CN114014812A - 一种以芴为核的化合物及其制备方法和应用 - Google Patents
一种以芴为核的化合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN114014812A CN114014812A CN202111277646.0A CN202111277646A CN114014812A CN 114014812 A CN114014812 A CN 114014812A CN 202111277646 A CN202111277646 A CN 202111277646A CN 114014812 A CN114014812 A CN 114014812A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- filtering
- extracting
- nitrogen
- dipropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 50
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 97
- 238000001914 filtration Methods 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 47
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 44
- 238000001816 cooling Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- 238000010898 silica gel chromatography Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 238000010992 reflux Methods 0.000 claims description 30
- -1 4- (2-bromophenyl) -5-phenyl-1, 3, 4-oxadiazole Chemical compound 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- XTSMCTWQYJCARH-UHFFFAOYSA-N CCCC1(CCC)C2=CC(Br)=CC=C2C(C=C2)=C1C=C2C(C=C1)=CC=C1N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCCC1(CCC)C2=CC(Br)=CC=C2C(C=C2)=C1C=C2C(C=C1)=CC=C1N(C1=CC=CC=C1)C1=CC=CC=C1 XTSMCTWQYJCARH-UHFFFAOYSA-N 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 22
- 239000007924 injection Substances 0.000 claims description 22
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 22
- QQTBEFPDRHYPLE-UHFFFAOYSA-N 2,7-dibromo-9,9-dipropylfluorene Chemical compound C1=C(Br)C=C2C(CCC)(CCC)C3=CC(Br)=CC=C3C2=C1 QQTBEFPDRHYPLE-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- QSKXKIRXGKSUNJ-UHFFFAOYSA-N N'-benzyl-4-bromobenzohydrazide Chemical compound C1=CC(Br)=CC=C1C(=O)NNCC1=CC=CC=C1 QSKXKIRXGKSUNJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000010926 purge Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 230000005525 hole transport Effects 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 11
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims description 11
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims description 11
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 11
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 235000011056 potassium acetate Nutrition 0.000 claims description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- KURRPQWVRLTHFJ-UHFFFAOYSA-N 3-(4-bromophenyl)-4,5-diphenyl-1,2,4-triazole Chemical compound C1=CC(Br)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=CC=C1 KURRPQWVRLTHFJ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- OEWAHVHQRNLQPY-UHFFFAOYSA-N N,N-diphenyl-4-[7-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9,9-dipropylfluoren-2-yl]aniline Chemical compound CCCC(CCC)(C1=C2)C(C=C(C=C3)C(C=C4)=CC=C4N(C4=CC=CC=C4)C4=CC=CC=C4)=C3C1=CC=C2C(C=C1)=CC=C1C1=NN=C(C2=CC=CC=C2)O1 OEWAHVHQRNLQPY-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 5
