml (250mmol) of 2.0M isopropylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 17.2g (60%) of white solid intermediate-6. MS(EI): 286(M + )
2)中间体-7的合成：2) Synthesis of Intermediate-7:
于100ml三口烧瓶中加入中间体-6 17g(59mmol)，硝基苯150ml后开启搅拌，室温下将48g(297mmol)溴素(Br
2)、1000ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-7 22.1g(60％)。MS(EI)：601(M
+)
Add 17g (59mmol) of Intermediate-6 and 150ml of nitrobenzene to a 100ml three-necked flask, and then start stirring. Mix 48g (297mmol) of bromine (Br 2 ) and 1000ml of nitrobenzene at room temperature and slowly add dropwise to the reaction solution. In the process, nitrogen is introduced to remove the HBr produced. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 22.1 g (60%) of Intermediate-7. MS(EI): 601(M + )
3)中间体-8的合成：3) Synthesis of Intermediate-8:
氮气保护下，于1000ml三口烧瓶中加入21.3g(35.4mmol)中间体-7、24g(70mmol)化合物-3、叔丁醇钠6.73g(70mmol)、0.5g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、200g硅胶粉拌样后过柱得纯度较低的中间体-8，将中间体 -8使用制备色谱进行提纯后得高纯度的中间体-8 16.5g(41％)。MS(EI)：1127(M
+)
Under nitrogen protection, add 21.3g (35.4mmol) Intermediate-7, 24g (70mmol) Compound-3, 6.73g (70mmol) of sodium tert-butoxide, 0.5g (0.56mmol) Pd 2 (dba) into a 1000ml three-necked flask 3. 350ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 200g silica gel powder, the intermediate-8 is obtained with lower purity, and 16.5g (41%) of the intermediate-8 with high purity is obtained after the intermediate-8 is purified by preparative chromatography. MS(EI): 1127(M + )
4)化合物G90的合成：4) Synthesis of compound G90:
氮气保护下，于1000ml三口烧瓶中加入16g(14.2mmol)中间体-8、Pd(dppf)Cl
20.5g(0.71mmol)，ZnCl
2 5g(36mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁18ml(36mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固7.1g，使用20倍甲苯进行重结晶三次后得黄绿色固体5g(35％)。MS(EI)：997(M
+)。
Under the protection of nitrogen, add 16g (14.2mmol) of Intermediate-8, Pd(dppf)Cl 2 0.5g (0.71mmol), and ZnCl 2 5g (36mmol) in 400ml dry tetrahydrofuran into a 1000ml three-necked flask. The temperature was lowered to -25°C, and 18ml (36mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex: EA=10:1 to obtain a yellow-green solid 7.1g. After recrystallization with 20 times toluene for three times, a yellow-green solid 5g (35%) ). MS (EI): 997 (M + ).
实施例4：化合物G105Example 4: Compound G105
1)中间体-9的合成：1) Synthesis of Intermediate-9:
氮气保护下，于3000ml三口烧瓶中加入1,6-二溴芘72g(200mmol)、苯硼酸61g(500mmol)、四三苯基膦钯11.5g(10mmol)、碳酸钾138g(1mol)、1500ml甲苯、300ml乙醇、400ml水，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应， 降温至室温后过滤得滤饼，滤饼使用2000ml甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体-9 42.5g(60％)。MS(EI)：354(M
+)。
Under the protection of nitrogen, add 72g (200mmol) of 1,6-dibromopyrene, 61g (500mmol) of phenylboronic acid, 11.5g (10mmol) of tetratriphenylphosphine palladium, 138g (1mol) of potassium carbonate, 1500ml of toluene into a 3000ml three-necked flask , 300ml ethanol, 400ml water, after the addition, the temperature is raised to reflux for 5 hours. After the completion of the reaction detected by HPLC, the reaction was stopped, cooled to room temperature and filtered to obtain a filter cake. The filter cake was heated to dissolve with 2000ml of toluene and passed through the activated carbon funnel to obtain a filtrate. 9 42.5g (60%). MS (EI): 354 (M + ).
2)中间体-10的合成：2) Synthesis of Intermediate-10:
于2000ml三口烧瓶中加入中间体-9 42g(63mmol)、硝基苯840ml后开启搅拌，室温下将50.4g(315mmol)溴素(Br
2)、1000ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-10 17.3g(41％)。MS(EI)：670(M
+)
Add 42g (63mmol) of Intermediate-9 and 840ml of nitrobenzene to a 2000ml three-necked flask and start stirring. Mix 50.4g (315mmol) of bromine (Br 2 ) and 1000ml of nitrobenzene at room temperature and then slowly add dropwise to the reaction. In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 17.3 g (41%) of Intermediate-10. MS(EI): 670(M + )
3)中间体-11的合成：3) Synthesis of Intermediate-11:
氮气保护下，于1000ml三口烧瓶中加入17g(25.4mmol)中间体-10、18.25g(63.5mmol)化合物-4、叔丁醇钠6.1g(63.5mmol)、Pd
2(dba)
31.16g(1.27mmol)、甲苯510ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-11，将中间体-11使用制备色谱进行提纯后得高纯度的中间体-11 11.5g(42％)。MS(EI)：1082(M
+)
Under nitrogen protection, add 17g (25.4mmol) Intermediate-10, 18.25g (63.5mmol) compound-4, 6.1g (63.5mmol) of sodium tert-butoxide, and Pd 2 (dba) 3 1.16g ( 1.27mmol), 510ml of toluene, after the addition, the temperature was raised to reflux for 5 hours. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 150g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-11 with lower purity. Intermediate-11 was purified by preparative chromatography to obtain 11.5g (42%) of Intermediate-11 with high purity. MS(EI): 1082(M + )
4)化合物G105的合成：4) Synthesis of compound G105:
氮气保护下，于1000ml三口烧瓶中加入11g(10.1mmol)中间体-11、Pd(dppf)Cl
20.37g(0.505mmol)，ZnCl
2 3.44g(25.25mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁12.6ml(25.25mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固7.1g，使用20倍甲苯进行重结晶三次后得黄绿色固体5g(35％)。MS(EI)：997(M
+)。
Under the protection of nitrogen, add 11g (10.1mmol) of Intermediate-11, Pd(dppf)Cl 2 0.37g (0.505mmol), ZnCl 2 3.44g (25.25mmol) in 400ml dry tetrahydrofuran in a 1000ml three-necked flask, and The reaction solution was lowered to -25°C, and 12.6ml (25.25mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex: EA=10:1 to obtain a yellow-green solid 7.1g. After recrystallization with 20 times toluene for three times, a yellow-green solid 5g (35%) ). MS (EI): 997 (M + ).
实施例5：化合物G113Example 5: Compound G113
1)中间体-12的合成：1) Synthesis of Intermediate-12:
于2000ml三口烧瓶中加入1,6-二氯芘27.1g(100mmol)、二氯甲烷270ml后开启搅拌，室温下将35.2g(220mmol)溴素(Br
2)、350ml二氯甲烷混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌24小时，反应完毕后，停止反应，将反应液过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-12 21.5g(50％)。MS(EI)：428(M
+)
Add 27.1g (100mmol) of 1,6-dichloropyrene and 270ml of dichloromethane into a 2000ml three-necked flask, and then start stirring. Mix 35.2g (220mmol) of bromine (Br 2 ) and 350ml of dichloromethane at room temperature and then slowly Add dropwise to the reaction solution and blow in nitrogen to remove the HBr produced. After the addition is complete, stir at room temperature for 24 hours. After the reaction is complete, stop the reaction. The reaction solution is filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The obtained crude product is prepared by HPLC to prepare Intermediate-12 21.5g (50%). MS(EI): 428(M + )
2)中间体-13的合成：2) Synthesis of Intermediate-13:
于1000ml三口烧瓶中加入中间体-12 21g(49mmol)，硝基苯150ml后开启搅拌，室温下将27.36g(108mmol)碘(I
2)、500ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HI。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-13 17g(50％)。MS(EI)：680(M
+)
Add 21g (49mmol) of Intermediate-12 and 150ml of nitrobenzene into a 1000ml three-necked flask, and then start stirring. Mix 27.36g (108mmol) of iodine (I 2 ) and 500ml of nitrobenzene at room temperature and slowly add dropwise to the reaction solution. In, nitrogen gas is introduced to remove the HI generated. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 17 g (50%) of Intermediate-13. MS(EI): 680(M + )
3)中间体-14的合成：3) Synthesis of Intermediate-14:
氮气保护下，于3000ml三口烧瓶中加入中间体-13 17g(25mmol)、苯硼酸6.4g(52.5mmol)、四三苯基膦钯1.5g(1.25mmol)、碳酸钾8.6g(62.5mmol)、340ml甲苯、64ml乙醇、24ml水，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应，降温至室温后过滤得滤饼，滤饼使用2000ml甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体-14粗品52.5g，将该粗品使用高效液相制备色谱进行分离后得纯度较高的中间体-14 6.1g(42％)MS(EI)：581(M+)。Under the protection of nitrogen, in a 3000ml three-necked flask, add 17g (25mmol) of Intermediate-13, 6.4g (52.5mmol) of phenylboronic acid, 1.5g (1.25mmol) of tetrakistriphenylphosphine palladium, 8.6g (62.5mmol) of potassium carbonate, 340ml of toluene, 64ml of ethanol, 24ml of water, after the addition, the temperature was raised to reflux for 5 hours. After the completion of the reaction detected by HPLC, the reaction was stopped, cooled to room temperature and filtered to obtain a filter cake. The filter cake was heated and dissolved in 2000ml of toluene and passed through the activated carbon funnel to obtain the filtrate. After the filtrate was rotary evaporated to remove the toluene, the intermediate was recrystallized with toluene- 14 crude product 52.5g, the crude product was separated by high performance liquid chromatography to obtain 6.1g (42%) of intermediate-14 with higher purity MS(EI):581(M+).
