CN114195808B - Boron-doped or phosphorus-doped fused ring compound containing binaphthyl ring, preparation method thereof and light-emitting device - Google Patents
Boron-doped or phosphorus-doped fused ring compound containing binaphthyl ring, preparation method thereof and light-emitting device Download PDFInfo
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- CN114195808B CN114195808B CN202111609561.8A CN202111609561A CN114195808B CN 114195808 B CN114195808 B CN 114195808B CN 202111609561 A CN202111609561 A CN 202111609561A CN 114195808 B CN114195808 B CN 114195808B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 173
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 71
- 238000006243 chemical reaction Methods 0.000 claims description 56
- -1 phosphorus heterocyclic compound Chemical class 0.000 claims description 54
- 239000012295 chemical reaction liquid Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 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 13
- 239000010409 thin film Substances 0.000 claims description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 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
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 17
- 230000003111 delayed effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 230000005281 excited state Effects 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 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
- 238000000926 separation method Methods 0.000 abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 2
- 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 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 261
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 249
- 238000012360 testing method Methods 0.000 description 168
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 166
- 238000000921 elemental analysis Methods 0.000 description 165
- 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
- 239000012074 organic phase Substances 0.000 description 136
- 239000000243 solution Substances 0.000 description 127
- 239000000047 product Substances 0.000 description 122
- 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
- 239000008367 deionised water Substances 0.000 description 88
- 229910021641 deionized water Inorganic materials 0.000 description 88
- 239000002904 solvent Substances 0.000 description 84
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 54
- 239000000741 silica gel Substances 0.000 description 54
- 229910002027 silica gel Inorganic materials 0.000 description 54
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 49
- 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
- 238000005516 engineering process Methods 0.000 description 30
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- 238000004440 column chromatography Methods 0.000 description 22
- 239000002244 precipitate Substances 0.000 description 22
- 239000012141 concentrate Substances 0.000 description 20
- 239000012452 mother liquor Substances 0.000 description 18
- 238000007738 vacuum evaporation Methods 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 15
- 229910014265 BrCl Inorganic materials 0.000 description 13
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 13
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 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
- 239000000203 mixture Substances 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- YPSXFMHXRZAGTG-UHFFFAOYSA-N 4-methoxy-2-[2-(5-methoxy-2-nitrosophenyl)ethyl]-1-nitrosobenzene Chemical compound COC1=CC=C(N=O)C(CCC=2C(=CC=C(OC)C=2)N=O)=C1 YPSXFMHXRZAGTG-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229910052760 oxygen Inorganic materials 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
- 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
- 239000010408 film Substances 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
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000006749 (C6-C60) aryl group Chemical group 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 125000004414 alkyl thio group Chemical group 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
- 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
- 229910052739 hydrogen Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007645 offset printing Methods 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
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000000137 annealing Methods 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
- QNZKEYXZEFCOMR-UHFFFAOYSA-N bromo(chloro)boron Chemical compound Cl[B]Br QNZKEYXZEFCOMR-UHFFFAOYSA-N 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
- 239000003153 chemical reaction reagent 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
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type 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
- 230000003287 optical effect Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 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
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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- 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
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- 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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- 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
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- 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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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- 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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- H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract
The invention relates to a boron or phosphorus fused ring compound containing binaphthyl ring, a preparation method thereof and a luminescent device, belonging to the technical field of organic luminescent materials. The condensed-cyclic compound of the present invention has a structure represented by any one of formulas (I) to (II). The boron-doped or phosphorus-doped fused ring compound containing binaphthyl ring can utilize the rigid skeleton structure of binaphthyl ring to reduce the relaxation degree of excited state structure, thereby realizing narrower half-peak width; on the other hand, the resonance effect between boron atoms or phosphorus atoms and hetero atoms is utilized to realize the separation of HOMO and LUMO, thereby realizing smaller delta E ST And TADF effect, thereby achieving high luminous efficiency. Meanwhile, by changing the kind of the aromatic ring or the heteroaromatic ring contained in the condensed-cyclic compound, further adjustment of the delayed fluorescence lifetime and half-width can be achieved.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a boron-doped or phosphorus-doped fused ring compound containing binaphthyl rings, a preparation method thereof and a luminescent device.
Background
Organic Light Emitting Devices (OLEDs) have the characteristics of rich color, thin thickness, wide viewing angle, rapid response, and the like, and can be used for preparing flexible devices, and are considered to be the next generation flat panel display and solid lighting technology with the most 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 excitons (expton) are formed by combining holes (Hole) injected from the anode and the cathode on an organic thin film with electrons (electrons) and releasing energy in the form of luminescence when the excitons return to a stable ground state from an excited state to emit light.
However, due to the limitation of the statistical law of spin quantum, the traditional fluorescent material can only utilize singlet excitons accounting for 25% of the total exciton number in the electroluminescent process, and the rest 75% of triplet excitons are deactivated in a non-radiative transition manner, so that the maximum value of the quantum efficiency (IQE) in the device is 25%. The phosphorescent metal complex can convert triplet excitons into photons by utilizing the orbital coupling action of heavy metal atoms, so that the triplet excitons are utilized, the internal quantum efficiency of 100% is realized, and the problem of high price of the phosphorescent metal complex is faced by the approach.
Thermally activated delayed fluorescence (thermally activated delayed fluorescence, TADF) materials are third generation organic luminescent materials following conventional fluorescent and phosphorescent materials, which generally have a small singlet-triplet energy level difference (Δe) ST ) The triplet state excitons are transferred to the singlet state excitons to emit fluorescence by utilizing a thermally activated reverse intersystem crossing (RISC) process, so that the full utilization of the singlet state excitons and the triplet state excitons is realized, and the internal quantum efficiency of 100% is realized. 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 the device. The main implementation way of TADF molecules at present is to introduce an electron donor (D) andan electron acceptor (A) unit, such that the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) are separated, thereby achieving a small ΔE ST . However, such D-a structures exhibit large Stokes shift due to a remarkable vibrational relaxation of the excited state, and have a wide luminescence spectrum, a full width at half maximum (FWHM) of typically 70 to 100nm, and in practical applications, it is generally necessary to use a filter or configure an optical microcavity to improve color purity, which may lead to a decrease in external quantum efficiency of the device or a complexity of the device structure.
Therefore, how to develop a luminescent material with both TADF effect and narrow half-width spectral characteristics by reasonable chemical structural design, and solve the defect of wider half-width faced by the above materials has become one of the problems to be solved by many prospective researchers in the field.
Disclosure of Invention
In view of the above, the present invention has an object to provide a boron or phosphorus fused ring compound containing binaphthyl ring, a method for producing the same, and a light emitting device, the fused ring compound having both TADF effect and narrow half-width spectral characteristics.
The boron or phosphorus fused ring compound containing binaphthyl ring provided by the invention has a structure shown in any one of formulas (I) to (II):
wherein X is 1 And X 2 Independently selected from B, P =o or p=s; y is Y 1 And Y 2 Independently selected from N (R) 1 )、O、S、Se、Te、B(R 1 )、C(R 1 R 2 ) Or Si (R) 1 R 2 )；
Ar 1 ～Ar 3 Independently selected from a substituted or unsubstituted C6 to C60 aryl ring, or a substituted or unsubstituted C3 to C60 heteroaryl ring; the substitution is D, F, cl, br, I, -CN, -NO 2 、-CF 3 C1-C30 straight-chain hydrocarbon group, C1-C30 branched-chain hydrocarbon group, C3-C30 cycloalkyl group, C1-C30 alkaneAn oxy group, a C1-C30 alkylthio group, a substituted or unsubstituted C6-C60 aryl ether group, a C3-C60 heteroaryl group, or a substituted or unsubstituted C3-C60 heteroaryl ether group; wherein the heteroatoms of the heteroaromatic groups are independently selected from Si, ge, N, P, O, S or Se;
R 1 ～R 2 Independently selected from H, D, F, cl, br, I, -CN, -CF 3 、-NO 2 、
A substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C5-C60 heteroaromatic group;
the R is 1 ～R 3 Selected from the group consisting of a straight chain hydrocarbon group of H, D, C to C30, a branched chain hydrocarbon group of C1 to C30, a cycloalkyl group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C60, and a substituted or unsubstituted heteroaryl group of C3 to C60; the heteroatoms of the heteroaryl groups are independently selected from Si, ge, N, P, O, S or Se; and R is 1 、R 2 And R is 3 Between every two, R 1 With Ar 1 ～Ar 3 Any one substituent group can also pass through single bond, -C (R a R b )-、-(C＝O)-、-Si(R a R b )-、-N(R a )-、-PO(R a ) -O-, -S-, or-Se-; the R is a And R is b Independently is a C1-C30 straight chain hydrocarbon group, a C1-C30 branched chain hydrocarbon group, a C3-C30 cycloalkyl group, a C1-C30 alkoxy group, a C1-C30 alkylthio group, a substituted or unsubstituted C6-C60 aryl ether groupA substituted or unsubstituted C5 to C60 heteroaryl group or a substituted or unsubstituted C5 to C60 heteroaryl ether group;
n 1 ～n 2 Is an integer of 0 to 4.
Preferably, the binaphthyl ring-containing boron or phosphorus fused ring compound has a structure as shown in any one of the following:
preferably, the X 1 And X 2 And are all B.
Preferably, said Y 1 And Y 2 Independently selected from N (R) 1 ) O, S or Se.
Preferably, the X 1 And X 2 Are all B, and the Y 1 And Y 2 Independently selected from N (R) 1 ) O, S or Se.
Most preferably, the binaphthyl ring-containing boron or phosphorus fused ring compound is selected from one of the following structures:
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the invention also provides a preparation method of the boron-doped or phosphorus-doped fused ring compound containing binaphthyl ring, which comprises the following steps:
when X is 1 And X 2 When independently selected from B or p=s, the preparation method comprises the steps of:
under argon atmosphere, putting A-1 or A-2 and o-xylene into a three-neck flask, cooling, dropwise adding a pentane solution of tert-butyllithium into the reaction solution, heating the reaction solution after the dropwise adding is finished, and stirring; after the reaction is finished, cooling the reaction liquid again, dropwise adding boron trihalide or phosphorus trihalide and sulfur powder into the reaction liquid, and heating the reaction liquid to continuously stir after the raw materials are added; 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 a boron impurity or phosphorus impurity fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II);
When X is 1 And X 2 Independently selected from p=o, the preparation method comprises the steps of:
under argon atmosphere, X is added into a two-neck flask 1 And X 2 Independently selected from a fused ring compound prepared when p=s, m-chloroperoxybenzoic acid and dried dichloromethane, stirring the reaction liquid at room temperature, placing the reaction liquid in methanol for sedimentation after the reaction is finished, filtering out solid separated out, and separating by silica gel column chromatography to obtain a boron-doped or phosphorus-doped fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II);
hereinafter, X is only 1 And X 2 Independently selected from B, gives a synthetic route to a binaphthyl ring-containing boron or phosphorus fused ring compound of formula (I), formula (II), respectively, as follows:
wherein Z is selected from one of Cl, br and I; other code numbers are the same as those described above, and are not repeated here.
Preferably, a specific embodiment of the preparation method of the boron or phosphorus fused ring compound containing binaphthyl ring is as follows:
when X is 1 And X 2 When independently selected from B or p=s, the preparation method comprises the steps of:
under argon atmosphere, putting A-1 or A-2 and o-xylene into a 500mL three-neck flask, cooling for 20 minutes at minus 30 ℃, dropwise adding 2.5M/L of a pentane solution of tert-butyllithium into the reaction solution, heating the reaction solution to 50 ℃ after the dropwise adding is finished, and stirring for 1 hour; cooling the reaction liquid to minus 30 ℃ again after 1 hour, dropwise adding boron trihalide or phosphorus trihalide and sulfur powder into the reaction liquid, heating the reaction liquid to 40 ℃ after the raw materials are added, and stirring for 1 hour; cooling the reaction solution to 0 ℃, dropwise adding N, N-diisopropylethylamine into the reaction solution, heating to 125 ℃ after the dropwise adding is finished, 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 under reduced pressure at 80 ℃ to obtain the boron or phosphorus heterocyclic compound containing binaphthyl ring shown in the formulas (I) and (II);
When X is 1 And X 2 Independently selected from p=o, the preparation method comprises the steps of:
x was added to a 250mL two-necked flask under an argon atmosphere 1 And X 2 Independently selected from the group consisting of a fused ring compound prepared when p=s, m-chloroperoxybenzoic acid and dried dichloromethane, stirring for 24 hours at room temperature, then placing the reaction solution in 500mL of methanol for sedimentation, filtering out the precipitated solid, and separating by silica gel column chromatography to obtain a boron or phosphorus fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II).
The invention also provides an application of the boron or phosphorus fused ring compound containing binaphthyl ring as shown in the formula (I) or (II) as a luminescent material, in particular to an application in an organic electroluminescent device.
The invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic film layer positioned between the anode and the cathode; the organic film layer comprises a boron or phosphorus heterocyclic compound containing binaphthyl ring as shown in the formula (I) or the formula (II).
Preferably, the organic thin film layer includes a light emitting layer; the light-emitting layer includes a boron or phosphorus fused ring compound containing a binaphthyl ring as shown in formula (I) or formula (II).
The structure of the organic electroluminescent device is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the application situation, quality requirements and product requirements by using a conventional organic electroluminescent device well known to the person skilled in the art, and the structure of the organic electroluminescent device preferably comprises: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.
The thickness of the substrate is preferably 0.3 to 0.7mm, more preferably 0.4 to 0.6mm; the choice of the substrate is not particularly limited and may be any substrate known to those skilled in the art for conventional organic electroluminescent devices, and may be chosen and adjusted by those skilled in the art according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.