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 5
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 claims description 4
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 claims description 4
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019213 POCl3 Inorganic materials 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- QSCMTUDPSASZKR-UHFFFAOYSA-N 2-[4-[7-(4-carbazol-9-ylphenyl)-9,9-dipropylfluoren-2-yl]phenyl]-5-phenyl-1,3,4-oxadiazole Chemical compound CCCC1(CCC)C2=CC(C(C=C3)=CC=C3N3C(C=CC=C4)=C4C4=CC=CC=C34)=CC=C2C(C=C2)=C1C=C2C(C=C1)=CC=C1C1=NN=C(C2=CC=CC=C2)O1 QSCMTUDPSASZKR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 2
- RZMCPQKABSLOFL-UHFFFAOYSA-N B1(OC(C(O1)(C)C)(C)C)C2=CC=C(C=C2)C3=NN=C(N3C4=CC=CC=C4)C5=CC=CC=C5 Chemical compound B1(OC(C(O1)(C)C)(C)C)C2=CC=C(C=C2)C3=NN=C(N3C4=CC=CC=C4)C5=CC=CC=C5 RZMCPQKABSLOFL-UHFFFAOYSA-N 0.000 description 6
- NKCCSKDFAZERTE-UHFFFAOYSA-N CCCC1(CCC)C2=CC(Br)=CC=C2C(C=C2)=C1C=C2C(C=C1)=CC=C1N1C2=CC=CC=C2C2=C1C=CC=C2 Chemical compound CCCC1(CCC)C2=CC(Br)=CC=C2C(C=C2)=C1C=C2C(C=C1)=CC=C1N1C2=CC=CC=C2C2=C1C=CC=C2 NKCCSKDFAZERTE-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 108091006149 Electron carriers Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明涉及有机电致发光显示技术领域,特别涉及一种以芴为核的化合物及其制备方法和应用。本发明通过给受体种类、键接位置的改变得到了一系列的蓝色发光分子并且有着高效率和高迁移率的电致发光器件,且器件结构简单,可大量制备节省时间和成本。本发明还包括一种以芴为核的化合物的应用,所述化合物用于作为有机发光二极管材料或用于制备有机电致发光器件。本发明制备的化合物经过在四氢呋喃和薄膜状态下的光谱测试呈现为蓝光发射,其热性能优异,成膜性良好,蒸镀器件后的电致发光光谱依然为蓝光发射。
Description
技术领域
本发明涉及有机电致发光显示技术领域,特别涉及一种以芴为核的化合物及其制备方法和应用。
背景技术
电致发光器件由于其亮度高、视角宽、对比度高、响应快、工作温度范围宽、可柔性大面积制备等优势逐渐吸引起人们的兴趣。虽然有机电致发光领域已经取得了很大进展,由于蓝色发光材料固有的宽带隙带来的跃迁困难等问题,使得高效率、低CIE坐标、高纯度的蓝色有机电致发光材料仍然很稀缺。
众所周知,蓝色光不仅是三原色之一,而且可以光源引发其他辐射。在蓝光分子结构的设计中D和A单元的选择在电致发光材料的光色和性质方面起着至关重要的作用,但不是所有的D和A组合体都可以得到为高效的蓝色EL发光材料,设计上的冲突使得高效率的蓝色电致发光材料仍然稀缺并在制作上极具挑战性。
因此目前亟需一种结构简单,可大量制备,具有一系列的蓝色发光分子并且有着高效率和高迁移率的电致发光器件。
发明内容
针对现有技术存在的不足,本发明提供一种以芴为核的化合物及其制备方法和应用,通过给受体种类、键接位置的改变得到了一系列的蓝色发光分子并且有着高效率和高迁移率的电致发光器件,且器件结构简单,可大量制备节省时间和成本。
本发明为实现上述目的采用的技术方案是:一种以芴为核的化合物,该化合物的结构如式1所示,
所述式1中:
两条烷基链长度各为CnH2n+1,其中n=1-8;
R1、R2为以下结构中的一种,R1和R2不相同:
或,R1、R2为以下结构中的一种,R1和R2不相同:
进一步的,所述式1所示化合物结构如下:
本发明还包括一种以芴为核的化合物的制备方法,所述合成方法包括如下步骤:
(1)将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌反应,用水洗涤抽滤后,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
(2)将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,加热反应后,加入上一步产物M1,在一定温度下搅拌反应,在去离子水中搅拌30分钟,抽滤后纯化,得到白色粉末R2-Br;
或,将M1加入POCl3中,氮气氛围下,加热反应,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为R2-Br;
(3)将R2-Br加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热反应,然后冷却至室温,萃取、过滤、纯化得到白色固体为R2-B(OH)2(M5,M6);
(4)将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,纯化后得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