4)中间体-15的合成：4) Synthesis of Intermediate-15:
氮气保护下，于1000ml三口烧瓶中加入6g(10.3mmol)中间体-14、7g(21mmol)化合物-6、叔丁醇钠2.2g(23mmol)、Pd
2(dba)
30.4g(0.52mmol)、甲苯160ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入500ml二氯甲烷、50g硅胶粉拌样后过柱得纯度较低的中间体-15，将中间体-15使用制备色谱进行提纯后得高纯度的中间体-15 5g(45％)。MS(EI)：1078(M
+)。
Under nitrogen protection, add 6g (10.3mmol) of Intermediate-14, 7g (21mmol) of Compound-6, sodium tert-butoxide 2.2g (23mmol), and Pd 2 (dba) 3 0.4g (0.52mmol) into a 1000ml three-necked flask. , 160ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, the temperature is reduced to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 50g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-15 with lower purity. Intermediate-15 was purified by preparative chromatography to obtain 5g (45%) of Intermediate-15 with high purity. MS (EI): 1078 (M + ).
5)化合物G113的合成：5) Synthesis of compound G113:
氮气保护下，于500ml三口烧瓶中加入5g(4.64mmol)中间体-15、Pd(dppf)Cl
20.2g(0.232mmol)，ZnCl
2 1.6g(11.6mmol)溶于200ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁6.3ml(11.6mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入100ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入50g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固4.1g，使用20倍甲苯进行重结晶三次后得黄绿色固体2.6g(55％)。MS(EI)：1037(M
+)。
Under nitrogen protection, add 5g (4.64mmol) Intermediate-15, Pd(dppf)Cl 2 0.2g (0.232mmol), and ZnCl 2 1.6g (11.6mmol) in 200ml dry tetrahydrofuran in a 500ml three-necked flask. The reaction solution was lowered to -25°C, and 6.3ml (11.6mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and 100ml of diluted hydrochloric acid (5%) was slowly added. After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was spin-dried and added 50g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex: EA=10:1 to obtain a yellow-green solid 4.1g. After recrystallization with 20 times toluene three times, a yellow-green solid 2.6g (55 %). MS (EI): 1037 (M + ).
实施例6：化合物G114Example 6: Compound G114
1)中间体-16的合成：1) Synthesis of Intermediate-16:
于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、二氯甲烷270ml后开启搅拌，室温下将56g(220mmol)碘(I
2)、350ml二氯甲烷混匀后缓慢滴加到反应液中，通入氮气去除产生的HI。滴加完毕后室温搅拌24小时，反应完毕后，停止反应，将反应液过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-16 31g(51％)。MS(EI)：612(M
+)
Add 36g (100mmol) of 1,6-dibromopyrene and 270ml of dichloromethane into a 2000ml three-necked flask, and then start stirring. Mix 56g (220mmol) of iodine (I 2 ) and 350ml of dichloromethane at room temperature and slowly add dropwise to In the reaction liquid, nitrogen gas was introduced to remove the generated HI. After the addition is complete, stir at room temperature for 24 hours. After the reaction is complete, stop the reaction. The reaction solution is filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The obtained crude product is prepared by HPLC to prepare Intermediate-16 31g (51%). MS(EI): 612(M + )
2)中间体-17的合成：2) Synthesis of Intermediate-17:
于1000ml三口烧瓶中加入中间体-16 31g(51mmol)，硝基苯650ml后开启搅拌，持续通入氯气，是整个反应系统维持氯气氛围，氯气置换完毕后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-17 15g(43％)。MS(EI)：680(M
+)
Add 31g (51mmol) of Intermediate-16 and 650ml of nitrobenzene to a 1000ml three-necked flask, then turn on the stirring and continue to inject chlorine. The entire reaction system maintains a chlorine atmosphere. After the chlorine is replaced, the temperature is raised to 80°C and the reaction is continued for 5 hours. After completion, the reaction was stopped, the reaction solution was cooled to room temperature and then filtered to obtain a solid. The solid was recrystallized with 5 times toluene to obtain a crude product. The crude product obtained was prepared by high performance liquid chromatography to prepare Intermediate-17 15g (43%). MS(EI): 680(M + )
3)中间体-18的合成：3) Synthesis of Intermediate-18:
氮气保护下，于1000ml三口烧瓶中加入15g(22mmol)中间体-17、12g(46mmol)化合物-7、叔丁醇钠5.1g(53mmol)、Pd
2(dba)
31g(1.1mmol)、甲苯300ml，加料完毕后升 温至80℃反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入2000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-18，将中间体-18使用制备色谱进行提纯后得高纯度的中间体-18 8.7g(42％)。MS(EI)：943(M
+)。
Under the protection of nitrogen, 15g (22mmol) of Intermediate-17, 12g (46mmol) of Compound-7, 5.1g (53mmol) of sodium tert-butoxide, Pd 2 (dba) 3 1g (1.1mmol), toluene were added to a 1000ml three-necked flask. 300ml, after the addition, the temperature was raised to 80°C for 5 hours. After the reaction is completed, the temperature is reduced to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is filtered and the filtrate is separated to obtain the organic phase. The organic phase is dried with 50g anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 150g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-18 with lower purity. Intermediate-18 was purified by preparative chromatography to obtain 8.7g (42%) of Intermediate-18 with high purity. MS (EI): 943 (M + ).
4)中间体-19的合成：4) Synthesis of Intermediate-19:
氮气保护下，于1000ml三口烧瓶中加入8g(8.5mmol)中间体-18、7g(18mmol)化合物-8、叔丁醇钠1.8g(19mmol)、Pd
2(dba)
30.4g(0.43mmol)、甲苯160ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入500ml二氯甲烷、50g硅胶粉拌样后过柱得纯度较低的中间体-19，将中间体-19使用制备色谱进行提纯后得高纯度的中间体-19 4g(40％)。MS(EI)：1176(M
+)。
Under nitrogen protection, add 8g (8.5mmol) of Intermediate-18, 7g (18mmol) of Compound-8, 1.8g (19mmol) of sodium tert-butoxide, and 0.4g (0.43mmol) of Pd 2 (dba) 3 into a 1000ml three-necked flask. , 160ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, the temperature is reduced to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 50 g silica gel powder, the intermediate -19 was obtained by passing through the column, and the intermediate -19 was purified by preparative chromatography to obtain 4 g (40%) of the high-purity intermediate -19. MS (EI): 1176 (M + ).
