CN114195808A - Binaphthalene ring-containing boron-doped or phosphorus-doped fused ring compound, preparation method thereof and light-emitting device - Google Patents
Binaphthalene ring-containing boron-doped or phosphorus-doped fused ring compound, preparation method thereof and light-emitting device Download PDFInfo
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- CN114195808A CN114195808A CN202111609561.8A CN202111609561A CN114195808A CN 114195808 A CN114195808 A CN 114195808A CN 202111609561 A CN202111609561 A CN 202111609561A CN 114195808 A CN114195808 A CN 114195808A
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- fused ring
- ring compound
- maldi
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 185
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 129
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 117
- 238000010898 silica gel chromatography Methods 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- GGLALOILOBJLRX-UHFFFAOYSA-N [Li]C(C)(C)C.CCCCC Chemical compound [Li]C(C)(C)C.CCCCC GGLALOILOBJLRX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- 125000005013 aryl ether group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003111 delayed effect Effects 0.000 abstract description 6
- 230000005281 excited state Effects 0.000 abstract description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 264
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 249
- 239000012074 organic phase Substances 0.000 description 168
- 238000000921 elemental analysis Methods 0.000 description 166
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 166
- 238000012360 testing method Methods 0.000 description 166
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 148
- 239000010410 layer Substances 0.000 description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 142
- 239000000243 solution Substances 0.000 description 107
- 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 98
- 239000002904 solvent Substances 0.000 description 90
- 239000008367 deionised water Substances 0.000 description 88
- 229910021641 deionized water Inorganic materials 0.000 description 88
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 83
- 229910000027 potassium carbonate Inorganic materials 0.000 description 74
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 74
- 239000000047 product Substances 0.000 description 73
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 41
- -1 heteroaryl ether Chemical compound 0.000 description 40
- 239000012467 final product Substances 0.000 description 31
- 238000005516 engineering process Methods 0.000 description 30
- 238000010129 solution processing Methods 0.000 description 29
- 239000002244 precipitate Substances 0.000 description 23
- 239000012141 concentrate Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 21
- 239000012452 mother liquor Substances 0.000 description 18
- 238000007738 vacuum evaporation Methods 0.000 description 18
- 229910020257 Cl2F2 Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 8
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000001194 electroluminescence spectrum Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 3
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000338 selenium disulfide Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6578—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
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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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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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
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- 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
- H10K85/636—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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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Abstract
The invention relates to a boron-doped or phosphorus-doped fused ring compound containing a binaphthyl ring, a preparation method thereof and a luminescent device, and belongs to the technical field of organic luminescent materials. The fused ring compound of the present invention has a structure represented by any one of formulas (I) to (II). The boron hetero or phosphorus hetero condensed ring compound containing binaphthyl ring provided by the invention can utilize binaphthylThe rigid skeleton structure of the naphthalene ring reduces the relaxation degree of an excited state structure, so that narrower half-peak width is realized; on the other hand, resonance effect between boron atom or phosphorus atom and heteroatom is utilized to realize separation of HOMO and LUMO, thereby realizing smaller Delta ESTAnd TADF effect, thereby achieving high luminous efficiency. Meanwhile, the delayed fluorescence lifetime and the half-peak width can be further adjusted by changing the types of the aromatic ring or the heteroaromatic ring contained in the fused ring compound.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound, a preparation method thereof and a luminescent device.
Background
Organic Light Emitting Devices (OLEDs) have the characteristics of rich colors, thin thickness, wide viewing angle, fast response, and the like, and can be used for manufacturing flexible devices, and are considered to be the next generation of flat panel display and solid illumination technologies with the greatest development prospects. OLEDs are generally composed of an ITO anode, a Hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1 to 2 organic layers may be omitted as needed, and an Exciton (exiton) is formed by combining a Hole (Hole) injected from a positive electrode and a negative electrode on an organic thin film and an Electron (Electron), and emits light by releasing energy in the form of light emission when the Exciton returns from an excited state to a stable ground state.
However, due to the limitation of the statistical law of spin quantum, the conventional fluorescent material can only utilize singlet excitons accounting for 25% of the total excitons in the electroluminescent process, and the rest 75% of the triplet excitons are inactivated by non-radiative transition, so that the maximum value of the Internal Quantum Efficiency (IQE) of the device is 25%. The phosphorescent metal complex can convert triplet excitons into photons by utilizing the spin-orbit coupling effect of heavy metal atoms, so that the utilization of the triplet excitons is realized, and the internal quantum efficiency of 100% is realized, but the path faces the problem that the phosphorescent metal complex is expensive.
TADF (thermally activated delayed fluorescence) materials are third-generation organic luminescent materials following traditional fluorescent and phosphorescent materials, and generally have smaller singlet-triplet energy level difference (delta E)ST) The triplet excitons are transferred to the singlet excitons to emit fluorescence by utilizing a thermally activated reverse intersystem crossing (RISC) process, thereby realizing the full utilization of the singlet and triplet excitons and realizing 100% internal quantum efficiency. Meanwhile, the material also has higher fluorescence quantum efficiency (PLQY) so as to promote the attenuation of singlet excitons in a light form and improve the efficiency of devices. The main approach to the current realization of TADF molecules is to introduce electron donor (D) and electron acceptor (a) units such that the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) are separated, thereby achieving a small Δ EST. However, the D-a structure exhibits a large Stokes shift due to a significant vibrational relaxation of an excited state, and has a broad emission spectrum, a full width at half maximum (FWHM) of generally 70-100 nm, and in practical applications, a filter or an optical microcavity is usually required to be configured to improve color purity, which may cause a reduction in external quantum efficiency of the device or a complexity of the device structure.
Therefore, how to develop a light emitting material having both TADF effect and narrow half-peak width spectral characteristic by reasonable chemical structure design to solve the defect of wide half-peak width faced by the above materials has become one of the problems to be solved by a great deal of prospective researchers in the field.
Disclosure of Invention
In view of the above, the present invention provides a boron-doped or phosphorus-doped fused ring compound containing a binaphthyl ring, which has both a TADF effect and a narrow half-peak broadband spectrum characteristic, a method for preparing the same, and a light-emitting device.
The boron-doped or phosphorus-doped fused ring compound containing the binaphthyl ring provided by the invention has a structure shown in any one of formulas (I) to (II):
wherein, X1And X2Independently selected from B, P ═ O or P ═ S; y is1And Y2Independently selected from N (R)1)、O、S、Se、Te、B(R1)、C(R1R2) Or Si (R)1R2)；
Ar1～Ar3Independently selected from a substituted or unsubstituted C6-C60 aryl ring, or a substituted or unsubstituted C3-C60 heteroaryl ring; the substitution is D, F, Cl, Br, I, -CN, -NO2、-CF3Straight chain alkyl of C1-C30, branched chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C30, alkylthio of C1-C30, substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted aryl ether of C6-C60, heteroaryl of C3-C60 or substituted or unsubstituted heteroaryl ether of C3-C60; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
R1～R2independently selected from H, D, F, Cl, Br, I, -CN, -CF3、-NO2、
the R is1～R3Selected from H,D. Linear alkyl of C1-C30, branched alkyl of C1-C30, cycloalkyl of C3-C30, substituted or unsubstituted aryl of C6-C60 or substituted or unsubstituted heteroaryl of C3-C60; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se; and R is1、R2And R3Between two and R1And Ar1～Ar3Any one of the substituent groups can also pass through a single bond, -C (R)aRb)-、-(C＝O)-、-Si(RaRb)-、-N(Ra)-、-PO(Ra) -, -O-, -S-or-Se-is linked; the R isaAnd RbIndependently straight-chain alkyl of C1-C30, branched-chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C30, alkylthio of C1-C30, substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted aryl ether of C6-C60, substituted or unsubstituted heteroaryl of C5-C60 or substituted or unsubstituted heteroaryl ether of C5-C60;
n1～n2is an integer of 0 to 4.
Preferably, the binaphthyl ring-containing boron-or phospha-fused ring compound has a structure represented by any one of the following:
preferably, X is1And X2Are all B.
Preferably, said Y is1And Y2Independently selected from N (R)1) O, S or Se.
Preferably, X is1And X2Are both B, and the Y1And Y2Independently selected from N (R)1) O, S or Se.
Most preferably, the bora-or phospha-fused ring compound containing a binaphthyl ring is selected from one of the following structures:
the invention also provides a preparation method of the boron-doped or phosphorus-doped fused ring compound containing the binaphthyl ring, which comprises the following steps:
when X is present1And X2When independently selected from B or P ═ S, the preparation process comprises the steps of:
under the argon atmosphere, placing A-1 or A-2 and o-xylene into a three-neck flask, cooling, dropwise adding a pentane solution of tert-butyl lithium into the reaction solution, heating the reaction solution after dropwise adding, and stirring; after the reaction is finished, cooling the reaction solution again, dropwise adding boron trihalide or phosphorus trihalide and adding sulfur powder into the reaction solution, and after the raw materials are added, heating the reaction solution and continuously stirring; cooling the reaction liquid after the reaction is finished, dropwise adding N, N-diisopropylethylamine into the reaction liquid, heating after the dropwise adding is finished, continuously stirring the reaction liquid, cooling the reaction liquid to room temperature, filtering solids separated out from the reaction liquid, washing with methanol, and drying the product to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped condensed ring compound shown in the formula (I) and the formula (II);
when X is present1And X2When independently selected from P ═ O, the preparation process comprises the steps of:
adding X into a double-neck flask under the argon atmosphere1And X2Independently selecting a fused ring compound prepared when P ═ S, m-chloroperoxybenzoic acid and dried dichloromethane, stirring the reaction solution at room temperature, then placing the reaction solution into methanol for sedimentation after the reaction is finished, filtering the precipitated solid, and separating by silica gel column chromatography to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in the formula (I) and the formula (II);
hereinafter, X alone1And X2Independently selected from B, and the synthetic routes of the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compounds shown in the formula (I) and the formula (II) are respectively as follows:
wherein Z is selected from one of Cl, Br and I; other codes are the same as those described above, and are not described herein again.
Preferably, one specific embodiment of the preparation method of the boron-doped or phosphorus-doped fused ring compound containing the binaphthyl ring is as follows:
when X is present1And X2When independently selected from B or P ═ S, the preparation process comprises the steps of:
under the argon atmosphere, placing A-1 or A-2 and o-xylene into a 500mL three-neck flask, cooling at minus 30 ℃ for 20 minutes, dropwise adding 2.5M/L of tert-butyl lithium pentane solution into the reaction solution, heating the reaction solution to 50 ℃ after the dropwise adding is finished, and stirring for 1 hour; after 1 hour, cooling the reaction solution to-30 ℃ again, dropwise adding boron trihalide or phosphorus trihalide and adding sulfur powder into the reaction solution, after the raw materials are added, heating the reaction solution to 40 ℃, and stirring for 1 hour; cooling the temperature of the reaction solution to 0 ℃, dropwise adding N, N-diisopropylethylamine into the reaction solution, and heating to 125 ℃ after dropwise adding, and stirring for 12 hours; finally, cooling the reaction liquid to room temperature, filtering the solid precipitated in the reaction liquid, washing with methanol, and drying the product at 80 ℃ under reduced pressure to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in the formula (I) and the formula (II);
when X is present1And X2When independently selected from P ═ O, the preparation process comprises the steps of:
under argon atmosphere, adding X into a 250mL double-neck flask1And X2Independently selected from the fused ring compound prepared when P ═ S, m-chloroperoxybenzoic acid and dried dichloromethane, is stirred at room temperature for 24 hours, the reaction solution is placed in 500mL of methanol for sedimentation, and the precipitated solid is filtered and separated by silica gel column chromatography to obtain the binaphthyl ring-containing boron hetero or phosphorus hetero fused ring compound represented by formula (I) or formula (II).
The invention also provides application of the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in the formula (I) or (II) as a luminescent material, in particular application to an organic electroluminescent device.
The invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode; the organic thin film layer comprises a binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound represented by the formula (I) or (II).
Preferably, the organic thin film layer includes a light emitting layer; the light-emitting layer comprises a binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in formula (I) or formula (II).
The structure of the organic electroluminescent device is not particularly limited in the present invention, and may be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art may select and adjust the structure according to the application, quality requirements and product requirements, and the structure of the organic electroluminescent device of the present invention preferably includes: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.
The thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm; the choice of the substrate is not particularly limited by the present invention, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, which may be selected and adjusted according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.
According to the invention, the anode is preferably a material susceptible to hole injection, more preferably a conductive metal or conductive metal oxide, and even more preferably indium tin oxide.
The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light emitting layer; the light-emitting layer includes a condensed ring compound represented by the above formula (I) or formula (II); the condensed ring compound shown in the formula (I) or the formula (II) provided by the invention is used as a luminescent material to directly form an organic electroluminescent layer.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light emitting layer and the cathode preferably further includes one or more of a hole blocking layer and an electron injection layer and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the preparation processes of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer, and is preferably prepared by a process of vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing and stereolithography.
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers including a light emitting layer on the anode; forming a cathode on the organic thin film layer;
the light-emitting layer includes one or more compounds represented by formula (I) or formula (II).
The structure and material of the organic electroluminescent device in the preparation method, and the corresponding preferred principle, and the corresponding material and structure in the organic electroluminescent device, and the corresponding preferred principle may be corresponding, and are not described in detail herein.
The present invention first forms an anode on a substrate, and the present invention does not specifically limit the manner of forming the anode, and may be performed according to a method known to those skilled in the art. The present invention is not particularly limited in the form of the light-emitting layer and the organic thin film layer below and above the light-emitting layer, and the organic thin film layer can be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. After the organic layer is formed, a cathode is prepared on the surface thereof, and the cathode is formed by a method known to those skilled in the art, including but not limited to vacuum deposition.