According to the present invention, the anode is preferably a material that facilitates hole injection, more preferably a conductive metal or conductive metal oxide, and still more preferably indium tin oxide.
The organic film layer can be one layer or a plurality of layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light emitting layer; the light-emitting layer comprises a condensed ring compound shown in the formula (I) or the formula (II); the condensed-cyclic 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 process of preparing 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 preferably, the present invention is prepared by using processes of vacuum evaporation, solution spin coating, solution doctor blading, inkjet printing, offset printing and three-dimensional printing.
The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, including a light emitting layer; forming a cathode on the organic thin film layer;
The light-emitting layer comprises one or more compounds shown as a formula (I) or a formula (II).
The structure and the materials of the organic electroluminescent device and the corresponding preferred principles of the preparation method of the invention can correspond to the corresponding materials and structures of the organic electroluminescent device and the corresponding preferred principles, and are not described in detail herein.
The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. The present invention is not particularly limited in the manner of forming the light emitting layer and the organic thin film layers below and above the light emitting layer, and may be formed on the anode by vacuum evaporation, solution spin coating, solution knife coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited as to the manner of forming the cathode after the organic layer is formed, and is preferably a method known to those skilled in the art, including but not limited to vacuum deposition, to prepare the cathode on the surface thereof.
The beneficial effects of the invention are as follows:
the boron-doped or phosphorus-doped fused ring compound containing binaphthyl ring can utilize the rigid skeleton structure of binaphthyl ring to reduce the relaxation degree of excited state structure, thereby realizing narrower half-peak width; on the other hand, the resonance effect between boron atoms or phosphorus atoms and hetero atoms is utilized to realize the separation of HOMO and LUMO, thereby realizing smaller delta E ST And TADF effect, thereby achieving high luminous efficiency. Meanwhile, by changing the kind of the aromatic ring or the heteroaromatic ring contained in the condensed-cyclic compound, further adjustment of the delayed fluorescence lifetime and half-width can be achieved.
The fused ring compound provided by the invention is used as a light-emitting layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized without a filter and a microcavity structure, but also the high external quantum efficiency of the device can be realized. Experimental results also show that: the device prepared by the fused ring compound provided by the invention has very narrow electroluminescent spectrum, the half-peak width is smaller than 40nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wider (70-100 nm) is solved. Meanwhile, the 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 boron or phosphorus fused ring compound containing binaphthyl ring provided by the invention has the advantages of simple preparation method and mild condition.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The reagents used in the examples below are all commercially available.
Example 1
1-1 (20.0 g,52.6 mmol), 1-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 1-3 (18.2 g, yield: 78%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.63; h,4.72.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
1-3 (15.0 g,33.8 mmol), 1-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 1-5 (15.3 g, yield: 81%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.12; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
1-5 (10.0 g,17.9 mmol), 1-6 (8.3 g,39.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (10.4 g,35.9 mmol), sodium t-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give the product 1-7 (13.2 g, yield: 90%).
Elemental analysis of the structure (C) 56 H 46 Cl 2 N 2 ): theoretical value: c,82.24; h,5.67; n,3.43; test value: c,82.28; h,5.61; n,3.39.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
1-7 (4.0 g,4.9 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a solution of t-butyllithium in n-pentane (8.3 mL,1.3M,10.8 mmol) was added dropwise at-30℃and after the addition was completed, the reaction solution was stirred at 50℃for 1 hour, the reaction solution was cooled again to-30℃and boron tribromide (2.9 g,1.1mL,11.7 mmol) was added dropwise to the reaction solution and the mixture was stirred at room temperature for 1 hour after the addition was completed. The temperature was lowered to 0℃again, N-diisopropylethylamine (1.6 g,2.2mL,12.7 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at 125℃for 20 hours after the completion of the addition. After the reaction solution was cooled to room temperature, the solid precipitated in the reaction solution was filtered, washed with methanol, and subjected to column chromatography on silica gel to give the product I-1-2 (2.3 g, yield: 62%).
Elemental analysis structure (C) 56 H 42 B 2 N 2 ): theoretical value: c,87.97; h,5.54; n,3.66; test value: c,88.01; h,5.48; n,3.72.
MALDI-TOF-MS: theoretical value 764.4; experimental value 764.4.
Example 2
2-1 (20.0 g,35.9 mmol), 2-2 (16.5 g,79.0 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (20.8 g,71.8 mmol), sodium t-butoxide (6.9 g,71.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 2-3 (18.2 g, yield: 74%).
Elemental analysis of the structure (C) 40 H 24 BrCl 2 NO): theoretical value: c,70.09; h,3.53; n,2.04; test value C,70.12; h,3.58; n,2.01.
MALDI-TOF-MS: theoretical value 683.0; experimental value 683.0.
2-3 (15.0 g,21.9 mmol), 2-4 (8.1 g,48.1 mmol), tris (dibenzylideneacetone) dipalladium (0.8 g,0.9 mmol), tri-tert-butylphosphinothioborate (12.7 g,43.8 mmol), sodium tert-butoxide (4.2 g,43.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 2-5 (13.2 g, 78% yield).
Elemental analysis of the structure (C) 52 H 34 Cl 2 N 2 O): theoretical value: c,80.72; h,4.43; n,3.62; test value: c,80.78; h,4.39; n,3.59.
MALDI-TOF-MS: theoretical value 772.2; experimental value 772.2.
Reference example 1, starting from 2-5 (10.0 g,12.9 mmol), finally gives the product I-1-14 (8.2 g, yield: 88%).
Elemental analysis structure (C) 52 H 30 B 2 N 2 O): theoretical value: c,86.69; h,4.20; n,3.89; test value: c,86.73; h,4.22; n,3.81.
MALDI-TOF-MS: theoretical value 720.3; experimental 720.3.
Example 3
3-1 (20.0 g,50.7 mmol), 3-2 (19.3 g,60.9 mmol), tetrakis (triphenylphosphine) palladium (4.7 g,4.1 mmol), potassium carbonate (28.1 g,203.0 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 3-3 (19.3 g, yield: 83%).
Elemental analysis of the structure (C) 23 H 23 BBrClO 2 ): theoretical value: c,60.37; h,5.07; test value: c,60.43; h,5.02.
MALDI-TOF-MS: theoretical value 456.1; experimental value 456.1.
3-3 (15.0 g,32.8 mmol), 3-4 (14.5 g,39.3 mmol), tetrakis (triphenylphosphine) palladium (3.0 g,2.6 mmol), potassium carbonate (18.1 g,131.1 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 3-5 (16.2 g, yield: 87%).
Elemental analysis of the structure (C) 27 H 16 Br 2 Cl 2 ): theoretical value: c,56.78; h,2.82; test value: c,56.83; h,2.79.
MALDI-TOF-MS: theoretical 567.9; experimental 567.9.
3-5 (10.0 g,17.5 mmol), 3-6 (4.2 g,38.5 mmol), tris (dibenzylideneacetone) dipalladium (0.6 g,0.7 mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (20.3 g,35.0 mmol), N-diisopropylethylamine (4.5 g,6.1mL,35.0 mmol) and 250mL of 1, 4-dioxane were placed in a 500mL three-necked flask under argon atmosphere, stirred at 105℃for 8 hours and then cooled to room temperature, and the resultant concentrate was subjected to column chromatography on silica gel to give 3-7 (10.2 g, yield: 93%).
Elemental analysis of the structure (C) 39 H 26 Cl 2 S 2 ): theoretical value: c,74.39; h,4.16; s,10.18; test value: c,74.45; h,4.11; s,10.12.
MALDI-TOF-MS: theoretical value 628.1; experimental value 628.1.
Reference example 1, starting from 3-7 (10.0 g,15.9 mmol), finally gives the product I-1-15 (6.5 g, yield: 71%).
Elemental analysis structure (C) 39 H 22 B 2 S 2 ): theoretical value: c,81.28; h,3.85; s,11.13; test value: c,81.32; h,3.88; s,11.07.
MALDI-TOF-MS: theoretical value 576.1; experimental value 576.1.
Example 4
4-1 (20.0 g,35.9 mmol), 4-2 (4.1 g,43.1 mmol), cesium carbonate (23.4 g,71.8 mmol), 2, 6-tetramethyl-3, 5-heptanedione (0.3 g,1.4 mmol), cuprous iodide (0.3 g,1.4 mmol) and 250mLN, N-dimethylformamide were added to a 500mL three-necked flask under argon atmosphere, the mixture was stirred at 180℃for 8 hours and cooled to room temperature, the reaction mixture was poured into 2000mL of methanol to settle, and the precipitated precipitate was filtered to obtain the product 4-3 (17.2 g, yield: 84%) by silica gel column chromatography.
Elemental analysis of the structure (C) 32 H 19 BrCl 2 O): theoretical value: c,67.39; h,3.36; test value: c,67.41; h,3.33.
MALDI-TOF-MS: theoretical value 568.0; experimental value 568.0.
4-3 (15.0 g,26.3 mmol), 4-4 (8.8 g,31.6 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tri-tert-butylphosphinothioborate (15.3 g,52.6 mmol), sodium tert-butoxide (5.1 g,52.6 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 4-5 (17.1 g, yield: 85%).
Elemental analysis of the structure (C) 52 H 43 Cl 2 NO): theoretical value: c,81.24; h,5.64; n,1.82; test value: c,81.28; h,5.61; n,1.85.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
4-5 (10.0 g,13.0 mmol) and dry toluene (70 mL) were placed in a 250mL two-necked flask under argon atmosphere, a solution of tert-butyllithium in n-pentane (22.0 mL,1.3M,28.6 mmol) was dropwise added at-30℃and stirred at 50℃for 1 hour after the dropwise addition, cooled again to-30℃and phosphorus trichloride (PCl) was dropwise added to the reaction solution 3 ) (4.3 g,2.7mL,31.2 mmol) and stirred at room temperature for 1 hour after the completion of the dropwise addition. Cooling to 0 deg.C again, adding aluminium trichloride (6.9 g,52.0 mmol), heating to 125 deg.C after the raw materials are added, and stirring for 1 hr. After the reaction was cooled to room temperature again, S was then added 8 (1.1 g,33.8 mmol) was added to the reaction solution, and stirred for 2And 0h. In the work-up, the solid precipitated in the reaction mixture was filtered, washed with methanol and separated by column chromatography on silica gel to give the product 4-6 (8.2 g, yield: 77%).
Elemental analysis structure (C) 52 H 39 NOP 2 S 2 ): theoretical value: c,76.17; h,4.79; n,1.71; s,7.82; test value: c,76.21; h,4.72; n,1.75; s,7.83.
MALDI-TOF-MS: theoretical value 819.2; experimental value 819.2.
4-6 (4.0 g,4.9 mmol), m-chloroperoxybenzoic acid (MCPBA) (1.9 g,10.7 mmol) and dried methylene chloride (70 mL) were added to a 250mL two-necked flask under argon atmosphere, and after stirring at room temperature for 24 hours, the reaction solution was settled in 500mL methanol, and the precipitated solid was filtered and separated by silica gel column chromatography to give the product I-1-16 (2.8 g, yield: 73%).
Elemental analysis structure (C) 52 H 39 NO 3 P 2 ): theoretical value: c,79.28; h,4.99; n,1.78; test value: c,79.28; h,4.99; n,1.78.
MALDI-TOF-MS: theoretical value 787.2; experimental value 787.2.
Example 5
5-1 (20.0 g,52.6 mmol), 5-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, then cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 5-3 (16.5 g, yield: 71%).
Elemental analysis structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.52; h,4.79.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
5-3 (15.0 g,33.8 mmol), 5-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 30mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, reacted at 120℃for 8 hours, then cooled to room temperature, 150mL of ethyl acetate was added, 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 the solvent removal of the organic phase was subjected to column chromatography on silica gel to obtain a product 5-5 (15.3 g, yield: 81%).
Elemental analysis structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.09; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
5-5 (15.0 g,26.9 mmol), 5-6 (16.7 g,59.2 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give the product 5-7 (18.5 g, yield: 72%).
Elemental analysis of the structure (C) 66 H 66 Cl 2 N 2 ): theoretical value: c,82.73; h,6.94; n,2.92; test value: c,82.77; h,6.91; n,2.87.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
Reference example 1, starting from 5-7 (4.0 g,4.2 mmol), finally gives the product I-2-2 (2.8 g, yield: 74%).
Elemental analysis structure (C) 66 H 62 B 2 N 2 ): theoretical value: c,87.61; h,6.91; n,3.10; test value: c,87.68; h,6.85; n,3.12.
MALDI-TOF-MS: theoretical value 904.5; experimental value 904.5.
Example 6
6-1 (15.0 g,26.9 mmol), 6-2 (12.4 g,59.2 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 6-3 (16.8 g, 77% yield).
Elemental analysis of the structure (C) 56 H 42 Cl 2 N 2 ): theoretical value: c,88.44; h,5.04; n,3.68; test value: c,88.47; h,5.01; n,3.61.
MALDI-TOF-MS: theoretical 760.3; experimental 760.3.
Reference example 1, starting from 6-3 (4.0 g,4.9 mmol), finally gives the product I-2-5 (3.4 g, yield: 91%).
Elemental analysis structure (C) 56 H 38 B 2 N 2 ): theoretical value: c,88.44; h,5.04; n,3.68; test value: c,88.46; h,5.01; n,3.62.
MALDI-TOF-MS: theoretical 760.3; experimental 760.3.
Example 7
7-1 (15.0 g,26.9 mmol), 7-2 (12.4 g,59.2 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 7-3 (17.3 g, 79% yield).