5)化合物G114的合成：5) Synthesis of compound G114:
氮气保护下，于500ml三口烧瓶中加入4g(3.4mmol)中间体-19、Pd(dppf)Cl
20.13g(0.17mmol)，ZnCl
2 1.2g(8.5mmol)溶于100ml无水四氢呋喃中，将反应液降至-25℃， 在烧瓶内缓慢滴加2.0M/L甲基氯化镁4.25ml(8.5mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入100ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入50g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固3.3g，使用20倍甲苯进行重结晶三次后得黄绿色固体2.1g(55％)。MS(EI)：1135(M
+)。
Under the protection of nitrogen, 4g (3.4mmol) Intermediate-19, Pd(dppf)Cl 2 0.13g (0.17mmol), ZnCl 2 1.2g (8.5mmol) were dissolved in 100ml anhydrous tetrahydrofuran in a 500ml three-necked flask. The reaction solution was lowered to -25°C, and 4.25ml (8.5mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and 100ml of diluted hydrochloric acid (5%) was slowly added. After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was spin-dried and added 50g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex:EA=10:1 to obtain 3.3g of yellow-green solid, and after recrystallization with 20 times toluene three times, the yellow-green solid 2.1g (55 %). MS (EI): 1135 (M + ).
实施例7：化合物G129Example 7: Compound G129
1)中间体-20的合成：1) Synthesis of Intermediate-20:
氮气保护下，于1000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
2 13.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M叔丁基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-20 15.1g(48％)。MS(EI)：314(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 1000ml three-necked flask. The reaction solution was lowered to -25°C, and 125ml (250mmol) of 2.0M tert-butylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 15.1g (48%) of a white solid intermediate-20. MS(EI): 314(M + )
2)中间体-21的合成：2) Synthesis of Intermediate-21:
于1000ml三口烧瓶中加入中间体-20 15g(48mmol)，硝基苯150ml后开启搅拌，室温下将34.56g(216mmol)溴素(Br
2)、200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-21 12.7g(42％)。MS(EI)：630(M
+)
Add 15g (48mmol) of Intermediate-20 and 150ml of nitrobenzene into a 1000ml three-necked flask, and then start stirring. Mix 34.56g (216mmol) of bromine (Br 2 ) and 200ml of nitrobenzene at room temperature and slowly add dropwise to the reaction. In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 12.7 g (42%) of Intermediate-21. MS(EI): 630(M + )
3)中间体-22的合成：3) Synthesis of Intermediate-22:
氮气保护下，于500ml三口烧瓶中加入12g(19mmol)中间体-21、14g(40mmol)化合物-9、叔丁醇钠4.4g(45.6mmol)、1g(1mmol)Pd
2(dba)
3、甲苯240ml，加料完毕后升温至回流反应10小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤饼，滤饼使用500倍二氯甲烷溶解后加入500ml水进行萃取后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-22，将中间体-22使用制备色谱进行提纯后得高纯度的中间体-22 8.9g(40％)。MS(EI)：1167(M
+)
Under the protection of nitrogen, add 12g (19mmol) of Intermediate-21, 14g (40mmol) of Compound-9, 4.4g (45.6mmol) of sodium tert-butoxide, 1g (1mmol) of Pd 2 (dba) 3 and toluene into a 500ml three-necked flask. 240ml, after the addition, the temperature was raised to reflux and reacted for 10 hours. After the reaction was completed, it was cooled to room temperature and 100ml of water was added and stirred for 15 minutes to obtain a filter cake. The filter cake was dissolved with 500 times of dichloromethane and 500ml of water was added for extraction to obtain an organic phase. The organic phase was dried with 50g anhydrous magnesium sulfate. After a short silica gel column, the filtrate is obtained. The filtrate is spin-dried and mixed with 1000ml of dichloromethane and 150g of silica gel powder. The sample is passed through the column to obtain Intermediate-22 with lower purity. Intermediate-22 is purified by preparative chromatography to obtain high purity. Intermediate-22 8.9 g (40%). MS(EI): 1167(M + )
4)化合物G129的合成：4) Synthesis of compound G129:
氮气保护下，于500ml三口烧瓶中加入8.8g(7.5mmol)中间体-22、Pd(dppf) Cl
20.3g(0.4mmol)，ZnCl
2 2.6g(19mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁9.5ml(19mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入100ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入100g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固6.5g，使用20倍甲苯进行重结晶后得黄绿色固体4g(52％)。MS(EI)：1037(M
+)。
Under nitrogen protection, add 8.8g (7.5mmol) Intermediate-22, Pd(dppf) Cl 2 0.3g (0.4mmol), ZnCl 2 2.6g (19mmol) in 400ml dry tetrahydrofuran in a 500ml three-necked flask. The reaction solution was reduced to -25°C, and 9.5ml (19mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 100ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 100g The silica powder was mixed and passed through the chromatography column, and the eluent was eluted with Hex:EA=10:1 to obtain 6.5g of yellow-green solid, and 4g (52%) of yellow-green solid was recrystallized with 20 times toluene. . MS (EI): 1037 (M + ).
实施例8：化合物G222的合成Example 8: Synthesis of compound G222
1)中间体-23的合成：1) Synthesis of Intermediate-23:
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
2 13.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M三氘代甲基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-23 19g(80.5％)。MS(EI)：236(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was lowered to -25°C, and 125ml (250mmol) of 2.0M trideuteromethylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 19g (80.5%) of white solid intermediate -23. MS(EI): 236(M + )
2)中间体-24的合成：2) Synthesis of Intermediate-24:
于1000ml三口烧瓶中加入中间体-23 18.5g(78mmol)，硝基苯150ml后开启搅拌，室温下将62.4g(390mmol)溴素(Br
2)、1200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕 后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-24 16g(34％)。MS(EI)：551(M
+)
Add 18.5g (78mmol) of Intermediate-23 and 150ml of nitrobenzene into a 1000ml three-necked flask, and then start stirring. Mix 62.4g (390mmol) of bromine (Br 2 ) and 1200ml of nitrobenzene at room temperature and then slowly add dropwise to In the reaction solution, nitrogen gas was introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 16 g (34%) of Intermediate-24. MS(EI): 551(M + )
3)中间体-25的合成：3) Synthesis of Intermediate-25:
氮气保护下，于1000ml三口烧瓶中加入15.4g(28mmol)中间体-24、22.6g(62mmol)化合物-10、叔丁醇钠6.5g(67mmol)、5.4g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、220g硅胶粉拌样后过柱得到纯度较低的中间体-25，将中间体-25使用制备色谱进行提纯后得高纯度的中间体-25白色固体19g(61％)。MS(EI)：1120(M
+)
Under the protection of nitrogen, add 15.4g (28mmol) of Intermediate-24, 22.6g (62mmol) of Compound-10, 6.5g (67mmol) of sodium tert-butoxide, 5.4g (0.56mmol) of Pd 2 (dba) into a 1000ml three-necked flask under nitrogen 3. 350ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 220 g of silica gel powder, the intermediate-25 was passed through a column to obtain Intermediate-25 with lower purity. Intermediate-25 was purified by preparative chromatography to obtain 19g (61%) of white solid with high purity Intermediate-25. MS(EI): 1120(M + )
4)化合物G222的合成：4) Synthesis of compound G222:
氮气保护下，于1000ml三口烧瓶中加入18g(16.1mmol)中间体-25、Pd(dppf)Cl
20.6g(0.8mmol)，ZnCl
2 5.5g(40.3mmol)溶于400ml无水四氢呋喃中，将反应液降至- 25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁20.3ml(40.5mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入150g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固8.4g，使用20倍甲苯进行重结晶三次后得黄绿色固体5.6g(35％)。MS(EI)：991(M
+)。
Under the protection of nitrogen, add 18g (16.1mmol) Intermediate-25, Pd(dppf)Cl 2 0.6g (0.8mmol), ZnCl 2 5.5g (40.3mmol) into 400ml dry tetrahydrofuran in a 1000ml three-necked flask, and The reaction solution was reduced to -25°C, and 20.3ml (40.5mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 150g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=10:1 to obtain a yellow-green solid 8.4g, and after recrystallization with 20 times toluene three times, a yellow-green solid 5.6g (35%) was obtained. . MS (EI): 991 (M + ).