The invention has the beneficial effects that:
according to the boron-doped or phosphorus-doped fused ring compound containing the binaphthyl ring, on one hand, the relaxation degree of an excited state structure can be reduced by using a rigid skeleton structure of the binaphthyl ring, so that narrower half-peak width is realized; on the other hand, resonance effect between boron atom or phosphorus atom and heteroatom is utilized to realize separation of HOMO and LUMO, thereby realizing smaller Delta ESTAnd TADF effect, thereby achieving high luminous efficiency. Meanwhile, the delayed fluorescence lifetime and the half-peak width can be further adjusted by changing the types of the aromatic ring or the heteroaromatic ring contained in the fused ring compound.
The fused ring compound provided by the invention is used as a light emitting layer of an electroluminescent device, so that the narrow electroluminescent half-peak width can be realized under the condition of no need of an optical filter and a microcavity structure, and the high external quantum efficiency of the device can be realized. The experimental results also show that: the device prepared from the condensed ring compound provided by the invention has a very narrow electroluminescent spectrum, the half-peak width of the device is less than 40nm, and the problem that the electroluminescent spectrum of a TADF compound with a traditional D-A structure is wide (70-100 nm) is solved. Meanwhile, devices prepared by the compound provided by the invention have higher device efficiency, and the maximum external quantum efficiency reaches 35.1%.
The preparation method of the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound provided by the invention is simple in preparation method and mild in conditions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the following examples are all commercially available.
Example 1
1-1(20.0g, 52.6mmol), 1-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 1-3(18.2g, yield: 78%) as a product.
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.63; h, 4.72.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
1-3(15.0g, 33.8mmol), 1-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 1-5(15.3g, yield: 81%) of the product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.12; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
1-5(10.0g, 17.9mmol), 1-6(8.3g, 39.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 1-7(13.2g, yield: 90%).
Elemental analysis of its Structure (C)56H46Cl2N2): theoretical value: c, 82.24; h, 5.67; n, 3.43; test values are: c, 82.28; h, 5.61; and N, 3.39.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
Under argon atmosphere, 1-7(4.0g,4.9mmol) and dry o-xylene (70mL) are added into a 250mL double-neck flask, n-pentane solution of tert-butyllithium (8.3mL,1.3M,10.8mmol) is dropwise added at minus 30 ℃, after the dropwise addition, the reaction solution is stirred for 1 hour at 50 ℃, the reaction solution is cooled to minus 30 ℃ again, boron tribromide (2.9g,1.1mL,11.7mmol) is dropwise added into the reaction solution, and the reaction solution is returned to room temperature and stirred for 1 hour after the dropwise addition. The temperature is again reduced to 0 ℃, N-diisopropylethylamine (1.6g,2.2mL,12.7mmol) is dropwise added into the reaction solution, and after the dropwise addition is finished, the temperature is raised to 125 ℃ and the mixture is stirred for 20 hours. After the reaction solution was cooled to room temperature, the solid precipitated in the reaction solution was filtered, washed with methanol and then separated by silica gel column chromatography to give the product I-1-2(2.3g, yield: 62%).
Elemental analysis Structure (C)56H42B2N2): theoretical value: c, 87.97; h, 5.54; n, 3.66; test values are: c, 88.01; h, 5.48; and N, 3.72.
MALDI-TOF-MS: theoretical value 764.4; experimental value 764.4.
Example 2
2-1(20.0g, 35.9mmol), 2-2(16.5g, 79.0mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (20.8g, 71.8mmol), sodium tert-butoxide (6.9g, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 2-3(18.2g, yield: 74%).
Elemental analysis of its Structure (C)40H24BrCl2NO): theoretical value: c, 70.09; h, 3.53; n, 2.04; test value C, 70.12; h, 3.58; and N, 2.01.
MALDI-TOF-MS: theoretical value 683.0; experimental value 683.0.
In a 500mL three-necked flask, under an argon atmosphere, 2-3(15.0g, 21.9mmol), 2-4(8.1g, 48.1mmol), tris (dibenzylideneacetone) dipalladium (0.8g, 0.9mmol), tri-tert-butylphosphine tetrafluoroborate (12.7g, 43.8mmol), sodium tert-butoxide (4.2g, 43.8mmol) and 250mL of toluene were added, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 2-5(13.2g, yield: 78%).
Elemental analysis of its Structure (C)52H34Cl2N2O): theoretical value: c, 80.72; h, 4.43; n, 3.62; test values are: c, 80.78; h, 4.39; and N, 3.59.
MALDI-TOF-MS: theoretical value 772.2; experimental value 772.2.
Referring to example 1, starting from 2-5(10.0g, 12.9mmol), the final product, I-1-14(8.2g, yield: 88%).
Elemental analysis Structure (C)52H30B2N2O): theoretical value: c, 86.69; h, 4.20; n, 3.89; test values are: c, 86.73; h, 4.22; and N, 3.81.
MALDI-TOF-MS: theoretical value 720.3; experimental value 720.3.
Example 3
In a 500mL three-necked flask, 3-1(20.0g, 50.7mmol), 3-2(19.3g,60.9mmol), tetrakis (triphenylphosphine) palladium (4.7g,4.1mmol), potassium carbonate (28.1g,203.0mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 3-3(19.3g, yield: 83%).
Elemental analysis of its Structure (C)23H23BBrClO2): theoretical value: c, 60.37; h, 5.07; test values are: c, 60.43; h, 5.02.
MALDI-TOF-MS: theoretical value 456.1; experimental value 456.1.
In a 500mL three-necked flask, 3-3(15.0g, 32.8mmol), 3-4(14.5g,39.3mmol), tetrakis (triphenylphosphine) palladium (3.0g,2.6mmol), potassium carbonate (18.1g,131.1mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 3-5(16.2g, yield: 87%).
Elemental analysis of its Structure (C)27H16Br2Cl2): theoretical value: c, 56.78; h, 2.82; test values are: c, 56.83; h, 2.79.
MALDI-TOF-MS: theoretical value 567.9; experimental value 567.9.
In a 500mL three-necked flask, 3-5(10.0g, 17.5mmol), 3-6(4.2g, 38.5mmol), tris (dibenzylideneacetone) dipalladium (0.6g, 0.7mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (20.3g, 35.0mmol), N-diisopropylethylamine (4.5g, 6.1mL, 35.0mmol) and 250mL of 1, 4-dioxane were added under an argon atmosphere, and after stirring at 105 ℃ for 8 hours, the mixture was cooled to room temperature, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 3-7(10.2g, yield: 93%).
Elemental analysis of its Structure (C)39H26Cl2S2): theoretical value: c, 74.39; h, 4.16; s, 10.18; test values are: c, 74.45; h, 4.11; and S, 10.12.
MALDI-TOF-MS: theoretical value 628.1; experimental value 628.1.
Referring to example 1, starting from 3-7(10.0g, 15.9mmol), the final product, I-1-15(6.5g, yield: 71%), was obtained.
Elemental analysis Structure (C)39H22B2S2): theoretical value: c, 81.28; h, 3.85; s, 11.13; test values are: c, 81.32; h, 3.88; and S, 11.07.
MALDI-TOF-MS: theoretical value 576.1; experimental value 576.1.
Example 4
Under an argon atmosphere, 4-1(20.0g, 35.9mmol), 4-2(4.1g, 43.1mmol), cesium carbonate (23.4g, 71.8mmol), 2,6, 6-tetramethyl-3, 5-heptanedione (0.3g, 1.4mmol), cuprous iodide (0.3g, 1.4mmol) and 250mLN, N-dimethylformamide were charged into a 500mL three-necked flask, stirred at 180 ℃ for 8 hours, cooled to room temperature, the reaction solution was poured into 2000mL of methanol to precipitate, the precipitated precipitate was filtered, and the product 4-3(17.2g, yield: 84%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)32H19BrCl2O): theoretical value: c, 67.39; h, 3.36; test values are: c, 67.41; h, 3.33.
MALDI-TOF-MS: theoretical value 568.0; experimental value 568.0.
In a 500mL three-necked flask, 4-3(15.0g, 26.3mmol), 4-4(8.8g, 31.6mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (15.3g, 52.6mmol), sodium tert-butoxide (5.1g, 52.6mmol) and 250mL of toluene were added under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 4-5(17.1g, yield: 85%).
Elemental analysis of its Structure (C)52H43Cl2NO): theoretical value: c, 81.24; h, 5.64; n, 1.82; test values are: c, 81.28; h, 5.61; n, 1.85.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
4-5(10.0g,13.0mmol) and dry toluene (70mL) are added to a 250mL two-necked flask under argon atmosphere, a n-pentane solution of tert-butyllithium (22.0mL,1.3M,28.6mmol) is added dropwise at-30 ℃, after the addition is completed, the mixture is stirred at 50 ℃ for 1 hour, cooled again to-30 ℃, and phosphorus trichloride (PCl) is added dropwise to the reaction mixture3) (4.3g,2.7mL,31.2mmol), and after the addition was complete, stirred at room temperature for 1 hour. The temperature is again reduced to 0 ℃, aluminum trichloride (6.9g,52.0mmol) is added, and after the raw material is added, the temperature is raised to 125 ℃ and stirring is carried out for 1 hour. After the reaction was cooled to room temperature again, S was added8(1.1g,33.8mmol) was added to the reaction solution and stirred for 20 h. In the case of the post-treatment, the solid precipitated in the reaction solution was filtered, washed with methanol, and then separated by silica gel column chromatography to obtain 4-6(8.2g, yield: 77%).
Elemental analysis Structure (C)52H39NOP2S2): theoretical value: c, 76.17; h, 4.79; n, 1.71; s, 7.82; test values are: c, 76.21; h, 4.72; n, 1.75; and S, 7.83.
MALDI-TOF-MS: theoretical value 819.2; experimental value 819.2.
4-6(4.0g,4.9mmol), m-chloroperoxybenzoic acid (MCPBA) (1.9g,10.7mmol) and dried methylene chloride (70mL) were charged in a 250mL two-necked flask under an argon atmosphere, and after stirring at room temperature for 24 hours, the reaction mixture was precipitated in 500mL of methanol, and the precipitated solid was filtered off to obtain product I-1-16(2.8g, yield: 73%) by silica gel column chromatography.
Elemental analysis Structure (C)52H39NO3P2): theoretical value: c, 79.28; h, 4.99; n, 1.78; test values are: c, 79.28; h, 4.99; n, 1.78.
MALDI-TOF-MS: theoretical value 787.2; experimental value 787.2.
Example 5
In a 500mL three-necked flask, 5-1(20.0g, 52.6mmol), 5-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added under an argon atmosphere, and stirred at 120 ℃ for 8 hours, followed by cooling to room temperature, addition of 150mL of ethyl acetate, washing of the organic phase with deionized water 3 times (100 mL. times.3), drying over anhydrous magnesium sulfate, and column chromatography of the concentrate from which the solvent was removed to give 5-3(16.5g, yield: 71%) as a product.
Elemental analysis Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.52; h, 4.79.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
In a 500mL three-necked flask, 5-3(15.0g, 33.8mmol), 5-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 30mL of water, 50mg of Aliquant-336 and 200mL of toluene were added under an argon atmosphere to react at 120 ℃ for 8 hours, followed by cooling to room temperature, then cooling to room temperature, adding 150mL of ethyl acetate, washing the organic phase with deionized water 3 times (100 mL. times.3), drying over anhydrous magnesium sulfate, and separating the concentrate obtained after removing the solvent from the organic phase by silica gel column chromatography to obtain 5-5(15.3g, yield: 81%).
Elemental analysis Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.09; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
5-5(15.0g, 26.9mmol), 5-6(16.7g, 59.2mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 5-7(18.5g, yield: 72%).
Elemental analysis of its Structure (C)66H66Cl2N2): theoretical value: c, 82.73; h, 6.94; n, 2.92; test values are: c, 82.77; h, 6.91; and N, 2.87.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
Referring to example 1, starting from 5-7(4.0g, 4.2mmol), the product I-2-2 was finally obtained (2.8g, yield: 74%).
Elemental analysis Structure (C)66H62B2N2): theoretical value: c, 87.61; h, 6.91; n, 3.10; test values are: c, 87.68; h, 6.85; and N, 3.12.
MALDI-TOF-MS: theoretical value 904.5; experimental value 904.5.
Example 6
6-1(15.0g, 26.9mmol), 6-2(12.4g, 59.2mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 6-3(16.8g, yield: 77%).
Elemental analysis of its Structure (C)56H42Cl2N2): theoretical value: c, 88.44; h, 5.04; n, 3.68; test values are: c, 88.47; h, 5.01; and N, 3.61.
MALDI-TOF-MS: theoretical value 760.3; experimental value 760.3.
Referring to example 1, starting from 6-3(4.0g, 4.9mmol), the product I-2-5 was finally obtained (3.4g, yield: 91%).
Elemental analysis Structure (C)56H38B2N2): theoretical value: c, 88.44; h, performing a chemical reaction on the mixture of the hydrogen peroxide and the nitrogen peroxide,5.04; n, 3.68; test values are: c, 88.46; h, 5.01; and N, 3.62.
MALDI-TOF-MS: theoretical value 760.3; experimental value 760.3.
Example 7
In a 500mL three-necked flask, 7-1(15.0g, 26.9mmol), 7-2(12.4g, 59.2mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 7-3(17.3g, yield: 79%).
Elemental analysis of its Structure (C)54H34Cl2N2O2): theoretical value: c, 79.70; h, 4.21; n, 3.44; test values are: c, 79.75; h, 4.16; and N, 3.47.
MALDI-TOF-MS: theoretical value 812.2; experimental value 812.2.
Referring to example 1, starting from 7-3(4.0g, 4.9mmol), the final product, I-2-10(3.2g, yield: 86%), was obtained.