Elemental analysis of the structure (C) 54 H 34 Cl 2 N 2 O 2 ): theoretical value: c,79.70; h,4.21; n,3.44; test value: c,79.75; h,4.16; n,3.47.
MALDI-TOF-MS: theoretical value 812.2; experimental value 812.2.
Reference example 1, starting from 7-3 (4.0 g,4.9 mmol), finally gives the product I-2-10 (3.2 g, yield: 86%).
Elemental analysis structure (C) 54 H 30 B 2 N 2 O 2 ): theoretical value: c,85.29; h,3.98; n,3.68; test value: c,85.32; h,3.92; n,3.69.
MALDI-TOF-MS: theoretical 760.3; experimental 760.3.
Example 8
8-1 (15.0 g,26.9 mmol), 8-2 (18.0 g,59.2 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 8-3 (22.2 g, 82% yield).
Elemental analysis of the structure (C) 66 H 46 Cl 2 N 2 S 2 ): theoretical value: c,79.10; h,4.63; n,2.80; s,6.40; test value: c,79.18; h,4.59; n,2.82; s,6.37.
MALDI-TOF-MS: theoretical value 1000.3; experimental value 1000.3.
Reference example 1, starting from 8-3 (4.0 g,4.0 mmol), finally gives the product I-2-18 (2.1 g, yield: 55%).
Elemental analysis structure (C) 66 H 42 B 2 N 2 S 2 ): theoretical value: c,83.55; h,4.46; n,2.95; s,6.76; test value: 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
9-1 (20.0 g,52.6 mmol), 9-2 (13.2 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, then cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 9-3 (18.2 g, yield: 90%).
Elemental analysis structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.52; h,4.79.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
9-3 (15.0 g,39.2 mmol), 9-4 (12.2 g,47.0 mmol), tetrakis (triphenylphosphine) palladium (3.6 g,3.1 mmol), potassium carbonate (21.7 g,156.8 mmol), 30mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere and reacted at 120℃for 8 hours, then cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after the solvent removal of the organic phase was separated by silica gel column chromatography to obtain a product 9-5 (15.1 g, yield: 88%).
Elemental analysis structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.09; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
9-5 (15.0 g,34.5 mmol), 9-6 (13.4 g,41.4 mmol), potassium carbonate (19.1 g,137.8 mmol) and N-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere and stirred at 180℃for 8 hours. Sedimentation was performed in 2000mL of water, and the precipitated solid was filtered and washed with methanol, followed by column chromatography on silica gel to give 9-7 (20.1 g, 79%).
Elemental analysis of the structure (C) 44 H 28 Cl 2 FNSe): theoretical value: c,71.46; h,3.82; n,1.89; test value: c,71.52; h,3.87; n,1.82.
MALDI-TOF-MS: theoretical value 739.1; experimental value 739.1.
9-7 (10.0 g,13.5 mmol), 9-8 (4.2 g,16.2 mmol), potassium carbonate (7.5 g,54.1 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, the mother liquor was poured into 1000mL methanol for sedimentation, the precipitated precipitate was filtered and washed with methanol, and then the product 9-9 (12.2 g, yield: 92%) was obtained by separation by silica gel column chromatography.
Elemental analysis of the structure (C) 62 H 42 Cl 2 N 2 OSe): theoretical value: c,75.92; h,4.32; n,2.86; test value: c,75.98; h,4.27; n,2.82.
MALDI-TOF-MS: theoretical value 980.2; experimental value 980.2.
Reference example 1, starting from 9-9 (4.0 g,4.1 mmol), finally gives the product I-2-57 (2.6 g, yield: 69%).
Elemental analysis structure (C) 62 H 38 B 2 N 2 OSe): theoretical value: c,80.28; h,4.13; n,3.02; test value: c,80.28; h,4.13; n,3.02.
MALDI-TOF-MS: theoretical value 928.2; experimental value 928.2.
Example 10
10-1 (20.0 g,26.9 mmol), 10-2 (16.7 g,59.2 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were placed in a 500mL three-necked flask under argon atmosphere, and stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 10-3 (19.2 g, yield: 74%).
Elemental analysis of the structure (C) 62 H 50 Cl 2 N 2 S 2 ): theoretical value: c,77.72; h,5.26; n,2.92; s,6.69; test value: c,77.78; h,5.21; n,2.94; s,6.63.
MALDI-TOF-MS: theoretical value 956.3; experimental value 956.3.
Reference example 4, starting from 10-3 (10.0 g,10.4 mmol), finally gives the product 10-4 (8.6 g, yield: 82%).
Elemental analysis structure (C) 62 H 46 N 2 P 2 S 4 ): theoretical value: c,73.79; h,4.59; n,2.78; s,12.71; test value: c,73.83; h,4.52; n,2.73; s,12.78
MALDI-TOF-MS: theoretical value 1008.2; experimental value 1008.2.
Reference example 4, starting from 10-4 (4.0 g,4.0 mmol), finally gives the product I-2-58 (3.3 g, yield: 72%).
Elemental analysis structure (C) 62 H 46 N 2 O 2 P 2 S 2 ): theoretical value: c,76.21; h,4.75; n,2.87; s,6.56; test value: 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
11-1 (20.0 g,52.6 mmol), 11-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give 11-3 (17.2 g, yield: 74%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.63; h,4.72.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
11-3 (15.0 g,33.8 mmol), 11-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 11-5 (14.3 g, yield: 76%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.12; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
11-5 (10.0 g,17.9 mmol), 11-6 (6.7 g,39.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (10.4 g,35.9 mmol), sodium t-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 11-7 (11.8 g, yield: 90%).
Elemental analysis of the structure (C) 50 H 34 Cl 2 N 2 ): theoretical value: c,81.85; h,4.67; n,3.82; test value: c,81.88; h,4.62; n,3.83.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
Reference example 1, starting from 11-7 (4.0 g,5.5 mmol), finally gives the product I-3-1 (2.3 g, yield: 62%).
Elemental analysis structure (C) 50 H 30 B 2 N 2 ): theoretical value: c,88.26; h,4.44; n,4.12; test value: c,88.35; h,4.41; n,4.16.
MALDI-TOF-MS: theoretical 680.3; experimental value 680.3.
Example 12
12-1 (15.0 g,26.9 mmol), 12-2 (8.7 g,32.3 mmol), tris (dibenzylideneacetone) dipalladium (1.0 g,1.1 mmol), tri-tert-butylphosphinothioborate (15.6 g,53.8 mmol), sodium tert-butoxide (5.2 g,53.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 12-3 (15.6 g, yield: 78%).
Elemental analysis of the structure (C) 46 H 28 BrCl 2 N): theoretical value: c,74.11; h,3.79; n,1.88; test value: c,74.18; h,3.72; n,1.85.
MALDI-TOF-MS: theoretical value 743.1; experimental value 743.1.
12-3 (15.0 g,20.1 mmol), 12-4 (12.5 g,44.3 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.8 mmol), tri-tert-butylphosphinothioborate (11.7 g,40.2 mmol), sodium tert-butoxide (3.9 g,40.2 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 12-5 (14.3 g, 75% yield).
Elemental analysis of the structure (C) 66 H 54 Cl 2 N 2 ): theoretical value: c,83.79; h,5.75; n,2.96; test value: c,83.81; h,5.73; n,2.98.
MALDI-TOF-MS: theoretical value 944.4; experimental value 944.4.
Reference example 1, starting from 12-5 (4.0 g,4.2 mmol), finally gives the product I-3-37 (2.1 g, yield: 56%).
Elemental analysis structure (C) 66 H 50 B 2 N 2 ): theoretical value: c,88.79; h,5.65; n,3.14; test value: c,88.81; h,5.61; n,3.17.
MALDI-TOF-MS: theoretical value 892.4; experimental value 892.4.
Example 13
13-1 (20.0 g,52.6 mmol), 13-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 13-3 (17.2 g, yield: 74%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.63; h,4.72.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
13-3 (15.0 g,33.8 mmol), 13-4 (12.4 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 13-5 (15.1 g, yield: 90%).
Elemental analysis of the structure (C) 26 H 14 BrCl 2 F) The method comprises the following steps Theoretical value: c,62.94; h,2.84; test value: c,62.91; h,2.87.
MALDI-TOF-MS: theoretical value 494.0; experimental value 494.0.
13-5 (10.0 g,20.2 mmol), 13-6 (14.8 g,44.3 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.8 mmol), tris (t-butylphosphinothioyl tetrafluoroborate (11.7 g,40.3 mmol), sodium t-butoxide (3.9 g,40.3 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give the product 13-7 (12.1 g, yield: 80%).
Elemental analysis of the structure (C) 51 H 32 Cl 2 FN): theoretical value: c,81.81; h,4.31; n,1.87; test value: c,81.88; h,4.26; n,1.88.
MALDI-TOF-MS: theoretical value 747.2; experimental value 747.2.
13-7 (10.0 g,13.4 mmol), 13-8 (4.6 g,29.4 mmol), potassium carbonate (3.7 g,26.7 mmol) and 50 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, settled in 500mL water, and separated by silica gel column chromatography after washing the precipitated precipitate with methanol to obtain 13-9 (8.5 g, yield: 72%).
Elemental analysis of the structure (C) 57 H 37 Cl 2 NSe): theoretical value: c,77.29; h,4.21; n,1.58; test value: c,77.24; h,4.25; n,1.54.
MALDI-TOF-MS: theoretical value 885.2; experimental value 885.2.
Reference example 1, starting from 13-9 (4.0 g,4.5 mmol), finally gives the product I-3-38 (3.2 g, yield: 85%).
Elemental analysis structure (C) 57 H 33 B 2 NSe): theoretical value: c,82.24; h,4.00; n,1.68; test value: c,82.28; h,4.08; n,1.61.
MALDI-TOF-MS: theoretical value 833.2; experimental value 833.2.
Example 14
14-1 (20.0 g,35.9 mmol), 14-2 (22.2 g,79.0 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (20.8 g,71.8 mmol), sodium t-butoxide (6.9 g,71.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 14-3 (18.2 g, 67% yield).
Elemental analysis of the structure (C) 46 H 40 BrCl 2 N): theoretical value: c,72.92; h,5.32; n,1.85; test value: c,72.98; h,5.27; n,1.88.
MALDI-TOF-MS: theoretical value 755.2; experimental value 755.2.
14-3 (15.0 g,19.8 mmol), 14-4 (7.2 g,43.6 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.8 mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (22.9 g,39.6 mmol), N-diisopropylethylamine (5.1 g,6.9mL,39.6 mmol) and 250mL of 1, 4-dioxane were placed in a 500mL three-necked flask under argon atmosphere, stirred at 105℃for 8 hours and then cooled to room temperature, and the resultant concentrate was subjected to silica gel column chromatography to give 14-5 (10.2 g, yield: 93%) as a product.
Elemental analysis of the structure (C) 54 H 45 Cl 2 NS 2 ): theoretical value: c,76.94; h,5.38; n,1.66; s,7.61; test value: c,76.91; h,5.32; n,1.69; s,7.58.
MALDI-TOF-MS: theoretical value 841.2; experimental value 841.2.
Reference example 1, starting from 14-5 (4.0 g,4.7 mmol), finally gives the product I-3-39 (2.1 g, yield: 56%).
Elemental analysis structure (C) 54 H 41 B 2 NS 2 ): theoretical value: c,82.13; h,5.23; n,1.77; s,8.12; test value: c,82.15; h,5.18; n,1.79; s,8.08.
MALDI-TOF-MS: theoretical value 789.3; experimental value 789.3.
Example 15
15-1 (20.0 g,52.6 mmol), 15-2 (13.2 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give 15-3 (17.4 g, yield: 86%).
Elemental analysis of the structure (C) 22 H 21 BClFO 2 ): theoretical value: c,69.05; h,5.53; test value: c,69.06; h,5.49.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
15-3 (15.0 g,39.2 mmol), 15-4 (12.2 g,47.0 mmol), tetrakis (triphenylphosphine) palladium (3.6 g,3.1 mmol), potassium carbonate (21.7 g,156.8 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 15-5 (12.8 g, yield: 75%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24; test value: c,71.79; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
15-5 (10.0 g,23.0 mmol), 15-6 (6.5 g,50.5 mmol), potassium carbonate (6.3 g,45.9 mmol) and 250-mLN-methylpyrrolidone were added to 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 water, the precipitate precipitated in the solution was filtered and washed with methanol, and the product 15-7 (11.3 g, yield: 75%) was obtained by silica gel column chromatography.
Elemental analysis of the structure (C) 38 H 22 Cl 2 F 2 S 2 ): theoretical value: c,70.04; h,3.40; s,9.84; test value: c,70.08; h,3.32; s,9.88.
MALDI-TOF-MS: theoretical value 650.1; experimental value 650.1.
Reference example 4, starting from 15-7 (4.0 g,6.1 mmol), finally gives the product I-3-40 (2.8 g, yield: 65%).
Elemental analysis structure (C) 38 H 18 F 2 P 2 S 4 ): theoretical value: c,64.95; h,2.58; s,18.25; test value: c,64.91; h,2.59; s,18.15.
MALDI-TOF-MS: theoretical value 702.0; experimental value 702.0.
Example 16
16-1 (20.0 g,52.6 mmol), 16-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 16-3 (14.3 g, yield: 61%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.52; h,4.78.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
16-3 (15.0 g,33.8 mmol), 16-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 16-5 (16.2 g, yield: 86%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.48.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
16-5 (10.0 g,17.9 mmol), 16-6 (11.1 g,39.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (10.4 g,35.9 mmol), sodium t-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 16-7 (13.3 g, yield: 77%).
