CN114213441B - Boron or phosphorus fused ring compound, preparation method thereof and light-emitting device - Google Patents
Boron or phosphorus fused ring compound, preparation method thereof and light-emitting device Download PDFInfo
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- CN114213441B CN114213441B CN202111610292.7A CN202111610292A CN114213441B CN 114213441 B CN114213441 B CN 114213441B CN 202111610292 A CN202111610292 A CN 202111610292A CN 114213441 B CN114213441 B CN 114213441B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 167
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 title claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 10
- 239000011574 phosphorus Substances 0.000 title claims description 10
- 239000012043 crude product Substances 0.000 claims description 129
- 239000012300 argon atmosphere Substances 0.000 claims description 128
- 238000006243 chemical reaction Methods 0.000 claims description 120
- 238000010898 silica gel chromatography Methods 0.000 claims description 117
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 93
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 88
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 88
- 239000002904 solvent Substances 0.000 claims description 87
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 73
- 239000012074 organic phase Substances 0.000 claims description 72
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 52
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- -1 alkyl lithium Chemical compound 0.000 claims description 8
- 239000012047 saturated solution Substances 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 150000001923 cyclic compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000003111 delayed effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 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 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 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
- 239000010410 layer Substances 0.000 description 145
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 138
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 129
- 238000012360 testing method Methods 0.000 description 129
- 238000000921 elemental analysis Methods 0.000 description 126
- 239000000047 product Substances 0.000 description 125
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 117
- 238000001816 cooling Methods 0.000 description 117
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 108
- 229940078552 o-xylene Drugs 0.000 description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 67
- 239000008367 deionised water Substances 0.000 description 62
- 229910021641 deionized water Inorganic materials 0.000 description 62
- 239000000243 solution Substances 0.000 description 59
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 56
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 54
- 238000001914 filtration Methods 0.000 description 51
- 230000008569 process Effects 0.000 description 47
- 239000007787 solid Substances 0.000 description 45
- 238000007738 vacuum evaporation Methods 0.000 description 45
- 229910000027 potassium carbonate Inorganic materials 0.000 description 28
- 101150003085 Pdcl gene Proteins 0.000 description 27
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 22
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910014265 BrCl Inorganic materials 0.000 description 5
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NHPPIJMARIVBGU-UHFFFAOYSA-N 1-iodonaphthalene Chemical compound C1=CC=C2C(I)=CC=CC2=C1 NHPPIJMARIVBGU-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
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000000605 extraction Methods 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
- STERKHRCDZPNRE-UHFFFAOYSA-N 4-iodoquinoline Chemical compound C1=CC=C2C(I)=CC=NC2=C1 STERKHRCDZPNRE-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
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 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
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- XFUCRHYSJRXATP-UHFFFAOYSA-N 1-(naphthalen-1-yldiselanyl)naphthalene Chemical compound C1=CC=C2C([Se][Se]C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 XFUCRHYSJRXATP-UHFFFAOYSA-N 0.000 description 2
- BKPDQETYXNGMRE-UHFFFAOYSA-N 1-tert-butyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C(C)(C)C)=CC=C2 BKPDQETYXNGMRE-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy 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
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- BCIDDURGCAHERU-UHFFFAOYSA-N 1,2-dibromo-4,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(Br)C=C1C BCIDDURGCAHERU-UHFFFAOYSA-N 0.000 description 1
- CFWJTWLWDMJECT-UHFFFAOYSA-N 1,2-dibromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C(Br)=C1 CFWJTWLWDMJECT-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- GLVMLJCMUBZVTJ-UHFFFAOYSA-N 1,4-dibromo-2,5-difluorobenzene Chemical compound FC1=CC(Br)=C(F)C=C1Br GLVMLJCMUBZVTJ-UHFFFAOYSA-N 0.000 description 1
- OJYLWCYRSGYMPP-UHFFFAOYSA-N 1-bromo-4-[(4-bromophenyl)diselanyl]benzene Chemical compound C1=CC(Br)=CC=C1[Se][Se]C1=CC=C(Br)C=C1 OJYLWCYRSGYMPP-UHFFFAOYSA-N 0.000 description 1
- ZXUNTMVJYICFPW-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-dithiol Chemical compound CC1=CC(S)=C(C)C=C1S ZXUNTMVJYICFPW-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000005013 aryl ether group Chemical group 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
- AYGAKGHUCUNBHE-UHFFFAOYSA-N benzenethiol;fluorobenzene Chemical compound FC1=CC=CC=C1.SC1=CC=CC=C1 AYGAKGHUCUNBHE-UHFFFAOYSA-N 0.000 description 1
- BGXZJSLTGNPDDH-UHFFFAOYSA-N benzenethiol;sodium Chemical compound [Na].SC1=CC=CC=C1 BGXZJSLTGNPDDH-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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 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
- VRLFOXMNTSYGMX-UHFFFAOYSA-N diphenyl ditelluride Chemical compound C=1C=CC=CC=1[Te][Te]C1=CC=CC=C1 VRLFOXMNTSYGMX-UHFFFAOYSA-N 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 108010023700 galanin-(1-13)-bradykinin-(2-9)-amide Proteins 0.000 description 1
- 108700039708 galantide Proteins 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
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon 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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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a boron-doped or phosphorus-doped fused ring compound, a preparation method thereof and a light-emitting device, and belongs to the technical field of organic light-emitting materials. The condensed-cyclic compound of the present invention has any one of structures represented by the formulas (I) to (VI). On one hand, the rigid framework structure of the condensed-cyclic compound can be utilized to reduce the relaxation degree of the excited state structure, so that the narrower half-peak width is realized; 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, 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 condensed ring compound provided by the invention is used as a light-emitting layer of an organic electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized under the condition that an optical filter and a microcavity structure are not needed, but also the high external quantum efficiency of the device can be realized.
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, 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.
The thermally activated delayed fluorescence (thermally activated delayed fluorescence, TADF) material is a third generation organic luminescent material subsequent to the traditional fluorescent and phosphorescent materials, and the material generally has a small singlet-triplet energy level difference (deltaest), and the triplet excitons are transferred to the singlet excitons to emit fluorescence by using a thermally activated reverse intersystem crossing (RISC) process, so that the full utilization of the singlet and triplet 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 is at present to introduce electron donor (D) and electron acceptor (a) units such that the highest occupied orbitals (HOMO) and the lowest unoccupied orbitals (LUMO) are separated, thus achieving a small Δest. 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 technical problem to be solved by the present invention is to provide a boron or phosphorus fused ring compound having both TADF effect and narrow half-width spectral characteristics, a method for preparing the same, and a light-emitting device.
The invention provides a boron-doped or phosphorus-doped fused ring compound, which has any one structure shown in formulas (I) to (VI):
wherein X is 1 And X 2 Independently selected from B, P =o or p=s;
Y 1 and Y 2 Independently selected from N (R) 1 )、O、S、Se、Te、B(R 1 )、(R 1 )P＝O、(R 1 )P＝S、C(R 1 R 2 ) Or Si (R) 1 R 2 )；
Ar 2 ～Ar 6 Independently selected from a substituted or unsubstituted C6 to C60 aryl ring, or a substituted or unsubstituted C3 to C60 heteroaryl ring; and Ar is Ar 4 With Ar 5 Between, ar 6 With Ar 7 Forming a condensed structure by sharing at least one carbon atom; 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 alkoxy group Alkylthio of C1-C30, aryl of substituted or unsubstituted C6-C60, aryl ether of substituted or unsubstituted C6-C60, heteroaryl of C3-C60 or heteroaryl ether of substituted or unsubstituted C3-C60; 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;
R 1 ～R 3 independently 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, an alkoxy group of C1 to C30, an alkylthio group of C1 to C30, a substituted or unsubstituted aryl group of C6 to C60, a substituted or unsubstituted aryl ether group of C6 to C60, a substituted or unsubstituted heteroaryl group of C5 to C60, and a substituted or unsubstituted heteroaryl ether group of C5 to C60; wherein the heteroatoms of the heteroaromatic 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 6 Optionally substituted groups can also be substituted by single bonds, -C (R a R b )-、-(C＝O)-、-Si(R a R b )-、-N(R a )-、-PO(R a ) -O-, -S-and-Se-, are linked; 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, or a C1-to-ultrahighAlkylthio of C30, substituted or unsubstituted aryl of C6 to C60, substituted or unsubstituted aryl ether of C6 to C60, substituted or unsubstituted heteroaryl of C5 to C60, or substituted or unsubstituted heteroaryl ether of C5 to C60.
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, se or Te.
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, se or Te.
Preferably, the X 1 And X 2 Are all B, and the Y 1 And Y 2 Independently selected from N (R) 1 ) O or S.
Preferably, the boron or phosphorus fused ring compound is selected from any 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, 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:
reacting a compound shown in a formula (I-1), a formula (II-1), a formula (III-1), a formula (IV-1), a formula (V-1) or a formula (VI-1) with alkyl lithium, and then reacting with boron trihalide, or phosphorus trihalide and sulfur powder, aluminum chloride and organic amine to obtain a fused ring compound shown in a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V) or a formula (VI);
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 and methylene chloride, adding m-chloroperbenzoic acid thereto, and stirring at room temperature to react; after the reaction is finished, adding m-chloroperbenzoic acid into the reaction system, and continuing stirring reaction at room temperature; adding sodium sulfite saturated solution into the mixture after the reaction is finished, drying the obtained organic phase by using anhydrous sodium sulfate, removing the solvent, and separating the crude product by silica gel column chromatography to obtain a fused ring compound shown in the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V) or the formula (VI);
Lu 1 and Lu 2 Hydrogen or halogen; other code numbers are the same as those described above, and are not repeated here.
Preferably, the alkyl lithium is one or more of butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium and ethyl lithium; the boron trihalide is one or more of boron trifluoride, boron trichloride, boron tribromide and boron triiodide; the organic amine is one or more of N, N-diisopropylethylamine, triethylamine and tri-N-butylamine.
The invention also provides application of the fused ring compound shown in any one of the formulas (I) - (VI) as a luminescent material, in particular to application in an organic electroluminescent device.
The organic electroluminescent device comprises an anode, a cathode and an organic film layer positioned between the anode and the cathode; the organic thin film layer comprises a fused ring compound shown in any one of formulas (I) - (VI) in the invention.
Preferably, the organic thin film layer includes a light emitting layer; the light-emitting layer includes a condensed ring compound represented by any one of the formulas (I) to (VI) of the present invention.