Elemental analysis Structure (C)54H30B2N2O2): theoretical value: c, 85.29; h, 3.98; n, 3.68; test values are: c, 85.32; h, 3.92; and N, 3.69.
MALDI-TOF-MS: theoretical value 760.3; experimental value 760.3.
Example 8
In a 500mL three-necked flask under an argon atmosphere, 8-1(15.0g, 26.9mmol), 8-2(18.0g, 59.2mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain a product 8-3(22.2g, yield: 82%).
Elemental analysis of its Structure (C)66H46Cl2N2S2): theoretical value: c, 79.10; h, 4.63; n, 2.80; s, 6.40; test values are: c, 79.18; h, 4.59; n, 2.82; s, 6.37.
MALDI-TOF-MS: theoretical value 1000.3; experimental value 1000.3.
Referring to example 1, starting from 8-3(4.0g, 4.0mmol), the product I-2-18 was finally obtained (2.1g, yield: 55%).
Elemental analysis Structure (C)66H42B2N2S2): theoretical value: c, 83.55; h, 4.46; n, 2.95; s, 6.76; test values are: c, 83.56; h, 4.41; n, 2.98; s, 6.77.
MALDI-TOF-MS: theoretical value 948.3; experimental value 948.3.
Example 9
In a 500mL three-necked flask under an argon atmosphere, 9-1(20.0g, 52.6mmol), 9-2(13.2g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were stirred at 120 ℃ for 8 hours, then cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), then dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 9-3(18.2g, yield: 90%).
Elemental analysis Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.52; h, 4.79.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
In a 500mL three-necked flask, 9-3(15.0g, 39.2mmol), 9-4(12.2g,47.0mmol), tetrakis (triphenylphosphine) palladium (3.6g,3.1mmol), potassium carbonate (21.7g,156.8mmol), 30mL of water, 50mg of Aliquant-336 and 200mL of toluene were added under an argon atmosphere to react at 120 ℃ for 8 hours, followed by cooling to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate was subjected to silica gel column chromatography to remove the solvent to obtain 9-5(15.1g, yield: 88%).
Elemental analysis Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.09; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
9-5(15.0g, 34.5mmol), 9-6(13.4g, 41.4mmol), potassium carbonate (19.1g, 137.8mmol) and N-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, and stirred at 180 ℃ for 8 hours. The precipitate was precipitated in 2000mL of water, and the precipitated solid was filtered, washed with methanol, and subjected to silica gel column chromatography to give 9-7(20.1g, 79%).
Elemental analysis of its Structure (C)44H28Cl2FNSe): theoretical value: c, 71.46; h, 3.82; n, 1.89; test values are: c, 71.52; h, 3.87; n, 1.82.
MALDI-TOF-MS: theoretical value 739.1; experimental value 739.1.
9-7(10.0g, 13.5mmol), 9-8(4.2g, 16.2mmol), potassium carbonate (7.5g, 54.1mmol) and 250mL of LN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 1000mL of methanol to be settled, the precipitated precipitate was filtered and washed with methanol, and then, the product was separated by column chromatography on silica gel to obtain 9-9(12.2g, yield: 92%).
Elemental analysis of its Structure (C)62H42Cl2N2OSe): theoretical value: c, 75.92; h, 4.32; n, 2.86; test values are: c, 75.98; h, 4.27; and N, 2.82.
MALDI-TOF-MS: theoretical value 980.2; experimental value 980.2.
Referring to example 1, starting from 9-9(4.0g, 4.1mmol), the final product, I-2-57(2.6g, yield: 69%), was obtained.
Elemental analysis Structure (C)62H38B2N2OSe): theoretical value: c, 80.28; h, 4.13; n, 3.02; test values are: c, 80.28; h, 4.13; and N, 3.02.
MALDI-TOF-MS: theoretical value 928.2; experimental value 928.2.
Example 10
In a 500mL three-necked flask, 10-1(20.0g, 26.9mmol), 10-2(16.7g, 59.2mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain a product 10-3(19.2g, yield: 74%).
Elemental analysis of its Structure (C)62H50Cl2N2S2): theoretical value: c, 77.72; h, 5.26; n, 2.92; s, 6.69; test values are: c, 77.78; h, 5.21; n, 2.94; and S, 6.63.
MALDI-TOF-MS: theoretical value 956.3; experimental value 956.3.
Referring to example 4, starting from 10-3(10.0g, 10.4mmol), the product 10-4(8.6g, yield: 82%) was finally obtained.
Elemental analysis Structure (C)62H46N2P2S4): theoretical value: c, 73.79; h, 4.59; n, 2.78; s, 12.71; test values are: c, 73.83; h, 4.52; n, 2.73; s,12.78
MALDI-TOF-MS: theoretical value 1008.2; experimental value 1008.2.
Referring to example 4, starting from 10-4(4.0g, 4.0mmol), the product I-2-58 was finally obtained (3.3g, yield: 72%).
Elemental analysis Structure (C)62H46N2O2P2S2): theoretical value: c, 76.21; h, 4.75; n, 2.87; s, 6.56; test values are: c, 76.18; h, 4.78; n, 2.89; s, 6.53.
MALDI-TOF-MS: theoretical value 976.3; experimental value 976.3.
Example 11
In a 500mL three-necked flask under an argon atmosphere, 11-1(20.0g, 52.6mmol), 11-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was charged, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 11-3(17.2g, yield: 74%).
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.63; h, 4.72.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
In a 500mL three-necked flask under an argon atmosphere, 11-3(15.0g, 33.8mmol), 11-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 11-5(14.3g, yield: 76%).
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c,56.12；H,2.51。
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
In a 500mL three-necked flask, under an argon atmosphere, 11-5(10.0g, 17.9mmol), 11-6(6.7g, 39.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to give the product 11-7(11.8g, yield: 90%).
Elemental analysis of its Structure (C)50H34Cl2N2): theoretical value: c, 81.85; h, 4.67; n, 3.82; test values are: c, 81.88; h, 4.62; and N, 3.83.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
Referring to example 1, starting from 11-7(4.0g, 5.5mmol), the product I-3-1 was finally obtained (2.3g, yield: 62%).
Elemental analysis Structure (C)50H30B2N2): theoretical value: c, 88.26; h, 4.44; n, 4.12; test values are: c, 88.35; h, 4.41; and N, 4.16.
MALDI-TOF-MS: theoretical value 680.3; experimental value 680.3.
Example 12
12-1(15.0g, 26.9mmol), 12-2(8.7g, 32.3mmol), tris (dibenzylideneacetone) dipalladium (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (15.6g, 53.8mmol), sodium tert-butoxide (5.2g, 53.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 12-3(15.6g, yield: 78%).
Elemental analysis of its Structure (C)46H28BrCl2N): theoretical value: c, 74.11; h, 3.79; n, 1.88; test values are: c, 74.18; h, 3.72; n, 1.85.
MALDI-TOF-MS: theoretical value 743.1; experimental value 743.1.
12-3(15.0g, 20.1mmol), 12-4(12.5g, 44.3mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.8mmol), tri-tert-butylphosphine tetrafluoroborate (11.7g, 40.2mmol), sodium tert-butoxide (3.9g, 40.2mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 12-5(14.3g, yield: 75%).
Elemental analysis of its Structure (C)66H54Cl2N2): theoretical value: c, 83.79; h, 5.75; n, 2.96; test values are: c, 83.81; h, 5.73; and N, 2.98.
MALDI-TOF-MS: theoretical value 944.4; experimental value 944.4.
Referring to example 1, starting from 12-5(4.0g, 4.2mmol), the final product, I-3-37(2.1g, yield: 56%).
Elemental analysis Structure (C)66H50B2N2): theoretical value: c, 88.79; h, 5.65; n, 3.14; test values are: c, 88.81; h, 5.61; and N, 3.17.
MALDI-TOF-MS: theoretical value 892.4; experimental value 892.4.
Example 13
13-1(20.0g, 52.6mmol), 13-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 13-3(17.2g, yield: 74%) as a product.
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.63; h, 4.72.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
13-3(15.0g, 33.8mmol), 13-4(12.4g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 13-5(15.1g, yield: 90%) as a product.
Elemental analysis of its Structure (C)26H14BrCl2F) The method comprises the following steps Theoretical value: c, 62.94; h, 2.84; test values are: c, 62.91; h, 2.87.
MALDI-TOF-MS: theoretical value 494.0; experimental value is 494.0.
13-5(10.0g, 20.2mmol), 13-6(14.8g, 44.3mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.8mmol), tri-tert-butylphosphine tetrafluoroborate (11.7g, 40.3mmol), sodium tert-butoxide (3.9g, 40.3mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent of the organic phase was subjected to silica gel column chromatography to obtain a product 13-7(12.1g, yield: 80%).
Elemental analysis of its Structure (C)51H32Cl2FN): theoretical value: c, 81.81; h, 4.31; n, 1.87; test values are: c, 81.88; h, 4.26; n, 1.88.
MALDI-TOF-MS: theoretical value 747.2; experimental value 747.2.
13-7(10.0g, 13.4mmol), 13-8(4.6g, 29.4mmol), potassium carbonate (3.7g, 26.7mmol) and 50mL of N-methylpyrrolidone were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, settled in 500mL of water, and the precipitated precipitate was washed with methanol and then separated by silica gel column chromatography to give 13-9(8.5g, yield: 72%).
Elemental analysis of its Structure (C)57H37Cl2NSe): theoretical value: c, 77.29; h, 4.21; n, 1.58; test values are: c, 77.24; h, 4.25; n, 1.54.
MALDI-TOF-MS: theoretical value 885.2; experimental value 885.2.
Referring to example 1, starting from 13-9(4.0g, 4.5mmol), the product I-3-38 was finally obtained (3.2g, yield: 85%).
Elemental analysis Structure (C)57H33B2NSe): theoretical value: c, 82.24; h, 4.00; n, 1.68; test values are: c, 82.28; h, 4.08; n, 1.61.
MALDI-TOF-MS: theoretical value 833.2; experimental value 833.2.
Example 14
14-1(20.0g, 35.9mmol), 14-2(22.2g, 79.0mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (20.8g, 71.8mmol), sodium tert-butoxide (6.9g, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 14-3(18.2g, yield: 67%).
Elemental analysis of its Structure (C)46H40BrCl2N): theoretical value: c, 72.92; h, 5.32; n, 1.85; test values are: c, 72.98; h, 5.27; n, 1.88.
MALDI-TOF-MS: theoretical value 755.2; experimental value 755.2.
14-3(15.0g, 19.8mmol), 14-4(7.2g, 43.6mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.8mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (22.9g, 39.6mmol), N-diisopropylethylamine (5.1g, 6.9mL, 39.6mmol) and 250mL of 1, 4-dioxane were added to a 500mL three-necked flask under an argon atmosphere, and after stirring at 105 ℃ for 8 hours, the mixture was cooled to room temperature, and the solvent was removed from the organic phase to obtain a concentrated solution, which was subjected to silica gel column chromatography to obtain 14-5(10.2g, yield: 93%).
Elemental analysis of its Structure (C)54H45Cl2NS2): theoretical value: c, 76.94; h, 5.38; n, 1.66; s, 7.61; test values are: c, 76.91; h, 5.32; n, 1.69; and S, 7.58.
MALDI-TOF-MS: theoretical value 841.2; experimental value 841.2.
Referring to example 1, starting from 14-5(4.0g, 4.7mmol), the final product, I-3-39(2.1g, yield: 56%).
Elemental analysis Structure (C)54H41B2NS2): theoretical value: c, 82.13; h, 5.23; n, 1.77; s, 8.12; test values are: c, 82.15; h, 5.18; n, 1.79; and S, 8.08.
MALDI-TOF-MS: theoretical value 789.3; experimental value 789.3.
Example 15
15-1(20.0g, 52.6mmol), 15-2(13.2g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 15-3(17.4g, yield: 86%) as a product.
Elemental analysis of its Structure (C)22H21BClFO2): theoretical value: c, 69.05; h, 5.53; test values are: c, 69.06; h, 5.49.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
15-3(15.0g, 39.2mmol), 15-4(12.2g,47.0mmol), tetrakis (triphenylphosphine) palladium (3.6g,3.1mmol), potassium carbonate (21.7g,156.8mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 15-5(12.8g, yield: 75%) as a product.
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.79; h, 3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
15-5(10.0g, 23.0mmol), 15-6(6.5g, 50.5mmol), potassium carbonate (6.3g, 45.9mmol) and 250mL of LN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the reaction solution was settled in 500mL of water, the precipitate precipitated in the solution was filtered and washed with methanol, and the product 15-7(11.3g, yield: 75%) was isolated by silica gel column chromatography.
Elemental analysis of its Structure (C)38H22Cl2F2S2): theoretical value: c, 70.04; h, 3.40; s, 9.84; test values are: c, 70.08; h, 3.32; and S, 9.88.
MALDI-TOF-MS: theoretical value 650.1; experimental value 650.1.
Referring to example 4, starting from 15-7(4.0g, 6.1mmol), the final product, I-3-40(2.8g, yield: 65%).
Elemental analysis Structure (C)38H18F2P2S4): theoretical value: c, 64.95; h, 2.58; s, 18.25; test values are: c, 64.91; h, 2.59; and S, 18.15.
MALDI-TOF-MS: theoretical value 702.0; experimental value 702.0.
Example 16
16-1(20.0g, 52.6mmol), 16-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 16-3(14.3g, yield: 61%) as a product.
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.52; h, 4.78.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
16-3(15.0g, 33.8mmol), 16-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 16-5(16.2g, yield: 86%) as a product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.48.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
16-5(10.0g, 17.9mmol), 16-6(11.1g, 39.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 16-7(13.3g, yield: 77%).