实施例9：化合物G223的合成Example 9: Synthesis of compound G223
1)中间体-26的合成1) Synthesis of Intermediate-26
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
213.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M乙基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-26 19.2g(74％)。MS(EI)：258(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was lowered to -25°C, and 125ml (250mmol) of 2.0M ethylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 19.2g (74%) of white solid intermediate-26. MS(EI): 258(M + )
2)中间体-27的合成2) Synthesis of Intermediate-27
于1000ml三口烧瓶中加入中间体-26 19g(73mmol)，硝基苯150ml后开启搅拌，室温下将62.4g(390mmol)溴素(Br
2)、1200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-27 26.8g(64％)。MS(EI)：569(M
+)
Add 19g (73mmol) of Intermediate-26 and 150ml of nitrobenzene into a 1000ml three-necked flask, and then start stirring. Mix 62.4g (390mmol) of bromine (Br 2 ) and 1200ml of nitrobenzene at room temperature and slowly add dropwise to the reaction. In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 26.8 g (64%) of Intermediate-27. MS(EI): 569(M + )
3)中间体-28的合成3) Synthesis of Intermediate-28
氮气保护下，于1000ml三口烧瓶中加入26g(45mmol)中间体-27、30g(100mmol)化合物-11、叔丁醇钠10.2g(107mmol)、5.8g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、220g硅胶粉拌样后过柱得到纯度较低的中间体-28，将中间体-28使用制备色谱进行提纯后得高纯度的中间体-28白色固体25.8g(56％)。MS(EI)：1010(M
+)
Under the protection of nitrogen, add 26g (45mmol) Intermediate-27, 30g (100mmol) Compound-11, Sodium tert-butoxide 10.2g (107mmol), 5.8g (0.56mmol) Pd 2 (dba) 3 , 350ml of toluene, the temperature was raised to reflux for 5 hours after the addition was completed. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 220 g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-28 with lower purity. Intermediate-28 was purified by preparative chromatography to obtain 25.8g (56%) of white solid with high purity Intermediate-28. MS(EI): 1010(M + )
4)化合物G223的合成：4) Synthesis of compound G223:
氮气保护下，于1000ml三口烧瓶中加入25g(24.7mmol)中间体-28、Pd(dppf)Cl
20.92g(1.262mmol)，ZnCl
2 8.6g(63.12mmol)溶于500ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁31.5ml(63.12mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入400ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入400g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝12:1进行洗脱后得黄绿色固体8.2g，使用20倍甲苯进行重结晶三次后得黄绿色固体5.5g(25％)。MS(EI)：882(M
+)。
Under the protection of nitrogen, add 25g (24.7mmol) Intermediate-28, Pd(dppf)Cl 2 0.92g (1.262mmol), ZnCl 2 8.6g (63.12mmol) in 500ml dry tetrahydrofuran into a 1000ml three-necked flask, and The reaction solution was reduced to -25°C, and 31.5ml (63.12mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and 400ml of diluted hydrochloric acid (5%) was slowly added. The organic phase was extracted after separation. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was spin-dried and added to 400g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex:EA=12:1 to obtain 8.2g of yellow-green solid. After recrystallization with 20 times toluene three times, 5.5g of yellow-green solid was obtained (25 %). MS (EI): 882 (M + ).
实施例10：化合物G224的合成Example 10: Synthesis of compound G224
1)中间体-29的合成1) Synthesis of Intermediate-29
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
213.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M氘代异丙基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-29 19.5g(67％)。MS(EI)：288(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was reduced to -25°C, and 125ml (250mmol) of 2.0M deuterated isopropyl magnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 19.5 g (67%) of white solid intermediate -29. MS(EI): 288(M + )
2)中间体-30的合成2) Synthesis of Intermediate-30
于1000ml三口烧瓶中加入中间体-29 19g(66mmol)，硝基苯150ml后开启搅拌，室温下将52.4g(330mmol)溴素(Br
2)、1200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-30 24.1g(61％)。MS(EI)：599(M
+)
Add 19g (66mmol) of Intermediate-29 and 150ml of nitrobenzene into a 1000ml three-necked flask, then start stirring. Mix 52.4g (330mmol) of bromine (Br 2 ) and 1200ml of nitrobenzene at room temperature and then slowly add dropwise to the reaction. In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 24.1 g (61%) of Intermediate-30. MS(EI): 599(M + )
3)中间体-31的合成3) Synthesis of Intermediate-31
氮气保护下，于1000ml三口烧瓶中加入24g(40mmol)中间体-30、32.1g(88mmol)化合物-12、叔丁醇钠9.8g(88mmol)、1.6g(1.76mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、220g硅胶粉拌样后过柱得到纯度较低的中间体-31，将中间体-31使用制备色谱进行提纯后得高纯度的中间体-31白色固体22.6g(53％)。MS(EI)：1070(M
+)
Under nitrogen protection, add 24g (40mmol) Intermediate-30, 32.1g (88mmol) Compound-12, 9.8g (88mmol) of sodium tert-butoxide, 1.6g (1.76mmol) Pd 2 (dba) 3 into a 1000ml three-necked flask. , 350ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 220g silica gel powder, the intermediate-31 with lower purity was obtained by passing through the column, and the intermediate-31 was purified by preparative chromatography to obtain 22.6g (53%) of high-purity intermediate-31 as a white solid. MS(EI): 1070(M + )
4)化合物G224的合成：4) Synthesis of compound G224:
氮气保护下，于1000ml三口烧瓶中加入22g(21.1mmol)中间体-31、Pd(dppf)Cl
20.966g(1.055mmol)，ZnCl
2 8.6g(52.75mmol)溶于500ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁31.5m(52.75mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入400ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入400g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝12:1进行洗脱后得黄绿色固体8.2g，使用20倍甲苯进行重结晶三次后得黄绿色固体5.05g(23％)。MS(EI)：1042(M
+)。
Under the protection of nitrogen, add 22g (21.1mmol) of Intermediate-31, Pd(dppf)Cl 2 0.966g (1.055mmol), and 8.6g (52.75mmol) of ZnCl 2 to 500ml of dry tetrahydrofuran in a 1000ml three-necked flask. The reaction solution was reduced to -25°C, and 2.0M/L methylmagnesium chloride 31.5m (52.75mmol) was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and 400ml of diluted hydrochloric acid (5%) was slowly added. The organic phase was extracted after separation. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was spin-dried and added to 400g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex: EA=12:1 to obtain 8.2 g of yellow-green solid. After recrystallization with 20 times toluene three times, 5.05 g of yellow-green solid was obtained (23 %). MS (EI): 1042 (M + ).