(6)将R2-B(OH)2(M5,M6)与混合,然后加入5:1的四氢呋喃和去离子水,和碳酸钾,抽换氮气三次后,加入催化剂,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,纯化后得到产物
进一步的,
所述步骤(5)和步骤(6)中的催化剂为:Pd(PPh3)4。
进一步的,具体制备方法如下:
(1)将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
(2)将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,100℃加热1小时后,加入上一步产物M1,在180℃条件下搅拌12h,在去离子水中搅拌30分钟,抽滤后用硅胶柱层析进一步纯化,得到白色粉末3-(4-溴苯基)-4,5-二苯基-1,2,4-三唑(M2);
或,将M1加入50mL POCl3中,氮气氛围下,90℃加热12小时,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为4-(2-溴苯基)-5-苯基-1,3,4-噁二唑(M3);
(3)将M2或M3分别加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5)或2-苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-1,3,4-噁二唑(M6);
(4)将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
(5)将M4与4-(9H-咔唑-9-基)苯硼酸,或(9-苯基-9H-咔唑-3-基)硼酸,或4-硼酸三苯胺分别组合,然后和碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体分别为9-(4-(7-溴-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑(Z1),或2-(7-溴-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑(Z2),或4-(7-溴-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺(Z3);
(6)将M5或M6与Z1,Z2或Z3分别组合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物分别为9-(4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑、2-(4-(7-(4-(9H-咔唑-9-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-5-苯基-1,3,4-噁二唑、2-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑、2-苯基-5-(4-(7-(9-苯基-9H-咔唑-2-基)-9,9-二丙基-9H-芴-2-基)苯基)-1,3,4-噁二唑、4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺,或N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺。
本发明还包括一种以芴为核的化合物的应用,所述化合物用于作为有机发光二极管材料或用于制备有机电致发光器件。
进一步的,所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层和阴极层组成。
进一步的,
所述透明基片的材料为玻璃或柔性基片;
所述阳极的材料为无机材料或有机导电材料,其中所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜;
所述空穴注入层的材料为溶液加工的PEDOT:PSS,结构式为:
所述空穴传输层的材料为TCTA,结构式为:
所述有机发光层的材料为式1所示化合物;
所述电子传输层的材料为TPBI,结构式为:
所述电子注入层的材料为LiF;
所述阴极层的材料为铝。
进一步的,
所述空穴注入层厚度为40nm;
所述空穴传输层厚度为20nm;
所述有机发光层厚度为20nm;
所述电子传输层厚度为30nm;
所述电子注入层厚度为1nm;
所述阴极层厚度为100nm。
进一步的,所述有机电致发光器件的制备方法为:
(1)清洗ITO基片:丙酮、ITO洗液、去离子水各超声35分钟以上,然后清洗烘干待用;
(2)空穴注入层PEDOT:PSS的旋涂:将plasma处理过的ITO基片放置在旋涂仪上,然后用针管滴加PEDOT:PSS溶液,待完全铺展后,以3000转/分钟旋转30秒,静置后用沾有去离子水的棉签擦去与正极探针接触的范围,然后150摄氏度下加热20分钟,退火冷却至室温后待用;
(3)蒸镀空穴传输层TCTA20 nm,速度为0.1nm/s;
(4)蒸镀所述有机发光层20nm,速度为0.1nm/s;
(5)蒸镀电子传输层TPBI 30nm,速度为0.1nm/s;
(6)蒸镀电子注入层LiF 1nm,速度为0.01nm/s;
(7)蒸镀阴极层Al 100nm,先以0.1nm/s的速度蒸镀,然后缓慢增加至0.3-0.4nm/s。
本发明以芴为核的化合物及其制备方法和应用的有益效果是:本发明制备的化合物经过在四氢呋喃和薄膜状态下的光谱测试呈现为蓝光发射,其热性能优异,成膜性良好,蒸镀器件后的电致发光光谱依然为蓝光发射。
附图说明
图1是本发明实施例化合物的合成路线图;
图2是本发明实施例的器件结构示意图;
图3是本发明实施例2中化合物的合成路线图;
图4是本发明实施例2中化合物的四氢呋喃溶液和薄膜状态下的紫外吸收与荧光发射图;
图5是本发明实施例2中化合物的电流密度-电压-亮度曲线图;
图6是本发明实施例2中化合物的外量子效率-亮度曲线图;
图7是本发明实施例2中化合物的器件光谱图;
图8是本发明实施例2中化合物的电流效率-亮度-功率效率曲线图;
图9是本发明实施例2中化合物的亮度-电流密度曲线图。
具体实施方式
下面结合附图与具体实施方式对本发明作进一步详细描述:
实施例1:
一种以芴为核的化合物,该化合物的结构如式1所示,
所述式1中:
两条烷基链长度各为CnH2n+1,其中n=1-8;