Elemental analysis of the structure (C) 66 H 66 Cl 2 N 2 ): theoretical value: c,82.73; h,6.94; n,2.92; test value: c,82.75; h,6.91; n,2.87.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
Reference example 1, starting from 16-7 (4.0 g,4.2 mmol), finally gives the product I-4-22 (1.2 g, yield: 32%).
Elemental analysis structure (C) 66 H 62 B 2 N 2 ): theoretical value: c,87.61; h,6.91; n,3.10; test value: c,87.64; h,6.86; n,3.13.
MALDI-TOF-MS: theoretical value 904.5; experimental value 904.5.
Example 17
17-1 (20.0 g,35.9 mmol), 17-2 (15.7 g,79.0 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (20.8 g,71.8 mmol), sodium t-butoxide (6.9 g,71.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 17-3 (22.5 g, yield: 79%).
Elemental analysis of the structure (C) 52 H 40 Cl 2 N 4 ): theoretical value: c,78.88; h,5.09; n,7.08; test value: c,78.89; h,5.06; n,7.02.
MALDI-TOF-MS: theoretical value 790.3; experimental value 790.3.
Reference example 1, starting from 17-3 (8.0 g,10.1 mmol), finally gives the product I-4-23 (2.5 g, yield: 34%).
Elemental analysis structure (C) 52 H 36 B 2 N 4 ): theoretical value: c,84.57; h,4.91; n,7.59; test value: c,84.59; h,4.86; n,7.52.
MALDI-TOF-MS: theoretical value 738.3; experimental value 738.3.
Example 18
18-1 (20.0 g,48.8 mmol), 18-2 (12.3 g,58.5 mmol), tetrakis (triphenylphosphine) palladium (4.5 g,3.9 mmol), potassium carbonate (27.0 g,195.1 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 18-3 (15.2 g, yield: 76%).
Elemental analysis of the structure (C) 23 H 23 BClFO 3 ): theoretical value: c,66.94; h,5.62; test value: c,66.91; h,5.68.
MALDI-TOF-MS: theoretical value 412.1; experimental value 412.1.
18-3 (15.0 g,36.3 mmol), 18-4 (11.3 g,43.6 mmol), tetrakis (triphenylphosphine) palladium (3.4 g,2.9 mmol), potassium carbonate (20.1 g,145.4 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 18-5 (11.3 g, yield: 81%).
Elemental analysis of the structure (C) 27 H 16 Cl 2 F 2 O): theoretical value: c,69.69; h,3.47; test value: c,69.61; h,3.42.
MALDI-TOF-MS: theoretical value 464.1; experimental value 464.1.
18-5 (10.0 g,21.5 mmol), 18-6 (11.9 g,47.3 mmol), potassium carbonate (5.9 g,43.0 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 18-7 (12.5 g, yield: 89%).
Elemental analysis of the structure (C) 47 H 33 Cl 2 Not): theoretical value: c,68.32; h,4.03; n,1.70; test value: c,68.38; h,3.92; n,1.75.
MALDI-TOF-MS: theoretical value 827.1; experimental value 827.1.
18-7 (10.0 g,15.4 mmol), 18-8 (6.6 g,33.8 mmol), potassium carbonate (4.2 g,30.7 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitate precipitated in the solution was filtered and separated by silica gel column chromatography to give the product 18-9 (9.2 g, yield: 72%).
Elemental analysis of the structure (C) 47 H 29 B 2 Not): theoretical value: c,73.03; h,3.78; n,1.81; test value: c,73.05; h,3.72; n,1.83.
MALDI-TOF-MS: theoretical 775.2; experimental value 775.2.
Reference example 1, starting from 18-9 (8.0 g,9.7 mmol), finally gives the product I-4-24 (3.9 g, yield: 52%).
Elemental analysis structure (C) 47 H 29 B 2 Not): theoretical value: c,73.03; h,3.78; n,1.81; test value: c,73.09; h,3.71; n,1.85.
MALDI-TOF-MS: theoretical 775.2; experimental value 775.2.
Example 19
19-1 (20.0 g,50.7 mmol), 19-2 (15.6 g,60.9 mmol), tetrakis (triphenylphosphine) palladium (4.7 g,4.1 mmol), potassium carbonate (28.1 g,203.0 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 19-3 (16.2 g, yield: 80%).
Elemental analysis of the structure (C) 23 H 23 BclFO 2 ): theoretical value: c,69.64; h,5.84; test value: c,69.68; h,5.82.
MALDI-TOF-MS: theoretical 396.2; experimental 396.2.
19-3 (15.0 g,37.8 mmol), 19-4 (13.9 g,45.4 mmol), tetrakis (triphenylphosphine) palladium (3.5 g,3.0 mmol), potassium carbonate (20.9 g,151.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 19-5 (14.2 g, yield: 84%).
Elemental analysis of the structure (C) 27 H 16 Cl 2 F 2 ): theoretical value: c,72.17; h,3.59; test value: c,72.19; h,3.53.
MALDI-TOF-MS: theoretical value 448.1; experimental value 448.1.
19-5 (10.0 g,22.3 mmol), 19-6 (4.0 g,26.7 mmol), potassium carbonate (6.2 g,44.5 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 19-7 (12.2 g, yield: 86%).
Elemental analysis of the structure (C) 37 H 29 Cl 2 FO): theoretical value: c,76.68; h,5.04; test value: c,76.62; h,5.07.
MALDI-TOF-MS: theoretical value 578.2; experimental value 578.2.
19-7 (10.0 g,17.3 mmol), 19-8 (7.3 g,34.4 mmol), potassium carbonate (4.3 g,31.2 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitate precipitated in the solution was filtered and separated by silica gel column chromatography to give the product 19-9 (9.8 g, yield: 81%).
Elemental analysis of the structure (C) 47 H 38 OP 2 S 2 Se): theoretical value: c,68.52; h,4.65; s,7.78; test value: c,68.56; h,4.61; s,7.79.
MALDI-TOF-MS: theoretical value 824.1; experimental value 824.1.
Reference example 4, starting from 19-9 (10.0 g,12.9 mmol), finally gives the product 19-10 (8.2 g, yield: 77%).
Elemental analysis of the structure (C) 47 H 29 B 2 Not): theoretical value: c,73.03; h,3.78; n,1.81; test value: c,73.05; h,3.72; n,1.83.
MALDI-TOF-MS: theoretical 775.2; experimental value 775.2.
Reference example 4, starting from 19-10 (4.0 g,4.9 mmol), finally gives the product I-4-25 (1.3 g, yield: 34%).
Elemental analysis of the structure (C) 47 H 38 O 3 P 2 Se): theoretical value: c,71.30; h,4.84; test value: c,71.35; h,4.81.
MALDI-TOF-MS: theoretical value 792.2; experimental value 792.2.
Example 20
20-1 (20.0 g,52.6 mmol), 20-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 20-3 (16.6 g, yield: 71%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.52; h,4.79.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
20-3 (15.0 g,33.8 mmol), 20-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 20-5 (15.2 g, yield: 81%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
20-5 (10.0 g,17.9 mmol), 20-6 (12.7 g,39.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (10.4 g,35.9 mmol), sodium t-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent was chromatographed on silica gel to give 20-7 (13.2 g, yield: 71%).
Elemental analysis of the structure (C) 74 H 50 Cl 2 N 2 ): theoretical value: c,85.62; h,4.85; n,2.70; test value: c,85.68; h,4.81; n,2.72.
MALDI-TOF-MS: theoretical value 1036.3; experimental value 1036.3.
Reference example 1, starting from 20-7 (4.0 g,4.9 mmol), finally gives the product I-5-26 (1.3 g, yield: 34%).
Elemental analysis of the structure (C) 74 H 46 B 2 N 2 ): theoretical value: c,90.25; h,4.71; n,2.84; test value: c,90.28; h,4.72; n,2.85.
MALDI-TOF-MS: theoretical value 984.4; experimental value 984.4.
Example 21
21-1 (20.0 g,52.6 mmol), 21-2 (13.2 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 21-3 (16.7 g, yield: 83%).
Elemental analysis of the structure (C) 22 H 21 BClFO 2 ): theoretical value: c,69.05; h,5.53; test value: c,69.08; h,5.47.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
21-3 (15.0 g,39.2 mmol), 21-4 (12.2 g,47.0 mmol), tetrakis (triphenylphosphine) palladium (3.6 g,3.1 mmol), potassium carbonate (21.7 g,156.8 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 21-5 (13.2 g, yield: 77%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24; test value: c,71.78; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
21-5 (10.0 g,23.0 mmol), 21-6 (14.1 g,50.5 mmol), potassium carbonate (6.3 g,45.9 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 21-7 (13.8 g, yield: 86%).
Elemental analysis of the structure (C) 46 H 38 Cl 2 FN): theoretical value: c,79.53; h,5.51; n,2.02; test value: c,79.58; h,5.47; n,2.04.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
21-7 (10.0 g,14.4 mmol), 21-8 (4.8 g,31.7 mmol), potassium carbonate (4.0 g,28.8 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 21-9 (8.3 g, yield: 70%).
Elemental analysis of the structure (C) 54 H 43 Cl 2 NOS): theoretical value: c,78.63; h,5.25; n,1.70; s,3.89; test value: c,78.68; h,5.21; n,1.67; s,3.92.
MALDI-TOF-MS: theoretical 823.2; experimental value 823.2.
Reference example 1, starting from 21-9 (8.0 g,9.7 mmol), finally gives the product I-5-27 (4.2 g, yield: 56%).
Elemental analysis of the structure (C) 54 H 39 B 2 NOS): theoretical value: c,84.06; h,5.09; n,1.82; s,4.16; test value: c,84.12; h,5.07; n,1.89; s,4.13.
MALDI-TOF-MS: theoretical value 771.3; experimental value 771.3.
Example 22
22-1 (20.0 g,35.9 mmol), 22-2 (27.5 g,79.0 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (41.5 g,71.8 mmol), N-diisopropylethylamine (9.3 g,12.5mL,71.8 mmol) and 250mL of 1, 4-dioxane were placed in a 500mL three-necked flask under argon atmosphere, stirred at 105℃for 8 hours and then cooled to room temperature, and the resultant concentrated solution was subjected to silica gel column chromatography to give 22-3 (33.1 g, yield: 84%) as a product.
Elemental analysis of the structure (C) 76 H 44 Cl 2 S 2 ): theoretical value: c,83.58; h,4.06; s,5.87; test value: c,83.62; h,4.00; s,5.82.
MALDI-TOF-MS: theoretical value 1090.2; experimental value 1090.2.
Reference example 1, starting from 22-3 (8.0 g,7.3 mmol), finally gives the product I-5-28 (4.6 g, yield: 60%).
Elemental analysis of the structure (C) 76 H 40 B 2 S 2 ): theoretical value: c,87.87; h,3.88; s,6.17; test value: c,87.87; h,3.88; s,6.17.
MALDI-TOF-MS: theoretical value 1038.3; experimental value 1038.3.
Example 23
To a 500mL three-necked flask, 23-1 (20.0 g,35.9 mmol), 23-2 (22.1 g,79.0 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tris (t-butylphosphinothioborate (41.5 g,71.8 mmol), sodium t-butoxide (9.3 g,12.5mL,71.8 mmol) and 250mL toluene were added under argon atmosphere, and after stirring at 120℃for 8 hours, the mixture was cooled to room temperature, 100mL 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 with anhydrous magnesium sulfate, and the resulting concentrate after removal of the solvent from the organic phase was chromatographed on a silica gel column to give the product 23-3 (33.1 g, yield: 84%).
Elemental analysis of the structure (C) 46 H 38 BrCl 2 N): theoretical value: c,73.12; h,5.07; n,1.85; test value: c,73.15; h,5.02; n,1.88.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
23-3 (20.0 g,26.5 mmol), 23-4 (5.5 g,58.2 mmol), cuprous iodide (0.2 g,1.1 mmol), 2, 6-tetramethyl-3, 5-heptanedione (0.2 g,1.1 mmol), cesium carbonate (17.2 g,52.9 mmol) and 100mLN, N-dimethylformamide were added to a 500mL three-necked flask under argon atmosphere, stirred at 80℃for 8 hours, cooled to room temperature, settled in 500mL water, and the solid precipitated in the solution was filtered, followed by column chromatography on silica gel to obtain the product 23-5 (17.2 g, yield: 85%).
Elemental analysis of the structure (C) 52 H 43 Cl 2 NO): theoretical value: c,81.24; h,5.64; n,1.82; test value: c,81.28; h,5.59; n,1.88.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
Reference example 10, starting from 23-5 (10.0 g,13.0 mmol), finally gives the product I-5-25 (8.5 g, yield: 80%).
Elemental analysis of the structure (C) 52 H 39 NOP 2 S 2 ): theoretical value: c,76.17; h,4.79; n,1.71; s,7.82; test value: 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
24-1 (20.0 g,52.6 mmol), 24-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 24-3 (15.2 g, yield: 75%).
Elemental analysis of the structure (C) 22 H 21 BClFO 2 ): theoretical value: c,69.05; h,5.53; test value: c,69.08; h,5.58.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
24-3 (15.0 g,39.2 mmol), 24-4 (17.3 g,47.0 mmol), tetrakis (triphenylphosphine) palladium (3.6 g,3.1 mmol), potassium carbonate (21.7 g,156.8 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give 24-5 (14.7 g, yield: 67%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.49.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
24-5 (10.0 g,17.9 mmol), 24-6 (6.8 g,15.7 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (10.4 g,35.9 mmol), sodium tert-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 24-7 (9.8 g, yield: 79%).
Elemental analysis of the structure (C) 46 H 38 BrCl 2 N): theoretical value: c,73.12; h,5.07; n,1.85; test value: c,73.15; h,5.02; n,1.88.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
24-7 (9.0 g,13.1 mmol), 24-8 (6.8 g,15.7 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.5 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (7.6 g,26.2 mmol), sodium tert-butoxide (2.5 g,26.2 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 24-9 (10.2 g, 75% yield).
Elemental analysis of the structure (C) 73 H 62 Cl 2 N 2 ): theoretical value: c,84.42; h,6.08; n,2.68; test value: c,84.39; h,6.12; n,2.62.
MALDI-TOF-MS: theoretical value 1036.4; experimental value 1036.4.
Reference example 1, starting from 24-9 (8.0 g,7.7 mmol), finally gives the product I-6-11 (3.9 g, yield: 51%).
Elemental analysis structure (C) 73 H 58 B 2 N 2 ): theoretical value: c,89.02; h,5.94; n,2.84; test value: c,89.12; h,5.91; n,2.80.
MALDI-TOF-MS: theoretical value 984.5; experimental value 984.5.
Example 25
Into a 500mL three-necked flask, 25-1 (10.0 g,17.9 mmol), 25-2 (2.4 g,21.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (20.8 g,35.9 mmol), N-diisopropylethylamine (4.6 g,6.3mL,35.9 mmol) and 150mL 1, 4-dioxane were charged under argon atmosphere, and after stirring at 105℃for 8 hours, the mixture was cooled to room temperature, and the resultant concentrated solution was subjected to silica gel column chromatography to give 25-3 (8.2 g, yield: 78%).
Elemental analysis of the structure (C) 32 H 19 BrCl 2 S is 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.
To a 500mL three-necked flask, 25-3 (8.0 g,13.6 mmol), 25-4 (7.1 g,16.4 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.5 mmol), tri-tert-butylphosphinothioborate (7.9 g,27.3 mmol), sodium tert-butoxide (2.6 g,27.3 mmol) and 250mL toluene were added under argon atmosphere, the mixture was 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 resultant concentrated solution was separated by silica gel column chromatography to give 25-5 (9.3 g, yield: 73%).
Elemental analysis of the structure (C) 64 H 51 Cl 2 NS): theoretical value C,82.03; h,5.49; n,1.49; s,3.42 test value C,82.08; h,5.42; n,1.42; s,3.47.
MALDI-TOF-MS: theoretical value 935.3; experimental value 935.3.
Reference example 1, starting from 25-5 (8.0 g,8.5 mmol), finally gives the product I-6-12 (2.3 g, yield: 30%).
Elemental analysis structure (C) 64 H 47 B 2 NS): theoretical C,86.98; h,5.36; n,1.58; s,3.63 test C,86.92; h,5.38; n,1.51; s,3.67.
MALDI-TOF-MS: theoretical value 883.4; experimental value 883.4.
Example 26
26-1 (20.0 g,52.6 mmol), 26-2 (20.0 g,63.1 mmol), tetrakis (triphenylphosphine) palladium (4.9 g,4.2 mmol), potassium carbonate (29.1 g,210.5 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 26-3 (16.6 g, yield: 71%).
Elemental analysis of the structure (C) 22 H 21 BBrClO 2 ): theoretical value: c,59.57; h,4.77; test value: c,59.52; h,4.79.
MALDI-TOF-MS: theoretical 442.1; experimental 442.1.
26-3 (15.0 g,33.8 mmol), 26-4 (14.9 g,40.6 mmol), tetrakis (triphenylphosphine) palladium (3.1 g,2.7 mmol), potassium carbonate (18.7 g,135.3 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 26-5 (15.2 g, yield: 81%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
26-5 (20.0 g,35.9 mmol), 26-6 (9.1 g,43.1 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (20.8 g,71.8 mmol), sodium t-butoxide (6.9 g,71.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, and after stirring at 120℃for 8 hours, cooled to room temperature, and the organic phase was freed from the solvent to give a concentrated solution of the product 26-7 (18.2 g, yield: 81%) by silica gel column chromatography.
Elemental analysis of the structure (C) 40 H 26 Cl 2 FNO): theoretical value: c,76.68; h,4.18; n,2.24; test value: c,76.69; h,4.166; n,2.21.
MALDI-TOF-MS: theoretical value 625.1; experimental value 625.1.
26-7 (10.0 g,16.0 mmol), 26-8 (4.0 g,19.2 mmol), tris (dibenzylideneacetone) dipalladium (0.6 g,0.6 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (9.3 g,31.9 mmol), sodium t-butoxide (3.1 g,31.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, and the organic phase was freed from the solvent to give a concentrated solution, which was subjected to column chromatography on silica gel to give the product 26-9 (11.1 g, yield: 85%).
Elemental analysis of the structure (C) 55 H 42 Cl 2 N 2 O): theoretical value: c,80.77; h,5.18; n,3.43; test value: c,80.78; h,5.16; n,3.41.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
Reference example 1, starting from 26-9 (8.0 g,9.8 mmol), finally gives the product I-7-29 (3.2 g, yield: 43%).
Elemental analysis structure (C) 55 H 38 B 2 N 2 O): theoretical value: c,86.41; h,5.01; n,3.66; test value: c,86.37; h,5.05; n,3.68.
MALDI-TOF-MS: theoretical value 764.3; experimental value 764.3.
Example 27
27-1 (20.0 g,45.1 mmol), 27-2 (14.0 g,54.1 mmol), tetrakis (triphenylphosphine) palladium (4.2 g,3.6 mmol), potassium carbonate (24.9 g,180.4 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give the product 27-3 (18.2 g, yield: 81%).
Elemental analysis of the structure (C) 26 H 14 BrCl 2 F) The method comprises the following steps Theoretical value: c,62.94; h,2.84; test value: c,62.95; h,2.81.
MALDI-TOF-MS: theoretical value 494.0; experimental value 494.0.
27-3 (10.0 g,20.2 mmol), 27-4 (4.8 g,24.2 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.8 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (11.7 g,40.3 mmol), sodium tert-butoxide (3.9 g,40.3 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 27-5 (11.1 g, yield: 90%).
Elemental analysis of the structure (C) 47 H 35 Cl 2 NSe): theoretical value: c,73.92; h,4.62; n,1.83; test value: c,73.94; h,4.65; n,1.79.
MALDI-TOF-MS: theoretical value 763.1; experimental value 763.1.
27-5 (10.0 g,16.3 mmol), 27-6 (6.1 g,35.9 mmol), potassium carbonate (4.5 g,32.6 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 27-7 (10.1 g, yield: 81%).
Elemental analysis of the structure (C) 46 H 38 Cl 2 FN): theoretical value: c,79.53; h,5.51; n,2.02; test value: c,79.58; h,5.47; n,2.04.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
Reference example 1, starting from 27-7 (8.0 g,10.5 mmol), finally gives the product I-7-30 (2.9 g, yield: 39%).
Elemental analysis structure (C) 47 H 31 B 2 NSe): theoretical value: c,79.47; h,4.40; n,1.97; test value: c,79.52; h,4.38; n,2.02.
MALDI-TOF-MS: theoretical value 711.2; experimental value 711.2.
Example 28
Reference example 4, starting with 28-1 (10.0 g,13.1 mmol), finally gives product 28-2 (8.7 g, yield: 82%).
Elemental analysis structure (C) 47 H 31 NP 2 S 2 Se): theoretical value: c,69.28; h,3.83; n,1.72; s,7.87; test value: c,69.32; h,3.81; n,1.76; s,7.81.
MALDI-TOF-MS: theoretical value 815.1; experimental value 815.1.
Reference example 4, starting from 28-2 (4.0 g,4.9 mmol), finally gives the product I-7-31 (2.8 g, yield: 73%).
Elemental analysis structure (C) 47 H 31 NOP 2 Se): theoretical value: c,73.63; h,4.08; n,1.83; test value: c,73.65; h,4.02; n,1.79.
MALDI-TOF-MS: theoretical 767.1; experimental 767.1.
Example 29
29-1 (10.0 g,17.9 mmol), 29-2 (6.1 g,21.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (10.4 g,35.9 mmol), sodium t-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel to give 29-3 (10.3 g, yield: 76%).
Elemental analysis of the structure (C) 46 H 40 Cl 2 FN): theoretical value: c,72.92; h,5.32; n,1.85; test value: c,72.94; h,5.28; n,1.87.
MALDI-TOF-MS: theoretical value 755.2; experimental value 755.2.
29-3 (10.0 g,13.2 mmol), 29-4 (2.7 g,15.8 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.5 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (7.7 g,26.4 mmol), sodium tert-butoxide (2.5 g,26.4 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 29-5 (8.2 g, yield: 73%).
Elemental analysis of the structure (C) 58 H 50 Cl 2 N 2 ): theoretical value: c,82.35; h,5.96; n,3.31; test value: c,82.38; h,5.91; n,3.33.
MALDI-TOF-MS: theoretical value 844.3; experimental value 844.3.
Reference example 1, starting from 29-5 (4.0 g,4.7 mmol), finally gives the product I-8-7 (3.1 g, yield: 83%).
Elemental analysis structure (C) 58 H 46 B 2 N 2 ): theoretical value: c,87.89; h,5.85; n,3.53; test value: c,87.86; h,5.89; n,3.49.
MALDI-TOF-MS: theoretical value 792.4; experimental value 792.4.
Example 30
30-1 (30.0 g,78.9 mmol), 30-2 (19.8 g,94.7 mmol), tetrakis (triphenylphosphine) palladium (7.3 g,6.3 mmol), potassium carbonate (43.6 g,315.7 mmol), 50mL of water, 50mg of aliquat-336 and 300mL of toluene were put into a 500mL three-necked flask under argon atmosphere, 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 3 times with deionized water (200 mL. Times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after the solvent removal of the organic phase was subjected to silica gel column chromatography to obtain a product 30-3 (28.2 g, yield: 93%).
Elemental analysis of the structure (C) 22 H 21 BClFO 2 ): theoretical value: c,69.05; h,5.53; test value: c,69.08; h,5.49.
MALDI-TOF-MS: theoretical value 382.1; experimental value 382.1.
30-3 (28.0 g,73.2 mmol), 30-4 (22.8 g,87.8 mmol), tetrakis (triphenylphosphine) palladium (6.8 g,5.9 mmol), potassium carbonate (40.5 g,292.7 mmol), 50mL of water, 50mg of aliquat-336 and 300mL of toluene were added to a 500mL three-necked flask under argon atmosphere, 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 3 times with deionized water (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 column chromatography on silica gel to obtain a product 30-5 (25.3 g, yield: 79%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24; test value: c,71.78; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
30-5 (12.0 g,27.6 mmol), 30-6 (7.6 g,33.1 mmol), potassium carbonate (15.2 g,110.3 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 30-7 (14.3 g, yield: 81%).
Elemental analysis of the structure (C) 41 H 29 Cl 2 FS): theoretical value: c,76.51; h,4.54; s,4.98; test value: c,76.47; h,4.51; s,5.02.
MALDI-TOF-MS: theoretical value 642.1; experimental value 642.1.
30-7 (12.0 g,18.6 mmol), 30-8 (2.5 g,22.4 mmol), potassium carbonate (10.3 g,74.6 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 30-9 (12.2 g, yield: 89%).
Elemental analysis of the structure (C) 47 H 34 Cl 2 S 2 ): theoretical value: c,76.93; h,4.67; s,8.74; test value: c,76.96; h,4.61; s,8.77.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
Reference example 1, starting from 30-9 (4.0 g,5.5 mmol), finally gives the product I-8-8 (2.9 g, yield: 78%).
Elemental analysis structure (C) 47 H 30 B 2 S 2 ): theoretical value: c,82.96; h,4.44; s,9.42; test value: c,82.98; h,4.40; s,9.39.
MALDI-TOF-MS: theoretical 680.2; experimental value 680.2.
Example 31
31-1 (20.0 g,40.5 mmol), 31-2 (15.4 g,48.6 mmol), tetrakis (triphenylphosphine) palladium (3.7 g,3.2 mmol), potassium carbonate (22.4 g,162.1 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 31-3 (18.6 g, yield: 82%).
Elemental analysis of the structure (C) 22 H 19 BBr 2 Cl 2 O 2 ): theoretical value: c,47.45; h,3.44; test value: c,47.48; h,3.41.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
31-3 (15.0 g,26.9 mmol), 31-4 (6.7 g,32.3 mmol), tetrakis (triphenylphosphine) palladium (2.5 g,2.2 mmol), potassium carbonate (14.9 g,107.7 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 31-5 (11.2 g, yield: 75%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.49.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
31-5 (10.0 g,17.9 mmol), 31-6 (4.6 g,21.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tri-tert-butylphosphinothioborate (10.4 g,35.9 mmol), sodium tert-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 31-7 (8.2 g, yield: 56%).
Elemental analysis of the structure (C) 56 H 46 Cl 2 N 2 ): theoretical value: c,82.24; h,5.67; n,3.43; test value: c,82.28; h,5.61; n,3.45.
MALDI-TOF-MS: theoretical value 816.3; experimental value 816.3.
Reference example 1, starting from 31-7 (8.0 g,9.8 mmol), finally gives the product II-1-10 (2.9 g, yield: 78%).
Elemental analysis structure (C) 56 H 42 B 2 N 2 ): theoretical value: c,87.97; h,5.54; n,3.66; test value: c,87.98; h,5.51; n,3.69.
MALDI-TOF-MS: theoretical value 764.4; experimental value 764.4.
Example 32
Under argon atmosphere, 32-1 (20.0 g,35.9 mmol), 32-2 (12.0 g,43.1 mmol), tris (dibenzylideneacetone) dipalladium (1.3 g,1.4 mmol), tri-tert-butylphosphinothioborate (20.8 g,71.8 mmol), sodium tert-butoxide (6.9 g,71.8 mmol) and 250mL toluene were added to a 500mL three-necked flask, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 32-3 (22.8 g, 84% yield).
Elemental analysis structure (C) 46 H 38 BrCl 2 N): theoretical value: c,73.12; h,5.07; n,1.85; test value: c,73.18; h,5.02; n,1.86.
MALDI-TOF-MS: theoretical value 753.2; experimental value 753.2.
Under argon atmosphere, 32-3 (10.0 g,13.2 mmol), 32-4 (3.6 g,15.9 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.5 mmol), tri-tert-butylphosphinothioborate (7.7 g,26.5 mmol), sodium tert-butoxide (2.5 g,26.5 mmol) and 250mL toluene were added to a 500mL three-necked flask, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 32-5 (9.8 g, 82% yield).
Element separationAnalysis structure (C) 60 H 48 Cl 2 N 2 S): theoretical value: c,80.07; h,5.38; n,3.11; s,3.56; test value: c,80.09; h,5.32; n,3.05; s,3.59.
MALDI-TOF-MS: theoretical value 898.3; experimental value 898.3.
Reference example 1, starting from 32-5 (8.0 g,8.9 mmol), finally gives the product II-1-11 (2.9 g, yield: 39%).
Elemental analysis structure (C) 60 H 44 B 2 N 2 S): theoretical value: c,85.11; h,5.24; n,3.31; s,3.79; test value: c,85.15; h,5.21; n,3.35; s,3.83.
MALDI-TOF-MS: theoretical value 846.3; experimental value 846.3.
Example 33
33-1 (20.0 g,35.9 mmol), 33-2 (16.8 g,79.0 mmol), cuprous iodide (0.2 g,1.1 mmol), 2, 6-tetramethyl-3, 5-heptanedione (0.2 g,1.1 mmol), cesium carbonate (17.2 g,52.9 mmol) and 100mLN, N-dimethylformamide were added to a 500mL three-necked flask under 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 the product 33-3 (15.2 g, 83% yield) was obtained by silica gel column chromatography.
Elemental analysis structure (C) 41 H 29 BrCl 2 O): theoretical value: c,71.53; h,4.25; test value: c,71.58; h,4.21.
MALDI-TOF-MS: theoretical value 686.1; experimental value 686.1.
33-3 (10.0 g,13.2 mmol), 33-4 (3.6 g,17.4 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.6 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (8.4 g,29.0 mmol), sodium t-butoxide (2.8 g,29.0 mmol) and 250mL toluene were added to a 500mL three-necked flask under an argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL 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 resulting concentrated solution was separated by silica gel column chromatography to give a product 33-5 (8.6 g, yield: 72%).
Elemental analysis structure (C) 56 H 43 Cl 2 NO): theoretical value: c,82.34; h,5.31; cl,8.68; n,1.71; test value: c,82.37; h,5.28; cl,8.69; n,1.68.
MALDI-TOF-MS: theoretical value 815.3; experimental value 815.3.
Reference example 1, starting from 33-5 (8.0 g,9.8 mmol), finally gives the product II-1-12 (3.3 g, yield: 44%).
Elemental analysis structure (C) 56 H 39 B 2 NO): theoretical value: c,88.09; h,5.15; b,2.83; n,1.83; test value: 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
34-1 (20.0 g,46.2 mmol), 34-2 (12.5 g,48.6 mmol), tetrakis (triphenylphosphine) palladium (3.7 g,3.2 mmol), potassium carbonate (22.4 g,162.1 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 34-3 (15.2 g, yield: 86%).
Elemental analysis of the structure (C) 22 H 19 BBrCl 2 FO 2 ): theoretical value: c,53.27; h,3.86; test value: c,53.28; h,3.82.
MALDI-TOF-MS: theoretical value 494.0; experimental value 494.0.
34-3 (15.0 g,34.5 mmol), 34-4 (8.6 g,41.4 mmol), tetrakis (triphenylphosphine) palladium (3.2 g,2.8 mmol), potassium carbonate (19.1 g,137.9 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 34-5 (12.3 g, yield: 82%).
Elemental analysis of the structure (C) 26 H 14 BrCl 2 F) The method comprises the following steps Theoretical value: c,62.94; h,2.84; test value: c,62.98; h,2.82.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
34-5 (10.0 g,23.0 mmol), 34-6 (9.6 g,27.6 mmol), tris (dibenzylideneacetone) dipalladium (0.8 g,0.9 mmol), tri-tert-butylphosphinothioborate (13.3 g,45.9 mmol), sodium tert-butoxide (4.4 g,45.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 34-7 (12.7 g, yield: 85%).
Elemental analysis structure (C) 50 H 30 Cl 2 FNSi): theoretical value: c,78.73; h,3.96; n,1.84; test value: c,78.78; h,3.92; n,1.87.
MALDI-TOF-MS: theoretical value 761.2; experimental value 761.2.
34-7 (10.0 g,13.1 mmol), 34-8 (4.5 g,28.8 mmol), potassium carbonate (3.6 g,26.2 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol for sedimentation, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give 34-9 (9.2 g, yield: 78%).
Elemental analysis of the structure (C) 56 H 35 Cl 2 NSeSi): theoretical value: c,74.75; h,3.92; n,1.56; test value: c,74.78; h,3.86; n,1.58.
MALDI-TOF-MS: theoretical value 899.1; experimental value 899.1.
Reference example 1, starting from 34-9 (8.0 g,8.9 mmol), finally gives the product II-1-13 (3.2 g, yield: 43%).
Elemental analysis structure (C) 56 H 31 B 2 NSeSi): theoretical value: c,79.45; h,3.69; n,1.65; test value: c,79.51; h,3.72; n,1.68.
MALDI-TOF-MS: theoretical value 847.2; experimental value 847.2.
Example 35
35-1 (20.0 g,46.2 mmol), 35-2 (14.2 g,55.5 mmol), tetrakis (triphenylphosphine) palladium (4.3 g,3.7 mmol), potassium carbonate (25.6 g,185.0 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 35-3 (18.2 g, yield: 90%).
Elemental analysis of the structure (C) 22 H 19 BCl 2 F 2 O 2 ): theoretical value: c,60.73; h,4.40; test value: c,60.78; h,4.37.
MALDI-TOF-MS: theoretical 434.1; experimental 434.1.
35-3 (15.0 g,34.5 mmol), 35-4 (8.6 g,41.4 mmol), tetrakis (triphenylphosphine) palladium (3.2 g,2.8 mmol), potassium carbonate (19.1 g,137.9 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 35-5 (11.4 g, yield: 76%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24; test value: c,71.78; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
35-5 (10.0 g,23.0 mmol), 35-6 (3.0 g,50.5 mmol), potassium carbonate (6.3 g,45.9 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 35-7 (10.2 g, yield: 84%).
Elemental analysis of the structure (C) 32 H 19 Cl 2 FS): theoretical value: c,73.15; h,3.64; s,6.10; test value: c,73.18; h,3.61; s,6.07.
MALDI-TOF-MS: theoretical value 524.1; experimental value 524.1.
35-7 (10.0 g,19.0 mmol), 35-8 (7.8 g,22.8 mmol), potassium carbonate (5.3 g,38.1 mmol) and 250-mLN-methylpyrrolidone were put into a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give 35-9 (13.5 g, yield: 84%).
Elemental analysis of the structure (C) 53 H 33 Cl 2 N 3 S 2 ): theoretical value: c,75.17; h,3.93; n,4.96; s,7.57; test value: c,75.19; h,3.91; n,4.93; s,7.58.
MALDI-TOF-MS: theoretical value 845.2; experimental value 845.2.
Reference example 4, starting from 35-9 (8.0 g,9.4 mmol), finally gives the product II-1-14 (3.2 g, yield: 38%).
Elemental analysis structure (C) 53 H 29 N 3 P 2 S 4 ): theoretical value: c,70.89; h,3.26; n,4.68; s,14.28; test value: 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 (20.0 g,46.2 mmol), 36-2 (11.6 g,55.5 mmol), tetrakis (triphenylphosphine) palladium (4.3 g,3.7 mmol), potassium carbonate (25.6 g,185.0 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was subjected to column chromatography on silica gel to give 36-3 (15.4 g, yield: 77%).
Elemental analysis of the structure (C) 22 H 19 BCl 2 F 2 O 2 ): theoretical value: c,60.73; h,4.40; test value: c,60.78; h,4.37.
MALDI-TOF-MS: theoretical 434.1; experimental 434.1.
36-3 (16.8 g,38.7 mmol), 36-4 (9.6 g,46.4 mmol), tetrakis (triphenylphosphine) palladium (3.6 g,3.1 mmol), potassium carbonate (21.4 g,154.6 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 36-5 (13.5 g, yield: 80%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24; test value: c,71.78; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
36-5 (10.0 g,23.0 mmol), 36-6 (7.7 g,27.6 mmol), potassium carbonate (6.3 g,45.9 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 36-7 (12.5 g, yield: 78%).
Elemental analysis of the structure (C) 46 H 38 Cl 2 FN): theoretical value: c,79.53; h,5.51; n,2.02; test value: c,79.58; h,5.42; n,2.12.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
36-7 (8.0 g,11.5 mmol), 36-8 (1.3 g,13.8 mmol), potassium carbonate (3.2 g,23.0 mmol) and 250-mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 2000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 36-9 (7.8 g, yield: 88%).
Elemental analysis of the structure (C) 52 H 43 Cl 2 NO): theoretical value: c,81.24; h,5.64; n,1.82; test value: c,81.26; h,5.61; n,1.79.
MALDI-TOF-MS: theoretical value 767.3; experimental value 767.3.
Reference example 1, starting from 36-9 (8.0 g,10.4 mmol), finally gives the product II-2-18 (6.1 g, yield: 82%).
Elemental analysis structure (C) 52 H 39 B 2 NO): theoretical value: c,87.29; h,5.49; n,1.96; test value: c,87.32; h,5.42; n,2.05.
MALDI-TOF-MS: theoretical value 715.3; experimental value 715.3.
Example 37
37-1 (20.0 g,28.8 mmol), 37-2 (6.6 g,69.0 mmol), potassium carbonate (8.0 g,57.6 mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 1000mL methanol to settle, and the precipitated precipitate was filtered and separated by silica gel column chromatography to obtain a product 37-3 (18.2 g, yield: 82%).
Elemental analysis structure (C) 56 H 44 Cl 2 S 2 ): theoretical value: c,78.95; h,5.21; s,7.53; test value: c,78.99; h,5.15; s,7.59.
MALDI-TOF-MS: theoretical value 850.2; experimental value 850.2.
Reference example 1, starting from 37-3 (10.0 g,13.0 mmol), finally gives the product II-2-19 (2.9 g, yield: 31%).
Elemental analysis structure (C) 56 H 40 B 2 S 2 ): theoretical value: c,84.22; h,5.05; s,8.03; test value: c,84.28; h,5.01; s,7.96.
MALDI-TOF-MS: theoretical value 798.3; experimental value 798.3.
Example 38
38-1 (20.0 g,40.5 mmol), 38-2 (15.4 g,48.6 mmol), tetrakis (triphenylphosphine) palladium (3.7 g,3.2 mmol), potassium carbonate (22.4 g,162.2 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 38-3 (18.2 g, yield: 81%).
Elemental analysis of the structure (C) 22 H 19 BBr 2 Cl 2 O 2 ): theoretical value: c,47.45; h,3.44; test value: c,47.48; h,3.42.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
38-3 (15.0 g,26.9 mmol), 38-4 (8.2 g,32.3 mmol), tetrakis (triphenylphosphine) palladium (2.5 g,2.2 mmol), potassium carbonate (14.9 g,107.8 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 38-5 (11.2 g, yield: 75%).
Elemental analysis of the structure (C) 46 H 40 Cl 2 FN): theoretical value: c,79.30; h,5.79; n,2.01; test value: c,79.35; h,5.72; n,2.08.
MALDI-TOF-MS: theoretical value 695.3; experimental value 695.3.
38-5 (10.0 g,17.9 mmol), 38-6 (6.1 g,21.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tri-tert-butylphosphinothioborate (10.4 g,35.9 mmol), sodium tert-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 38-7 (10.7 g, yield: 84%).
Elemental analysis structure (C) 46 H 40 Cl 2 FN): theoretical value: c,79.30; h,5.79; n,2.01; test value: c,79.27; h,5.71; n,2.08.
MALDI-TOF-MS: theoretical value 695.3; experimental value 695.3.
38-7 (10.0 g,10.5 mmol), 38-8 (4.8 g,17.2 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.6 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (8.3 g,28.7 mmol), sodium tert-butoxide (2.8 g,28.7 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 38-9 (11.2 g, 82% yield).
Elemental analysis structure (C) 66 H 64 Cl 2 N 2 ): theoretical value: c,82.91; h,6.75; n,2.93; test value: c,82.98; h,6.72; n,2.91.
MALDI-TOF-MS: theoretical value 954.4; experimental value 954.4.
Reference example 4, starting from 38-9 (10.0 g,10.5 mmol), finally gives the product 38-10 (7.5 g, yield: 71%).
Elemental analysis structure (C) 66 H 60 N 2 P 2 S2): theoretical value: c,78.70; h,6.00; n,2.78; s,6.37; test value: c,78.68; h,6.02; n,2.72; s,6.31.