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 any structure of the formulas (I) - (VI); the condensed-cyclic compounds shown in the formulas (I) - (VI) provided by the invention are taken as luminescent materials 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 condensed ring compounds shown in any structure of formulas (I) - (VI).
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 provided by the invention can utilize the rigid framework structure of the fused ring compound to reduce the relaxation degree of the excited state structure, thereby realizing higherNarrow half-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 boron-doped or phosphorus-doped fused ring compound provided by the invention is used as a light-emitting layer of an organic electroluminescent device, so that the narrow electroluminescent half-peak width can be realized under the condition that a filter and a microcavity structure are not needed, and the high external quantum efficiency of the device can be realized. Experimental results also show that the device prepared from the boron-doped or phosphorus-doped fused ring compound provided by the invention has a 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 34.3%.
The preparation method of the boron-doped or phosphorus-doped fused ring compound has the advantages of simple steps and mild conditions.
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
Under argon atmosphere, m-1 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) are added into a 48mL single-port reaction flask and uniformly mixed, 1-iodonaphthalene (11.4 g,45.0 mmol) is added into the mixture and uniformly mixed, and the mixture is heated at 235 ℃ for 20min after tube sealing. After cooling to room temperature, the reaction flask was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-2 (1.0 g, yield: 20%).
Elemental analysis structure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.14; h,2.52.
Matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS): theoretical value 553.9; experimental value 553.9.
Into a 250mL two-necked flask under argon atmosphere were charged m-2 (5.6 g,10.0 mmol), diphenylamine (3.7 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and (AMPHOS) 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was separated by silica gel column chromatography to give product m-3 (4.8 g, yield: 65%).
Elemental analysis structure (C) 50 H 34 Cl 2 N 2 ): theoretical value: c,81.85; h,4.67; n,3.82; test value: c,81.76; h,4.70; n,3.81.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
M-3 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 1-1 (0.8 g, yield: 30%).
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,88.23; h,4.46; n,4.14.
MALDI-TOF-MS: theoretical 680.3; experimental value 680.3.
Example 2
In a 250mL two-necked flask, m-2 (5.6 g,10.0 mmol), tert-butylcarbazole (6.1 g,22.0 mmol) and cesium carbonate (13.0 g,40.0 mmol) were added under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-4 (6.4 g, yield: 67%).
Elemental analysis structure (C) 66 H 62 Cl 2 N 2 ): theoretical value: c,83.08; h,6.55; n,2.94; test value: c,83.02; h,6.52; n,2.99.
MALDI-TOF-MS: theoretical value 952.4; experimental value 952.4.
M-4 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, an aqueous sodium acetate solution was added to the reaction system, and extraction was performed with ethyl acetate, so that an organic phase was dried over anhydrous sodium sulfate, the organic solvent was removed after filtration, and the crude product was separated by silica gel column chromatography to obtain a product 1-4 (1.2 g, yield: 33%).
Elemental analysis structure (C) 66 H 58 B 2 N 2 ): theoretical value: c,88.00; h,6.49; n,3.11; test value: c,88.03; h,6.52; n,3.14.
MALDI-TOF-MS: theoretical 900.5; experimental 900.5.
Example 3
In a 250mL two-necked flask, m-2 (5.6 g,10.0 mmol), acridine (4.6 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol), tri-t-butylphosphine tetrafluoroborate (0.6 g,2.0 mmol) and Pd were charged under an argon atmosphere 2 (dba) 3 (0.46 g,0.5 mmol) and 60mL of toluene were added and the system was reacted at 105℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-5 (5.4 g, yield: 66%).
Elemental analysis structure (C) 56 H 42 Cl 2 N 2 ): theoretical value: c,82.64; h,5.20; n,3.44; test value: c,82.62; h,5.21; n,3.47.
MALDI-TOF-MS: theoretical value 812.3; experimental value 812.3.
M-5 (3.3 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-5 (1.0 g, yield: 32%).
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,88.42; h,5.07; n (N),3.62。
MALDI-TOF-MS: theoretical 760.3; experimental 760.3.
Example 4
In a 250mL two-necked flask under argon atmosphere, m-2 (5.6 g,10.0 mmol), m-6 (5.8 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-7 (5.0 g, yield: 54%).
Elemental analysis structure (C) 62 H 50 Cl 2 N 2 O 2 ): theoretical value: c,80.42; h,5.44; n,3.03; test value: c,80.29; h,5.41; n,3.09.
MALDI-TOF-MS: theoretical value 924.3; experimental value 924.3.
M-7 (3.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, an aqueous sodium acetate solution was added to the reaction system, and extraction was performed with ethyl acetate, so that an organic phase was dried over anhydrous sodium sulfate, the organic solvent was removed after filtration, and the crude product was separated by silica gel column chromatography to obtain a product 1-8 (0.8 g, yield: 23%).
Elemental analysis structure (C) 62 H 46 B 2 N 2 O 2 ): theoretical value: c,85.33; h,5.31; n,3.21; test value: c,85.35; h,5.32; n,3.29.
MALDI-TOF-MS: theoretical 872.4; experimental value 872.4.
Example 5
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Under argon atmosphere, m-8 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) are added into a 48mL single-port reaction bottle, uniformly mixed, and then m-9 (11.7 g,45.0 mmol) is added into the mixture, uniformly mixed, and the mixture is heated at 235 ℃ for 20min after tube sealing. After cooling to room temperature, the tube was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-10 (1.0 g, yield: 19%).
Elemental analysis structure (C) 22 H 10 Br 2 Cl 2 S 2 ): theoretical value: c,46.43; h,1.77; s,11.27; test value: c,46.41; h,1.73; s,11.29.
MALDI-TOF-MS: theoretical value 565.8; experimental value 565.8.
In a 250mL two-necked flask under argon atmosphere, m-10 (5.7 g,10.0 mmol), diphenylamine (5.8 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-11 (4.1 g, yield: 55%).
Elemental analysis structure (C) 46 H 30 Cl 2 N 2 S 2 ): theoretical value: c,74.08; h,4.05; n,3.76; s,8.60; test value: c,74.18; h,4.08; n,3.72; s,8.62.
MALDI-TOF-MS: theoretical 744.1; experimental 744.1.
M-11 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-15 (0.7 g, yield: 27%).
Elemental analysis structure (C) 46 H 26 B 2 N 2 S 2 ): theoretical value: c,79.79; h,3.78; n,4.05; s,9.26; test value: c,79.72; h,3.75; n,4.08; s,9.26.
MALDI-TOF-MS: theoretical value 692.2; experimental value 692.2.
Example 6
Under argon atmosphere, m-8 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added into a 48mL single-port reaction flask, and mixed well, 4-iodoquinoline (11.5 g,45.0 mmol) was added thereto, and the mixture was heated at 235℃for 20min after sealing. After cooling to room temperature, the tube was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-12 (1.1 g, yield: 21%).
Elemental analysis structure (C) 24 H 12 Br 2 Cl 2 N 2 ): theoretical value: c,51.56; h,2.16; n,5.01; test value: c,51.52; h,2.18; n,5.04.
MALDI-TOF-MS: theoretical value 555.9; experimental value 555.9.
Into a 250mL two-necked flask under argon atmosphere were charged m-12 (5.6 g,10.0 mmol), diphenylamine (5.8 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and (AMPHOS) 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto to give an organic phaseDrying over anhydrous sodium sulfate, concentrating, and removing the solvent, the crude product was subjected to silica gel column chromatography to give the product m-13 (3.8 g, yield: 51%).
Elemental analysis structure (C) 48 H 32 Cl 2 N 4 ): theoretical value: c,78.36; h,4.38; n,7.62; test value: c,78.35; h,4.34; n,7.63.
MALDI-TOF-MS: theoretical 734.2; experimental 734.2.
M-13 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give products 1-19 (0.8 g, yield: 29%).
Elemental analysis structure (C) 48 H 28 B 2 N 4 ): theoretical value: c,84.49; h,4.14; n,8.21; test value: c,84.41; h,4.11; n,8.24.
MALDI-TOF-MS: theoretical value 682.3; experimental value 682.3.
Example 7
In a 250mL two-necked flask under argon atmosphere, m-2 (5.6 g,10.0 mmol), m-14 (12.3 g,22.0 mmol), sodium t-butoxide (3.8 g,40.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-15 (6.8 g, yield：45％)。
Elemental analysis structure (C) 106 H 86 Cl 2 N 6 ): theoretical value: c,84.05; h,5.72; n,5.55; test value: c,84.05; h,5.72; n,5.55.
MALDI-TOF-MS: theoretical value 1512.6; experimental value 1512.6.
M-15 (6.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, an aqueous sodium acetate solution was added to the reaction system, and extraction was performed with ethyl acetate, so that an organic phase was dried over anhydrous sodium sulfate, the organic solvent was removed after filtration, and the crude product was separated by silica gel column chromatography to obtain products 1 to 29 (1.3 g, yield: 22%).
Elemental analysis structure (C) 106 H 82 B 2 N 6 ): theoretical value: c,87.11; h,5.66; n,5.75; test value: c,87.17; h,5.64; n,5.71.
MALDI-TOF-MS: theoretical value 1460.7; experimental value 1460.7.
Example 8
In a 250mL two-necked flask, m-2 (5.6 g,10.0 mmol), phenol (2.8 g,22.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, 60mL of NMP was added, and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-16 (4.5 g, yield: 77%).
Elemental analysis structure(C 38 H 24 Cl 2 O 2 ): theoretical value: c,78.22; h,4.15; test value: c,78.24; h,4.11.
MALDI-TOF-MS: theoretical value 582.1; experimental value 582.1.
M-16 (2.3 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-32 (0.8 g, yield: 36%).
Elemental analysis structure (C) 38 H 20 B 2 O 2 ): theoretical value: c,86.08; h,3.80; test value: c,86.01; h,3.84.
MALDI-TOF-MS: theoretical 530.2; experimental value 530.2.
Example 9
Under argon atmosphere, m-8 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added into a 48mL single-port reaction flask, and mixed uniformly, m-17 (12.6 g,45.0 mmol) was added thereto, and the flask was sealed and heated at 235℃for 20min. After cooling to room temperature, the tube was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-18 (1.1 g, yield: 20%).
Elemental analysis structure (C) 30 H 18 Br 2 Cl 2 ): theoretical value: c,59.15; h,2.98; test value: c,59.16; h,2.93.
MALDI-TOF-MS: theoretical value 605.9; experimental value 605.9.
In a 250mL two-necked flask, m-18 (6.1 g,10.0 mmol), m-fluorobenzene thiophenol (2.8 g,22.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, 60mL of NMP was added, and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-19 (5.0 g, yield: 67%).
Elemental analysis structure (C) 38 H 22 Br 2 F 2 S 2 ): theoretical value: c,61.63; h,2.99; s,8.66; test value: c,61.68; h,2.96; s,8.62.
MALDI-TOF-MS: theoretical value 738.0; experimental value 738.0.
M-19 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give products 1-106 (0.7 g, yield: 26%).
Elemental analysis structure (C) 42 H 22 B 2 F 2 S 2 ): theoretical value: c,77.56; h,3.41; s,9.86; test value: c,77.51; h,3.44; s,9.83.
MALDI-TOF-MS: theoretical value 650.1; experimental value 650.1.
Example 10
Dinaphthyldiselenide (26.4 g,64.0 mmol), sodium borohydride (4.9 g,128.0 mmol) and 300mL DMF are added into a 250mL three-necked flask under argon atmosphere to react for 4 hours at room temperature, m-2 (35.7 g,64.0 mmol) is added into the system under argon protection, stirring is carried out at 80 ℃ for 24 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water (3000 mL), solid is filtered out, the solvent is removed, and the crude product is separated by silica gel column chromatography to obtain a product m-20 (17.8 g, yield: 34%).
Elemental analysis structure (C) 46 H 28 Cl 2 Se 2 ): theoretical value: c,68.25; h,3.49; test value: c,68.32; h,3.46.
MALDI-TOF-MS: theoretical value 810.0; experimental 810.0.
M-20 (3.2 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-67 (0.8 g, yield: 25%).
Elemental analysis structure (C) 46 H 24 B 2 Se 2 ): theoretical value: c,73.06; h,3.20; test value: c,73.09; h,3.22.
MALDI-TOF-MS: theoretical value 758.0; experimental value 758.0.
Example 11
Diphenyl ditelluride (13.1 g,32.0 mmol), sodium borohydride (2.5 g,64.0 mmol) and 300mL DMF are added into a 250mL three-neck flask under argon atmosphere to react for 4 hours at room temperature, m-2 (35.7 g,64.0 mmol) is added into the system under argon protection, stirring is carried out at 80 ℃ for 24 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water (3000 mL), solid is filtered out, the solvent is removed, and the crude product is separated by silica gel column chromatography to obtain a product m-21 (10.0 g, yield: 23%).
Elemental analysis structure (C) 32 H 19 BrCl 2 Te): theoretical value: c,56.36; h,2.81; test value: c,56.32; h,2.80.
MALDI-TOF-MS: theoretical value 681.9; experimental value 681.9.
In a 250mL two-necked flask under argon atmosphere, m-21 (6.8 g,10.0 mmol), diphenylamine (2.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-22 (4.2 g, yield: 55%).
Elemental analysis structure (C) 44 H 29 Cl 2 NTe): theoretical value: c,68.61; h,3.80; n,1.82; test value: c,68.63; h,3.86; n,1.81.
MALDI-TOF-MS: theoretical value 771.1; experimental value 771.1.
M-22 (3.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-87 (0.6 g, yield: 21%).
Elemental analysis structure (C) 44 H 25 B 2 NTe): theoretical value: c,73.72; h,3.52; n,1.95; test value: c,73.76; h,3.45; n,1.91.
MALDI-TOF-MS: theoretical value 719.1; experimental value 719.1.
Example 12
Into a 250mL two-necked flask under argon atmosphere were charged m-2 (5.6 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the obtained organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was separated by silica gel column chromatography to obtain the product m-23 (4.2 g, yield: 65%).
Elemental analysis structure (C) 38 H 24 BrCl 2 N): theoretical value: c,70.72; h,3.75; n,2.17; test value: c,70.71; h,3.72; n,2.11.
MALDI-TOF-MS: theoretical value 643.1; experimental value 643.1.
In a 250mL two-necked flask, m-23 (6.5 g,10.0 mmol) and sodium thiophenol (1.5 g,11.0 mmol) were charged under argon atmosphere, 60mL of NMP was added, and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was separated by silica gel column chromatography to give product m-24 (5.0 g, yield: 67%).
Elemental analysis structure (C) 44 H 29 Cl 2 NS): theoretical value: c,78.33; h,4.33; n,2.08; s,4.75; test value: c,78.31; h,4.36; n,2.09; s,4.72.
MALDI-TOF-MS: theoretical value 673.1; experimental value 673.1.
M-24 (2.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to minus 30 ℃, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60℃for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 1-97 (0.5 g, yield: 19%). Elemental analysis structure (C) 44 H 25 NP 2 S 3 ): theoretical value: c,72.81; h,3.47; n,1.93; s,13.25; test value: c,72.83; h,3.42; n,1.93; s,13.26.
MALDI-TOF-MS: theoretical value 725.1; experimental value 725.1.
Example 13
In a 250mL two-necked flask, m-2 (5.6 g,10.0 mmol), tert-butylcarbazole (6.1 g,22.0 mmol) and cesium carbonate (13.0 g,40.0 mmol) were added under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was separated by silica gel column chromatography to give product m-25 (6.4 g, yield: 67%).
Elemental analysis structure (C) 66 H 62 Cl 2 N 2 ): theoretical value: c,83.08; h,6.55; n,2.94; test value: c,83.02; h,6.52; n,2.99.
MALDI-TOF-MS: theoretical value 952.4; experimental value 952.4.
M-25 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product m-26 (0.8 g, yield: 18%).
Elemental analysis structure (C) 66 H 58 N 2 P 2 S 2 ): theoretical value: c,78.86; h,5.82; n,2.79; s,6.38; test value: c,78.81; h,5.85; n,2.81; s,6.35.
MALDI-TOF-MS: theoretical value 1004.4; experimental value 1004.4.
M-26 (5.6 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was separated by silica gel column chromatography to give a product 1-90 (3.1 g, yield: 32%).
Elemental analysis structure (C) 66 H 58 N 2 O 2 P 2 ): theoretical value: c,81.46; h,6.01; n,2.88; test value: c,81.41; h,6.03; n,2.85.
MALDI-TOF-MS: theoretical value 972.4; experimental value 972.4.
Example 14
In a 250mL two-necked flask, m-27 (3.3 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 mL) was added thereto * 3) The obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to obtain the product m-28 (2.3 g, yield: 69%).
Elemental analysis structure (C) 22 H 16 ClN): theoretical value: c,80.12; h,4.89; n,4.25; test value: c,80.03; h,4.84; n,4.29.
MALDI-TOF-MS: theoretical value 329.1; experimental value 329.1.
In a 250mL two-necked flask under argon atmosphere, m-28 (3.3 g,10.0 mmol), p-dibromobenzene (1.2 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-29 (4.1 g, yield: 56%).
Elemental analysis structure (C) 50 H 34 Cl 2 N 2 ): theoretical value: c,81.85; h,4.67; n,3.82; test value: c,81.81; h,4.64; n,3.89.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
M-29 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give product 2-1 (0.9 g, yield: 33%).
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,88.21; h,4.45; n,4.16.
MALDI-TOF-MS: theoretical 680.3; experimental value 680.3.
Example 15
In a 250mL two-necked flask, m-30 (3.3 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-31 (2.1 g, yield: 62%).
Elemental analysis structure (C) 21 H 15 ClN 2 ): theoretical value: c,76.25; h,4.57; n,8.47; test value: c,76.21; h,4.61; n,8.46.
MALDI-TOF-MS: theoretical value 330.1; experimental value 330.1.
In a 250mL two-necked flask under argon atmosphere, m-31 (3.3 g,10.0 mmol), 1, 4-dibromo-2, 5-difluorobenzene (1.4 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-32 (3.2 g, yield: 43%).
Elemental analysis structure (C) 48 H 30 Cl 2 F 2 N 4 ): theoretical value: c,74.71; h,3.92; n,7.26; a test value; c,74.74; h,3.91; n,7.23.
MALDI-TOF-MS: theoretical value 770.2; experimental value 770.2.
M-32 (3.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 2-12 (0.8 g, yield: 23%).
Elemental analysis structure (C) 48 H 26 B 2 F 2 N 4 ): theoretical value: c,80.25; h,3.65; n,7.80; test value: c,80.21; h,3.63; n,7.82.
MALDI-TOF-MS: theoretical value 718.2; experimental value 718.2.
Example 16
In a 250mL two-necked flask, m-33 (4.8 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-34 (2.9 g, yield: 61%).
Elemental analysis structure (C) 32 H 27 ClFN): theoretical value: c,80.07; h,5.67; n,2.92; test value: c,80.03; h,5.69; n,2.95.
MALDI-TOF-MS: theoretical value 479.2; experimental value 479.2.
In a 250mL two-necked flask under argon atmosphere, m-34 (4.8 g,10.0 mmol), 2, 5-dimethyl-benzene-1, 4-dithiol (0.9 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water was added thereto, and the organic phase obtained by extraction was used withoutDrying over sodium sulfate, removing the solvent, and separating the crude product by silica gel column chromatography to obtain the product m-35 (2.2 g, yield: 41%).
Elemental analysis structure (C) 72 H 62 C l2 N 2 S 2 ): theoretical value: c,79.32; h,5.73; n,2.57; s,5.88; test value: c,79.31; h,5.76; n,2.55; s,5.85.
MALDI-TOF-MS: theoretical value 1088.4; experimental value 1088.4.
M-35 (4.4 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 2-40 (1.1 g, yield: 27%).
Elemental analysis structure (C) 72 H 58 B 2 N 2 S 2 ): theoretical value: c,83.39; h,5.64; n,2.70; s,6.18; test value: c,83.33; h,5.68; n,2.72; s,6.14.
MALDI-TOF-MS: theoretical value 1036.4; experimental value 1036.4.
Example 17
In a 250mL two-necked flask, m-36 (2.6 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, and the solvent was removed to give a crude product The product m-37 (1.7 g, yield: 65%) was obtained by column chromatography on silica gel.
Elemental analysis structure (C) 16 H 10 ClF): theoretical value: c,74.86; h,3.93; test value: c,74.82; h,3.91.
MALDI-TOF-MS: theoretical value 256.1; experimental value 256.1.
Di (4-bromophenyl) diselenide (15.0 g,32.0 mmol), sodium borohydride (2.5 g,64.0 mmol) and 300mL of DMF were added to a 250mL three-necked flask under argon atmosphere to react for 4 hours at room temperature, m-37 (16.4 g,64.0 mmol) was added to the system under argon protection, the reaction was stirred for 24 hours at 80 ℃, then cooled to room temperature, the reaction solution was poured into water (3000 mL), the solid was filtered out, the solvent was removed, and the crude product was separated by silica gel column chromatography to obtain the product m-38 (9.1 g, yield: 30%).
Elemental analysis structure (C) 22 H 14 BrClSe): theoretical value: c,55.90; h,2.99; test value: c,55.95; h,2.92.
MALDI-TOF-MS: theoretical value 471.9; experimental value 471.9.
In a 250mL two-necked flask under argon atmosphere, m-38 (4.7 g,10.0 mmol), m-28 (3.6 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-39 (3.1 g, yield: 43%).
Elemental analysis structure (C) 44 H 29 Cl 2 NSe): theoretical value: c,73.24; h,4.05; n,1.94; test value: c,73.26; h,4.02; n,1.92.
MALDI-TOF-MS: theoretical value 721.1; experimental value 721.1.
M-39 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 2-52 (0.7 g, yield: 28%).
Elemental analysis structure (C) 44 H 25 B 2 NSe): theoretical value: c,79.08; h,3.77; n,2.10; test value: c,79.05; h,3.78; n,2.13.
MALDI-TOF-MS: theoretical value 669.1; experimental value 669.1.
Example 18
In a 250mL two-necked flask, m-40 (4.4 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-41 (1.9 g, yield: 43%).
Elemental analysis structure (C) 30 H 32 ClN): theoretical value: c,81.51; h,7.30; n,3.17; test value: c,81.53; h,7.35; n,3.11.
MALDI-TOF-MS: theoretical value 441.2; experimental value 441.2.
In a 250mL two-necked flask under argon atmosphere, m-41 (4.4 g,10.0 mmol), p-dibromobenzene (1.2 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.35 g,0.5 mmol) was added to 60mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-42 (3.9 g, yield)The rate is as follows: 41%).
Elemental analysis structure (C) 66 H 66 Cl 2 N 2 ): theoretical value: c,82.73; h,6.94; n,2.92; test value: c,82.71; h,6.92; n,2.95.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
M-42 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product m-43 (0.6 g, yield: 16%). Elemental analysis structure (C) 66 H 62 N 2 P 2 S 2 ): theoretical value: c,78.54; h,6.19; n,2.78; s,6.35; test value: c,78.51; h,6.13; n,2.79; s,6.36.
MALDI-TOF-MS: theoretical value 1008.4; experimental value 1008.4.
M-43 (10.1 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was separated by silica gel column chromatography to give a product 2-55 (3.2 g, yield: 33%).
Elemental analysis structure (C) 66 H 62 N 2 O 2 P 2 ): theoretical value: c,81.12; h,6.40; n,2.87; test value: c,81.03; h,6.43; n,2.84。
MALDI-TOF-MS: theoretical value 976.4; experimental value 976.4.
Example 19
In a 250mL two-necked flask, m-44 (2.9 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-45 (1.3 g, yield: 44%).
Elemental analysis structure (C) 17 H 12 ClFO): theoretical value: c,71.21; h,4.22; test value: c,71.25; h,4.20.
MALDI-TOF-MS: theoretical value 286.1; experimental value 286.1.
In a 250mL two-necked flask, m-45 (2.9 g,10.0 mmol), p-diphenylthiol (0.7 g,5.0 mmol) and cesium carbonate (6.5 g,20.0 mmol) were charged under argon atmosphere, and the system was reacted at 120℃for 5 hours. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-46 (2.7 g, yield: 41%).
Elemental analysis structure (C) 40 H 28 Cl 2 O 2 S 2 ): theoretical value: c,71.10; h,4.18; s,9.49; test value: c,71.17; h,4.15; s,9.44.
MALDI-TOF-MS: theoretical value 674.1; experimental value 674.1.
M-46 (2.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to minus 30 ℃, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system and the mixture was droppedAfter 20 minutes of addition, stirring was carried out at 60℃for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 2-70 (0.6 g, yield: 19%). Elemental analysis structure (C) 40 H 24 O 2 P 2 S 4 ): theoretical value: c,66.10; h,3.33; s,17.64; test value: c,66.14; h,3.31; s,17.62.
MALDI-TOF-MS: theoretical value 726.0; experimental 726.0.
Example 20
In a 250mL two-necked flask, m-47 (4.8 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-48 (2.0 g, yield: 41%).
Elemental analysis structure (C) 30 H 30 BrN): theoretical value: c,74.37; h,6.24; n,2.89; test value: c,74.32; h,6.26; n,2.83.
MALDI-TOF-MS: theoretical value 483.2; experimental value 483.2.
In a 250mL two-necked flask, m-48 (4.8 g,10.0 mmol), m-49 (5.8 g,10.0 mmol) and cesium carbonate (6.5 g,20.0 mmol) were added under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-50 (5.6 g, yield: 54%).
Elemental analysis structure (C) 66 H 62 Br 2 N 2 ): theoretical value: c,76.00; h,5.99; n,2.69; test value: c,76.05; h,5.93; n,2.72.
MALDI-TOF-MS: theoretical value 1040.3; experimental value 1040.3.
M-50 (4.2 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 3-3 (1.4 g, yield: 38%).
Elemental analysis structure (C) 66 H 58 B 2 N 2 ): theoretical value: c,88.00; h,6.49; n,3.11; test value: c,88.05; h,6.44; n,3.12.
MALDI-TOF-MS: theoretical 900.5; experimental 900.5.
Example 21
In a 250mL two-necked flask, m-51 (3.3 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-52 (1.5 g, yield: 44%).
Elemental analysis structure(C 22 H 16 ClN): theoretical value: c,80.12; h,4.89; n,4.25; test value: c,80.10; h,4.85; n,4.22.
MALDI-TOF-MS: theoretical value 329.1; experimental value 329.1.
In a 250mL two-necked flask under argon atmosphere, m-52 (3.3 g,10.0 mmol), m-53 (5.4 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-54 (3.0 g, yield: 40%).
Elemental analysis structure (C) 48 H 32 Cl 2 N 2 S): theoretical value: c,77.93; h,4.36; n,3.79; s,4.33; test value: c,77.97; h,4.32; n,3.72; s,4.35.
MALDI-TOF-MS: theoretical value 738.2; experimental value 738.2.
M-54 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give 3-7 (0.9 g, yield: 31%).
Elemental analysis structure (C) 48 H 28 B 2 N 2 S): theoretical value: c,83.99; h,4.11; n,4.08; s,4.67; test value: c,83.95; h,4.13; n,4.05; s,4.62.
MALDI-TOF-MS: theoretical value 686.2; experimental value 686.2.
Example 22
Under argon atmosphere, m-55 (4.1 g,9.3 mmol) and copper powder (7.0 g,111.0 mmol) are added into a 48mL single-port reaction flask, and mixed uniformly, 1-iodonaphthalene (5.7 g,22.5 mmol) is added into the flask, the flask is sealed, and the flask is heated at 235 ℃ for 20min. After cooling to room temperature, the tube was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-56 (0.9 g, yield: 21%).
Elemental analysis structure (C) 24 H 19 BrClN): theoretical value: c,66.00; h,4.38; n,3.21; test value: c,66.02; h,4.35; n,3.24.
MALDI-TOF-MS: theoretical value 435.0; experimental value 435.0.
In a 250mL two-necked flask under argon atmosphere, m-56 (4.4 g,10.0 mmol), m-57 (2.2 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-58 (2.3 g, yield: 41%).
Elemental analysis structure (C) 38 H 33 ClN 2 ): theoretical value: c,82.51; h,6.01; n,5.06; test value: c,82.55; h,6.04; n,5.03.
MALDI-TOF-MS: theoretical value 552.2; experimental value 552.2.
In a 250mL two-necked flask under argon atmosphere, m-58 (5.5 g,10.0 mmol), m-59 (7.8 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-60 (3.8 g, yield: 32%).
Element separationAnalysis structure (C) 82 H 68 Cl 2 N 4 ): theoretical value: c,83.44; h,5.81; n,4.75; test value: c,83.41; h,5.83; n,4.79.
MALDI-TOF-MS: theoretical value 1178.5; experimental value 1178.5.
M-60 (4.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 3-18 (1.4 g, yield: 30%).
Elemental analysis structure (C) 82 H 64 B 2 N 4 ): theoretical value: c,87.39; h,5.72; n,4.97; test value: c,87.37; h,5.71; n,4.92.
MALDI-TOF-MS: theoretical value 1126.5; experimental value 1126.5.
Example 23
In a 250mL two-necked flask, m-61 (3.3 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-62 (1.5 g, yield: 45%).
Elemental analysis structure (C) 17 H 11 BrF 2 ): theoretical value: c,61.29; h,3.33; test value: c,61.23；H,3.34。
MALDI-TOF-MS: theoretical 332.0; experimental 332.0.
In a 250mL two-necked flask, m-62 (3.3 g,10.0 mmol), m-63 (3.4 g,10.0 mmol) and potassium carbonate (2.8 g,20.0 mmol) were charged under argon atmosphere, and 30mL of DMF was added and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-64 (4.1 g, yield: 63%).
Elemental analysis structure (C) 38 H 25 BrFN 3 S): theoretical value: c,69.72; h,3.85; n,6.42; s,4.90; test value: c,69.74; h,3.87; n,6.40; s,4.93.
MALDI-TOF-MS: theoretical value 653.1; experimental value 653.1.
In a 250mL two-necked flask, m-64 (6.5 g,10.0 mmol), m-65 (3.2 g,10.0 mmol) and potassium carbonate (2.8 g,20.0 mmol) were charged under argon atmosphere, and 30mL of DMF was added and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-66 (5.1 g, yield: 54%).
Elemental analysis structure (C) 54 H 35 Br 2 N 3 S 2 ): theoretical value: c,68.29; h,3.71; n,4.42; s,6.75; test value: c,68.25; h,3.73; n,4.45; s,6.72.
MALDI-TOF-MS: theoretical value 947.1; experimental value 947.1.
M-66 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 3-64 (1.0 g, yield: 31%).
Elemental analysis structure (C) 54 H 31 B 2 N 3 S 2 ): theoretical value: c,80.31; h,3.87; n,5.20; s,7.94; test value: c,80.34; h,3.84; n,5.22; s,7.97.
MALDI-TOF-MS: theoretical value 807.2; experimental value 807.2.
Example 24
In a 250mL two-necked flask, m-67 (4.4 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-68 (1.9 g, yield: 42%).
Elemental analysis structure (C) 30 H 32 ClN): theoretical value: c,81.51; h,7.30; n,3.17; test value: c,81.55; h,7.32; n,3.13.
MALDI-TOF-MS: theoretical value 441.2; experimental value 441.2.
In a 250mL two-necked flask under argon atmosphere, m-68 (4.4 g,10.0 mmol), m-69 (5.3 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-70 (3.8 g, yield: 40%).
Elemental analysis structure (C) 66 H 66 Cl 2 N 2 ): theoretical value: c,82.73; h,6.94; n,2.92; test value: c,82.71; h,6.97; n,2.93.
MALDI-TOF-MS: theoretical value 956.5; experimental value 956.5.
M-70 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product m-71 (1.0 g, yield: 26%). Elemental analysis structure (C) 66 H 62 N 2 P 2 S 2 ): theoretical value: c,78.54; h,6.19; n,2.78; s,6.35; test value: c,78.51; h,6.16; n,2.73; s,6.32.
MALDI-TOF-MS: theoretical value 1008.4; experimental value 1008.4.
M-71 (10.1 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to obtain a product 3-49 (3.0 g, yield: 31%).
Elemental analysis structure (C) 66 H 62 N 2 O 2 P 2 ): theoretical value: c,81.12; h,6.40; n,2.87; test value: c,81.15; h,6.41; n,2.84.
MALDI-TOF-MS: theoretical value 976.4; experimental value 976.4.
Example 25
In a 250mL two-necked flask, m-72 (4.0 g,10.0 mmol), naphthalene 1-borate (1.9 g,11.0 mmol), potassium carbonate (1.9 g,20.0 mmol) and Pd (PPh) were charged under an argon atmosphere 3 ) 2 Cl 2 (0.18 g,0.25 mmol) and 30mL of toluene were added and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-73 (1.6 g, yield: 41%).
Elemental analysis structure (C) 16 H 9 Br 2 Cl): theoretical value: c,48.47; h,2.29; test value: c,48.44; h,2.23.
MALDI-TOF-MS: theoretical value 393.9; experimental value 393.9.
Into a 250mL two-necked flask under argon atmosphere were charged m-73 (4.0 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-74 (2.0 g, yield: 42%).
Elemental analysis structure (C) 28 H 19 BrClN): theoretical value: c,69.37; h,3.95; n,2.89; test value: c,69.39; h,3.93; n,2.87.
MALDI-TOF-MS: theoretical 483.0; experimental 483.0.
In a 250mL two-necked flask, m-74 (4.8 g,10.0 mmol), m-75 (2.7 g,10.0 mmol) and cesium carbonate (6.5 g,20.0 mmol) were added under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-76 (3.4 g, yield: 52%).
Elemental analysis structure (C) 44 H 29 Cl 2 NO): theoretical value: c,80.24; h,4.44; n,2.13; test value: c,80.29; h,4.43; n,2.11.
MALDI-TOF-MS: theoretical value 657.2; experimental value 657.2.
M-76 (2.6 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was obtained by separating the product 3-62 by silica gel column chromatography (0.7 g, yield: 23%).
Elemental analysis structure (C) 44 H 25 NOP 2 S 2 ): theoretical value: c,74.46; h,3.55; n,1.97; s,9.03; test value: c,74.48; h,3.57; n,1.93; s,9.06.
MALDI-TOF-MS: theoretical 709.1; experimental 709.1.
Example 26
Under argon atmosphere, m-77 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added into a 48mL single-port reaction flask, mixed well, 1-iodonaphthalene (11.4 g,45.0 mmol) was added thereto, mixed well, and the mixture was heated at 235℃for 20min after sealing. After cooling to room temperature, the tube was opened, toluene was added thereto, filtration was performed, the residue was washed with toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-78 (1.1 g, yield: 22%).
Elemental analysis junctionStructure (C) 26 H 14 Br 2 Cl 2 ): theoretical value: c,56.06; h,2.53; test value: c,56.03; h,2.51.
Matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS): theoretical value 553.9; experimental value 553.9.
Into a 250mL two-necked flask under argon atmosphere were charged m-78 (5.6 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-79 (2.9 g, yield: 40%).
Elemental analysis structure (C) 50 H 34 Cl 2 N 2 ): theoretical value: c,81.85; h,4.67; n,3.82; test value: c,81.82; h,4.64; n,3.81.
MALDI-TOF-MS: theoretical value 732.2; experimental value 732.2.
M-79 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was obtained by separating by silica gel column chromatography to give product 4-1 (0.8 g, yield: 30%).
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,88.27; h,4.42; n,4.10.
MALDI-TOF-MS: theoretical 680.3; experimental value 680.3.
Example 27
In a 250mL two-necked flask, m-80 (5.6 g,10.0 mmol), p-tert-butylphenol (1.7 g,10.0 mmol), m-81 (1.7 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF 60mL was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-82 (3.1 g, yield: 43%).
Elemental analysis structure (C) 44 H 32 Cl 2 S 3 ): theoretical value: c,72.61; h,4.43; s,13.21; test value: c,72.66; h,4.41; s,13.20.
MALDI-TOF-MS: theoretical value 726.1; experimental value 726.1.
M-82 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 4-47 (0.7 g, yield: 25%).
Elemental analysis structure (C) 44 H 28 B 2 S 3 ): theoretical value: c,78.35; h,4.18; s,14.26; test value: c,78.38; h,4.13; s,14.22.
MALDI-TOF-MS: theoretical value 674.2; experimental value 674.2.
Example 28
Under argon atmosphere, m-83 (5.2 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) are added into a 48mL single-port reaction flask and uniformly mixed, then m-84 (12.6 g,45.0 mmol) is added into the flask and uniformly mixed, and the flask is heated at 235 ℃ for 20min after tube sealing. After cooling to room temperature, the tube was carefully opened, toluene was added thereto, filtration, washing of the residue with toluene, removal of the solvent, and separation of the crude product by silica gel column chromatography gave the product m-85 (1.3 g, yield: 23%).
Elemental analysis structure (C) 30 H 18 Br 2 Cl 2 ): theoretical value: c,59.15; h,2.98; test value: c,59.16; h,2.99.
MALDI-TOF-MS: theoretical value 605.9; experimental value 605.9.
Dinaphthyldiselenide (26.4 g,64.0 mmol), sodium borohydride (4.9 g,128.0 mmol) and 300mL DMF are added into a 250mL three-necked flask under argon atmosphere to react for 4 hours at room temperature, m-85 (39.0 g,64.0 mmol) is added into the system under argon protection to react for 24 hours at 80 ℃, then the reaction solution is cooled to room temperature, the reaction solution is poured into water (3000 mL), solid is filtered out, the solvent is removed, and the crude product is separated by silica gel column chromatography to obtain a product m-86 (15.1 g, yield: 31%).
Elemental analysis structure (C) 42 H 28 Cl 2 Se 2 ): theoretical value: c,66.24; h,3.71; test value: c,66.25; h,3.76.
MALDI-TOF-MS: theoretical value 762.0; experimental value 762.0.
M-86 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 4-28 (0.6 g, yield: 23%).
Elemental analysis structure (C) 42 H 24 B 2 Se 2 ): theoretical value: c,71.23; h,3.42; test value: c,71.21; h,3.45.
MALDI-TOF-MS: theoretical value 710.0; experimental value 710.0.
Example 29
Into a 250mL two-necked flask under argon atmosphere were charged m-87 (5.6 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-88 (2.2 g, yield: 34%).
Elemental analysis structure (C) 38 H 24 BrCl 2 N): theoretical value: c,70.72; h,3.75; n,2.17; test value: c,70.78; h,3.73; n,2.13.
MALDI-TOF-MS: theoretical value 643.1; experimental value 643.1.
Dinaphthylditelluride (13.1 g,32.0 mmol), sodium borohydride (2.5 g,64.0 mmol) and 300mL DMF are added into a 250mL three-neck flask under argon atmosphere to react for 4 hours at room temperature, m-88 (41.3 g,64.0 mmol) is added into the system under argon protection, stirring is carried out at 80 ℃ for 24 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water (3000 mL), solid is filtered out, the solvent is removed by pumping, and the crude product is separated by a column to obtain a product m-89 (15.8 g, yield: 32%).
Elemental analysis structure (C) 44 H 29 Cl 2 NTe): theoretical value: c,68.61; h,3.80; n,1.82; test value: c,68.61; h,3.80; n,1.82.
MALDI-TOF-MS: theoretical value 771.1; experimental value 771.1.
M-89 (3.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give 4-36 (0.8 g, yield: 27%).
Elemental analysis structure (C) 44 H 25 B 2 NTe): theoretical value: c,73.72; h,3.52; n,1.95; test value: c,73.70; h,3.51; n,1.92.
MALDI-TOF-MS: theoretical value 719.1; experimental value 719.1.
Example 30
In a 250mL two-necked flask, m-90 (5.6 g,10.0 mmol), m-91 (4.6 g,20.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-92 (2.8 g, yield: 33%).
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,78.98; h,5.24; s,7.51.
MALDI-TOF-MS: theoretical value 850.2; experimental value 850.2.
M-92 (3.4 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃.Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 mmol,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product m-93 (0.8 g, yield: 22%). Elemental analysis structure (C) 56 H 40 P 2 S 4 ): theoretical value: c,74.48; h,4.46; s,14.20; test value: c,74.43; h,4.49; s,14.21.
MALDI-TOF-MS: theoretical value 902.1; experimental value 902.1.
M-93 (9.0 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give a product 4-48 (2.9 g, yield: 32%).
Elemental analysis structure (C) 56 H 40 O 2 P 2 S 2 ): theoretical value: c,77.22; h,4.63; s,7.36; test value: c,77.24; h,4.61; s,7.32.
MALDI-TOF-MS: theoretical value 870.2; experimental value 870.2.
Example 31
In a 250mL two-necked flask, m-94 (5.6 g,10.0 mmol), m-95 (1.8 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-96 (2.2 g, yield: 34%).
Elemental analysis structure (C) 37 H 25 BrCl 2 S): theoretical value: c,68.11; h,3.86; s,4.91; test value: c,68.10; h,3.83; s,4.92.
MALDI-TOF-MS: theoretical value 650.0; experimental value 650.0.
Into a 250mL two-necked flask under argon atmosphere were charged m-96 (6.5 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-97 (3.0 g, yield: 41%).
Elemental analysis structure (C) 49 H 35 Cl 2 NS): theoretical value: c,79.45; h,4.76; n,1.89; s,4.33; test value: c,79.43; h,4.73; n,1.86; s,4.31.
MALDI-TOF-MS: theoretical value 739.2; experimental value 739.2.
M-97 (3.0 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 mmol,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 4-49 (0.7 g, yield: 21%). Elemental analysis structure (C) 49 H 31 NP 2 S 3 ): theoretical value: c,74.32; h,3.95; n,1.77; s,12.15; test value: c,74.36; h,3.93; n,1.74; s,12.13.
MALDI-TOF-MS: theoretical value 791.1; experimental value 791.1.
Example 32
Under argon atmosphere, m-98 (3, 7g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) are added into a 48mL single-port reaction bottle, uniformly mixed, 4-iodoquinoline (11.5 g,45.0 mmol) is added into the mixture, uniformly mixed, and the mixture is heated at 235 ℃ for 20min after tube sealing. After cooling to room temperature, the tube was carefully opened, toluene was added thereto, filtration, washing of the filter residue with toluene, removal of the solvent, and separation of the crude product by silica gel column chromatography gave the product m-99 (0.9 g, yield: 24%).
Elemental analysis structure (C) 15 H 8 Br 2 ClN): theoretical value: c,45.33; h,2.03; n,3.52; test value: c,45.30; h,2.06; n,3.51.
MALDI-TOF-MS: theoretical value 394.9; experimental value 394.9.
In a 250mL two-necked flask, m-99 (4.0 g,10.0 mmol), m-100 (3.6 g,11.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged under argon atmosphere 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-101 (2.8 g, yield: 44%).
Elemental analysis structure (C) 37 H 23 BrCl 2 N 2 ): theoretical value: c,68.75; h,3.59; n,4.33; test value: c,68.78; h,3.53; n,4.35.
MALDI-TOF-MS: theoretical value 644.0; experimental value 644.0.
In a 250mL two-necked flask, m-101 (6.5 g,10.0 mmol), diphenylamine (1.9 g,11.0 mmol) and t-butanol were charged under argon atmosphereSodium (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-102 (3.0 g, yield: 41%).
Elemental analysis structure (C) 48 H 32 Cl 2 N 4 ): theoretical value: c,78.36; h,4.38; n,7.62; test value: c,78.33; h,4.36; n,7.60.
MALDI-TOF-MS: theoretical 734.2; experimental 734.2.
M-102 (2.9 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give a product 5-49 (0.6 g, yield: 22%).
Elemental analysis structure (C) 48 H 28 B 2 N 4 ): theoretical value: c,84.49; h,4.14; n,8.21; test value: c,84.43; h,4.16; n,8.24.
MALDI-TOF-MS: theoretical value 682.3; experimental value 682.3.
Example 33
In a 250mL two-necked flask, m-103 (3.2 g,10.0 mmol), m-104 (3.2 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF 60mL was added and the system was reacted at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-105 (1.9 g, yield: 31%).
Elemental analysis structure (C) 32 H 19 Br 2 FS): theoretical value: c,62.56; h,3.12; s,5.22; test value: c,62.52; h,3.14; s,5.25.
MALDI-TOF-MS: theoretical value 612.0; experimental value 612.0.
In a 250mL two-necked flask, m-105 (6.1 g,10.0 mmol), m-106 (5.2 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-107 (3.4 g, yield: 31%).
Elemental analysis structure (C) 68 H 42 Br 2 N 2 S 2 ): theoretical value: c,73.51; h,3.81; n,2.52; s,5.77; test value: c,73.52; h,3.83; n,2.55; s,5.71.
MALDI-TOF-MS: theoretical value 1108.1; experimental value 1108.1.
M-107 (4.4 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give a product 5-50 (1.1 g, yield: 29%).
Elemental analysis structure (C) 68 H 38 B 2 N 2 S 2 ): theoretical value: c,84.30; h,3.95; n,2.89; s,6.62; test value: c,84.30; h,3.92; n is a number of the N,2.84；S,6.60。
MALDI-TOF-MS: theoretical value 968.3; experimental value 968.3.
Example 34
In a 250mL two-necked flask, m-108 (4.8 g,10.0 mmol), m-109 (3.2 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-110 (2.4 g, yield: 31%).
Elemental analysis structure (C) 47 H 32 Cl 2 N 2 Se): theoretical value: c,72.87; h,4.16; n,3.62; test value: c,72.87; h,4.18; n,3.69.
MALDI-TOF-MS: theoretical value 774.1; experimental value 774.1.
M-110 (3.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give a product 5-51 (0.7 g, yield: 25%).
Elemental analysis structure (C) 47 H 28 B 2 N 2 Se): theoretical value: c,78.26; h,3.91; n,3.88 test value: c,78.23; h,3.94; n,3.85.
MALDI-TOF-MS: theoretical 722.2; experimental value 722.2.
Example 35
In a 250mL two-necked flask, m-111 (4.2 g,10.0 mmol), m-112 (2.7 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-113 (2.2 g, yield: 32%).
Elemental analysis structure (C) 44 H 29 Cl 2 NS): theoretical value: c,78.33; h,4.33; n,2.08; s,4.75; test value: c,78.31; h,4.38; n,2.04; s,4.72.
MALDI-TOF-MS: theoretical value 673.1; experimental value 673.1.
M-113 (2.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product m-114 (0.6 g, yield: 20%). Elemental analysis structure (C) 44 H 25 NP 2 S 3 ): theoretical value: c,72.81; h,3.47; n,1.93; s,13.25; test value: c,72.82; h,3.46; n,1.97; s,13.21.
MALDI-TOF-MS: theoretical value 725.1; experimental value 725.1.
M-114 (7.3 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give a product 5-43 (2.6 g, yield: 37%).
Elemental analysis structure (C) 44 H 25 NO 2 P 2 S): theoretical value: c,76.18; h,3.63; n,2.02; s,4.62; test value: c,76.13; h,3.62; n,2.06; s,4.64.
MALDI-TOF-MS: theoretical value 693.1; experimental value 693.1.
Example 36
In a 250mL two-necked flask, m-115 (3.2 g,10.0 mmol), m-116 (3.6 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-117 (2.2 g, yield: 34%).
Elemental analysis structure (C) 32 H 19 Br 2 FSe): theoretical value: c,58.12; h,2.90; test value: c,58.14; h,2.92.
MALDI-TOF-MS: theoretical value 659.9; experimental value 659.9.
In a 250mL two-necked flask, m-117 (6.6 g,10.0 mmol), m-117-2 (3.1 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-118 (2.9 g, yield: 31%).
Elemental analysis structure (C) 49 H 42 Br 2 Se 2 ): theoretical value: c,62.04; h,4.46; test value: c,62.08; h,4.42.
MALDI-TOF-MS: theoretical value 948.0; experimental value 948.0.
M-118 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give a product 5-52 (0.8 g, yield: 21%).
Elemental analysis structure (C) 49 H 38 P 2 S 2 Se 2 ): theoretical value: c,64.61; h,4.21; s,7.04; test value: c,64.61; h,4.20; s,7.03.
MALDI-TOF-MS: theoretical value 912.0; experimental value 912.0.
Example 37
M-119 (3.1 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added to a 48mL pressure-resistant tube under argon atmosphere, and mixed uniformly, and then 4-iodoquinoline (11.5 g,45.0 mmol) was added thereto, and the tube was sealed and heated at 235℃for 20min. After air cooling for 2min, the tube was carefully opened, toluene was added thereto, the mixture was filtered while it was still hot, the residue was washed with hot toluene, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-120 (0.8 g, yield: 25%).
Elemental analysis structure (C) 21 H 15 ClN 2 ): theoretical value: c,76.25; h,4.57; n,8.47; test value: c,76.27; h,4.55; n,8.44.
MALDI-TOF-MS: theoretical value 330.1; experimental value 330.1.
In a 250mL two-necked flask under argon atmosphere, m-120 (3.3 g,10.0 mmol), 1, 2-dibromo-4, 5-dimethylbenzene (1.3 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-121 (1.6 g, yield: 41%).
Elemental analysis structure (C) 50 H 36 Cl 2 N 4 ): theoretical value: c,78.63; h,4.75; n,7.34; test value: c,78.61; h,4.73; n,7.32.
MALDI-TOF-MS: theoretical value 762.2; experimental value 762.2.
M-121 (3.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give a product 6-59 (0.8 g, yield: 28%).
Elemental analysis structure (C) 50 H 32 B 2 N 4 ): theoretical value: c,84.53; h,4.54; n,7.89; test value: c,84.56; h,4.52; n,7.85.
MALDI-TOF-MS: theoretical value 710.3; experimental value 710.3.
Example 38
Into a 250mL two-necked flask under argon atmosphere were charged m-122 (3.4 g,10.0 mmol), diphenylamine (1.7 g,10.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-123 (1.8 g, yield: 42%).
Elemental analysis structure (C) 28 H 19 ClFN): theoretical value: c,79.33; h,4.52; n,3.30; test value: c,79.31; h,4.54; n,3.32.
MALDI-TOF-MS: theoretical value 423.1; experimental value 423.1.
In a 250mL two-necked flask, m-123 (4.2 g,10.0 mmol), o-diphenylthiol (0.7 g,5.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were added under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-124 (3.5 g, yield: 37%).
Elemental analysis structure (C) 62 H 42 Cl 2 N 2 S 2 ): theoretical value: c,78.38; h,4.46; n,2.95; s,6.75; test value: c,78.32; h,4.44; n,2.94; s,6.72.
MALDI-TOF-MS: theoretical value 948.2; experimental value 948.2.
M-124 (3.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give the product 6-28 (0.9 g, yield: 25%).
Elemental analysis structure (C) 62 H 38 B 2 N 2 S 2 ): theoretical value: c,83.04; h,4.27; n,3.12; s,7.15; test value: c,83.01; h,4.29; n,3.14; s,7.12.
MALDI-TOF-MS: theoretical 896.3; experimental value 896.3.
Example 39
In a 250mL two-necked flask under argon atmosphere, m-125 (2.8 g,10.0 mmol), o-bromophenol (1.7 g,10.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) were charged 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give the product m-126 (2.3 g, yield: 52%).