R1、R2为以下结构中的一种,R1和R2不相同:
或,R1、R2为以下结构中的一种,R1和R2不相同:
所述式1所示化合物结构如下:
本发明还包括一种以芴为核的化合物的制备方法,如图1所示,所述合成方法包括如下步骤:
(1)将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌反应,用水洗涤抽滤后,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
(2)将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,加热反应后,加入上一步产物M1,在一定温度下搅拌反应,在去离子水中搅拌30分钟,抽滤后纯化,得到白色粉末R2-Br;
或,将M1加入POCl3中,氮气氛围下,加热反应,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为R2-Br;
(3)将R2-Br加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热反应,然后冷却至室温,萃取、过滤、纯化得到白色固体为R2-B(OH)2(M5,M6);
(4)将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,纯化后得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
(6)将R2-B(OH)2(M5,M6)与混合,然后加入5:1的四氢呋喃和去离子水,和碳酸钾,抽换氮气三次后,加入催化剂,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,纯化后得到产物
所述步骤(5)和步骤(6)中的催化剂为:Pd(PPh3)4。
本发明还包括一种以芴为核的化合物的应用,所述化合物用于作为有机发光二极管材料或用于制备有机电致发光器件。
如图2所示,所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层和阴极层组成。
所述透明基片的材料为玻璃或柔性基片;
所述阳极的材料为无机材料或有机导电材料,其中所述无机材料为氧化铟锡、氧化锌、氧化锡锌、金、银或铜;
所述空穴注入层的材料为溶液加工的PEDOT:PSS,结构式为:
所述空穴传输层的材料为TCTA,结构式为:
所述有机发光层的材料为式1所示化合物;
所述电子传输层的材料为TPBI,结构式为:
所述电子注入层的材料为LiF;
所述阴极层的材料为铝。
所述空穴注入层厚度为40nm;
所述空穴传输层厚度为20nm;
所述有机发光层厚度为20nm;
所述电子传输层厚度为30nm;
所述电子注入层厚度为1nm;
所述阴极层厚度为100nm。
所述有机电致发光器件的制备方法为:
(1)清洗ITO基片:丙酮、ITO洗液、去离子水各超声35分钟以上,然后清洗烘干待用;
(2)空穴注入层PEDOT:PSS的旋涂:将plasma处理过的ITO基片放置在旋涂仪上,然后用针管滴加PEDOT:PSS溶液,待完全铺展后,以3000转/分钟旋转30秒,静置后用沾有去离子水的棉签擦去与正极探针接触的范围,然后150摄氏度下加热20分钟,退火冷却至室温后待用;
(3)蒸镀空穴传输层TCTA 20nm,速度为0.1nm/s;
(4)蒸镀所述有机发光层20nm,速度为0.1nm/s;
(5)蒸镀电子传输层TPBI 30nm,速度为0.1nm/s;
(6)蒸镀电子注入层LiF 1nm,速度为0.01nm/s;
(7)蒸镀阴极层Al 100nm,先以0.1nm/s的速度蒸镀,然后缓慢增加至0.3-0.4nm/s。
实施例2:
如图3所示,N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺的制备方法:
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入250mL圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后萃取、过滤,硅胶柱层析法得到的白色固体为2,7-二溴-9,9-二丙基-9H-芴,然后将所得产物、4-硼酸三苯胺、碳酸钾加入250ml圆底烧瓶中,溶剂为四氢呋喃和去离子水5:1,加入催化剂Pd(PPh3)4,在氮气氛围下90℃下回流24h反应,然后萃取过滤,柱层析法得到4-(7-溴-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺(M1);
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中。所得到的混合物在室温下搅拌4h,提纯得到白色粉末N’-苄基-4-溴苯甲酰肼,然后加入50mL三氯氧磷中,90℃加热12小时,加入冰水浴然后析出白色沉淀,提纯后即为4-(2-溴苯基)-5-苯基-1,3,4-噁二唑,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,[1,1'-双(二苯基膦基)二茂铁]二氯化钯为催化剂,加热至90℃反应12小时,提纯后得到白色固体为2-苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-1,3,4-噁二唑(M2);
最后将M1、M2、碳酸钾加入250ml圆底烧瓶中,溶剂为四氢呋喃和去离子水5:1,加入催化剂Pd(PPh3)4,在氮气氛围下90℃下回流24h反应,提纯后得到N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺,该产物为白色固体,产率为82%。
将N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺用于制备有机电致发光器件。
N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺的性质检测:
对N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺进行紫外吸收和荧光发射测试,所得结果如图4所示,四氢呋喃溶液中发射峰为477纳米,薄膜状态下则为458纳米的蓝光发射。