Elemental analysis of its Structure (C)66H66Cl2N2): theoretical value: c, 82.73; h, 6.94; n, 2.92; test values are: c, 82.75; h, 6.91; and N, 2.87.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
Referring to example 1, starting from 16-7(4.0g, 4.2mmol), the final product, I-4-22(1.2g, yield: 32%), was obtained.
Elemental analysis Structure (C)66H62B2N2): theoretical value: c, 87.61; h, 6.91; n, 3.10; test values are: c, 87.64; h, 6.86; and N, 3.13.
MALDI-TOF-MS: theoretical value 904.5; experimental value 904.5.
Example 17
17-1(20.0g, 35.9mmol), 17-2(15.7g, 79.0mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (20.8g, 71.8mmol), sodium tert-butoxide (6.9g, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and then cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 17-3(22.5g, yield: 79%).
Elemental analysis of its Structure (C)52H40Cl2N4): theoretical value: c, 78.88; h, 5.09; n, 7.08; test values are: c, 78.89; h, 5.06; and N, 7.02.
MALDI-TOF-MS: theoretical value 790.3; experimental value 790.3.
Referring to example 1, starting from 17-3(8.0g, 10.1mmol), the product I-4-23 was finally obtained (2.5g, yield: 34%).
Elemental analysis Structure (C)52H36B2N4): theoretical value: c, 84.57; h, 4.91; n, 7.59; test values are: c, 84.59; h, 4.86; and N, 7.52.
MALDI-TOF-MS: theoretical value 738.3; experimental value 738.3.
Example 18
18-1(20.0g, 48.8mmol), 18-2(12.3g,58.5mmol), tetrakis (triphenylphosphine) palladium (4.5g,3.9mmol), potassium carbonate (27.0g,195.1mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 18-3(15.2g, yield: 76%) as a product.
Elemental analysis of its Structure (C)23H23BClFO3): theoretical value: c, 66.94; h, 5.62; test values are: c, 66.91; h, 5.68.
MALDI-TOF-MS: theoretical value 412.1; experimental value 412.1.
18-3(15.0g, 36.3mmol), 18-4(11.3g,43.6mmol), tetrakis (triphenylphosphine) palladium (3.4g,2.9mmol), potassium carbonate (20.1g,145.4mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 18-5(11.3g, yield: 81%) as a product.
Elemental analysis of its Structure (C)27H16Cl2F2O): theoretical value: c, 69.69; h, 3.47; test values are: c, 69.61; h, 3.42.
MALDI-TOF-MS: theoretical value 464.1; experimental value 464.1.
18-5(10.0g, 21.5mmol), 18-6(11.9g, 47.3mmol), potassium carbonate (5.9g, 43.0mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain 18-7(12.5g, yield: 89%).
Elemental analysis of its Structure (C)47H33Cl2NOTE): theoretical value: c, 68.32; h, 4.03; n, 1.70; test values are: c, 68.38; h, 3.92; n, 1.75.
MALDI-TOF-MS: theoretical value 827.1; experimental value 827.1.
18-7(10.0g, 15.4mmol), 18-8(6.6g, 33.8mmol), potassium carbonate (4.2g, 30.7mmol) and 250mL of LN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitate precipitated from the solution was filtered and then separated by silica gel column chromatography to obtain 18-9(9.2g, yield: 72%).
Elemental analysis of its Structure (C)47H29B2NOTE): theoretical value: c, 73.03; h, 3.78; n, 1.81; test values are: c, 73.05; h, 3.72; n, 1.83.
MALDI-TOF-MS: theoretical value 775.2; experimental value 775.2.
Referring to example 1, starting from 18-9(8.0g, 9.7mmol), the final product, I-4-24, was obtained (3.9g, yield: 52%).
Elemental analysis Structure (C)47H29B2NOTE): theoretical value: c, 73.03; h, 3.78; n, 1.81; test values are: c, 73.09; h, 3.71; n, 1.85.
MALDI-TOF-MS: theoretical value 775.2; experimental value 775.2.
Example 19
19-1(20.0g, 50.7mmol), 19-2(15.6g,60.9mmol), tetrakis (triphenylphosphine) palladium (4.7g,4.1mmol), potassium carbonate (28.1g,203.0mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 19-3(16.2g, yield: 80%) as a product.
Elemental analysis of its Structure (C)23H23BclFO2): theoretical value: c, 69.64; h, 5.84; test values are: c, 69.68; h, 5.82.
MALDI-TOF-MS: theoretical value 396.2; experimental value 396.2.
19-3(15.0g, 37.8mmol), 19-4(13.9g,45.4mmol), tetrakis (triphenylphosphine) palladium (3.5g,3.0mmol), potassium carbonate (20.9g,151.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 19-5(14.2g, yield: 84%) as a product.
Elemental analysis of its Structure (C)27H16Cl2F2): theoretical value: c, 72.17; h, 3.59; test values are: c, 72.19; h, 3.53.
MALDI-TOF-MS: theoretical value 448.1; experimental value 448.1.
19-5(10.0g, 22.3mmol), 19-6(4.0g, 26.7mmol), potassium carbonate (6.2g, 44.5mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain 19-7(12.2g, yield: 86%).
Elemental analysis of its Structure (C)37H29Cl2FO): theoretical value: c, 76.68; h, 5.04; test values are: c, 76.62; h, 5.07.
MALDI-TOF-MS: theoretical value 578.2; experimental value 578.2.
19-7(10.0g, 17.3mmol), 19-8(7.3g, 34.4mmol), potassium carbonate (4.3g, 31.2mmol) and 250mL of LN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitate precipitated from the solution was filtered and then separated by silica gel column chromatography to obtain 19-9(9.8g, yield: 81%).
Elemental analysis of its Structure (C)47H38OP2S2Se): theoretical value: c, 68.52; h, 4.65; s, 7.78; test values are: c, 68.56; h, 4.61; s, 7.79.
MALDI-TOF-MS: theoretical value 824.1; experimental value 824.1.
Referring to example 4, starting from 19-9(10.0g, 12.9mmol), the final product, 19-10(8.2g, yield: 77%), was obtained.
Elemental analysis of its Structure (C)47H29B2NOTE): theoretical value: c, 73.03; h, 3.78; n, 1.81; test values are: c, 73.05; h, 3.72; n, 1.83.
MALDI-TOF-MS: theoretical value 775.2; experimental value 775.2.
Referring to example 4, starting from 19-10(4.0g, 4.9mmol), the final product, I-4-25(1.3g, yield: 34%), was obtained.
Elemental analysis of its Structure (C)47H38O3P2Se): theoretical value: c, 71.30; h, 4.84; test values are: c, 71.35; h, 4.81.
MALDI-TOF-MS: theoretical value 792.2; experimental value 792.2.
Example 20
20-1(20.0g, 52.6mmol), 20-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 20-3(16.6g, yield: 71%) as a product.
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.52; h, 4.79.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
20-3(15.0g, 33.8mmol), 20-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 20-5(15.2g, yield: 81%) as a product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
20-5(10.0g, 17.9mmol), 20-6(12.7g, 39.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 20-7(13.2g, yield: 71%).
Elemental analysis of its Structure (C)74H50Cl2N2): theoretical value: c, 85.62; h, 4.85; n, 2.70; test values are: c, 85.68; h, 4.81; and N, 2.72.
MALDI-TOF-MS: theoretical value 1036.3; experimental value 1036.3.
Referring to example 1, starting from 20-7(4.0g, 4.9mmol), the final product, I-5-26(1.3g, yield: 34%), was obtained.
Elemental analysis of its Structure (C)74H46B2N2): theoretical value: c, 90.25; h, 4.71; n, 2.84; test values are: c, 90.28; h, 4.72; and N, 2.85.
MALDI-TOF-MS: theoretical value 984.4; experimental value 984.4.
Example 21
21-1(20.0g, 52.6mmol), 21-2(13.2g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 21-3(16.7g, yield: 83%) as a product.
Elemental analysis of its Structure (C)22H21BClFO2): theoretical value: c, 69.05; h, 5.53; test values are: c, 69.08; h, 5.47.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
21-3(15.0g, 39.2mmol), 21-4(12.2g,47.0mmol), tetrakis (triphenylphosphine) palladium (3.6g,3.1mmol), potassium carbonate (21.7g,156.8mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 21-5(13.2g, yield: 77%) as a product.
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.78;H,3.21。
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
21-5(10.0g, 23.0mmol), 21-6(14.1g, 50.5mmol), potassium carbonate (6.3g, 45.9mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain 21-7(13.8g, yield: 86%).
Elemental analysis of its Structure (C)46H38Cl2FN): theoretical value: c, 79.53; h, 5.51; n, 2.02; test values are: c, 79.58; h, 5.47; and N, 2.04.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
21-7(10.0g, 14.4mmol), 21-8(4.8g, 31.7mmol), potassium carbonate (4.0g, 28.8mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain 21-9(8.3g, yield: 70%) as a product.
Elemental analysis of its Structure (C)54H43Cl2NOS): theoretical value: c, 78.63; h, 5.25; n, 1.70; s, 3.89; test values are: c, 78.68; h, 5.21; n, 1.67; and S, 3.92.
MALDI-TOF-MS: a theoretical value of 823.2; the experimental value is 823.2.
Referring to example 1, starting from 21-9(8.0g, 9.7mmol), the final product, I-5-27(4.2g, yield: 56%).
Elemental analysis of its Structure (C)54H39B2NOS): theoretical value: c, 84.06; h, 5.09; n, 1.82; s, 4.16; test values are: c, 84.12; h, 5.07; n, 1.89; and S, 4.13.
MALDI-TOF-MS: theoretical value 771.3; experimental value 771.3.
Example 22
In a 500mL three-necked flask, under an argon atmosphere, 22-1(20.0g, 35.9mmol), 22-2(27.5g, 79.0mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (41.5g, 71.8mmol), N-diisopropylethylamine (9.3g, 12.5mL, 71.8mmol) and 250mL of 1, 4-dioxane were added, and after stirring at 105 ℃ for 8 hours, the mixture was cooled to room temperature, and the solvent was removed from the organic phase to obtain a concentrated solution, which was subjected to silica gel column chromatography to obtain 22-3(33.1g, yield: 84%).
Elemental analysis of its Structure (C)76H44Cl2S2): theoretical value: c, 83.58; h, 4.06; s, 5.87; test values are: c, 83.62; h, 4.00; and S, 5.82.
MALDI-TOF-MS: theoretical value 1090.2; experimental value 1090.2.
Referring to example 1, starting from 22-3(8.0g, 7.3mmol), the final product, I-5-28(4.6g, yield: 60%), was obtained.
Elemental analysis of its Structure (C)76H40B2S2): theoretical value: c, 87.87; h, 3.88; s, 6.17; test values are: c, 87.87; h, 3.88; and S, 6.17.
MALDI-TOF-MS: theoretical value 1038.3; experimental value 1038.3.
Example 23
23-1(20.0g, 35.9mmol), 23-2(22.1g, 79.0mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (41.5g, 71.8mmol), sodium tert-butoxide (9.3g, 12.5mL, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 23-3(33.1g, yield: 84%).
Elemental analysis of its Structure (C)46H38BrCl2N): theoretical value: c, 73.12; h, 5.07; n, 1.85; test values are: c, 73.15; h, 5.02; n, 1.88.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
23-3(20.0g, 26.5mmol), 23-4(5.5g, 58.2mmol), cuprous iodide (0.2g,1.1mmol), 2,6, 6-tetramethyl-3, 5-heptanedione (0.2g,1.1mmol), cesium carbonate (17.2g, 52.9mmol) and 100mLN, N-dimethylformamide were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 80 ℃ for 8 hours, cooled to room temperature, settled in 500mL of water, the solid precipitated in the solution was filtered, and then separated by silica gel column chromatography to obtain 23-5(17.2g, yield: 85%).
Elemental analysis of its Structure (C)52H43Cl2NO): theoretical value: c, 81.24; h, 5.64; n, 1.82; test values are: c, 81.28; h, 5.59; n, 1.88.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
Referring to example 10, starting from 23-5(10.0g, 13.0mmol), the final product, I-5-25(8.5g, yield: 80%), was obtained.
Elemental analysis of its Structure (C)52H39NOP2S2): theoretical value: c, 76.17; h, 4.79; n, 1.71; s, 7.82; test values are: c, 76.18; h, 4.72; n, 1.73; s, 7.79.
MALDI-TOF-MS: theoretical value 819.2; experimental value 819.2.
Example 24
In a 500mL three-necked flask under an argon atmosphere, 24-1(20.0g, 52.6mmol), 24-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was charged, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 24-3(15.2g, yield: 75%).
Elemental analysis of its Structure (C)22H21BClFO2): theoretical value: c, 69.05; h, 5.53; test values are: c, 69.08; h, 5.58.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
In a 500mL three-necked flask under an argon atmosphere, 24-3(15.0g, 39.2mmol), 24-4(17.3g,47.0mmol), tetrakis (triphenylphosphine) palladium (3.6g,3.1mmol), potassium carbonate (21.7g,156.8mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was charged, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 24-5(14.7g, yield: 67%).
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.49.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
In a 500mL three-necked flask, 24-5(10.0g, 17.9mmol), 24-6(6.8g, 15.7mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added under an argon atmosphere, stirred at 120 ℃ for 8 hours and then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 24-7(9.8g, yield: 79%).
Elemental analysis of its Structure (C)46H38BrCl2N): theoretical value: c, 73.12; h, 5.07; n, 1.85; test values are: c, 73.15; h, 5.02; n, 1.88.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
In a 500mL three-necked flask, 24-7(9.0g, 13.1mmol), 24-8(6.8g, 15.7mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (7.6g, 26.2mmol), sodium tert-butoxide (2.5g, 26.2mmol) and 250mL of toluene were added under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 24-9(10.2g, yield: 75%).
Elemental analysis of its Structure (C)73H62Cl2N2): theoretical value: c, 84.42; h, 6.08; n, 2.68; test values are: c, 84.39; h, 6.12; and N, 2.62.
MALDI-TOF-MS: theoretical value 1036.4; experimental value 1036.4.
Referring to example 1, starting from 24-9(8.0g, 7.7mmol), the final product, I-6-11, was obtained (3.9g, yield: 51%).
Elemental analysis Structure (C)73H58B2N2): theoretical value: c, 89.02; h, 5.94; n, 2.84; test values are: c, 89.12; h, 5.91; and N, 2.80.
MALDI-TOF-MS: theoretical value 984.5; experimental value 984.5.
Example 25
25-1(10.0g, 17.9mmol), 25-2(2.4g, 21.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (20.8g, 35.9mmol), N-diisopropylethylamine (4.6g, 6.3mL, 35.9mmol) and 150mL of 1, 4-dioxane were added to a 500mL three-necked flask under an argon atmosphere, and after stirring at 105 ℃ for 8 hours, the mixture was cooled to room temperature, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 25-3(8.2g, yield: 78%).
Elemental analysis of its Structure (C)32H19BrCl2S) theoretical value C, 65.55; h, 3.27; s,5.47 test value C, 65.58; h, 3.22; s, 5.41.
MALDI-TOF-MS: theoretical value 584.0; experimental value 584.0.
25-3(8.0g, 13.6mmol), 25-4(7.1g, 16.4mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (7.9g, 27.3mmol), sodium tert-butoxide (2.6g, 27.3mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 25-5(9.3g, yield: 73%).
Elemental analysis of its Structure (C)64H51Cl2NS) theoretical values C, 82.03; h, 5.49; n, 1.49; s,3.42 test value C, 82.08; h, 5.42; n, 1.42; and S, 3.47.
MALDI-TOF-MS: theoretical value 935.3; experimental value 935.3.
Referring to example 1, starting from 25-5(8.0g, 8.5mmol), the product I-6-12 was finally obtained (2.3g, yield: 30%).
Elemental analysis Structure (C)64H47B2NS) theoretical value C, 86.98; h, 5.36; n, 1.58; s,3.63 test C, 86.92; h, 5.38; n, 1.51; and S, 3.67.
MALDI-TOF-MS: theoretical value 883.4; experimental value 883.4.
Example 26
26-1(20.0g, 52.6mmol), 26-2(20.0g,63.1mmol), tetrakis (triphenylphosphine) palladium (4.9g,4.2mmol), potassium carbonate (29.1g,210.5mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 26-3(16.6g, yield: 71%).
Elemental analysis of its Structure (C)22H21BBrClO2): theoretical value: c, 59.57; h, 4.77; test values are: c, 59.52; h, 4.79.
MALDI-TOF-MS: theoretical value 442.1; experimental value 442.1.
26-3(15.0g, 33.8mmol), 26-4(14.9g,40.6mmol), tetrakis (triphenylphosphine) palladium (3.1g,2.7mmol), potassium carbonate (18.7g,135.3mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 26-5(15.2g, yield: 81%) as a product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
26-5(20.0g, 35.9mmol), 26-6(9.1g, 43.1mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (20.8g, 71.8mmol), sodium tert-butoxide (6.9g, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, and after stirring at 120 ℃ for 8 hours, the mixture was cooled to room temperature, and the resulting concentrate was subjected to solvent removal by silica gel column chromatography to give 26-7(18.2g, yield: 81%).
Elemental analysis of its Structure (C)40H26Cl2FNO): theoretical value: c, 76.68; h, 4.18; n, 2.24; test values are: c, 76.69; h, 4.166; n, 2.21.
MALDI-TOF-MS: theoretical value 625.1; experimental value 625.1.
26-7(10.0g, 16.0mmol), 26-8(4.0g, 19.2mmol), tris (dibenzylideneacetone) dipalladium (0.6g, 0.6mmol), tri-tert-butylphosphine tetrafluoroborate (9.3g, 31.9mmol), sodium tert-butoxide (3.1g, 31.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, and after stirring at 120 ℃ for 8 hours, the mixture was cooled to room temperature, and the resulting concentrate was subjected to solvent removal by silica gel column chromatography to give 26-9(11.1g, yield: 85%).
Elemental analysis of its Structure (C)55H42Cl2N2O): theoretical value: c, 80.77; h, 5.18; n, 3.43; test values are: c, 80.78; h, 5.16; n, 3.41.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
Referring to example 1, starting from 26-9(8.0g, 9.8mmol), the final product, I-7-29, was obtained (3.2g, yield: 43%).
Elemental analysis Structure (C)55H38B2N2O): theoretical value: c, 86.41; h, 5.01; n, 3.66; test values are: c, 86.37; h, 5.05; and N, 3.68.
MALDI-TOF-MS: theoretical value 764.3; experimental value 764.3.
Example 27
27-1(20.0g, 45.1mmol), 27-2(14.0g,54.1mmol), tetrakis (triphenylphosphine) palladium (4.2g,3.6mmol), potassium carbonate (24.9g,180.4mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 27-3(18.2g, yield: 81%) as a product.
Elemental analysis of its Structure (C)26H14BrCl2F) The method comprises the following steps Theoretical value: c, 62.94; h, 2.84; test values are: c, 62.95; h, 2.81.
MALDI-TOF-MS: theoretical value 494.0; experimental value is 494.0.
27-3(10.0g, 20.2mmol), 27-4(4.8g, 24.2mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.8mmol), tri-tert-butylphosphine tetrafluoroborate (11.7g, 40.3mmol), sodium tert-butoxide (3.9g, 40.3mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 27-5(11.1g, yield: 90%).
Elemental analysis of its Structure (C)47H35Cl2NSe): theoretical value: c, 73.92; h, 4.62; n, 1.83; test values are: c, 73.94; h, 4.65; n, 1.79.
MALDI-TOF-MS: theoretical value 763.1; experimental value 763.1.
27-5(10.0g, 16.3mmol), 27-6(6.1g, 35.9mmol), potassium carbonate (4.5g, 32.6mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain 27-7(10.1g, yield: 81%).
Elemental analysis of its Structure (C)46H38Cl2FN): theoretical value: c, 79.53; h, 5.51; n, 2.02; test values are: c, 79.58; h, 5.47; and N, 2.04.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
Referring to example 1, starting from 27-7(8.0g, 10.5mmol), the final product, I-7-30(2.9g, yield: 39%), was obtained.
Elemental analysis Structure (C)47H31B2NSe): theoretical value: c, 79.47; h, 4.40; n, 1.97; test values are: c, 79.52; h, 4.38; and N, 2.02.
MALDI-TOF-MS: theoretical value 711.2; experimental value 711.2.
Example 28
Referring to example 4, starting from 28-1(10.0g, 13.1mmol), the product 28-2 was finally obtained (8.7g, yield: 82%).
Elemental analysis Structure (C)47H31NP2S2Se): theoretical value: c, 69.28; h3.83; n, 1.72; s, 7.87; test values are: c, 69.32; h, 3.81; n, 1.76; s, 7.81.
MALDI-TOF-MS: theoretical value 815.1; experimental value 815.1.
Referring to example 4, starting from 28-2(4.0g, 4.9mmol), the final product, I-7-31(2.8g, yield: 73%), was obtained.
Elemental analysis Structure (C)47H31NOP2Se): theoretical value: c, 73.63; h, 4.08; n, 1.83; test values are: c, 73.65; h, 4.02; n, 1.79.
MALDI-TOF-MS: theoretical value 767.1; experimental value 767.1.
Example 29
29-1(10.0g, 17.9mmol), 29-2(6.1g, 21.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 29-3(10.3g, yield: 76%).
Elemental analysis of its Structure (C)46H40Cl2FN): theoretical value: c, 72.92; h, 5.32; n, 1.85; test values are: c, 72.94; h, 5.28; n, 1.87.
MALDI-TOF-MS: theoretical value 755.2; experimental value 755.2.
29-3(10.0g, 13.2mmol), 29-4(2.7g, 15.8mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (7.7g, 26.4mmol), sodium tert-butoxide (2.5g, 26.4mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 29-5(8.2g, yield: 73%).
Elemental analysis of its Structure (C)58H50Cl2N2): theoretical value: c, 82.35; h, 5.96; n, 3.31; test values are: c, 82.38; h, 5.91; n, 3.33.
MALDI-TOF-MS: theoretical value 844.3; experimental value 844.3.
Referring to example 1, starting from 29-5(4.0g, 4.7mmol), the final product, I-8-7(3.1g, yield: 83%).
Elemental analysis Structure (C)58H46B2N2): theoretical value: c, 87.89; h, 5.85; n, 3.53; test values are: c, 87.86; h, 5.89; and N, 3.49.
MALDI-TOF-MS: theoretical value 792.4; experimental value 792.4.
Example 30
In a 500mL three-necked flask under an argon atmosphere, 30-1(30.0g, 78.9mmol), 30-2(19.8g,94.7mmol), tetrakis (triphenylphosphine) palladium (7.3g,6.3mmol), potassium carbonate (43.6g,315.7mmol), 50mL of water, 50mg of Aliquant-336 and 300mL of toluene were stirred at 120 ℃ for 8 hours, then cooled to room temperature, 200mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (200 mL. times.3), and then dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to give 30-3(28.2g, yield: 93%).
Elemental analysis of its Structure (C)22H21BClFO2): theoretical value: c, 69.05; h, 5.53; test values are: c, 69.08; h, 5.49.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
In a 500mL three-necked flask, 30-3(28.0g, 73.2mmol), 30-4(22.8g,87.8mmol), tetrakis (triphenylphosphine) palladium (6.8g,5.9mmol), potassium carbonate (40.5g,292.7mmol), 50mL of water, 50mg of Aliquant-336 and 300mL of toluene were charged under an argon atmosphere and stirred at 120 ℃ for 8 hours, followed by cooling to room temperature, 200mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (200 mL. times.3) and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 30-5(25.3g, yield: 79%).
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.78; h, 3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
30-5(12.0g, 27.6mmol), 30-6(7.6g, 33.1mmol), potassium carbonate (15.2g, 110.3mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered, and the product 30-7(14.3g, yield: 81%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)41H29Cl2FS): theoretical value: c, 76.51; h, 4.54; s, 4.98; test values are: c, 76.47; h, 4.51; and S, 5.02.
MALDI-TOF-MS: theoretical value 642.1; experimental value 642.1.
30-7(12.0g, 18.6mmol), 30-8(2.5g, 22.4mmol), potassium carbonate (10.3g, 74.6mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered, and the product 30-9(12.2g, yield: 89%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)47H34Cl2S2): theoretical value: c, 76.93; h, 4.67; s, 8.74; test values are: c, 76.96; h, 4.61; s, 8.77.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
Referring to example 1, starting from 30-9(4.0g, 5.5mmol), the final product, I-8-8(2.9g, yield: 78%), was obtained.
Elemental analysis Structure (C)47H30B2S2): theoretical value: c, 82.96; h, 4.44; s, 9.42; test values are: c, 82.98; h, 4.40; s, 9.39.
MALDI-TOF-MS: theoretical value 680.2; experimental value 680.2.
Example 31
31-1(20.0g, 40.5mmol), 31-2(15.4g,48.6mmol), tetrakis (triphenylphosphine) palladium (3.7g,3.2mmol), potassium carbonate (22.4g,162.1mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 31-3(18.6g, yield: 82%) as a product.
Elemental analysis of its Structure (C)22H19BBr2Cl2O2): theoretical value: c, 47.45; h, 3.44; test values are: c, 47.48; h, 3.41.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
31-3(15.0g, 26.9mmol), 31-4(6.7g,32.3mmol), tetrakis (triphenylphosphine) palladium (2.5g,2.2mmol), potassium carbonate (14.9g,107.7mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 31-5(11.2g, yield: 75%) as a product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.49.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
31-5(10.0g, 17.9mmol), 31-6(4.6g, 21.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 31-7(8.2g, yield: 56%).
Elemental analysis of its Structure (C)56H46Cl2N2): theoretical value: c, 82.24; h, 5.67; n, 3.43; test values are: c, 82.28; h, 5.61; and N, 3.45.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
Referring to example 1, starting from 31-7(8.0g, 9.8mmol), the final product, II-1-10(2.9g, yield: 78%), was obtained.
Elemental analysis Structure (C)56H42B2N2): theoretical value: c, 87.97; h, 5.54; n, 3.66; test values are: c, 87.98; h, 5.51; and N, 3.69.
MALDI-TOF-MS: theoretical value 764.4; experimental value 764.4.
Example 32
32-1(20.0g, 35.9mmol), 32-2(12.0g, 43.1mmol), tris (dibenzylideneacetone) dipalladium (1.3g, 1.4mmol), tri-tert-butylphosphine tetrafluoroborate (20.8g, 71.8mmol), sodium tert-butoxide (6.9g, 71.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 32-3(22.8g, yield: 84%).
Elemental analysis Structure (C)46H38BrCl2N): theoretical value: c, 73.12; h, 5.07; n, 1.85; test values are: c, 73.18; h, 5.02; n, 1.86.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
32-3(10.0g, 13.2mmol), 32-4(3.6g, 15.9mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (7.7g, 26.5mmol), sodium tert-butoxide (2.5g, 26.5mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 32-5(9.8g, yield: 82%).
Elemental analysis Structure (C)60H48Cl2N2S): theoretical value: c, 80.07; h, 5.38; n, 3.11; s, 3.56; test values are: c, 80.09; h, 5.32; n, 3.05; and S, 3.59.
MALDI-TOF-MS: theoretical value 898.3; experimental value 898.3.