Elemental analysis structure (C) 24 H 16 BrClO): theoretical value: c,66.15; h,3.70; test value: c,66.11; h,3.73.
MALDI-TOF-MS: theoretical value 434.0; experimental value 434.0.
In a 250mL two-necked flask, m-126 (4.4 g,10.0 mmol), m-127 (3.6 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF 60mL was added to react at 120℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-128 (2.6 g, yield: 36%).
Elemental analysis structure (C) 48 H 33 Cl 2 NO): theoretical value: c,81.12; h,4.68; n,1.97; test value:C,81.13；H,4.65；N,1.92。
MALDI-TOF-MS: theoretical 709.2; experimental 709.2.
M-128 (2.8 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give product 6-42 (0.6 g, yield: 23%).
Elemental analysis structure (C) 48 H 29 B 2 NO): theoretical value: c,87.70; h,4.45; n,2.13; test value: c,87.71; h,4.43; n,2.15.
MALDI-TOF-MS: theoretical value 657.2; experimental value 657.2.
Example 40
M-129 (5.5 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added to a 48mL single port reaction flask under argon atmosphere, mixed well, m-130 (11.7 g,45.0 mmol) was added thereto, mixed well, and the mixture was heated at 235℃for 20min after sealing. After cooling to room temperature, the tube was carefully opened, toluene was added thereto, filtration, washing of the filter residue with toluene, removal of the solvent, and separation of the crude product by silica gel column chromatography gave the product m-131 (1.1 g, yield: 23%).
Elemental analysis structure (C) 32 H 20 BrFS): theoretical value: c,71.78; h,3.76; s,5.99; test value: c,71.76; h,3.74; s,5.92.
MALDI-TOF-MS: theoretical value 534.1; experimental value 534.1.
M-131 (5.4 g,10.0 mmol), o-diphenylselenophene (2.4 g,5.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were added to a 250mL two-necked flask under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5h. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was separated by silica gel column chromatography to give product m-132 (4.3 g, yield: 34%).
Elemental analysis structure (C) 70 H 44 Br 2 S 2 Se 2 ): theoretical value: c,66.36; h,3.50; s,5.06; test value: c,66.36; h,3.54; s,5.03.
MALDI-TOF-MS: theoretical value 1266.0; experimental value 1266.0.
M-132 (5.1 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 1 hour at 50℃and cooled again to-30℃again, and boron tribromide (2.5 g,1.0mL,10.0 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 deg.c again, dropping N, N-diisopropylethylamine (2.2 g,2.8ml,17.2 mmol) into the reaction system dropwise, and raising the temperature to 125 deg.c to react for 20 hr. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by silica gel column chromatography to give 6-60 (1.0 g, yield: 23%).
Elemental analysis structure (C) 70 H 40 B 2 S 2 Se 2 ): theoretical value: c,74.75; h,3.58; s,5.70; test value: c,74.72; h,3.56; s,5.72.
MALDI-TOF-MS: theoretical value 1126.1; experimental value 1126.1.
Example 41
Under argon atmosphere, m-133 (3.1 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added to a 48mL pressure-resistant tube, and mixed uniformly, and then m-134 (13.3 g,45.0 mmol) was added thereto, and the tube was sealed and heated at 235℃for 20 minutes. After air cooling for 2min, the tube was carefully opened, toluene was added thereto, the mixture was filtered while it was still hot, the residue was washed with hot toluene, the solvent was removed by suction, and the crude product was isolated in a column to give the product m-135 (0.7 g, yield: 21%).
Elemental analysis structure (C) 25 H 22 ClN): theoretical value: c,80.74; h,5.96; n,3.77; test value: c,80.77; h,5.93; n,3.75.
MALDI-TOF-MS: theoretical 371.1; experimental 371.1.
In a 250mL two-necked flask under argon atmosphere was charged m-135 (3.7 g,10.0 mmol), 1, 2-dibromo-4-trifluoromethylbenzene (1.5 g,5.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was isolated by column separation to give the product m-136 (1.9 g, yield: 43%).
Elemental analysis structure (C) 57 H 45 Cl 2 F 3 N 2 ): theoretical value: c,77.28; h,5.12; n,3.16; test value: c,77.28; h,5.10; n,3.13.
MALDI-TOF-MS: theoretical value 884.3; experimental value 884.3.
M-136 (3.5 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-neck flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by column to give the product m-137 (0.8 g, yield: 21%).
Elemental analysis structure (C) 57 H 41 F 3 N 2 P 2 S 2 ): theoretical value: c,73.06; h,4.41; n,2.99; s,6.84; test value: c,73.02; h,4.40; n,2.95; s,6.83.
MALDI-TOF-MS: theoretical value 936.2; experimental value 936.2.
M-137 (9.4 g,10.0 mmol) and methylene chloride (50 mL) were added to a 250mL two-necked flask under argon atmosphere, m-chloroperbenzoic acid (4.9 g,77wt%,22.0 mmol) was added thereto and stirred at room temperature for 5 hours, m-chloroperbenzoic acid (0.5 g,77wt%,2.2 mmol) was added thereto, the reaction system was stirred at room temperature for 16 hours, a saturated solution of sodium sulfite (50 mL) was added thereto, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was removed after concentration, and the crude product was isolated by column separation to give a product 6-61 (3.5 g, yield: 39%).
Elemental analysis structure (C) 57 H 41 F 3 N 2 O 2 P 2 ): theoretical value: c,75.66; h,4.57; n,3.10; test value: c,75.62; h,4.54; n,3.13.
MALDI-TOF-MS: theoretical value 904.3; experimental value 904.3.
Example 42
M-138 (3.1 g,9.3 mmol) and copper powder (14.1 g,222.0 mmol) were added to a 48mL pressure-resistant tube under argon atmosphere, and mixed uniformly, and 4-iodonaphthalene (11.4 g,45.0 mmol) was added thereto, and the tube was sealed and heated at 235℃for 20min. After air cooling for 2min, the tube was carefully opened, toluene was added thereto, the mixture was filtered while it was still hot, the residue was washed with hot toluene, the solvent was removed by suction, and the crude product was isolated in a column to give the product m-139 (0.8 g, yield: 22%).
Elemental analysis structure (C) 25 H 22 ClN): theoretical value: c,80.74; h,5.96; n,3.77; test value: c,80.77; h,5.92; n,3.73.
MALDI-TOF-MS: theoretical 371.1; experimental 371.1.
In a 250mL two-necked flask under argon atmosphere was charged m-139 (3.7 g,10.0 mmol), o-dibromobenzene (2.4 g,10.0 mmol), sodium t-butoxide (1.9 g,20.0 mmol) and (AMPHOS) 2 PdCl 2 (0.18 g,0.25 mmol) was added to 30mL of o-xylene and the system was reacted at 120℃for 5h. After cooling to room temperature, deionized water (30 ml. Times.3) was added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was isolated by column separation to give the product m-140 (1.9 g, yield: 39%).
Elemental analysis structure (C) 28 H 19 BrClN): theoretical value: c,69.37; h,3.95; n,2.89; test value: c,69.39; h,3.93; n,2.83.
MALDI-TOF-MS: theoretical 483.0; experimental 483.0.
In a 250mL two-necked flask, m-140 (4.8 g,10.0 mmol), m-141 (2.7 g,10.0 mmol) and potassium carbonate (5.5 g,40.0 mmol) were charged under argon atmosphere, and DMF (60 mL) was added to react at 120℃for 5 hours. After cooling to room temperature, dichloromethane (50 mL) and deionized water (30 mL x 3) were added thereto, and the resulting organic phase was dried over anhydrous sodium sulfate, concentrated, and the solvent was removed, and the crude product was isolated as m-142 (2.2 g, yield: 32%).
Elemental analysis structure (C) 44 H 29 Cl 2 NS): theoretical value: c,78.33; h,4.33; n,2.08; s,4.75; test value: c,78.35; h,4.36; n,2.04; s,4.73.
MALDI-TOF-MS: theoretical value 673.1; experimental value 673.1.
M-142 (2.7 g,4.0 mmol) and dried o-xylene (70 mL) were added dropwise to a 250mL two-necked flask under argon atmosphere, and a butyllithium solution (4.0 mL,2.5M,10.0 mmol) was added dropwise at-30℃and stirred for 10 hours at 50 ℃. Cooled again to-30deg.C, phosphorus trichloride (1.4 g,0.9mL,10.0 mmol) was added to the system, and after 20 minutes the mixture was stirred at 60deg.C for 1 hour. Cooling to-30deg.C again, adding sulfur powder (0.4 g,14.0 mmol) into the system, and stirring at 60deg.C for 1 hr after 20 min. Aluminum chloride (0.9 g,6.6 mmol) and N, N-diisopropylethylamine (2.2 g,2.8mL,17.2 mmol) were added to the reaction system again and the temperature was raised to 125℃for 20 hours. Cooling to room temperatureAfter that, a solid was precipitated in the filtration system and washed with methanol, and the crude product was separated by a column to obtain a product 6-58 (0.6 g, yield: 22%). Elemental analysis structure (C) 44 H 25 NP 2 S 3 ): theoretical value C,72.81; h,3.47; n,1.93; s,13.25; test value: c,72.83; h,3.49; n,1.95; s,13.22.
MALDI-TOF-MS: theoretical value 725.1; experimental value 725.1.
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 in polystyrene at a concentration of 1wt% to prepare a sample to be tested, and testing the sample with a time-resolved fluorescence spectrometer, the testing instrument being Edinburgh fluorescence spectrometer (FLS-980, UK).
As can be seen from Table 1, the fused ring compounds in the examples provided by the present invention exhibited delayed fluorescence effects with a delayed fluorescence lifetime of 46 to 102. Mu.s.
Device instance
The process for preparing the device by the organic light-emitting layer through the vacuum evaporation process comprises the following steps: on indium tin oxide supported on a glass substrate, 4×10 -4 Depositing TAPC, TCTA, EML (the mass ratio of the luminescent compound to SIMCP2 is 1:9), tmPyPB and LiF/Al cathode in sequence 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 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 on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating the inventive luminescent compound with SIMCP2 at a spin speed of 1500rpm in a mass ratio of 1:9, 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 43
Taking the fused ring compound 1-1 in the embodiment 1 as an implementation object, the fused ring compound 1-1 and SIMCP2 are subjected to the following mass ratio of 1:9 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 1-1 provided herein.
Example 44
Taking the fused ring compounds 1-5 in the embodiment 3 as implementation targets, the fused ring compounds 1-5 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-5 provided herein.
Example 45
Taking the fused ring compounds 1-15 in the embodiment 5 as implementation targets, the fused ring compounds 1-15 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-15 provided herein.
Example 46
Taking the fused ring compounds 1-19 in the embodiment 6 as implementation targets, the fused ring compounds 1-19 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-19 provided herein.
Example 47
Taking the fused ring compounds 1-32 in the embodiment 8 as implementation targets, mixing the fused ring compounds 1-32 with SIMCP2 according to a mass ratio of 1:9 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 1-32 provided herein.
Example 48
Taking the fused ring compounds 1-106 in the embodiment 9 as implementation targets, the fused ring compounds 1-106 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-106 provided herein.
Example 49
Taking the fused ring compounds 1-67 in the embodiment 10 as implementation targets, the fused ring compounds 1-67 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-67 provided herein.
Example 50
Taking the fused ring compounds 1-87 in the embodiment 11 as implementation targets, the fused ring compounds 1-87 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-87 provided herein.
Example 51
Taking the fused ring compounds 1-97 in the embodiment 12 as implementation targets, the fused ring compounds 1-97 and SIMCP2 are mixed according to the mass ratio of 1:9 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 1-97 provided herein.
Example 52
Taking the fused ring compound 2-1 in example 14 as an implementation object, the fused ring compound 2-1 and SIMCP2 are mixed according to a mass ratio of 1:9 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 2-1 provided herein.
Example 53
Taking the fused ring compounds 2-12 in the embodiment 15 as implementation targets, the fused ring compounds 2-12 and SIMCP2 are mixed according to the mass ratio of 1:9 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 2-12 provided herein.
Example 54
Taking the fused ring compounds 2-52 in the embodiment 17 as implementation targets, the fused ring compounds 2-52 and SIMCP2 are mixed according to the mass ratio of 1:9 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 2-52 provided herein.
Example 55
Taking the fused ring compounds 2-70 in the embodiment 19 as implementation targets, mixing the fused ring compounds 2-70 with SIMCP2 according to a mass ratio of 1:9 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 2-70 provided herein.
Example 56
Taking the fused ring compound 3-7 in the embodiment 21 as an implementation object, the fused ring compound 3-7 and SIMCP2 are mixed according to the mass ratio of 1:9 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 3-7 provided herein.
Example 57
Taking the fused ring compounds 3-64 in the embodiment 23 as implementation targets, the fused ring compounds 3-64 and SIMCP2 are mixed according to the mass ratio of 1:9 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 3-64 provided herein.
Example 58
Taking the fused ring compounds 3-62 in the embodiment 25 as implementation targets, the fused ring compounds 3-62 and SIMCP2 are mixed according to the mass ratio of 1:9 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 3-62 provided herein.
Example 59
Taking the fused ring compound 4-1 in the example 26 as an implementation object, the fused ring compound 4-1 and the SIMCP2 are subjected to the following mass ratio of 1:9 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 4-1 provided herein.
Example 60
Taking the fused ring compounds 4-47 in the embodiment 27 as implementation targets, the fused ring compounds 4-47 and SIMCP2 are mixed according to the mass ratio of 1:9 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 4-47 provided herein.
Example 61
Taking the fused ring compounds 4-28 in the embodiment 28 as implementation targets, the fused ring compounds 4-28 and SIMCP2 are mixed according to the mass ratio of 1:9 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 4-28 provided herein.
Example 62
Taking the fused ring compounds 4-36 in the embodiment 29 as implementation targets, the fused ring compounds 4-36 and SIMCP2 are mixed according to the mass ratio of 1:9 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 4-36 provided herein.
Example 63
Taking the fused ring compounds 4-48 in the embodiment 30 as implementation targets, the fused ring compounds 4-48 and SIMCP2 are mixed according to the mass ratio of 1:9 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 4-48 provided herein.
Example 64
Taking the fused ring compounds 4-49 in the embodiment 31 as implementation targets, the fused ring compounds 4-49 and SIMCP2 are mixed according to the mass ratio of 1:9 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 4-49 provided herein.
Example 65
Taking the fused ring compounds 5-49 in the embodiment 32 as implementation targets, the fused ring compounds 5-49 and SIMCP2 are mixed according to the mass ratio of 1:9 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 5-49 provided herein.
Example 66
Taking the fused ring compound 5-50 in the embodiment 33 as an implementation object, mixing the fused ring compound 5-50 with SIMCP2 according to a mass ratio of 1:9 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 5-50 provided herein.
Example 67
Taking the fused ring compounds 5-51 in the embodiment 34 as implementation targets, the fused ring compounds 5-51 and SIMCP2 are mixed according to the mass ratio of 1:9 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 5-51 provided herein.
Example 68
Taking the fused ring compounds 5-43 in the embodiment 35 as implementation targets, the fused ring compounds 5-43 and SIMCP2 are mixed according to the mass ratio of 1:9 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 5-43 provided herein.
Example 69
Taking the fused ring compounds 5-52 in the embodiment 36 as implementation targets, mixing the fused ring compounds 5-52 with SIMCP2 according to a mass ratio of 1:9 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 5-52 provided herein.
Example 70
Taking the fused ring compound 6-59 in example 37 as an implementation object, the fused ring compound 6-59 and SIMCP2 are mixed according to the mass ratio of 1:9 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 6-59 provided herein.
Example 71
Taking the fused ring compounds 6-28 in the embodiment 38 as implementation targets, the fused ring compounds 6-28 and SIMCP2 are mixed according to the mass ratio of 1:9 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 6-28 provided herein.
Example 72
Taking the fused ring compound 6-42 in the embodiment 39 as an implementation object, the fused ring compound 6-42 and SIMCP2 are mixed according to the mass ratio of 1:9 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 6-42 provided herein.
Example 73
Taking the fused ring compound 6-60 in the embodiment 40 as an implementation object, mixing the fused ring compound 6-60 with SIMCP2 according to a mass ratio of 1:9 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 6-60 provided herein.
Example 74
Taking the fused ring compound 6-61 in example 41 as an implementation object, the fused ring compound 6-61 and SIMCP2 are mixed according to the mass ratio of 1:9 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 6-61 provided herein.
Example 75
Taking the fused ring compounds 6-58 in the embodiment 42 as implementation targets, the fused ring compounds 6-58 and SIMCP2 are mixed according to the mass ratio of 1:9 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 6-58 provided herein.
Example 76
Taking the fused ring compounds 1-4 in the embodiment 2 as implementation targets, the fused ring compounds 1-4 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 1-4 provided herein.
Example 77
Taking the fused ring compounds 1-8 in the embodiment 4 as implementation targets, the fused ring compounds 1-8 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 1-8 provided herein.
Example 78
Taking the fused ring compounds 1-29 in the embodiment 7 as implementation targets, the fused ring compounds 1-29 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 1-29 provided herein.
Example 79
Taking the fused ring compounds 1-90 in the embodiment 13 as implementation targets, the fused ring compounds 1-90 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 1-90 provided herein.
Example 80
Taking the fused ring compounds 2-40 in the embodiment 16 as implementation targets, mixing the fused ring compounds 2-40 with SIMCP2 according to a mass ratio of 1:9 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 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 2-40 provided herein.
Example 81
Taking the fused ring compounds 2-55 in the embodiment 18 as implementation targets, the fused ring compounds 2-55 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 2-55 provided herein.
Example 82
Taking the fused ring compound 3-3 in the embodiment 20 as an implementation object, the fused ring compound 3-3 and SIMCP2 are mixed according to the mass ratio of 1:9 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 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 3-3 provided herein.
Example 83
Taking the fused ring compounds 3-18 in the embodiment 22 as implementation targets, mixing the fused ring compounds 3-18 with SIMCP2 according to a mass ratio of 1:9 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 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 3-18 provided herein.
Example 84
Taking the fused ring compounds 3-49 in the embodiment 24 as implementation targets, the fused ring compounds 3-49 and SIMCP2 are mixed according to the mass ratio of 1:9 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 B, and the obtained device is tested.
Referring to Table 2, table 2 provides the performance parameters of the electroluminescent devices prepared with 3-49 provided herein.
TABLE 2 Performance parameters of electroluminescent devices prepared from the fused Ring Compounds provided by the invention
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Note that: 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 boron-doped or phosphorus-doped fused ring compound provided by the invention has a 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 from the boron-doped or phosphorus-doped fused ring compound have higher device efficiency, and the maximum external quantum efficiency reaches 34.3%.
Claims (5)
1. A boron or phosphorus fused ring compound, characterized in that it is selected from any one of the following structures:
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2. a method of preparing a boron or phosphorus fused ring compound according to claim 1, wherein the boron or phosphorus fused ring compound has any one of structures represented by formulas (I) to (VI):
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:
reacting a compound shown in a formula (I-1), a formula (II-1), a formula (III-1), a formula (IV-1), a formula (V-1) or a formula (VI-1) with alkyl lithium, and then reacting with boron trihalide, or phosphorus trihalide and sulfur powder, aluminum chloride and organic amine to obtain a fused ring compound shown in a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V) or a formula (VI);
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 and methylene chloride, adding m-chloroperbenzoic acid thereto, and stirring at room temperature to react; after the reaction is finished, adding m-chloroperbenzoic acid into the reaction system, and continuing stirring reaction at room temperature; adding sodium sulfite saturated solution into the mixture after the reaction is finished, drying the obtained organic phase by using anhydrous sodium sulfate, removing the solvent, and separating the crude product by silica gel column chromatography to obtain a fused ring compound shown in the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V) or the formula (VI);
Lu 1 And Lu 2 Hydrogen or halogen; the other substituents correspond to substituents on each of the compounds of claim 1.
3. The method for producing a boron or phosphorus fused ring compound according to claim 2, wherein the alkyl lithium is one or more of butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium and ethyl lithium; the boron trihalide is one or more of boron trifluoride, boron trichloride, boron tribromide and boron triiodide; the organic amine is one or more of N, N-diisopropylethylamine, triethylamine and tri-N-butylamine.
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 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 condensed cyclic compound according to claim 1.
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| JPWO2010104047A1 (en) * | 2009-03-11 | 2012-09-13 | 国立大学法人京都大学 | Polycyclic aromatic compounds |
| CN113801151A (en) * | 2020-07-14 | 2021-12-17 | 北京八亿时空液晶科技股份有限公司 | Fused ring aromatic compound and application thereof |
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