由图5-图9可知,该开启电压为4.2V,亮度为25416cd·m-2,电流效率高达23.0cd·A-1、功率效率为15.1lm·W-1,外量子效率则高达14.6%且在1000亮度下外量子效率为12%,效率滚降较低,该材料空穴与电子载流子迁移率相近,注入平衡,电子迁移率在5.0×105V·cm-2下能达到6.6×10-5cm2·V-1·S-1,空穴迁移率则能达到5.6×10-5cm2·V-1·S-1,为新型传输材料。
本发明通过本实施例说明了N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺的制备方法及其在OLED器件中的应用,但不限于以上方法才能制备,本领域的技术人员应该明了,对本发明所述化合物进行改进,如原料替换和器件结构改良均在保护范围和公开范围内。
实施例3:
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,100℃加热1小时后,加入上一步产物M1,在180℃条件下搅拌12h,在去离子水中搅拌30分钟,抽滤后用硅胶柱层析进一步纯化,得到白色粉末3-(4-溴苯基)-4,5-二苯基-1,2,4-三唑(M2);
将M2加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5);
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
将M4与4-(9H-咔唑-9-基)苯硼酸混合,然后将碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体为9-(4-(7-溴-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑(Z1);
将M5与Z1混合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物为9-(4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑。
实施例4:
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
将M1加入50mLPOCl3中,氮气氛围下,90℃加热12小时,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为4-(2-溴苯基)-5-苯基-1,3,4-噁二唑(M3);
将M3加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5)或2-苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-1,3,4-噁二唑(M6);
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);将M4与4-(9H-咔唑-9-基)苯硼酸混合,然后将碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体为9-(4-(7-溴-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑(Z1);
将M6与Z1混合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物为2-(4-(7-(4-(9H-咔唑-9-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-5-苯基-1,3,4-噁二唑。
实施例5:
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,100℃加热1小时后,加入上一步产物M1,在180℃条件下搅拌12h,在去离子水中搅拌30分钟,抽滤后用硅胶柱层析进一步纯化,得到白色粉末3-(4-溴苯基)-4,5-二苯基-1,2,4-三唑(M2);
将M2加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5);
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
将M4与(9-苯基-9H-咔唑-3-基)硼酸混合,然后将碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体为2-(7-溴-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑(Z2)
将M5与Z2混合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物为2-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑。
实施例6:
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
将M1加入50mLPOCl3中,氮气氛围下,90℃加热12小时,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为4-(2-溴苯基)-5-苯基-1,3,4-噁二唑(M3);
将M3加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5)或2-苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-1,3,4-噁二唑(M6);
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);将M4与(9-苯基-9H-咔唑-3-基)硼酸混合,然后将碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体为2-(7-溴-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑(Z2);
将M6与Z2混合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物为2-苯基-5-(4-(7-(9-苯基-9H-咔唑-2-基)-9,9-二丙基-9H-芴-2-基)苯基)-1,3,4-噁二唑。
实施例7:
将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,100℃加热1小时后,加入上一步产物M1,在180℃条件下搅拌12h,在去离子水中搅拌30分钟,抽滤后用硅胶柱层析进一步纯化,得到白色粉末3-(4-溴苯基)-4,5-二苯基-1,2,4-三唑(M2);