MALDI-TOF-MS: theoretical value 1006.4; experimental value 1006.4.
Reference example 4, starting from 38-10 (4.0 g,4.0 mmol), finally gives the product II-2-20 (1.3 g, yield: 34%).
Elemental analysis structure (C) 66 H 60 N 2 O 2 P 2 ): theoretical value: c,81.29; h,6.20; n,2.87; test value: c,81.32; h,6.26; n,2.82.
MALDI-TOF-MS: theoretical value 974.4; experimental value 974.4.
Example 39
39-1 (20.0 g,40.5 mmol), 39-2 (15.4 g,48.6 mmol), tetrakis (triphenylphosphine) palladium (3.7 g,3.2 mmol), potassium carbonate (22.4 g,162.1 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 39-3 (17.2 g, yield: 76%).
Elemental analysis of the structure (C) 22 H 19 BBr 2 Cl 2 O 2 ): theoretical value: c,47.45; h,3.44; test value: c,47.48; h,3.42.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
39-3 (15.0 g,26.9 mmol), 39-4 (6.7 g,32.3 mmol), tetrakis (triphenylphosphine) palladium (2.5 g,2.2 mmol), potassium carbonate (14.9 g,107.7 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 39-5 (11.2 g, yield: 75%).
Elemental analysis of the structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.08; h,2.51.
MALDI-TOF-MS: theoretical value 553.9; experimental value 553.9.
39-5 (10.0 g,17.9 mmol), 39-6 (8.2 g,21.5 mmol), tris (dibenzylideneacetone) dipalladium (0.7 g,0.7 mmol), tri-tert-butylphosphinothioborate (10.4 g,35.9 mmol), sodium tert-butoxide (3.4 g,35.9 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on silica gel to give 39-7 (10.5 g, yield: 73%).
Elemental analysis structure (C) 54 H 44 BrCl 2 N): theoretical value: c,75.62; h,5.17; n,1.63; test value: c,75.68; h,5.12; n,1.65.
MALDI-TOF-MS: theoretical value 855.2; experimental value 855.2.
39-7 (10.0 g,12.5 mmol), 39-8 (4.2 g,15.1 mmol), tris (dibenzylideneacetone) dipalladium (0.5 g,0.5 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (7.3 g,25.1 mmol), sodium t-butoxide (2.4 g,25.1 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel column to give 39-9 (11.2 g, yield: 94%).
Elemental analysis structure (C) 66 H 64 Cl 2 N 2 ): theoretical value: c,82.91; h,6.75; n,2.93; test value: c,82.98; h,6.72; n,2.91.
MALDI-TOF-MS: theoretical value 954.4; experimental value 954.4.
Reference example 1, starting from 39-9 (10.0 g,10.6 mmol), finally gives the product II-3-6 (2.9 g, yield: 31%).
Elemental analysis structure (C) 56 H 40 B 2 S 2 ): theoretical value: c,84.22; h,5.05; s,8.03; test value: c,84.28; h,5.01; s,7.96.
MALDI-TOF-MS: theoretical value 798.3; experimental value 798.3.
Example 40
40-1 (20.0 g,46.2 mmol), 40-2 (11.6 g,55.5 mmol), tetrakis (triphenylphosphine) palladium (4.3 g,3.7 mmol), potassium carbonate (25.6 g,185.0 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 40-3 (18.2 g, yield: 90%).
Elemental analysis of the structure (C) 22 H 19 BCl 2 F 2 O 2 ): theoretical value: c,60.73; h,4.40; test value: c,60.75; h,4.37.
MALDI-TOF-MS: theoretical 434.1; experimental 434.1.
40-3 (15.0 g,34.5 mmol), 40-4 (8.6 g,41.4 mmol), tetrakis (triphenylphosphine) palladium (3.2 g,2.8 mmol), potassium carbonate (19.1 g,137.9 mmol), 40mL of water, 50mg of aliquat-336 and 200mL of toluene were put into a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL of ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give 40-5 (12.4 g, yield: 83%).
Elemental analysis of the structure (C) 26 H 14 Cl 2 F 2 ): theoretical value: c,71.74; h,3.24;test value: c,71.78; h,3.21.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
40-5 (8.0 g,18.4 mmol), 40-6 (4.5 g,22.1 mmol), potassium carbonate (5.1 g,36.8 mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, reacted at 180℃for 8 hours, cooled to room temperature, and the mother liquor was poured into 1000mL methanol for sedimentation, and the precipitated precipitate was filtered and separated by silica gel column chromatography to give a product 40-7 (8.3 g, yield: 73%).
Elemental analysis structure (C) 32 H 19 Cl 2 FTe): theoretical value: c,61.89; h,3.08; test value: c,61.82; h,3.11.
MALDI-TOF-MS: theoretical value 622.0; experimental value 622.0.
40-7 (10.0 g,16.1 mmol), 40-8 (5.4 g,19.3 mmol), tris (dibenzylideneacetone) dipalladium (0.6 g,0.6 mmol), tris (t-butylphosphinothioyl) tetrafluoroborate (9.3 g,32.2 mmol), sodium t-butoxide (3.1 g,32.2 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours and then cooled to room temperature, and the organic phase was freed from the solvent to obtain a concentrated solution, which was subjected to column chromatography on silica gel to give a product 40-9 (12.8 g, yield: 90%).
Elemental analysis structure (C) 52 H 45 Cl 2 NTe): theoretical value: c,70.78; h,5.14; n,1.59; test value: 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.
Reference example 1, starting from 40-9 (10.0 g,11.3 mmol), finally gives the product II-3-7 (1.1 g, yield: 47%).
Elemental analysis structure (C) 52 H 41 B2 NTe): theoretical value: c,75.33; h,4.98; n,1.69; test value: c,75.33; h,4.98; n,1.69.
MALDI-TOF-MS: theoretical value 831.3; experimental value 831.3.
Example 41
41-1 (20.0 g,45.9 mmol), 41-2 (11.0 g,55.1 mmol), potassium carbonate (12.7 g,91.9 mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL deionized water, the precipitated solid was filtered and washed with methanol, and then the product 41-3 (22.4 g, yield: 79%) was obtained by silica gel column chromatography.
Elemental analysis structure (C) 38 H 21 Cl 2 FOS): theoretical value: c,74.15; h,3.44; s,5.21; test value: c,74.25; h,3.42; s,5.25.
MALDI-TOF-MS: theoretical 614.1 experimental 614.1.
41-3 (20.0 g,32.5 mmol), 41-4 (5.9 g,39.0 mmol), potassium carbonate (9.0 g,65.0 mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL deionized water, the precipitated solid was filtered and washed with methanol, and then separated by silica gel column chromatography to obtain the product 41-5 (18.2 g, yield: 75%).
Elemental analysis structure (C) 47 H 32 Cl 2 OS 2 ): theoretical value: c,75.49; h,4.31; s,8.57; test value: c,75.53; h,4.28; s,9.04.
MALDI-TOF-MS: theoretical value 746.1; experimental value 746.1.
Reference example 1, starting from 41-5 (10.0 g,13.4 mmol), finally gives the product II-3-8 (4.2 g, yield: 45%).
Elemental analysis structure (C) 47 H 28 B 2 OS 2 ): theoretical value: c,81.29; h,4.06; s,9.23; test value: c,81.32; h,4.04; s,9.21.
MALDI-TOF-MS: theoretical 694.2; experimental 694.2.
Example 42
42-1 (20.0 g,42.1 mmol), 42-2 (10.6 g,50.6 mmol), tetrakis (triphenylphosphine) palladium (3.9 g,3.4 mmol), potassium carbonate (23.3 g,168.6 mmol), 50mg aliquat-336, 40mL deionized water and 100mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 42-3 (17.7 g, 88% yield).
Elemental analysis structure (C) 25 H 25 BCl 2 F 2 O 2 ): theoretical value: c,62.93; h,5.28; test value: c,62.98; h,5.22.
MALDI-TOF-MS: theoretical value 476.1; experimental value 476.1.
42-3 (15.0 g,31.4 mmol), 42-4 (9.4 g,37.7 mmol), tetrakis (triphenylphosphine) palladium (2.9 g,2.5 mmol), potassium carbonate (17.4 g,125.7 mmol), 50mg aliquat-336, 40mL deionized water and 100mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 150mL ethyl acetate was added, the organic phase was washed 3 times with deionized water (100 mL. Times.3), then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after removal of the solvent from the organic phase was separated by silica gel column chromatography to give the product 42-5 (13.3 g, yield 81%).
Elemental analysis structure (C) 32 H 26 Cl 2 F 2 ): theoretical value: c,73.99; h,5.05; test value: c,74.06; h,5.01
MALDI-TOF-MS: theoretical value 518.1; experimental value 518.1.
42-5 (15.0 g,28.9 mmol), 42-6 (10.0 g,34.7 mmol), tris (dibenzylideneacetone) dipalladium (1.1 g,1.2 mmol), tri-tert-butylphosphinothioyl tetrafluoroborate (16.8 g,57.8 mmol), sodium tert-butoxide (5.5 g,57.8 mmol) and 250mL toluene were added to a 500mL three-necked flask under argon atmosphere, stirred at 120℃for 8 hours, cooled to room temperature, 100mL ethyl acetate was added to the reaction solution, the organic phase was washed 3 times with deionized water (100 mL. Times.3), dried over anhydrous magnesium sulfate, and the resulting concentrated solution after removal of the solvent was chromatographed on a silica gel to give 42-7 (19.2 g, yield: 85%).
Elemental analysis structure (C) 52 H 41 Cl 2 FN 2 ): theoretical value: c,79.68; h,5.27; n,3.57; test value: c,79.69; h,5.22; n,3.59
MALDI-TOF-MS: theoretical value 782.3; experimental value 782.3.
42-7 (8.0 g,10.2 mmol), 42-8 (1.2 g,12.2 mmol), potassium carbonate (2.8 g,20.4 mmol) and 100 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, then cooled to room temperature, the reaction solution was settled in 500mL deionized water, the precipitated solid was filtered and washed with methanol, and then the product 42-9 (5.6 g, yield: 64%) was obtained by silica gel column chromatography.
Elemental analysis structure (C) 58 H 46 Cl 2 N 2 O): theoretical value: c,81.20; h,5.40; n,3.27; test value: c,81.25; h,5.32; n,3.29.
MALDI-TOF-MS: theoretical value 856.3; experimental value 856.3.
Reference example 1, starting from 42-9 (5.0 g,5.8 mmol), finally gives the product II-4-7 (3.1 g, yield: 66%).
Elemental analysis structure (C) 58 H 42 B 2 N 2 O): theoretical value: c,86.58; h,5.26; n,3.48; test value: c,86.56; h,5.28; n,3.47.
MALDI-TOF-MS: theoretical value 804.4; experimental value 804.4.
Example 43
43-1 (20.0 g,46.2 mmol), 43-2 (11.6 g,55.5 mmol), tetrakis (triphenylphosphine) palladium (4.3 g,3.7 mmol), potassium carbonate (25.6 g,185.0 mmol), 50mL of water, 50mg of aliquat-336 and 100mL of toluene were added to a 500mL three-necked flask under 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 3 times with deionized water (100 mL. Times.3), and then dried over anhydrous magnesium sulfate, and the concentrated solution obtained after the solvent removal of the organic phase was subjected to column chromatography on silica gel to obtain a product 43-3 (17.6 g, yield: 87%).
Elemental analysis structure (C) 46 H 38 Cl 2 FN): theoretical value: c,79.53; h,5.51; n,2.02; test value: c,79.57; h,5.45; n,2.08.
MALDI-TOF-MS: theoretical value 693.2; experimental value 693.2.
43-3 (15.0 g,34.5 mmol), 43-4 (8.6 g,41.4 mmol), tetrakis (triphenylphosphine) palladium (3.2 g,2.8 mmol), potassium carbonate (19.1 g,137.9 mmol), 50mL of water, 50mg of aliquat-336 and 100mL of toluene were added to a 500mL three-necked flask under 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 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 column chromatography on silica gel to obtain a product 43-5 (12.5 g, yield: 83%).
Elemental analysis structure (C) 52 H 43 Cl 2 NS): theoretical value: c,79.58; h,5.52; n,1.78; s,4.08; test value: c,79.62; h,5.58; n,1.69; s,4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
43-5 (8.0 g,18.4 mmol), 43-6 (6.2 g,22.1 mmol), potassium carbonate (5.1 g,36.8 mmol) and 150 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, then cooled to room temperature, the reaction solution was settled in 600mL of water, the precipitate precipitated in the solution was filtered and washed with methanol, and then the product 43-7 (9.3 g, yield: 73%) was obtained by silica gel column chromatography.
Elemental analysis structure (C) 52 H 43 Cl 2 NS): theoretical value: c,79.58; h,5.52; n,1.78; s,4.08; test value: c,79.62; h,5.58; n,1.69; s,4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
43-7 (8.0 g,11.5 mmol), 43-8 (1.5 g,13.8 mmol), potassium carbonate (3.2 g,23.0 mmol) and 150 mLN-methylpyrrolidone were added to a 500mL three-necked flask under argon atmosphere, stirred at 180℃for 8 hours, then cooled to room temperature, the reaction solution was settled in 600mL of water, the precipitate precipitated in the solution was filtered and washed with methanol, and then the product 43-9 (5.6 g, yield: 62%) was obtained by silica gel column chromatography.
Elemental analysis structure (C) 52 H 43 Cl 2 NS): theoretical value: c,79.58; h,5.52; n,1.78; s,4.08; test value: c,79.62; h,5.58; n,1.69; s,4.13.
MALDI-TOF-MS: theoretical value 783.3; experimental value 783.3.
Reference example 1, starting from 43-9 (5.0 g,6.4 mmol), finally gives the product II-4-8 (3.1 g, yield: 67%).
Elemental analysis structure (C) 52 H 39 B 2 NS): theoretical value: c,85.37; h,5.37; n,1.91; s,4.38; test value: c,85.39; h,5.35; n,1.97; s,4.32.
MALDI-TOF-MS: theoretical value 731.3; experimental value 731.3.
Referring to table 1, table 1 shows photophysical properties of the condensed-cyclic compounds prepared in the examples of the present invention.
TABLE 1 photophysical Properties of fused Ring Compounds prepared according to the examples of the invention
Note that the delayed fluorescence lifetime in the table is obtained by doping a compound at a concentration of 1wt% in polystyrene to prepare a sample to be tested, and testing the sample with a time resolved fluorescence spectrometer (FLS-980, UK) with a testing instrument of Edinburgh fluorescence spectrometer.
As can be seen from Table 1, the condensed-cyclic compounds in the examples provided by the present invention have a smaller ΔE ST (<0.2 eV), exhibits a thermally activated delayed fluorescence effect with a delayed fluorescence lifetime of 32 to 73 mus.
Device instance
Organic light-emitting layer is adoptedThe process for preparing the device by the vacuum evaporation process comprises the following steps: on indium tin oxide supported on a glass substrate, 4×10 -4 And (3) sequentially depositing TAPC, TCTA, EML (the luminescent compound and SIMCP2 and DPAc-DtCzBN are co-evaporated according to the mass ratio of 1:2:7), tmPyPB and LiF/Al cathodes under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein TAPC and TmPyPB are respectively used as a hole transport layer and an electron transport layer, and TCTA is an exciton blocking layer, and the structural formula is shown as follows:
the specific device structure (device structure a) is:
ITO/TAPC(50nm)/TCTA(5nm)/EML(30nm)/TmPyPB(30nm)/LiF(0.8nm)/Al(100nm)。
the organic light-emitting layer adopts the solution processing technology to prepare the device as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated onto indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating the inventive luminescent compound with SIMCP2 and DPAc-DtCzBN at a mass ratio of 1:2:7, and annealing at 80℃for 30 minutes, followed by 4X 10 -4 Sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the TSPO1 and the TmPyPB are respectively used as a hole blocking layer, an electron transport layer and a main material, and the structural formula is 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
Taking the fused ring compound I-1-2 in the example 1 as an implementation object, the fused ring compound I-1-2, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-1-2 provided herein.
Example 45
Taking the fused ring compounds I-1-14 in the example 2 as implementation targets, the fused ring compounds I-1-14, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-1-14 provided herein.
Example 46
Taking the fused ring compounds I-1-15 in the embodiment 3 as implementation targets, the fused ring compounds I-1-15, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-1-15 provided herein.
Example 47
Taking the fused ring compounds I-1-16 in the example 4 as implementation targets, the fused ring compounds I-1-16, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-1-16 provided herein.
Example 48
Taking the fused ring compound I-2-2 in the example 5 as an implementation object, the fused ring compound I-2-2, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-2 provided herein.
Example 49
Taking the fused ring compound I-2-5 in the example 6 as an implementation object, the fused ring compound I-2-5, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-5 provided herein.
Example 50
Taking the fused ring compound I-2-10 in the example 7 as an implementation object, the fused ring compound I-2-10, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-10 provided herein.
Example 51
Taking the fused ring compounds I-2-18 in the example 8 as implementation targets, the fused ring compounds I-2-18, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-18 provided herein.
Example 52
Taking the fused ring compounds I-2-57 in the example 9 as implementation targets, the fused ring compounds I-2-57, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-57 provided herein.
Example 53
Taking the fused ring compounds I-2-58 in the embodiment 10 as implementation targets, the fused ring compounds I-2-58, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-2-58 provided herein.
Example 54
Taking the fused ring compound I-3-1 in example 11 as an implementation object, the fused ring compound I-3-1, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-3-1 provided herein.
Example 55
Taking the fused ring compounds I-3-37 in the example 12 as implementation targets, the fused ring compounds I-3-37, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-3-37 provided herein.
Example 56
Taking the fused ring compound I-3-38 in example 13 as an implementation object, the fused ring compound I-3-38, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-3-38 provided herein.
Example 57
Taking the fused ring compounds I-3-39 in the embodiment 14 as implementation targets, the fused ring compounds I-3-39, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-3-39 provided herein.
Example 58
Taking the fused ring compound I-3-40 in example 15 as an implementation object, the fused ring compound I-3-40, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-3-40 provided herein.
Example 59
Taking the fused ring compound I-4-22 in example 16 as an implementation object, the fused ring compound I-4-22, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-4-22 provided herein.
Example 60
Taking the fused ring compound I-4-23 in example 17 as an implementation object, the fused ring compound I-4-23, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-4-23 provided herein.
Example 61
Taking the fused ring compound I-4-24 in the example 18 as an implementation object, the fused ring compound I-4-24, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-4-24 provided herein.
Example 62
Taking the fused ring compound I-4-25 in example 19 as an implementation object, the fused ring compound I-4-25, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-4-25 provided herein.
Example 63
Taking the fused ring compounds I-5-26 in the embodiment 20 as implementation targets, the fused ring compounds I-5-26, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-5-26 provided herein.
Example 64
Taking the fused ring compound I-5-27 in the example 21 as an implementation object, the fused ring compound I-5-27, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-5-27 provided herein.
Example 65
Taking the fused ring compound I-5-28 in the example 22 as an implementation object, the fused ring compound I-5-28, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-5-28 provided herein.
Example 66
Taking the fused ring compound I-5-25 in example 23 as an implementation object, the fused ring compound I-5-25, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-5-25 provided herein.
Example 67
Taking the fused ring compound I-6-11 in the example 24 as an implementation object, the fused ring compound I-6-11, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-6-11 provided herein.
Example 68
With the fused ring compound I-6-12 of example 25 as an implementation object, the fused ring compound I-6-12, SIMCP2 and DPAc-DtCzBN are mixed according to 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 using 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 I-6-12 provided herein.
Example 69
Taking the fused ring compounds I-7-29 in the example 26 as implementation targets, the fused ring compounds I-7-29, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-7-29 provided herein.
Example 70
Taking the fused ring compound I-7-30 in the embodiment 27 as an implementation object, the fused ring compound I-7-30, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-7-30 provided herein.
Example 71
Taking the fused ring compound I-7-31 in the example 28 as an implementation object, the fused ring compound I-7-31, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-7-31 provided herein.
Example 72
Taking the fused ring compound I-8-7 in the example 29 as an implementation object, the fused ring compound I-8-7, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-8-7 provided herein.
Example 73
Taking the fused ring compound I-8-8 in example 30 as an implementation object, the fused ring compound I-8-8, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 I-8-8 provided herein.
Example 74
Taking the fused ring compounds II-1-10 in the embodiment 31 as implementation targets, the fused ring compounds II-1-10, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 herein.
Example 75
Taking the fused ring compounds II-1-11 in the embodiment 32 as implementation targets, the fused ring compounds II-1-11, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 herein.
Example 76
Taking the fused ring compounds II-1-12 in the embodiment 33 as implementation targets, the fused ring compounds II-1-12, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 herein.
Example 77
With the condensed-ring compound II-1-13 of example 34 as an implementation object, the condensed-ring compound II-1-13, SIMCP2 and DPAc-DtCzBN were mixed according to 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 using 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 herein.
Example 78
Taking the fused ring compounds II-1-14 in the embodiment 35 as implementation targets, the fused ring compounds II-1-14, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 herein.
Example 79
Taking the fused ring compound II-2-18 in the embodiment 36 as an implementation object, the fused ring compound II-2-18, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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-2-18 provided herein.
Example 80
Taking the fused ring compounds II-2-19 in the embodiment 37 as implementation targets, the fused ring compounds II-2-19, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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 herein.
Example 81
Taking the fused ring compound II-2-20 in the example 38 as an implementation object, the fused ring compound II-2-20, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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-2-20 provided herein.
Example 82
With the condensed-ring compound II-3-6 of example 39 as an implementation object, the condensed-ring compound II-3-6, SIMCP2 and DPAc-DtCzBN are mixed according to 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 using 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-3-6 provided herein.
Example 83
Taking the fused ring compound II-3-7 in the example 40 as an implementation object, the fused ring compound II-3-7, SIMCP2 and DPAc-DtCzBN are mixed according to the 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 using 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-3-7 provided herein.
Example 84
With the condensed-cyclic compound II-3-8 of example 41 as an implementation object, the condensed-cyclic compound II-3-8, SIMCP2 and DPAc-DtCzBN were mixed according to 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 using 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-3-8 provided herein.
Example 85
With the condensed-ring compound II-4-7 of example 42 as an implementation object, the condensed-ring compound II-4-7, SIMCP2 and DPAc-DtCzBN are mixed according to 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 using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with II-4-7 provided herein.
Example 86
With the condensed-ring compound II-4-8 of example 43 as an implementation object, the condensed-ring compound II-4-8, SIMCP2 and DPAc-DtCzBN were mixed according to 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 using the structure of the device structure B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with II-4-8 provided herein.
TABLE 2 Performance parameters of electroluminescent devices prepared from the fused Ring Compounds provided by the invention
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And (3) injection: the luminance of the panel is 1cd m -2 The driving voltage of the device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device and the calculation method described in the literature (Jpn.J.appl.Phys.2001, 40, L783); the half-width is the width of the peak at half the peak height of the electroluminescent spectrum at room temperature, i.e. the midpoint of the peak height is taken as a straight line parallel to the bottom of the peak, which straight line intersects the distance between the two 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 very narrow electroluminescent spectrum, the half-peak width is smaller than 40nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wider (70-100 nm) is solved. Meanwhile, the devices prepared by the compound provided by the invention have higher device efficiency, and the maximum external quantum efficiency reaches 35.1%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. A boron or phosphorus fused ring compound containing a binaphthyl ring, characterized in that it is selected from one of the following structures:
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2. a process for preparing a binaphthyl ring-containing boron or phosphorus fused ring compound as claimed in claim 1,
the boron or phosphorus fused ring compound containing binaphthyl ring has a structure shown in any one of formulas (I) to (II):
the preparation method comprises the following steps:
when X is 1 And X 2 When independently selected from B or p=s, the preparation method comprises the steps of:
under argon atmosphere, putting A-1 or A-2 and o-xylene into a three-neck flask, cooling, dropwise adding a pentane solution of tert-butyllithium into the reaction solution, heating the reaction solution after the dropwise adding is finished, and stirring; after the reaction is finished, cooling the reaction liquid again, dropwise adding boron trihalide or phosphorus trihalide and sulfur powder into the reaction liquid, and heating the reaction liquid to continuously stir after the raw materials are added; 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 a boron impurity or phosphorus impurity fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II);
When X is 1 And X 2 Independently selected from p=o, the preparation method comprises the steps of:
under argon atmosphere, X is added into a two-neck flask 1 And X 2 Independently selected from a fused ring compound prepared when p=s, m-chloroperoxybenzoic acid and dried dichloromethane, stirring the reaction liquid at room temperature, placing the reaction liquid in methanol for sedimentation after the reaction is finished, filtering out solid separated out, and separating by silica gel column chromatography to obtain a boron-doped or phosphorus-doped fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II);
wherein Z is selected from one of Cl, br and I; the other substituents each correspond to a substituent on each of the compounds of claim 1.
3. The process for preparing a binaphthyl ring-containing boron or phosphorus fused ring compound according to claim 2, wherein one specific embodiment of the process is:
when X is 1 And X 2 When independently selected from B or p=s, the preparation method comprises the steps of:
under argon atmosphere, putting A-1 or A-2 and o-xylene into a 500mL three-neck flask, cooling for 20 minutes at minus 30 ℃, dropwise adding 2.5M/L of a pentane solution of tert-butyllithium into the reaction solution, heating the reaction solution to 50 ℃ after the dropwise adding is finished, and stirring for 1 hour; cooling the reaction liquid to minus 30 ℃ again after 1 hour, dropwise adding boron trihalide or phosphorus trihalide and sulfur powder into the reaction liquid, heating the reaction liquid to 40 ℃ after the raw materials are added, and stirring for 1 hour; cooling the reaction solution to 0 ℃, dropwise adding N, N-diisopropylethylamine into the reaction solution, heating to 125 ℃ after the dropwise adding is finished, 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 under reduced pressure at 80 ℃ to obtain the boron or phosphorus heterocyclic compound containing binaphthyl ring shown in the formulas (I) and (II);
When X is 1 And X 2 Independently selected from p=o, the preparation method comprises the steps of:
x was added to a 250mL two-necked flask under an argon atmosphere 1 And X 2 Independently selected from the group consisting of a fused ring compound prepared when p=s, m-chloroperoxybenzoic acid and dried dichloromethane, stirring for 24 hours at room temperature, then placing the reaction solution in 500mL of methanol for sedimentation, filtering out the precipitated solid, and separating by silica gel column chromatography to obtain a boron or phosphorus fused ring compound containing binaphthyl rings shown in the formula (I) and the formula (II).
4. An organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode; the organic thin film layer comprising the binaphthyl ring-containing boron or phosphorus fused ring compound according to claim 1.
5. The organic electroluminescent device according to claim 4, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer comprising the binaphthyl ring-containing boron or phosphorus fused ring compound according to claim 1.
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| CN115443280A (en) * | 2020-04-23 | 2022-12-06 | 三星显示有限公司 | Organic molecules for optoelectronic devices |
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