实施例11：化合物G225的合成Example 11: Synthesis of compound G225
1)中间体-32的合成1) Synthesis of Intermediate-32
氮气保护下，于2000ml三口烧瓶中加入1,6-二溴芘36g(100mmol)、Pd(dppf)Cl
23.7g(5mmol)，ZnCl
2 13.6g(250mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M三氘代甲基氯化镁125ml(250mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入1000ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝9:1进行洗脱后得白色固体中间体-32 19g (80.5％)。MS(EI)：236(M
+)
Under the protection of nitrogen, add 36g (100mmol) of 1,6-dibromopyrene, 3.7g (5mmol) of Pd(dppf)Cl 2 and 13.6g (250mmol) of ZnCl 2 into 400ml of dry tetrahydrofuran in a 2000ml three-necked flask. The reaction solution was lowered to -25°C, and 125ml (250mmol) of 2.0M trideuteromethylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 1000ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=9:1 to obtain 19g (80.5%) of a white solid intermediate-32. MS(EI): 236(M + )
2)中间体-33的合成2) Synthesis of Intermediate-33
于1000ml三口烧瓶中加入中间体-32 18g(78mmol)，硝基苯150ml后开启搅拌，室温下将62.4g(390mmol)溴素(Br
2)、1200ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-33 16g(34％)。MS(EI)：551(M
+)
Add 18g (78mmol) of Intermediate-32 to a 1000ml three-necked flask and 150ml of nitrobenzene, then start stirring. Mix 62.4g (390mmol) of bromine (Br 2 ) and 1200ml of nitrobenzene at room temperature and then slowly add dropwise to the reaction In the liquid, nitrogen gas is introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain Intermediate-33 16g (34%). MS(EI): 551(M + )
3)中间体-34的合成3) Synthesis of Intermediate-34
氮气保护下，于1000ml三口烧瓶中加入15.4g(28mmol)中间体-33、18.6g(62mmol)化合物-13、叔丁醇钠6.5g(67mmol)、5.4g(0.56mmol)Pd
2(dba)
3、甲苯350ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、220g硅胶粉拌样后过柱得到纯度较低的中间体-34，将中间体-34使用制备色谱进行提纯后得高纯度的中间体-34白色固体17.9g(65％)。MS(EI)：988(M
+)
Under the protection of nitrogen, add 15.4g (28mmol) of Intermediate-33, 18.6g (62mmol) of Compound-13, 6.5g (67mmol) of sodium tert-butoxide, 5.4g (0.56mmol) of Pd 2 (dba) into a 1000ml three-necked flask. 3. 350ml of toluene, the temperature is raised to reflux for 5 hours after the addition is complete. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 220 g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-34 with lower purity. Intermediate-34 was purified by preparative chromatography to obtain 17.9 g (65%) of white solid with high purity Intermediate-34. MS(EI): 988(M + )
4)化合物G225的合成4) Synthesis of compound G225
氮气保护下，于1000ml三口烧瓶中加入15.9g(16.1mmol)中间体-34、Pd(dppf)Cl
20.6g(0.8mmol)，ZnCl
2 5.5g(40.3mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁20.3ml(40.5mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入150g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固10g，使用20倍甲苯进行重结晶三次后得黄绿色固体5.5g(40％)。MS(EI)：860(M
+)
Under the protection of nitrogen, 15.9g (16.1mmol) of Intermediate-34, Pd(dppf)Cl 2 0.6g (0.8mmol), ZnCl 2 5.5g (40.3mmol) were dissolved in 400ml of dry tetrahydrofuran into a 1000ml three-necked flask. The reaction solution was lowered to -25°C, and 20.3ml (40.5mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 150g The silica powder was mixed and passed through the column, and the eluent was eluted with Hex:EA=10:1 to obtain 10 g of yellow-green solid, and after recrystallization with 20 times toluene three times, 5.5 g (40%) of yellow-green solid was obtained. MS(EI): 860(M + )
实施例12：化合物G226的合成Example 12: Synthesis of compound G226
1)中间体-35的合成1) Synthesis of Intermediate-35
氮气保护下，于3000ml三口烧瓶中加入1,6-二溴芘72g(200mmol)、间甲苯硼酸68g(500mmol)、四三苯基膦钯11.5g(10mmol)、碳酸钾138g(1mol)、1500ml甲苯、300ml乙醇、400ml水，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应，降温至室温后过滤得滤饼，滤饼使用2000ml甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体-35 50.4g(66％)。MS(EI)：382(M
+)。
Under nitrogen protection, add 72g (200mmol) of 1,6-dibromopyrene, 68g (500mmol) of m-toluene boronic acid, 11.5g (10mmol) of tetrakistriphenylphosphine palladium, 138g (1mol) of potassium carbonate, 1500ml in a 3000ml three-necked flask Toluene, 300ml ethanol, 400ml water, after the addition, the temperature was raised to reflux and reacted for 5 hours. After the completion of the reaction detected by HPLC, the reaction was stopped, cooled to room temperature and filtered to obtain a filter cake. The filter cake was heated and dissolved in 2000ml of toluene and passed through the activated carbon funnel to obtain the filtrate. After the filtrate was rotary evaporated to remove the toluene, the intermediate was recrystallized with toluene- 35 50.4g (66%). MS (EI): 382 (M + ).
2)中间体-36的合成2) Synthesis of Intermediate-36
于2000ml三口烧瓶中加入中间体-35 50g(130mmol)，硝基苯1000ml后开启搅拌，室温下将52g(650mmol)溴素(Br
2)、1040ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-36 38.7g(43％)。MS(EI)：693(M
+)
Add 50g (130mmol) of Intermediate-35 and 1000ml of nitrobenzene to a 2000ml three-necked flask, and then start stirring. Mix 52g (650mmol) of bromine (Br 2 ) and 1040ml of nitrobenzene at room temperature and then slowly add dropwise to the reaction solution. In the process, nitrogen is introduced to remove the HBr produced. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 38.7 g (43%) of Intermediate-36. MS(EI): 693(M + )
3)中间体-37的合成3) Synthesis of Intermediate-37
氮气保护下，于1000ml三口烧瓶中加入35g(50.5mmol)中间体-36、37.8g(126.25mmol)化合物-14、叔丁醇钠14.1g(126.25mmol)、Pd
2(dba)
32.52g(2.52mmol)、甲苯1050ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-37，将中间体-37使用制备色谱进行提纯后得高纯度的中间体-37 25.1g(44％)。MS(EI)：1134(M
+)
Under the protection of nitrogen, 35g (50.5mmol) of Intermediate-36, 37.8g (126.25mmol) of Compound-14, 14.1g (126.25mmol) of sodium tert-butoxide, Pd 2 (dba) 3 2.52g ( 2.52mmol), 1050ml of toluene, after the addition, the temperature was raised to reflux and reacted for 5 hours. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g of anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 150 g of silica gel powder were mixed with samples and passed through a column to obtain Intermediate-37 with lower purity. Intermediate-37 was purified by preparative chromatography to obtain 25.1 g (44%) of Intermediate-37 with high purity. MS(EI): 1134(M + )
4)化合物G226的合成4) Synthesis of compound G226
氮气保护下，于1000ml三口烧瓶中加入11.4g(10.1mmol)中间体-37、Pd(dppf)Cl
20.37g(0.505mmol)，ZnCl
2 3.44g(25.25mmol)溶于400ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁12.6ml(25.25mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝6:1进行洗脱后得黄绿色固7.1g，使用20倍甲苯进行重结晶三次后得黄绿色固体4.2g(42％)。MS(EI)：1006(M
+)。
Under nitrogen protection, add 11.4g (10.1mmol) of Intermediate-37, Pd(dppf)Cl 2 0.37g (0.505mmol), and ZnCl 2 3.44g (25.25mmol) into 400ml of dry tetrahydrofuran in a 1000ml three-necked flask. The reaction solution was reduced to -25°C, and 12.6ml (25.25mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica powder was mixed and passed through the chromatography column. The eluent was eluted with Hex:EA=6:1 to obtain a yellow-green solid 7.1g. After recrystallization with 20 times toluene three times, a yellow-green solid 4.2g (42 %). MS (EI): 1006 (M + ).
实施例13：化合物G227的合成Example 13: Synthesis of compound G227
1)中间体-38的合成1) Synthesis of Intermediate-38
氮气保护下，于3000ml三口烧瓶中加入1,6-二溴芘72g(200mmol)、三氟甲基对甲苯硼酸89g(500mmol)、四三苯基膦钯11.5g(10mmol)、碳酸钾138g(1mol)、1500ml甲苯、300ml乙醇、400ml水，加料完毕后升温至回流反应5小时。HPLC检测反应完全后， 停止反应，降温至室温(25±5℃)后过滤得滤饼，滤饼使用2000ml甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体-38 58.8g(60％)。MS(EI)：490(M
+)。
Under the protection of nitrogen, in a 3000ml three-necked flask were added 72g (200mmol) of 1,6-dibromopyrene, 89g (500mmol) of trifluoromethyl p-tolueneboronic acid, 11.5g (10mmol) of tetrakistriphenylphosphine palladium, and 138g of potassium carbonate ( 1mol), 1500ml of toluene, 300ml of ethanol, 400ml of water, after the addition is completed, the temperature is raised to reflux for 5 hours. After HPLC detects that the reaction is complete, stop the reaction, cool to room temperature (25±5°C), and filter to obtain a filter cake. The filter cake is heated and dissolved in 2000ml of toluene and passed through the activated carbon funnel to obtain the filtrate. After the filtrate is rotary evaporated to remove the toluene, use toluene. 58.8g (60%) of Intermediate-38 was obtained by recrystallization. MS (EI): 490 (M + ).