将M2加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5);
将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
将M4与4-硼酸三苯胺混合,然后将碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体为4-(7-溴-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺(Z3);
将M5与Z3混合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物为4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺。
在本发明的制备方法中,各种材料的加成顺序和具体反应步骤可由本领域技术人员进行调整,不仅适用于实验室的小规模制备,也适用于化工厂的工业化大规模生产。在工业批量生产中,具体反应参数可由本领域技术人员通过实验确定。
若无特殊说明,下述实施例中所用的实验方法,均为常规方法。
若无特殊说明,下述实施例中所用到的试剂、材料等,均可从商业途径获到或由商业途径所获原料合成。
上述实施例只是为了说明本发明的技术构思及特点,其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所做出的等效的变化或修饰,都应涵盖在本发明的保护范围内。
Claims (10)
3.一种根据权利要求1-2任一项所述的以芴为核的化合物的制备方法,其特征是:所述合成方法包括如下步骤:
(1)将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌反应,用水洗涤抽滤后,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
(2)将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,加热反应后,加入上一步产物M1,在一定温度下搅拌反应,在去离子水中搅拌30分钟,抽滤后纯化,得到白色粉末R2-Br;
或,将M1加入POCl3中,氮气氛围下,加热反应,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为R2-Br;
(3)将R2-Br加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热反应,然后冷却至室温,萃取、过滤、纯化得到白色固体为R2-B(OH)2(M5,M6);
(4)将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,纯化后得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
4.根据权利要求3所述的制备方法,其特征是:
所述步骤(5)和步骤(6)中的催化剂为:Pd(PPh3)4。
5.根据权利要求3或4任一项所述的制备方法,其特征是:具体制备方法如下:
(1)将4-溴苯甲酰氯溶于二氯甲烷,滴入苯甲酰肼和三乙胺的二氯甲烷溶液中,所得到的混合物在室温下搅拌4h,然后用水洗涤抽滤,再用无水乙醇重结晶提纯得到白色粉末N’-苄基-4-溴苯甲酰肼(M1);
(2)将苯胺和邻二氯苯加入到装有回流冷凝器的双颈圆底瓶中,PCl3在氮气氛围下滴加到瓶中,100℃加热1小时后,加入上一步产物M1,在180℃条件下搅拌12h,在去离子水中搅拌30分钟,抽滤后用硅胶柱层析进一步纯化,得到白色粉末3-(4-溴苯基)-4,5-二苯基-1,2,4-三唑(M2);
或,将M1加入50mLPOCl3中,氮气氛围下,90℃加热12小时,然后冷却至室温,将所得混合物加入到冰水,然后析出白色沉淀,萃取、过滤、重结晶,抽滤所得即为4-(2-溴苯基)-5-苯基-1,3,4-噁二唑(M3);
(3)将M2或M3分别加入圆底烧瓶,然后加入联硼酸频那醇酯、乙酸钾,以1,4-二氧六环为溶剂,抽换氮气3次,然后加入[1,1'-双(二苯基膦基)二茂铁]二氯化钯,再抽换氮气三次,加热至90℃反应12小时,然后冷却至室温,萃取、过滤,采用硅胶柱层析法得到白色固体为3,4-二苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-4H-1,2,4-三唑(M5)或2-苯基-5-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)苯基)-1,3,4-噁二唑(M6);
(4)将2,7-二溴芴、四丁基溴化铵、正丙基溴和50%氢氧化钠水溶液,以二甲基亚砜为溶剂加入圆底烧瓶中,氮气氛围下加热至90摄氏度,反应8小时后冷却至室温,然后萃取、过滤,采用硅胶柱层析法得到白色固体为2,7-二溴-9,9-二丙基-9H-芴(M4);
(5)将M4与4-(9H-咔唑-9-基)苯硼酸,或(9-苯基-9H-咔唑-3-基)硼酸,或4-硼酸三苯胺分别组合,然后和碳酸钾,四氢呋喃和去离子水5:1加入圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h;停止加热后萃取、过滤,采用硅胶柱层析法,得到白色固体分别为9-(4-(7-溴-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑(Z1),或2-(7-溴-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑(Z2),或4-(7-溴-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺(Z3);
(6)将M5或M6与Z1,Z2或Z3分别组合,然后将碳酸钾、四氢呋喃与去离子水比例为5:1加入250ml圆底烧瓶中,抽换氮气三次后,加入催化剂Pd(PPh3)4,90℃下回流24h,停止加热后静置,待冷却至室温后再用离子水和二氯甲烷萃取三次、过滤,以石油醚和二氯甲烷为淋洗剂,采用硅胶柱层析法,得到产物分别为9-(4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-9H-咔唑、2-(4-(7-(4-(9H-咔唑-9-基)苯基)-9,9-二丙基-9H-芴-2-基)苯基)-5-苯基-1,3,4-噁二唑、2-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-9-苯基-9H-咔唑、2-苯基-5-(4-(7-(9-苯基-9H-咔唑-2-基)-9,9-二丙基-9H-芴-2-基)苯基)-1,3,4-噁二唑、4-(7-(4-(4,5-二苯基-4H-1,2,4-三唑-3-基)苯基)-9,9-二丙基-9H-芴-2-基)-N,N-二苯基苯胺,或N,N-二苯基-4-(7-(4-(5-苯基-1,3,4-恶二唑-2-基)苯基)-9,9-二丙基-9H-芴-2-基)苯胺。