Referring to example 1, starting from 32-5(8.0g, 8.9mmol), the final product, II-1-11(2.9g, yield: 39%).
Elemental analysis Structure (C)60H44B2N2S): theoretical value: c, 85.11; h, 5.24; n, 3.31; s, 3.79; test values are: c, 85.15; h, 5.21; n, 3.35; and S, 3.83.
MALDI-TOF-MS: theoretical value 846.3; experimental value 846.3.
Example 33
33-1(20.0g, 35.9mmol), 33-2(16.8g,79.0mmol), cuprous iodide (0.2g,1.1mmol), 2,6, 6-tetramethyl-3, 5-heptanedione (0.2g,1.1mmol), cesium carbonate (17.2g, 52.9mmol), and 100mLN, N-dimethylformamide were added to a 500mL three-necked flask under an argon atmosphere, stirred at 80 ℃ for 8 hours, then cooled to room temperature, the mother liquor was settled in 500mL water, the precipitated solid was filtered and washed with methanol, and then separated by silica gel column chromatography to give 33-3(15.2g, 83% yield).
Elemental analysis Structure (C)41H29BrCl2O): theoretical value: c, 71.53; h, 4.25; test values are: c, 71.58; h, 4.21.
MALDI-TOF-MS: theoretical value 686.1; experimental value 686.1.
33-3(10.0g, 13.2mmol), 33-4(3.6g, 17.4mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.6mmol), tri-tert-butylphosphine tetrafluoroborate (8.4g, 29.0mmol), sodium tert-butoxide (2.8g, 29.0mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 33-5(8.6g, yield: 72%).
Elemental analysis Structure (C)56H43Cl2NO): theoretical value: c, 82.34; h, 5.31; cl, 8.68; n, 1.71; test values are: c, 82.37; h, 5.28; cl, 8.69; n, 1.68.
MALDI-TOF-MS: theoretical value 815.3; experimental value 815.3.
Referring to example 1, starting from 33-5(8.0g, 9.8mmol), the final product, II-1-12(3.3g, yield: 44%) was obtained.
Elemental analysis Structure (C)56H39B2NO): theoretical value: c, 88.09; h, 5.15; b, 2.83; n, 1.83; test values are: c, 88.02; h, 5.17; b, 2.85; n, 1.81.
MALDI-TOF-MS: theoretical value 763.3; experimental value 763.3.
Example 34
In a 500mL three-necked flask under an argon atmosphere, 34-1(20.0g, 46.2mmol), 34-2(12.5g,48.6mmol), tetrakis (triphenylphosphine) palladium (3.7g,3.2mmol), potassium carbonate (22.4g,162.1mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 34-3(15.2g, yield: 86%).
Elemental analysis of its Structure (C)22H19BBrCl2FO2): theoretical value: c, 53.27; h, 3.86; test values are: c, 53.28; h, 3.82.
MALDI-TOF-MS: theoretical value 494.0; experimental value is 494.0.
In a 500mL three-necked flask under an argon atmosphere, 34-3(15.0g, 34.5mmol), 34-4(8.6g,41.4mmol), tetrakis (triphenylphosphine) palladium (3.2g,2.8mmol), potassium carbonate (19.1g,137.9mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate which was subjected to silica gel column chromatography to obtain 34-5(12.3g, yield: 82%).
Elemental analysis of its Structure (C)26H14BrCl2F) The method comprises the following steps Theoretical value: c, 62.94; h, 2.84; test values are: c, 62.98; h, 2.82.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
34-5(10.0g, 23.0mmol), 34-6(9.6g, 27.6mmol), tris (dibenzylideneacetone) dipalladium (0.8g, 0.9mmol), tri-tert-butylphosphine tetrafluoroborate (13.3g, 45.9mmol), sodium tert-butoxide (4.4g, 45.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 34-7(12.7g, yield: 85%).
Elemental analysis Structure (C)50H30Cl2FNSi): theoretical value: c, 78.73; h, 3.96; n, 1.84; test values are: c, 78.78; h, 3.92; n, 1.87.
MALDI-TOF-MS: theoretical value 761.2; experimental value 761.2.
34-7(10.0g, 13.1mmol), 34-8(4.5g, 28.8mmol), potassium carbonate (3.6g, 26.2mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered off, and the product 34-9(9.2g, yield: 78%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)56H35Cl2NSeSi): theoretical value: c, 74.75; h, 3.92; n, 1.56; test values are: c, 74.78; h, 3.86; n, 1.58.
MALDI-TOF-MS: theoretical value 899.1; experimental value 899.1.
Referring to example 1, starting from 34-9(8.0g, 8.9mmol), the final product, II-1-13(3.2g, yield: 43%) was obtained.
Elemental analysis Structure (C)56H31B2NSeSi): theoretical value: c, 79.45; h, 3.69; n, 1.65; test values are: c, 79.51; h, 3.72; n, 1.68.
MALDI-TOF-MS: theoretical value 847.2; experimental value 847.2.
Example 35
35-1(20.0g, 46.2mmol), 35-2(14.2g,55.5mmol), tetrakis (triphenylphosphine) palladium (4.3g,3.7mmol), potassium carbonate (25.6g,185.0mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 35-3(18.2g, yield: 90%) as a product.
Elemental analysis of its Structure (C)22H19BCl2F2O2): theoretical value: c, 60.73; h, 4.40; test values are: c, 60.78; h, 4.37.
MALDI-TOF-MS: theoretical value 434.1; experimental value 434.1.
35-3(15.0g, 34.5mmol), 35-4(8.6g,41.4mmol), tetrakis (triphenylphosphine) palladium (3.2g,2.8mmol), potassium carbonate (19.1g,137.9mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 35-5(11.4g, yield: 76%) as a product.
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.78; h, 3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
35-5(10.0g, 23.0mmol), 35-6(3.0g, 50.5mmol), potassium carbonate (6.3g, 45.9mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered, and the product 35-7(10.2g, yield: 84%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)32H19Cl2FS): theoretical value: c, 73.15; h, 3.64; s, 6.10; test values are: c, 73.18; h, 3.61; and S, 6.07.
MALDI-TOF-MS: theoretical value 524.1; experimental value 524.1.
35-7(10.0g, 19.0mmol), 35-8(7.8g, 22.8mmol), potassium carbonate (5.3g, 38.1mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to be settled, the precipitated precipitate was filtered off, and the product 35-9(13.5g, yield: 84%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)53H33Cl2N3S2): theoretical value: c, 75.17; h, 3.93; n, 4.96; s, 7.57; test values are: c,75.19；H,3.91；N,4.93；S,7.58。
MALDI-TOF-MS: theoretical value 845.2; experimental value 845.2.
Referring to example 4, starting from 35-9(8.0g, 9.4mmol), the final product, II-1-14(3.2g, yield: 38%).
Elemental analysis Structure (C)53H29N3P2S4): theoretical value: c, 70.89; h, 3.26; n, 4.68; s, 14.28; test values are: c, 70.81; h, 3.31; n, 4.62; s, 14.29.
MALDI-TOF-MS: theoretical value 897.1; experimental value 897.1.
Example 36
36-1(20.0g, 46.2mmol), 36-2(11.6g,55.5mmol), tetrakis (triphenylphosphine) palladium (4.3g,3.7mmol), potassium carbonate (25.6g,185.0mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 36-3(15.4g, yield: 77%) as a product.
Elemental analysis of its Structure (C)22H19BCl2F2O2): theoretical value: c, 60.73; h, 4.40; test values are: c, 60.78; h, 4.37.
MALDI-TOF-MS: theoretical value 434.1; experimental value 434.1.
36-3(16.8g, 38.7mmol), 36-4(9.6g,46.4mmol), tetrakis (triphenylphosphine) palladium (3.6g,3.1mmol), potassium carbonate (21.4g,154.6mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 36-5(13.5g, yield: 80%) as a product.
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.78; h, 3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
36-5(10.0g, 23.0mmol), 36-6(7.7g, 27.6mmol), potassium carbonate (6.3g, 45.9mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered, and the product 36-7(12.5g, yield: 78%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)46H38Cl2FN): theoretical value: c, 79.53; h, 5.51; n, 2.02; test values are: c, 79.58; h, 5.42; and N, 2.12.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
36-7(8.0g, 11.5mmol), 36-8(1.3g, 13.8mmol), potassium carbonate (3.2g,23.0mmol) and 250mL of LN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 2000mL of methanol to settle, the precipitated precipitate was filtered, and the product 36-9(7.8g, yield: 88%) was obtained by silica gel column chromatography.
Elemental analysis of its Structure (C)52H43Cl2NO): theoretical value: c, 81.24; h, 5.64; n, 1.82; test values are: c, 81.26; h, 5.61; n, 1.79.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
Referring to example 1, starting from 36-9(8.0g, 10.4mmol), the final product, II-2-18(6.1g, yield: 82%), was obtained.
Elemental analysis Structure (C)52H39B2NO): theoretical value: c, 87.29; h, 5.49; n, 1.96; test values are: c, 87.32; h, 5.42; and N, 2.05.
MALDI-TOF-MS: theoretical value 715.3; experimental value 715.3.
Example 37
37-1(20.0g, 28.8mmol), 37-2(6.6g, 69.0mmol), potassium carbonate (8.0g, 57.6mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 1000mL of methanol to settle, the precipitated precipitate was filtered, and the product 37-3(18.2g, yield: 82%) was obtained by silica gel column chromatography.
Elemental analysis Structure (C)56H44Cl2S2): theoretical value: c, 78.95; h, 5.21; s, 7.53; test values are: c, 78.99; h, 5.15; and S, 7.59.
MALDI-TOF-MS: theoretical value 850.2; experimental value 850.2.
Referring to example 1, starting from 37-3(10.0g, 13.0mmol), the product II-2-19 was finally obtained (2.9g, yield: 31%).
Elemental analysis Structure (C)56H40B2S2): theoretical value: c, 84.22; h, 5.05; s, 8.03; test values are: c, 84.28; h, 5.01; and S, 7.96.
MALDI-TOF-MS: theoretical value 798.3; experimental value 798.3.
Example 38
38-1(20.0g, 40.5mmol), 38-2(15.4g,48.6mmol), tetrakis (triphenylphosphine) palladium (3.7g,3.2mmol), potassium carbonate (22.4g,162.2mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 38-3(18.2g, yield: 81%) as a product.
Elemental analysis of its Structure (C)22H19BBr2Cl2O2): theoretical value: c, 47.45; h, 3.44; test values are: c, 47.48; h, 3.42.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
38-3(15.0g, 26.9mmol), 38-4(8.2g,32.3mmol), tetrakis (triphenylphosphine) palladium (2.5g,2.2mmol), potassium carbonate (14.9g,107.8mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, added with 150mL of ethyl acetate, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 38-5(11.2g, yield: 75%) as a product.
Elemental analysis of its Structure (C)46H40Cl2FN): theoretical value: c, 79.30; h, 5.79; n, 2.01; test values are: c, 79.35; h, 5.72; and N, 2.08.
MALDI-TOF-MS: theoretical value 695.3; experimental value 695.3.
38-5(10.0g, 17.9mmol), 38-6(6.1g, 21.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 38-7(10.7g, yield: 84%).
Elemental analysis Structure (C)46H40Cl2FN): theoretical value: c, 79.30; h, 5.79; n, 2.01; test values are: c, 79.27; h, 5.71; and N, 2.08.
MALDI-TOF-MS: theoretical value 695.3; experimental value 695.3.
38-7(10.0g, 10.5mmol), 38-8(4.8g, 17.2mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.6mmol), tri-tert-butylphosphine tetrafluoroborate (8.3g, 28.7mmol), sodium tert-butoxide (2.8g, 28.7mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 38-9(11.2g, yield: 82%).
Elemental analysis Structure (C)66H64Cl2N2): theoretical value: c, 82.91; h, 6.75; n, 2.93; test values are: c, 82.98; h, 6.72; and N, 2.91.
MALDI-TOF-MS: theoretical value 954.4; experimental value 954.4.
Referring to example 4, starting from 38-9(10.0g, 10.5mmol), the final product was 38-10(7.5g, yield: 71%).
Elemental analysis Structure (C)66H60N2P2S2): theoretical value: c, 78.70; h, 6.00; n, 2.78; s, 6.37; test values are: c, 78.68; h, 6.02; n, 2.72; s, 6.31.
MALDI-TOF-MS: theoretical value 1006.4; experimental value 1006.4.
Referring to example 4, starting from 38-10(4.0g, 4.0mmol), the final product, II-2-20(1.3g, yield: 34%).
Elemental analysis Structure (C)66H60N2O2P2): theoretical value: c, 81.29; h, 6.20; n, 2.87; test values are: c, 81.32; h, 6.26; and N, 2.82.
MALDI-TOF-MS: theoretical value 974.4; experimental value 974.4.
Example 39
39-1(20.0g, 40.5mmol), 39-2(15.4g,48.6mmol), tetrakis (triphenylphosphine) palladium (3.7g,3.2mmol), potassium carbonate (22.4g,162.1mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 39-3(17.2g, yield: 76%) as a product.
Elemental analysis of its Structure (C)22H19BBr2Cl2O2): theoretical value: c, 47.45; h, 3.44; test values are: c, 47.48; h, 3.42.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
39-3(15.0g, 26.9mmol), 39-4(6.7g,32.3mmol), tetrakis (triphenylphosphine) palladium (2.5g,2.2mmol), potassium carbonate (14.9g,107.7mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 39-5(11.2g, yield: 75%) as a product.
Elemental analysis of its Structure (C)26H14Br2Cl2): theoretical value: c, 56.06; h, 2.53; test values are: c, 56.08; h, 2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
39-5(10.0g, 17.9mmol), 39-6(8.2g, 21.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g, 0.7mmol), tri-tert-butylphosphine tetrafluoroborate (10.4g, 35.9mmol), sodium tert-butoxide (3.4g, 35.9mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 39-7(10.5g, yield: 73%).
Elemental analysis Structure (C)54H44BrCl2N): theoretical value: c, 75.62; h, 5.17; n, 1.63; test values are: c, 75.68; h, 5.12; n, 1.65.
MALDI-TOF-MS: theoretical value 855.2; experimental value 855.2.
39-7(10.0g, 12.5mmol), 39-8(4.2g, 15.1mmol), tris (dibenzylideneacetone) dipalladium (0.5g, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (7.3g, 25.1mmol), sodium tert-butoxide (2.4g, 25.1mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 39-9(11.2g, yield: 94%).
Elemental analysis Structure (C)66H64Cl2N2): theoretical value: c, 82.91; h, 6.75; n, 2.93; test values are: c, 82.98; h, 6.72; and N, 2.91.
MALDI-TOF-MS: theoretical value 954.4; experimental value 954.4.
Referring to example 1, starting from 39-9(10.0g, 10.6mmol), the product II-3-6(2.9g, yield: 31%) was finally obtained.
Elemental analysis Structure (C)56H40B2S2): theoretical value: c, 84.22; h, 5.05; s, 8.03; test values are: c, 84.28; h, 5.01; and S, 7.96.
MALDI-TOF-MS: theoretical value 798.3; experimental value 798.3.
Example 40
40-1(20.0g, 46.2mmol), 40-2(11.6g,55.5mmol), tetrakis (triphenylphosphine) palladium (4.3g,3.7mmol), potassium carbonate (25.6g,185.0mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 40-3(18.2g, yield: 90%) as a product.
Elemental analysis of its Structure (C)22H19BCl2F2O2): theoretical value: c, 60.73; h, 4.40; test values are:C,60.75；H,4.37。
MALDI-TOF-MS: theoretical value 434.1; experimental value 434.1.
40-3(15.0g, 34.5mmol), 40-4(8.6g,41.4mmol), tetrakis (triphenylphosphine) palladium (3.2g,2.8mmol), potassium carbonate (19.1g,137.9mmol), 40mL of water, 50mg of Aliquant-336 and 200mL of toluene were charged in a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 40-5(12.4g, yield: 83%) as a product.
Elemental analysis of its Structure (C)26H14Cl2F2): theoretical value: c, 71.74; h, 3.24; test values are: c, 71.78; h, 3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
40-5(8.0g, 18.4mmol), 40-6(4.5g, 22.1mmol), potassium carbonate (5.1g,36.8mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, reacted at 180 ℃ for 8 hours, cooled to room temperature, the mother liquor was poured into 1000mL of methanol to settle, the precipitated precipitate was filtered, and the product 40-7(8.3g, yield: 73%) was obtained by silica gel column chromatography.
Elemental analysis Structure (C)32H19Cl2FTe): theoretical value: c, 61.89; h, 3.08; test values are: c, 61.82; h, 3.11.
MALDI-TOF-MS: theoretical value 622.0; experimental value 622.0.
40-7(10.0g, 16.1mmol), 40-8(5.4g, 19.3mmol), tris (dibenzylideneacetone) dipalladium (0.6g, 0.6mmol), tri-tert-butylphosphine tetrafluoroborate (9.3g, 32.2mmol), sodium tert-butoxide (3.1g, 32.2mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, and after stirring at 120 ℃ for 8 hours, the mixture was cooled to room temperature, and the resulting concentrate was subjected to silica gel column chromatography to remove the solvent, whereby 40-9(12.8g, yield: 90%) was obtained as a product.
Elemental analysis Structure (C)52H45Cl2NTe): theoretical value: c, 70.78; h, 5.14; n is added to the reaction solution to form a reaction solution,1.59; test values are: c, 78.99; h, 5.15; s,7.59C, 70.79; h, 5.12; n, 1.54.
MALDI-TOF-MS: theoretical value 883.2; experimental value 883.2.
Referring to example 1, starting from 40-9(10.0g, 11.3mmol), the product II-3-7 was finally obtained (1.1g, yield: 47%).
Elemental analysis Structure (C)52H41B2 NTe): theoretical value: c, 75.33; h, 4.98; n, 1.69; test values are: c, 75.33; h, 4.98; n, 1.69.
MALDI-TOF-MS: theoretical value 831.3; experimental value 831.3.
EXAMPLE 41
41-1(20.0g, 45.9mmol), 41-2(11.0g,55.1mmol), potassium carbonate (12.7g,91.9mmol) and 100 mLN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL of deionized water, the precipitated solid was filtered and washed with methanol, and then the product 41-3(22.4g, yield: 79%) was isolated by silica gel column chromatography.
Elemental analysis Structure (C)38H21Cl2FOS): theoretical value: c, 74.15; h, 3.44; s, 5.21; test values are: c, 74.25; h, 3.42; and S, 5.25.
MALDI-TOF-MS: theoretical 614.1 experimental 614.1.
41-3(20.0g, 32.5mmol), 41-4(5.9g,39.0mmol), potassium carbonate (9.0g,65.0mmol) and 100 mLN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL of deionized water, the precipitated solid was filtered and washed with methanol, and then the product 41-5(18.2g, yield: 75%) was isolated by silica gel column chromatography.
Elemental analysis Structure (C)47H32Cl2OS2): theoretical value: c, 75.49; h, 4.31; s, 8.57; test values are: c, 75.53; h, 4.28; and S, 9.04.
MALDI-TOF-MS: theoretical value 746.1; experimental value 746.1.
Referring to example 1, starting from 41-5(10.0g, 13.4mmol), the product II-3-8 was finally obtained (4.2g, yield: 45%).
Elemental analysis Structure (C)47H28B2OS2): theoretical value: c, 81.29; h, 4.06; s, 9.23; test values are: c, 81.32; h, 4.04; s, 9.21.
MALDI-TOF-MS: theoretical 694.2; experimental value 694.2.
Example 42
42-1(20.0g, 42.1mmol), 42-2(10.6g,50.6mmol), tetrakis (triphenylphosphine) palladium (3.9g,3.4mmol), potassium carbonate (23.3g,168.6mmol), 50mg aliquant-336, 40mL deionized water and 100mL toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to give 42-3(17.7g, 88% yield) as a product.
Elemental analysis Structure (C)25H25BCl2F2O2): theoretical value: c, 62.93; h, 5.28; test values are: c, 62.98; h, 5.22.
MALDI-TOF-MS: theoretical value 476.1; experimental value 476.1.
42-3(15.0g, 31.4mmol), 42-4(9.4g,37.7mmol), tetrakis (triphenylphosphine) palladium (2.9g,2.5mmol), potassium carbonate (17.4g,125.7mmol), 50mg of aliquant-336, 40mL of deionized water and 100mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed with deionized water 3 times (100 mL. times.3), dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 42-5(13.3g, 81% yield).
Elemental analysis structure(C32H26Cl2F2): theoretical value: c, 73.99; h, 5.05; test values are: c, 74.06; h,5.01
MALDI-TOF-MS: theoretical value 518.1; experimental value 518.1.
42-5(15.0g, 28.9mmol), 42-6(10.0g, 34.7mmol), tris (dibenzylideneacetone) dipalladium (1.1g, 1.2mmol), tri-tert-butylphosphine tetrafluoroborate (16.8g, 57.8mmol), sodium tert-butoxide (5.5g, 57.8mmol) and 250mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours and cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to silica gel column chromatography to obtain 42-7(19.2g, yield: 85%).
Elemental analysis Structure (C)52H41Cl2FN2): theoretical value: c, 79.68; h, 5.27; n, 3.57; test values are: c, 79.69; h, 5.22; n,3.59
MALDI-TOF-MS: theoretical value 782.3; experimental value 782.3.
42-7(8.0g, 10.2mmol), 42-8(1.2g,12.2mmol), potassium carbonate (2.8g,20.4mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL of deionized water, the precipitated solid was filtered and washed with methanol, and then the product 42-9(5.6g, yield: 64%) was isolated by silica gel column chromatography.
Elemental analysis Structure (C)58H46Cl2N2O): theoretical value: c, 81.20; h, 5.40; n, 3.27; test values are: c, 81.25; h, 5.32; and N, 3.29.
MALDI-TOF-MS: theoretical value 856.3; experimental value 856.3.
Referring to example 1, starting from 42-9(5.0g, 5.8mmol), the final product, II-4-7(3.1g, yield: 66%).
Elemental analysis Structure (C)58H42B2N2O): theoretical value: c, 86.58; h, 5.26; n, 3.48; test values are: c, 86.56; h, 5.28; and N, 3.47.
MALDI-TOF-MS: theoretical value 804.4; experimental value 804.4.
Example 43
43-1(20.0g, 46.2mmol), 43-2(11.6g,55.5mmol), tetrakis (triphenylphosphine) palladium (4.3g,3.7mmol), potassium carbonate (25.6g,185.0mmol), 50mL of water, 50mg of Aliquant-336 and 100mL of toluene were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 43-3(17.6g, yield: 87%).
Elemental analysis Structure (C)46H38Cl2FN): theoretical value: c, 79.53; h, 5.51; n, 2.02; test values are: c, 79.57; h, 5.45; and N, 2.08.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
43-3(15.0g, 34.5mmol), 43-4(8.6g,41.4mmol), tetrakis (triphenylphosphine) palladium (3.2g,2.8mmol), potassium carbonate (19.1g,137.9mmol), 50mL of water, 50mg of Aliquant-336 and 100mL of toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120 ℃ for 8 hours, then cooled to room temperature, 100mL of ethyl acetate was added to the reaction solution, the organic phase was washed with deionized water 3 times (100 mL. times.3), and then dried over anhydrous magnesium sulfate, and the solvent was removed from the organic phase to obtain a concentrate, which was subjected to silica gel column chromatography to obtain 43-5(12.5g, yield: 83%).
Elemental analysis Structure (C)52H43Cl2NS): theoretical value: c, 79.58; h, 5.52; n, 1.78; s, 4.08; test values are: c, 79.62; h, 5.58; n, 1.69; and S, 4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
43-5(8.0g, 18.4mmol), 43-6(6.2g,22.1mmol), potassium carbonate (5.1g,36.8mmol) and 150 mLN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, then cooled to room temperature, the reaction solution was precipitated in 600mL of water, the precipitate precipitated in the solution was filtered, washed with methanol, and then subjected to silica gel column chromatography to obtain 43-7(9.3g, yield: 73%).
Elemental analysis Structure (C)52H43Cl2NS): theoretical value: c, 79.58; h, 5.52; n, 1.78; s, 4.08; test values are: c, 79.62; h, 5.58; n, 1.69; and S, 4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
43-7(8.0g, 11.5mmol), 43-8(1.5g,13.8mmol), potassium carbonate (3.2g,23.0mmol) and 150 mLN-methylpyrrolidone were charged into a 500mL three-necked flask under an argon atmosphere, stirred at 180 ℃ for 8 hours, then cooled to room temperature, the reaction solution was precipitated in 600mL of water, the precipitate precipitated in the solution was filtered, washed with methanol, and then subjected to silica gel column chromatography to obtain 43-9(5.6g, yield: 62%).
Elemental analysis Structure (C)52H43Cl2NS): theoretical value: c, 79.58; h, 5.52; n, 1.78; s, 4.08; test values are: c, 79.62; h, 5.58; n, 1.69; and S, 4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
Referring to example 1, starting from 43-9(5.0g, 6.4mmol), the final product, II-4-8(3.1g, yield: 67%).
Elemental analysis Structure (C)52H39B2NS): theoretical value: c, 85.37; h, 5.37; n, 1.91; s, 4.38; test values are: c, 85.39; h, 5.35; n, 1.97; and S, 4.32.
MALDI-TOF-MS: theoretical value 731.3; experimental value 731.3.
Referring to table 1, table 1 shows the photophysical properties of the fused ring compounds prepared in the examples of the present invention.
TABLE 1 photophysical properties of fused ring compounds prepared in the examples of the present invention
Note that the delayed fluorescence lifetime in the table is obtained by doping a compound at a concentration of 1 wt% in polystyrene to prepare a sample to be tested and measuring the sample by using a time-resolved fluorescence spectrometer, and the measuring instrument is an Edinburgh fluorescence spectrometer (FLS-980, UK).
As can be seen from Table 1, the fused ring compounds in the examples provided by the present invention have smaller Δ EST(<0.2eV), the delayed fluorescence effect of thermal activation is shown, and the delayed fluorescence lifetime is 32-73 μ s.
Device examples
The process of preparing the device by the organic light-emitting layer by adopting a vacuum evaporation process is as follows: on indium tin oxide supported on a glass substrate, 4X 10-4Sequentially depositing TAPC, TCTA, EML (co-evaporation of the luminescent compound, SIMCP2 and DPAc-DtCzBN according to the mass ratio of 1: 2: 7), TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the TAPC and the TmPyPB are respectively used as a hole transport layer and an electron transport layer, and the TCTA is an exciton blocking layer and has the following structural formula:
the specific device structure (device structure a) is:
ITO/TAPC(50nm)/TCTA(5nm)/EML(30nm)/TmPyPB(30nm)/LiF(0.8nm)/Al(100nm)。
the process of preparing the device by adopting the solution processing technology for the organic light-emitting layer is as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and then spin-coated with SIMCP2 and DPAc-DtCzBN at a rotation speed of 1500rpm in a mass ratio of 1: 2: 7 the mixed toluene solution was annealed at 80 ℃ for 30 minutes for 1 minute, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and LiF/Al cathodes under Pa vacuum degree to obtain the organic electroluminescent deviceThe device, wherein TSPO1, TmPyPB are respectively used as hole blocking layer, electron transport layer and host material, and the structural formula is shown as follows:
the specific device structure (device structure B) is:
ITO/PEDOT:PSS(40nm)/EML(30nm)/TSPO1(8nm)/TmPyPB(42nm)/LiF(1nm)/Al(100nm)。
example 44
Using the fused ring compound I-1-2 in example 1 as an object, the fused ring compound I-1-2, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-1-2 provided by the present invention.