2)中间体-39的合成2) Synthesis of Intermediate-39
于2000ml三口烧瓶中加入中间体-38 30.8g(63mmol)，硝基苯616ml后开启搅拌，室温下将50.4g(315mmol)溴素(Br
2)、1000ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-39 21g(41％)。MS(EI)：816(M
+)
Add 30.8g (63mmol) of Intermediate-38 and 616ml of nitrobenzene to a 2000ml three-necked flask, and then start stirring. Mix 50.4g (315mmol) of bromine (Br 2 ) and 1000ml of nitrobenzene at room temperature and then slowly add dropwise to In the reaction solution, nitrogen gas was introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 21 g (41%) of Intermediate -39. MS(EI): 816(M + )
3)中间体-40的合成3) Synthesis of Intermediate-40
氮气保护下，于1000ml三口烧瓶中加入20.7g(25.4mmol)中间体-39、23.1g(63.5mmol)化合物-15、叔丁醇钠6.1g(63.5mmol)、Pd
2(dba)
31.16g(1.27mmol)、甲苯600ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短 柱后得滤液，滤液旋干后加入1000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-40，将中间体-40使用制备色谱进行提纯后得高纯度的中间体-40 11.5g(42％)。MS(EI)：1371(M
+)
Under nitrogen protection, add 20.7g (25.4mmol) of Intermediate-39, 23.1g (63.5mmol) of Compound-15, 6.1g (63.5mmol) of sodium tert-butoxide, and Pd 2 (dba) 3 1.16g into a 1000ml three-necked flask. (1.27mmol), 600ml of toluene, after the addition, the temperature was raised to reflux for 5 hours. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. Dichloromethane and 150g of silica gel powder were mixed with samples and passed through the column to obtain Intermediate-40 with lower purity. Intermediate-40 was purified by preparative chromatography to obtain 11.5g (42%) of Intermediate-40 with high purity. MS(EI): 1371(M + )
4)化合物G227的合成4) Synthesis of compound G227
氮气保护下，于1000ml三口烧瓶中加入11g(8mmol)中间体-40、Pd(dppf)Cl
20.29g(0.4mmol)，ZnCl
2 2.72g(20mmol)溶于220ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M/L甲基氯化镁10ml(20mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入200g硅胶粉进行拌样并过层析柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固7.1g，使用20倍甲苯进行重结晶三次后得黄绿色固体3.78g(38％)。MS(EI)：1244(M
+)。
Under nitrogen protection, add 11g (8mmol) Intermediate-40, Pd(dppf)Cl 2 0.29g (0.4mmol), and ZnCl 2 2.72g (20mmol) into 220ml dry tetrahydrofuran into a 1000ml three-necked flask. The temperature was reduced to -25°C, and 10ml (20mmol) of 2.0M/L methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 200g The silica gel powder was mixed and passed through the chromatography column. The eluent was eluted with Hex:EA=10:1 to obtain a yellow-green solid 7.1g. After recrystallization with 20 times toluene three times, a yellow-green solid 3.78g (38 %). MS (EI): 1244 (M + ).
实施例14：化合物G228的合成Example 14: Synthesis of compound G228
1)中间体-41的合成1) Synthesis of Intermediate-41
氮气保护下，于3000ml三口烧瓶中加入1,6-二溴芘72g(200mmol)、化合物-16 122g(500mmol)、四三苯基膦钯11.5g(10mmol)、碳酸钾138g(1mol)、1500ml甲苯、300ml乙醇、400ml水，加料完毕后升温至回流反应5小时。HPLC检测反应完全后，停止反应，降温至室温后过滤得滤饼，滤饼使用2000ml甲苯加热溶解后趁热过活性炭漏斗后得滤液，滤液旋蒸除去甲苯后，使用甲苯重结晶得中间体-41 65.7g(55％)。MS(EI)：598(M
+)。
Under nitrogen protection, add 72g (200mmol) of 1,6-dibromopyrene, 122g (500mmol) of compound-16, 11.5g (10mmol) of tetrakistriphenylphosphine palladium, 138g (1mol) of potassium carbonate, 1500ml in a 3000ml three-necked flask Toluene, 300ml ethanol, 400ml water, after the addition, the temperature was raised to reflux and reacted for 5 hours. After the completion of the reaction detected by HPLC, the reaction was stopped, cooled to room temperature and filtered to obtain a filter cake. The filter cake was heated to dissolve in 2000ml of toluene and passed through the activated carbon funnel to obtain the filtrate. 41 65.7 g (55%). MS (EI): 598 (M + ).
2)中间体-42的合成2) Synthesis of Intermediate-42
于2000ml三口烧瓶中加入中间体-41 37.6g(63mmol)，硝基苯750ml后开启搅拌，室温下将50.4g(315mmol)溴素(Br
2)、750ml硝基苯混匀后缓慢滴加到反应液中，通入氮气去除产生的HBr。滴加完毕后室温搅拌2小时后升温至80℃继续反应5小时，反应完毕后，停止反应，将反应液降至室温后过滤得固体，固体使用5倍甲苯重结晶后得粗品，将得到的粗品使用高效液相制备色谱制备得中间体-42 23.9g(41％)。MS(EI)：926(M
+)
Add 37.6g (63mmol) of Intermediate-41 and 750ml of nitrobenzene to a 2000ml three-necked flask, and then start stirring. Mix 50.4g (315mmol) of bromine (Br 2 ) and 750ml of nitrobenzene at room temperature and then slowly add dropwise to In the reaction solution, nitrogen gas was introduced to remove the generated HBr. After the dropwise addition is complete, stir at room temperature for 2 hours and then heat up to 80°C to continue the reaction for 5 hours. After the reaction is complete, stop the reaction. The reaction solution is cooled to room temperature and filtered to obtain a solid. The solid is recrystallized with 5 times toluene to obtain a crude product. The crude product was prepared by high performance liquid chromatography to obtain 23.9 g (41%) of Intermediate-42. MS(EI): 926(M + )
3)中间体-43的合成3) Synthesis of Intermediate-43
氮气保护下，于1000ml三口烧瓶中加入23.5g(25.4mmol)中间体-42、23.17g(63.5mmol)化合物-17、叔丁醇钠6.1g(63.5mmol)、Pd
2(dba)
31.16g(1.27mmol)、甲苯510ml，加料完毕后升温至回流反应5小时。反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用50g无水硫酸镁干燥后过硅胶短柱后得滤液，滤液旋干后加入1000ml二氯甲烷、150g硅胶粉拌样后过柱得纯度较低的中间体-43，将中间体-43使用制备色谱进行提纯后得高纯度的中间体-43 13.5g(36％)。MS(EI)：1480(M
+)
Under the protection of nitrogen, 23.5g (25.4mmol) of Intermediate-42, 23.17g (63.5mmol) of Compound-17, 6.1g (63.5mmol) of sodium tert-butoxide, and Pd 2 (dba) 3 1.16g were added to a 1000ml three-necked flask under nitrogen (1.27mmol), 510ml of toluene, the temperature was raised to reflux for 5 hours after the addition was completed. After the reaction is completed, it is cooled to room temperature and 100ml of water is added and stirred for 15 minutes. The filtrate is obtained by filtration. The organic phase is obtained after separation of the filtrate. The organic phase is dried with 50g anhydrous magnesium sulfate and passed through a silica gel short column to obtain the filtrate. After mixing samples with dichloromethane and 150g silica gel powder, pass through the column to obtain Intermediate-43 with lower purity. Intermediate-43 is purified by preparative chromatography to obtain 13.5g (36%) of Intermediate-43 with high purity. MS(EI): 1480(M + )
4)化合物G228的合成4) Synthesis of compound G228
氮气保护下，于1000ml三口烧瓶中加入13g(8mmol)中间体-43、Pd(dppf)Cl
20.29g(0.4mmol)，ZnCl
2 2.7g(20mmol)溶于260ml无水四氢呋喃中，将反应液降至-25℃，在烧瓶内缓慢滴加2.0M甲基氯化镁10.5ml(20mmol)，滴加完毕后缓慢升温至80℃搅拌4小时。反应结束后，将反应液降至室温后缓慢加入300ml稀盐酸(5％)，静置分层后萃取得有机相，有机相使用无水硫酸镁干燥后过滤得滤液，滤液旋干后加入150g硅胶粉进行拌样并过柱，淋洗液使用Hex：EA＝10:1进行洗脱后得黄绿色固10.2g，使用20倍甲苯进行重结晶三次后得黄绿色固体4.3g(44％)。MS(EI)：1352(M
+)。
Under the protection of nitrogen, add 13g (8mmol) of Intermediate-43, Pd(dppf)Cl 2 0.29g (0.4mmol), ZnCl 2 2.7g (20mmol) in 260ml dry tetrahydrofuran into a 1000ml three-necked flask. The temperature was lowered to -25°C, and 10.5ml (20mmol) of 2.0M methylmagnesium chloride was slowly added dropwise into the flask. After the addition, the temperature was slowly raised to 80°C and stirred for 4 hours. After the reaction, the reaction solution was cooled to room temperature and slowly added 300ml of dilute hydrochloric acid (5%). After standing for layering, the organic phase was extracted. The organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the filtrate. The filtrate was spin-dried and added 150g The silica gel powder was mixed and passed through the column. The eluent was eluted with Hex: EA=10:1 to obtain 10.2g of yellow-green solid, and after recrystallization with 20 times toluene three times, 4.3g (44%) of yellow-green solid was obtained. . MS (EI): 1352 (M + ).