6.一种以芴为核的化合物的应用,所述化合物具有权利要求1或2任一项所述的结构,或通过权利要求3-5任一项所述的方法制备,其特征在于:所述化合物用于作为有机发光二极管材料或用于制备有机电致发光器件。
7.根据权利要求6所述的应用,其特征是:所述有机电致发光器件由下至上依次由透明基片、阳极、空穴注入层、空穴传输层、有机发光层、电子传输层、电子注入层和阴极层组成。
9.根据权利要求7所述的应用,其特征是:
所述空穴注入层厚度为40nm;
所述空穴传输层厚度为20nm;
所述有机发光层厚度为20nm;
所述电子传输层厚度为30nm;
所述电子注入层厚度为1nm;
所述阴极层厚度为100nm。
10.根据权利要求7所述的应用,其特征是:所述有机电致发光器件的制备方法为:
(1)清洗ITO基片:丙酮、ITO洗液、去离子水各超声35分钟以上,然后清洗烘干待用;
(2)空穴注入层PEDOT:PSS的旋涂:将plasma处理过的ITO基片放置在旋涂仪上,然后用针管滴加PEDOT:PSS溶液,待完全铺展后,以3000转/分钟旋转30秒,静置后用沾有去离子水的棉签擦去与正极探针接触的范围,然后150摄氏度下加热20分钟,退火冷却至室温后待用;
(3)蒸镀空穴传输层TCTA 20nm,速度为0.1nm/s;
(4)蒸镀所述有机发光层20nm,速度为0.1nm/s;
(5)蒸镀电子传输层TPBI 30nm,速度为0.1nm/s;
(6)蒸镀电子注入层LiF 1nm,速度为0.01nm/s;
(7)蒸镀阴极层Al 100nm,先以0.1nm/s的速度蒸镀,然后缓慢增加至0.3-0.4nm/s。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111277646.0A CN114014812A (zh) | 2021-10-29 | 2021-10-29 | 一种以芴为核的化合物及其制备方法和应用 |
PCT/CN2021/128354 WO2023070700A1 (zh) | 2021-10-29 | 2021-11-03 | 一种以芴为核的化合物及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111277646.0A CN114014812A (zh) | 2021-10-29 | 2021-10-29 | 一种以芴为核的化合物及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114014812A true CN114014812A (zh) | 2022-02-08 |
Family
ID=80059044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111277646.0A Pending CN114014812A (zh) | 2021-10-29 | 2021-10-29 | 一种以芴为核的化合物及其制备方法和应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114014812A (zh) |
WO (1) | WO2023070700A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116283608B (zh) * | 2023-05-24 | 2023-08-29 | 吉林奥来德光电材料股份有限公司 | 一种发光辅助材料及其制备方法、发光器件 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040056255A1 (en) * | 2002-09-23 | 2004-03-25 | Robeson Lloyd Mahlon | Novel light emitting layers for LED devices based on high Tg polymer matrix compositions |
JP2009203176A (ja) * | 2008-02-27 | 2009-09-10 | Toyo Ink Mfg Co Ltd | 有機エレクトロルミネッセンス素子用材料および化合物 |
CN103304510A (zh) * | 2012-03-15 | 2013-09-18 | 海洋王照明科技股份有限公司 | 含芴的有机半导体材料及其制备方法和有机电致发光器件 |
CN103833507A (zh) * | 2013-12-25 | 2014-06-04 | 石家庄诚志永华显示材料有限公司 | 一系列有机电致发光材料及其制备方法与应用 |
CN104956206A (zh) * | 2012-12-04 | 2015-09-30 | 昆士兰大学 | 经由发光猝灭检测分析物的方法 |
CN106632269A (zh) * | 2016-10-10 | 2017-05-10 | 青岛科技大学 | 蓝色电致发光化合物及其在有机电致发光器件中的应用 |
CN107954921A (zh) * | 2017-11-29 | 2018-04-24 | 华南协同创新研究院 | 一种用9-苯基芴封端的电致发光材料及其制备方法与应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102675296A (zh) * | 2012-04-10 | 2012-09-19 | 苏州纳凯科技有限公司 | 用于有机电致发光器件中的双极性材料及其制备方法 |
-
2021
- 2021-10-29 CN CN202111277646.0A patent/CN114014812A/zh active Pending