Example 45
Using the fused ring compound I-1-14 in example 2 as an object, the fused ring compound I-1-14, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-1-14 provided by the present invention.
Example 46
Using the fused ring compound I-1-15 in example 3 as an object, the fused ring compound I-1-15, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-1-15 provided by the present invention.
Example 47
Using the fused ring compound I-1-16 in example 4 as an object, the fused ring compound I-1-16, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-1-16 provided by the present invention.
Example 48
Using the fused ring compound I-2-2 in example 5 as an object, the fused ring compound I-2-2, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-2 provided by the present invention.
Example 49
Using the fused ring compound I-2-5 in example 6 as an object, the fused ring compound I-2-5, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-5 provided by the present invention.
Example 50
Using the fused ring compound I-2-10 in example 7 as an object, the fused ring compound I-2-10, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-10 provided by the present invention.
Example 51
Using the fused ring compound I-2-18 in example 8 as an object, the fused ring compound I-2-18, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-18 provided by the present invention.
Example 52
Using the fused ring compound I-2-57 in example 9 as an object, the fused ring compound I-2-57, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to table 2, table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-57 provided by the present invention.
Example 53
Using the fused ring compound I-2-58 of example 10 as an object, the fused ring compound I-2-58, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-2-58 provided by the present invention.
Example 54
Using the fused ring compound I-3-1 in example 11 as an object, the fused ring compound I-3-1, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-3-1 provided by the present invention.
Example 55
Using the fused ring compound I-3-37 of example 12 as an object, the fused ring compound I-3-37, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-3-37 provided by the present invention.
Example 56
Using the fused ring compound I-3-38 in example 13 as an object, the fused ring compound I-3-38, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-3-38 provided by the present invention.
Example 57
Using the fused ring compound I-3-39 in example 14 as an object, the fused ring compound I-3-39, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-3-39 provided by the present invention.
Example 58
Using the fused ring compound I-3-40 in example 15 as an object, the fused ring compound I-3-40, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-3-40 provided by the present invention.
Example 59
Using the fused ring compound I-4-22 in example 16 as an object, the fused ring compound I-4-22, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-4-22 provided herein.
Example 60
Using the fused ring compound I-4-23 in example 17 as an object, the fused ring compound I-4-23, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-4-23 provided by the present invention.
Example 61
Using the fused ring compound I-4-24 in example 18 as an object, the fused ring compound I-4-24, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-4-24 provided by the present invention.
Example 62
Using the fused ring compound I-4-25 in example 19 as an object, the fused ring compound I-4-25, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-4-25 provided by the present invention.
Example 63
Using the fused ring compound I-5-26 in example 20 as an object, the fused ring compound I-5-26, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-5-26 provided by the present invention.
Example 64
Using the fused ring compound I-5-27 of example 21 as an object, the fused ring compound I-5-27, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-5-27 provided by the present invention.
Example 65
Using the fused ring compound I-5-28 of example 22 as a subject, the fused ring compound I-5-28, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-5-28 provided by the present invention.
Example 66
Using the fused ring compound I-5-25 in example 23 as an object, the fused ring compound I-5-25, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-5-25 provided by the present invention.
Example 67
Using the fused ring compound I-6-11 in example 24 as a subject, the fused ring compound I-6-11, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-6-11 provided by the present invention.
Example 68
Using the fused ring compound I-6-12 in example 25 as an object, the fused ring compound I-6-12, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with fused ring compounds I-6-12 provided by the present invention.
Example 69
Using the fused ring compound I-7-29 in example 26 as a subject, the fused ring compound I-7-29, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-7-29 provided by the present invention.
Example 70
Using the fused ring compound I-7-30 in example 27 as an object, the fused ring compound I-7-30, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-7-30 provided herein.
Example 71
Using the fused ring compound I-7-31 in example 28 as an object, the fused ring compound I-7-31, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-7-31 provided herein.
Example 72
Using the fused ring compound I-8-7 in example 29 as a subject, the fused ring compound I-8-7, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-8-7 provided by the present invention.
Example 73
Using the fused ring compound I-8-8 in example 30 as an object, the fused ring compound I-8-8, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds I-8-8 provided by the present invention.
Example 74
Using the fused ring compound II-1 to 10 in example 31 as an object, the fused ring compound II-1 to 10, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-10 provided by the present invention.
Example 75
Using the fused ring compound II-1-11 of example 32 as a subject, the fused ring compound II-1-11, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-11 provided by the present invention.
Example 76
Using the fused ring compound II-1-12 of example 33 as an object, the fused ring compound II-1-12, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-12 provided by the present invention.
Example 77
Using the fused ring compound II-1-13 of example 34 as an object, the fused ring compound II-1-13, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-13 provided by the present invention.
Example 78
Using the fused ring compound II-1-14 in example 35 as an object, the fused ring compound II-1-14, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-14 provided by the present invention.
Example 79
Using the fused ring compound II-2-18 in example 36 as a subject, the fused ring compound II-2-18, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds II-2-18 provided by the present invention.
Example 80
Using the fused ring compound II-2-19 in example 37 as an object, the fused ring compound II-2-19, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with the fused ring compounds II-1-19 provided by the present invention.
Example 81
Using the fused ring compound II-2-20 in example 38 as an object, the fused ring compound II-2-20, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to table 2, table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds II-2-20 provided by the present invention.
Example 82
Using the fused ring compound II-3-6 of example 39 as a subject, the fused ring compound II-3-6, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to table 2, table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds II-3-6 provided by the present invention.
Example 83
Using the fused ring compound II-3-7 in example 40 as an object, the fused ring compound II-3-7, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to table 2, table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds II-3-7 provided by the present invention.
Example 84
Using the fused ring compound II-3-8 in example 41 as an object, the fused ring compound II-3-8, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with fused ring compounds II-3-8 provided by the present invention.
Example 85
Using the fused ring compound II-4-7 of example 42 as a subject, the fused ring compound II-4-7, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with II-4-7 provided by the present invention.
Example 86
Using the fused ring compound II-4-8 of example 43 as a subject, the fused ring compound II-4-8, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1: 2: 7 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with II-4-8 provided by the present invention.
Table 2 performance parameters of electroluminescent devices prepared from fused ring compounds provided by the present invention
Note: the on-voltage in the table is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device by the calculation method described in the literature (Jpn.J.appl.Phys.2001,40, L783); the half-peak width is the peak width at half of the peak height of the electroluminescence spectrum at room temperature, i.e. a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the straight line is connected withDistance between two intersecting points on both sides of the peak.
As can be seen from Table 2, the device prepared from the fused ring compound provided by the invention has a very narrow electroluminescence spectrum, the half-peak width of the device is less than 40nm, and the problem that the traditional TADF compound with a D-A structure has a wider electroluminescence spectrum (70-100 nm) is solved. Meanwhile, devices prepared by the compound provided by the invention have higher device efficiency, and the maximum external quantum efficiency reaches 35.1%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A bora-or phospha-fused ring compound having a binaphthyl ring, characterized by having a structure represented by any one of formulae (I) to (II):
wherein, X1And X2Independently selected from B, P ═ O or P ═ S; y is1And Y2Independently selected from N (R)1)、O、S、Se、Te、B(R1)、C(R1R2) Or Si (R)1R2)；
Ar1～Ar3Independently selected from a substituted or unsubstituted C6-C60 aryl ring, or a substituted or unsubstituted C3-C60 heteroaryl ring; the substitution is D, F, Cl, Br, I, -CN, -NO2、-CF3Straight chain alkyl of C1-C30, branched chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C30, alkylthio of C1-C30, substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted aryl ether of C6-C60, heteroaryl of C3-C60 or substituted or unsubstituted C3C60 with a heteroaryl group; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;
R1～R2independently selected from H, D, F, Cl, Br, I, -CN, -CF3、-NO2、
-O-R1-S-R1、
-Se-R1、
-Te-R1、
Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group or substituted or unsubstituted C5-C60 heteroaromatic group;
the R is1～R3Selected from H, D, C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C3-C30 naphthenic base, substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C3-C60 heteroaryl; the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se; and R is1、R2And R3Between two and R1And Ar1～Ar3Any one of the substituent groups can also pass through a single bond, -C (R)aRb)-、-(C＝O)-、-Si(RaRb)-、-N(Ra)-、-PO(Ra) -, -O-, -S-or-Se-is linked; the R isaAnd RbIndependently a linear chain of C1-C30A hydrocarbon group, a branched hydrocarbon group of C1-C30, a naphthenic group of C3-C30, an alkoxyl group of C1-C30, an alkylthio group of C1-C30, a substituted or unsubstituted aryl group of C6-C60, a substituted or unsubstituted aryl ether group of C6-C60, a substituted or unsubstituted heteroaryl group of C5-C60 or a substituted or unsubstituted heteroaryl ether group of C5-C60;
n1～n2is an integer of 0 to 4.
2. The bora-or phospha-fused ring compound having a binaphthyl ring as claimed in claim 1, which has a structure represented by any one of the following:
3. the bora-or phospha-fused ring compound containing a binaphthyl ring as claimed in claim 1, wherein X is1And X2Are all B.
4. The bora-or phospha-fused ring compound containing a binaphthyl ring as claimed in claim 1, wherein Y is1And Y2Independently selected from N (R)1) O, S or Se.
5. The bora-or phospha-fused ring compound containing a binaphthyl ring as claimed in claim 1, wherein X is1And X2Are both B, and the Y1And Y2Independently selected from N (R)1) O, S or Se.
6. The bora-or phospha-fused ring compound containing a binaphthyl ring as claimed in claim 1, wherein it is selected from one of the following structures:
7. a method for producing a bora-or phospha-fused ring compound having a binaphthyl ring as set forth in any one of claims 1 to 6, comprising the steps of:
when X is present1And X2When independently selected from B or P ═ S, the preparation process comprises the steps of:
under the argon atmosphere, placing A-1 or A-2 and o-xylene into a three-neck flask, cooling, dropwise adding a pentane solution of tert-butyl lithium into the reaction solution, heating the reaction solution after dropwise adding, and stirring; after the reaction is finished, cooling the reaction solution again, dropwise adding boron trihalide or phosphorus trihalide and adding sulfur powder into the reaction solution, and after the raw materials are added, heating the reaction solution and continuously stirring; cooling the reaction liquid after the reaction is finished, dropwise adding N, N-diisopropylethylamine into the reaction liquid, heating after the dropwise adding is finished, continuously stirring the reaction liquid, cooling the reaction liquid to room temperature, filtering solids separated out from the reaction liquid, washing with methanol, and drying the product to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped condensed ring compound shown in the formula (I) and the formula (II);
when X is present1And X2When independently selected from P ═ O, the preparation process comprises the steps of:
adding X into a double-neck flask under the argon atmosphere1And X2Independently selecting a fused ring compound prepared when P ═ S, m-chloroperoxybenzoic acid and dried dichloromethane, stirring the reaction solution at room temperature, then placing the reaction solution into methanol for sedimentation after the reaction is finished, filtering the precipitated solid, and separating by silica gel column chromatography to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in the formula (I) and the formula (II);
wherein Z is selected from one of Cl, Br and I; the other symbols are as defined in claims 1-6.
8. The method for preparing a bora-or phospha-fused ring compound having a binaphthyl ring as claimed in claim 7, wherein one embodiment of the preparation method is:
when X is present1And X2When independently selected from B or P ═ S, the preparation process comprises the steps of:
under the argon atmosphere, placing A-1 or A-2 and o-xylene into a 500mL three-neck flask, cooling at minus 30 ℃ for 20 minutes, dropwise adding 2.5M/L of tert-butyl lithium pentane solution into the reaction solution, heating the reaction solution to 50 ℃ after the dropwise adding is finished, and stirring for 1 hour; after 1 hour, cooling the reaction solution to-30 ℃ again, dropwise adding boron trihalide or phosphorus trihalide and adding sulfur powder into the reaction solution, after the raw materials are added, heating the reaction solution to 40 ℃, and stirring for 1 hour; cooling the temperature of the reaction solution to 0 ℃, dropwise adding N, N-diisopropylethylamine into the reaction solution, and heating to 125 ℃ after dropwise adding, and stirring for 12 hours; finally, cooling the reaction liquid to room temperature, filtering the solid precipitated in the reaction liquid, washing with methanol, and drying the product at 80 ℃ under reduced pressure to obtain the binaphthyl ring-containing boron-doped or phosphorus-doped fused ring compound shown in the formula (I) and the formula (II);
when X is present1And X2When independently selected from P ═ O, the preparation process comprises the steps of:
under argon atmosphere, adding X into a 250mL double-neck flask1And X2Independently selected from the fused ring compound prepared when P ═ S, m-chloroperoxybenzoic acid and dried dichloromethane, is stirred at room temperature for 24 hours, the reaction solution is placed in 500mL of methanol for sedimentation, and the precipitated solid is filtered and separated by silica gel column chromatography to obtain the binaphthyl ring-containing boron hetero or phosphorus hetero fused ring compound represented by formula (I) or formula (II).
9. An organic electroluminescent device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode; wherein the organic thin film layer comprises the binaphthyl ring-containing boro-or phospha-fused ring compound according to any one of claims 1 to 6.
10. The organic electroluminescent device according to claim 9, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer includes the binaphthyl ring-containing boro-or phospha-fused ring compound of any one of claims 1 to 6.
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