其他化合物G1-G17、G19-G27、G29-G89、G91-G104、G106-G112、G115-G128、G130-G221，使用具体实施方式进行制备，并使用MS对产品结构进行确认。Other compounds G1-G17, G19-G27, G29-G89, G91-G104, G106-G112, G115-G128, G130-G221 were prepared using specific embodiments, and the product structure was confirmed using MS.
以下将通过实施例和对照例对本发明进行详细的说明。下属实施例于对照例只是为了举例说明本发明，本发明的范围并不限于下述实施例和对照例。Hereinafter, the present invention will be described in detail through examples and comparative examples. The following examples and comparative examples are only to illustrate the present invention, and the scope of the present invention is not limited to the following examples and comparative examples.
《有机电致发光器件的制造》"Manufacturing of Organic Electroluminescent Devices"
应用例1:Application example 1:
其采用ITO作为反射层阳极基板材料，,并以N2等离子或UV-Ozone对其进行表面处理.在阳极基板上方，向空穴注入层(HIL)沉积HAT-CN 10纳米厚度的HAT-CN，在其上方选使用NPD以120纳米厚度形成空穴传输层(HTL).在上述空穴传输层(HTL)上,真空蒸镀形成blue EML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光层，选择本发明化学式G1为dopant材料，掺杂约5％的25纳米厚度形成发光层，并在上方以1:1的比例混合蒸镀35纳米厚度的ETM和LiQ到电子输送层(ETL),之后在电子注入层(EIL)上以2纳米厚度的 LiQ进行蒸镀.此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。It uses ITO as the reflective layer anode substrate material, and uses N2 plasma or UV-Ozone for surface treatment. On the anode substrate, deposit HAT-CN 10 nanometers thick HAT-CN on the hole injection layer (HIL), The hole transport layer (HTL) is formed with a thickness of 120 nanometers using NPD. On the above hole transport layer (HTL), vacuum evaporation forms blue EML 9,10-Bis (2-naphthyl) anthraces (ADN). ) As the light-emitting layer, the chemical formula G1 of the present invention is selected as the dopant material, and the light-emitting layer is formed by doping about 5% with a thickness of 25 nanometers, and a mixture of ETM and LiQ with a thickness of 35 nanometers is deposited on the electron transport layer at a ratio of 1:1. (ETL), then on the electron injection layer (EIL) with a thickness of 2 nanometers of LiQ vapor deposition. After that, magnesium (Mg) and silver (Ag) are mixed in a ratio of 9:1 on the cathode and the thickness is 15 nanometers. Evaporation, deposit N4,N4′-BIS[4-BIS(3-methylphenyl)Aminophenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]- with a thickness of 65nm on the above cathode sealing layer 4,4'Diamin (DNTPD).
此外，在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封，以保护有机电致发光器件不被大气中的氧气或水分所影响至此制备获得有机电致发光器件。In addition, the surface of the cathode is sealed with a UV curable adhesive and a seal cap containing a desiccant to protect the organic electroluminescent device from being affected by oxygen or moisture in the atmosphere. The organic electroluminescent device is thus prepared.
应用例2-228Application example 2-228
分别以化合物G2-G228作为蓝光掺杂(BD)物质，其他部分与应用例1一致，据此制作出应用例2～228的有机电致发光器件。The compounds G2-G228 were used as blue light doping (BD) materials, and the other parts were the same as those in Application Example 1. Accordingly, organic electroluminescent devices of Application Examples 2 to 228 were fabricated.
对照例1Comparative example 1
与应用例1的区别在于，使用BD-1及BD-2代替本发明的化合物作为蓝光掺杂材料(blue dopant)，其余与应用例1相同。The difference from Application Example 1 is that BD-1 and BD-2 are used instead of the compound of the present invention as blue dopants, and the rest is the same as Application Example 1.
上述应用例制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm
2的条件下测定的，结果如表1所示。
The characteristics of the organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example were measured under the condition of a current density of 10 mA/cm 2. The results are shown in Table 1.
表1不同实验组器件性能测试结果：Table 1 Device performance test results of different experimental groups:
由如上表1的实验对比数据可知，采用本发明所述的化合物制备的有机电致发光器件的应用例1～228，与对照例相比，电压大幅度降低，发光效率显著提高，且色坐标蓝移，大大提高了OLED器件的蓝光色彩饱和度。由此可见，本发明的化合物能使器件的驱动电压大大降低，大幅度减少了电能的消耗、显著提高了发光效率。另外通过低驱动电压，高的色彩饱和度，有机电致发光器件的寿命有效提高，色彩更加鲜艳。From the experimental comparison data in Table 1 above, it can be seen that application examples 1 to 228 of organic electroluminescent devices prepared by using the compound of the present invention have greatly reduced voltage, significantly improved luminous efficiency, and color coordinates compared with the control example. The blue shift greatly improves the blue color saturation of the OLED device. It can be seen that the compound of the present invention can greatly reduce the driving voltage of the device, greatly reduce the power consumption, and significantly improve the luminous efficiency. In addition, through low driving voltage and high color saturation, the life span of the organic electroluminescent device is effectively improved, and the color is more vivid.
Claims (10)
- 一种有机电致发光化合物，其结构式如式(I)所示：An organic electroluminescent compound whose structural formula is shown in formula (I):
其中，Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的硅烷基或硅类衍生物基团、取代或未取代的C1-C40的直连或支链烷基、取代或未取代的C3-C40的环烷基、取代或未取代的C1-C40的杂烷基、取代或未取代的C2-C40的烯基、取代或未取代的C2-C40的炔基、取代或未取代的C6-C60的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基；Wherein, Ar1, Ar2, Ar3, Ar4 are each independently a substituted or unsubstituted silyl group or silicon derivative group, a substituted or unsubstituted C1-C40 straight or branched alkyl group, a substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C6-C60 aromatic hydrocarbon group, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon group;R1、R2、R3、R4各自独立的选自氰基、CF3、取代或未取代的硅烷基或硅类衍生物基团、取代或未取代的C1-C40的直连或支链烷基、取代或未取代的C3-C40的环烷基、取代或未取代的C1-C40的杂烷基、取代或未取代的C2-C40的烯基、取代或未取代的C2-C40的炔基、取代或未取代的C6-C60的芳香族烃基、取代或未取代的C5-C60的杂芳香族烃基。R1, R2, R3, and R4 are each independently selected from cyano, CF3, substituted or unsubstituted silyl or silicon derivative groups, substituted or unsubstituted C1-C40 straight or branched alkyl, substituted Or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted Or unsubstituted C6-C60 aromatic hydrocarbon groups, substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon groups. - 根据权利要求1所述的有机电致发光化合物，其特征在于，The organic electroluminescent compound according to claim 1, wherein:其中，Ar1、Ar2、Ar3、Ar4各自独立的为取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的3,5-二苯基苯基、取代或未取代的1,2-二苯基苯基、取代或未取代的萘基、取代或未取代的菲基、取代或未取代的蒽基、取代或未取代的咔唑基、取代或未取代9,9-螺二芴基团、取代或未取代的9,9-二甲基芴基团、取代或未取代的咔唑类及其衍生物基团、取代或未取代的呋喃类及其衍生物基团、取代或未取代的噻吩类及其衍生物基团、取代或未取代的萘类及其衍生物基团；Wherein, Ar1, Ar2, Ar3, Ar4 are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted 3,5-diphenyl Phenyl, substituted or unsubstituted 1,2-diphenylphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted carbazole Group, substituted or unsubstituted 9,9-spirobifluorene group, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted carbazole and its derivative group, substituted or unsubstituted Substituted furans and their derivative groups, substituted or unsubstituted thiophenes and their derivative groups, substituted or unsubstituted naphthalenes and their derivative groups;R1、R2、R3、R4各自独立的选自甲基、其中一个或多个氢被氘氢(D)取代或未取代的甲基、乙基、其中一个或多个氢被氘氢(D)取代或未取代的已基、异丙基、其中一个或多个氢被氘氢(D)取代或未取代的异丙基、叔丁基、其中一个或多个氢被氘氢(D)取代或未取代的叔丁基、取代或未取代的硅烷基或硅类衍生物基团、取代或为取代的苯基、取代或未取代甲苯基、取代或未取代的联苯基、取代或未取代的三联苯基、取代或未取代的各种芴类衍生物基团、取代或未取代的咔唑类及其衍生物基团、取代或未取代的呋喃类及其衍生物基团、取代或未取代的噻吩类及其衍生物基团。R1, R2, R3, and R4 are each independently selected from methyl, one or more hydrogens of which are substituted or unsubstituted by deuterium hydrogen (D), methyl, ethyl, and one or more of hydrogens are deuterated hydrogen (D) Substituted or unsubstituted hexyl, isopropyl, isopropyl, tert-butyl in which one or more hydrogens are replaced by deuterium hydrogen (D) or unsubstituted, in which one or more hydrogens are replaced by deuterium hydrogen (D) Or unsubstituted tert-butyl, substituted or unsubstituted silyl or silicon derivative groups, substituted or substituted phenyl, substituted or unsubstituted tolyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Substituted terphenyl, substituted or unsubstituted various fluorene derivative groups, substituted or unsubstituted carbazoles and their derivative groups, substituted or unsubstituted furans and their derivative groups, substituted Or unsubstituted thiophenes and their derivative groups.
- 根据权利要求1或2所述的有机电致发光化合物，其特征在于，The organic electroluminescent compound according to claim 1 or 2, characterized in that:其中，Ar1、Ar2、Ar3、Ar4各自独立的为苯基、甲基苯基、乙基苯基、异丙基苯基、叔丁基苯基、五氟苯基、4-氟苯基、4-氰基苯基、联苯基、1-萘基、2-萘基、二苯并呋喃基、4-甲基二苯并呋喃基、4-乙基二苯并呋喃基、4-异丙基二苯并呋喃基、4-叔丁基二苯并 呋喃基、咔唑基、二苯并噻吩基；Among them, Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4 -Cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyl Dibenzofuranyl, 4-tert-butyldibenzofuranyl, carbazolyl, dibenzothienyl;R1、R2、R3、R4各自独立的选自甲基、单氘代甲基、二氘代甲基、三氘代甲基、乙基、单氘代乙基、双氘代乙基、三氘代乙基、四氘代乙基、五氘代乙基、异丙基、单氘代异丙基、双氘代异丙基、三氘代异丙基、四氘代异丙基、五氘代异丙基、六氘代异丙基、七氘代异丙基、叔丁基、单氘代叔丁基、双氘代叔丁基、三氘代叔丁基、四氘代叔丁基、五氘代叔丁基、六氘代叔丁基、七氘代叔丁基、八氘代叔丁基、九氘代叔丁基、苯基、甲苯基、4-氟苯基、4-氰基苯基、五氟苯基、联苯基、三联苯基、4-三氟甲基苯基、3,5-二苯基苯基、1,2-二苯基苯基等基团、六氘代的9,9-二甲基芴基团、9,9-二苯基芴基团、9,9-螺二芴基团。R1, R2, R3, R4 are each independently selected from methyl, mono-deuterated methyl, di-deuterated methyl, tri-deuterated methyl, ethyl, mono-deuterated ethyl, double-deuterated ethyl, tri-deuterated Ethyl, tetra-deuterated ethyl, penta-deuterated ethyl, isopropyl, single deuterated isopropyl, double deuterated isopropyl, tri-deuterated isopropyl, tetra-deuterated isopropyl, pentadeuterium Isopropyl, six-deuterated isopropyl, seven-deuterated isopropyl, tert-butyl, single-deuterated tert-butyl, double-deuterated tert-butyl, tri-deuterated tert-butyl, tetradeuterated tert-butyl , Five deuterated tert-butyl, six deuterated tert-butyl, seven deuterated tert-butyl, eight deuterated tert-butyl, nine deuterated tert-butyl, phenyl, tolyl, 4-fluorophenyl, 4- Cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3,5-diphenylphenyl, 1,2-diphenylphenyl and other groups, Six-deuterated 9,9-dimethylfluorene group, 9,9-diphenylfluorene group, 9,9-spirobifluorene group.
- 根据权利要求3所述的有机电致发光化合物，其特征在于，The organic electroluminescent compound according to claim 3, wherein:其中，Ar1、Ar2、Ar3、Ar4各自独立的为苯基、甲基苯基、乙基苯基、异丙基苯基、叔丁基苯基、五氟苯基、4-氟苯基、4-氰基苯基、联苯基、1-萘基、2-萘基、二苯并呋喃基、4-甲基二苯并呋喃基、4-乙基二苯并呋喃基、4-异丙基二苯并呋喃基、4-叔丁基二苯并呋喃基、二苯并噻吩基；Among them, Ar1, Ar2, Ar3, Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4 -Cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyl Dibenzofuranyl, 4-tert-butyl dibenzofuranyl, dibenzothienyl;R1、R2、R3、R4各自独立的选自甲基、三氘代甲基、乙基、双氘代乙基、五氘代乙基、异丙基、单氘代异丙基、七氘代异丙基、叔丁基、九氘代叔丁基、苯基、甲苯基、4-氟苯基、4-氰基苯基、五氟苯基、联苯基、三联苯基、4-三氟甲基苯基、3,5-二苯基苯基、1,2-二苯基苯基、六氘代的9,9-二甲基芴基团、9,9-二苯基芴基团、9,9-螺二芴基团。R1, R2, R3, and R4 are each independently selected from methyl, tri-deuterated methyl, ethyl, double deuterated ethyl, pentadeuterated ethyl, isopropyl, single deuterated isopropyl, seven deuterated Isopropyl, tert-butyl, non-deuterated tert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, tert-phenyl, 4-tris Fluoromethylphenyl, 3,5-diphenylphenyl, 1,2-diphenylphenyl, hexadeuterated 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group Group, 9,9-spirobifluorene group.
- 根据权利要求1所述的有机电致发光化合物，其特征在于，该有机电致发光化合物为化合物G1至G228中任意一个：The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is any one of compounds G1 to G228:
- 一种包含权利要求1-5中任一项所述的有机电致发光化合物的有机电致发光器件。An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1-5.
- 根据权利要求6所述的有机电致发光器件，其特征在于，所述有机电致发光器件包 括：The organic electroluminescent device according to claim 6, wherein the organic electroluminescent device comprises:阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层以及阴极顺次堆积的构造；A structure in which anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer, electron injection layer and cathode are sequentially stacked;其中，阳极和发光层之间还设置有电子阻隔层；Wherein, an electron barrier layer is also provided between the anode and the light-emitting layer;阴极和发光层之间还设置有空穴阻隔层；A hole blocking layer is also arranged between the cathode and the light-emitting layer;阴极表面还设置有覆盖层。The surface of the cathode is also provided with a covering layer.
- 根据权利要求7所述的有机电致发光器件，其特征在于，所述空穴传输层、电子阻隔层、空穴阻隔层、电子传输层、发光层材料，或者覆盖层中的至少一层包含权利要求1-5中任一项所述的有机电致发光化合物。The organic electroluminescent device according to claim 7, wherein at least one of the hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, light emitting layer material, or covering layer comprises The organic electroluminescent compound of any one of claims 1-5.
- 一种包含权利要求6-8中任一项所述的有机电致发光器件的有机电致发光显示设备。An organic electroluminescence display device comprising the organic electroluminescence device according to any one of claims 6-8.
- 权利要求1-5中任一项所述化合物作为有机电致发光材料的应用。The use of the compound of any one of claims 1 to 5 as an organic electroluminescent material.
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| CN105359292A (en) * | 2013-07-17 | 2016-02-24 | 罗门哈斯电子材料韩国有限公司 | A combination of a dopant compound and a host compound and an organic electroluminescent device comprising the same |
| CN108558678A (en) * | 2017-12-29 | 2018-09-21 | 广州华睿光电材料有限公司 | Aromatic amine derivant and organic electronic device |
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| CN105359292A (en) * | 2013-07-17 | 2016-02-24 | 罗门哈斯电子材料韩国有限公司 | A combination of a dopant compound and a host compound and an organic electroluminescent device comprising the same |
| CN108727205A (en) * | 2017-04-19 | 2018-11-02 | 吉林奥来德光电材料股份有限公司 | One kind is containing pyrene compound and preparation method thereof and organic luminescent device |
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