- 2021-11-03 WO PCT/CN2021/128354 patent/WO2023070700A1/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040056255A1 (en) * | 2002-09-23 | 2004-03-25 | Robeson Lloyd Mahlon | Novel light emitting layers for LED devices based on high Tg polymer matrix compositions |
JP2009203176A (ja) * | 2008-02-27 | 2009-09-10 | Toyo Ink Mfg Co Ltd | 有機エレクトロルミネッセンス素子用材料および化合物 |
CN103304510A (zh) * | 2012-03-15 | 2013-09-18 | 海洋王照明科技股份有限公司 | 含芴的有机半导体材料及其制备方法和有机电致发光器件 |
CN104956206A (zh) * | 2012-12-04 | 2015-09-30 | 昆士兰大学 | 经由发光猝灭检测分析物的方法 |
CN103833507A (zh) * | 2013-12-25 | 2014-06-04 | 石家庄诚志永华显示材料有限公司 | 一系列有机电致发光材料及其制备方法与应用 |
CN106632269A (zh) * | 2016-10-10 | 2017-05-10 | 青岛科技大学 | 蓝色电致发光化合物及其在有机电致发光器件中的应用 |
CN107954921A (zh) * | 2017-11-29 | 2018-04-24 | 华南协同创新研究院 | 一种用9-苯基芴封端的电致发光材料及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
WO2023070700A1 (zh) | 2023-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Low turn-on voltage, high-power-efficiency, solution-processed deep-blue organic light-emitting diodes based on starburst oligofluorenes with diphenylamine end-capper to enhance the HOMO level | |
Huang et al. | Benzene-cored fluorophors with TPE peripheries: facile synthesis, crystallization-induced blue-shifted emission, and efficient blue luminogens for non-doped OLEDs | |
CN103833507B (zh) | 一系列有机电致发光材料及其制备方法与应用 | |
Wang et al. | Solution‐Processible 2, 2′‐Dimethyl‐biphenyl Cored Carbazole Dendrimers as Universal Hosts for Efficient Blue, Green, and Red Phosphorescent OLEDs | |
CN103951621B (zh) | 一种蓝色有机发光二极管材料 | |
Liu et al. | Triazatruxene-based thermally activated delayed fluorescence small molecules with aggregation-induced emission properties for solution-processable nondoped OLEDs with low efficiency roll-off | |
Ban et al. | Spirobifluorene/sulfone hybrid: highly efficient solution-processable material for UV–violet electrofluorescence, blue and green phosphorescent OLEDs | |
TWI431003B (zh) | 有機化合物及包含其之有機電激發光裝置 | |
Huang et al. | Construction of deep-blue AIE luminogens with TPE and oxadiazole units | |
CN108218891B (zh) | 一类电致发光化合物及其制备方法和应用 | |
CN109608383A (zh) | 一种有机电致发光材料及其制备方法与应用 | |
CN114014812A (zh) | 一种以芴为核的化合物及其制备方法和应用 | |
CN108203420B (zh) | 萘苯并呋喃和蒽的衍生物及其制备方法、应用和器件 | |
TWI619690B (zh) | 有機化合物及使用其的有機電激發光元件 | |
CN112125813A (zh) | 一种化合物、空穴传输材料和有机电致发光器件 | |
CN115028626B (zh) | 一种热致延迟荧光材料及其制备方法和应用 | |
TW201418217A (zh) | 有機化合物及包含其之有機電激發光裝置 | |
CN115636755A (zh) | 一种萘基取代双芳胺化合物及其应用 | |
CN112694433B (zh) | 一类有机小分子空穴传输材料及其制备方法和应用 | |
TWI602817B (zh) | 啡啉衍生物及使用其之有機電激發光裝置 | |
TWI601710B (zh) | 化合物及使用其的有機電激發光裝置 | |
KR102561467B1 (ko) | 유기 발광 다이오드 애플리케이션에 사용하는 시아노-유도 올리고노페닐아세틸렌-기반 형광 소분자 기판 및 유기 발광 다이오드 애플리케이션에 이들의 사용 | |
CN112940025A (zh) | 一种手性热活化延迟荧光材料、制备方法和用途 | |
CN113896724A (zh) | 基于苯并噻二唑-芘并咪唑的有机红光小分子及其在制备非掺杂有机电致发光器件中的应用 | |
CN106518688B (zh) | 一种9-苯基取代芴衍生物、制备方法及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |