CN105130877A - 基于芴与咔唑的高稠环一氮杂[7]螺烯化合物及其合成方法和应用 - Google Patents
基于芴与咔唑的高稠环一氮杂[7]螺烯化合物及其合成方法和应用 Download PDFInfo
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- CN105130877A CN105130877A CN201510465624.5A CN201510465624A CN105130877A CN 105130877 A CN105130877 A CN 105130877A CN 201510465624 A CN201510465624 A CN 201510465624A CN 105130877 A CN105130877 A CN 105130877A
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- hexyl
- azepine
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- carbazole
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title abstract 8
- 238000001308 synthesis method Methods 0.000 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000001716 carbazoles Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 63
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- -1 azepine [7] helicene compound Chemical class 0.000 claims description 22
- ZADYHNRFHQXTOH-UHFFFAOYSA-N heptahelicene Chemical compound C1=CC=C2C3=C(C=4C(=CC=C5C=CC=6C(C=45)=CC=CC=6)C=C4)C4=CC=C3C=CC2=C1 ZADYHNRFHQXTOH-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LNZBSVNIMBHSAG-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(methylamino)hexan-1-one Chemical compound CCCCC(NC)C(=O)c1ccc2OCOc2c1 LNZBSVNIMBHSAG-UHFFFAOYSA-N 0.000 claims description 14
- 238000010189 synthetic method Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- MDOAAHGPXOGVQG-UHFFFAOYSA-N ethene;propane Chemical compound C=C.CCC MDOAAHGPXOGVQG-UHFFFAOYSA-N 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 3
- 150000001538 azepines Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 3
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- PJAWEFMLSSLAIM-UHFFFAOYSA-N (2,3,4-trimethylphenyl)boron Chemical compound [B]C1=CC=C(C)C(C)=C1C PJAWEFMLSSLAIM-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 3
- 230000005669 field effect Effects 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 150000002220 fluorenes Chemical class 0.000 description 20
- 239000000126 substance Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 8
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- SHUQFBKCOHURJQ-UHFFFAOYSA-N 9-hexylcarbazole Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 SHUQFBKCOHURJQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OFEPZJNWQSMFOE-UHFFFAOYSA-N 3-ethenyl-9-hexylcarbazole Chemical compound C=CC1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 OFEPZJNWQSMFOE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- UNLWPTLNZBEHNF-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.[Br] Chemical class C1=CC=CC=2C3=CC=CC=C3CC12.[Br] UNLWPTLNZBEHNF-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C1)C=CC(c2c3cc(ccc4ccc(*(*)c5c-6cc(*)cc5)c-6c44)c4c2)=C1C3(I)I[*+] Chemical compound CC(C1)C=CC(c2c3cc(ccc4ccc(*(*)c5c-6cc(*)cc5)c-6c44)c4c2)=C1C3(I)I[*+] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- 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
- C07F5/027—Organoboranes and organoborohydrides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
本发明提供了一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物(Ⅰ)及其合成方法和应用。本发明以芴和咔唑衍生物为原料,采用光催化闭环的方法,制得一类具有良好OLED性能的高稠环一氮杂[7]螺烯化合物。本发明合成方法具有产率高、时间短、操作简单等优点,并且使用普通廉价的试剂,降低制备的成本,易于推广应用。本发明还提供一氮杂[7]螺烯化合物(Ⅰ)作为发光材料应用在有机发光二极管中。基于芴与咔唑的高稠环一氮杂[7]螺烯化合物(Ⅰ)可在有机电致发光、有机场效应管、有机二阶非线性、手性液晶以及生物医药等领域得到应用。
Description
技术领域
本发明涉及一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物及其合成方法和应用,具体涉及利用光催化闭环反应方法制备的高稠环一氮杂[7]螺烯化合物及其在有机发光二极管中的应用,属于化工技术领域。
背景技术
螺烯是一类由多个芳香环彼此以邻位稠合方式而形成的具有螺旋结构的多环芳香化合物,此类分子中存在扭曲面,是典型的手性螺旋分子。螺烯及其衍生物因其独特的结构和特殊的物理及化学性质被应用于有机电致发光、有机场效应管、有机二阶非线性、手性液晶以及生物医药等领域。
光催化闭环反应是合成螺烯衍生物一种非常重要的反应,此方法所用的前驱体合成步骤简单且产率较高。近年来,人们利用光催化闭环反应方法合成了一系列多稠环螺烯衍生物。然而,很多螺烯化合物的合成所需时间长、产率低,并且随着共轭体系的增加,具有刚性结构的螺烯,分子间的相互作用力增强,导致溶解性变差,有关报道参见L.Liu,etal.J.Org.Chem.1991,56,3769.;F.B.Mallory,etal.J.Am.Chem.Soc.1997,119,2119.此外,缺少引入功能团的活性位点也是合成螺烯衍生物过程中一个非常严重的问题(参见A.Rajca,etal.J.Org.Chem.2009,74,7504.)。通过引入合适的基团,不仅可以有效改善有机分子的溶解性而且可以调控分子的物化性能。以廉价的芴和咔唑为起始反应原料,通过光催化闭环反应,我们可以制备一类具有优良性能的高稠环一氮杂[7]螺烯化合物。现有材料中尚未见此类螺烯化合物及其在有机发光二极管中应用的报道。
发明内容
本发明旨在提供一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物及其合成方法和应用。
本发明通过以下技术方案实现:
1、基于芴与咔唑的高稠环一氮杂[7]螺烯化合物
本发明的一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物,结构通式Ⅰ如下:
其中,取代基R2、R5、R9、R10、R12各自独立的为C1-C6的烷基、Cl、Br、苯、二(三甲苯基)硼或吡啶;R1、R3-R4、R6-R8、R11、R13-R15为H。
优选的,上述通式Ⅰ化合物是下列之一:
5,11,11‐三己基一氮杂[7]螺烯Ⅰ(a)
2,13‐二溴‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(b)
13‐二(三甲苯基)硼基‐5,11,11-三己基一氮杂[7]螺烯Ⅰ(c)
13‐吡啶‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(d)
5,11,11‐三吡啶一氮杂[7]螺烯Ⅰ(e)
2、基于芴与咔唑的高稠环一氮杂[7]螺烯化合物(Ⅰ)的合成方法
本发明的一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物的其合成方法,以反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑衍生物为原料,通过光催化闭环反应制备而得;
化学反应式如下:
试剂与条件:苯;I2:碘;环氧丙烷;hv:紫外光。
一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物的合成方法,包括如下步骤:
(1)将有机溶剂用蒸馏法纯化,在惰性气氛下保存待用;
(2)将反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑衍生物和化学计量比的碘加入到步骤(1)纯化的有机溶剂中,边溶解边搅拌,完全溶解后使溶液中溶质的浓度均为0.01-1摩尔/升,通惰性气体30-60分钟;
(3)在持续搅拌情况下,将环氧丙烷加入步骤(2)所得的溶液中,使溶液中环氧丙烷的浓度为0.1-2.5摩尔/升;
(4)用250-500W的高压汞灯透过石英玻璃照射步骤(3)所得的溶液5-50分钟至反应结束,得到粗产物;
(5)真空旋蒸出溶剂,将所得的粗产物溶解在二氯甲烷中,依次用质量分数为10-35%的Na2S2O3溶液和蒸馏水洗涤得有机滤液;
(6)对步骤(5)的有机滤液进行分离提纯得到产物。
根据本发明优选的,
步骤(1)中所述的有机溶剂选自苯、甲苯、正己烷、四氢呋喃或二氯甲烷中的一种。
步骤(6)中的分离提纯是指对有机滤液进行萃取、洗涤、干燥、旋干、硅胶柱层析、重结晶分离后得产物。
根据本发明优选的,5,11,11‐三己基一氮杂[7]螺烯Ⅰ(a)的制备,包括如下步骤:
(1)将有机溶剂苯用常压蒸馏的方法进行纯化,在惰性气氛下保存待用;
(2)将反-9,9-二己基-2-(2-咔唑乙烯基)芴0.45mmol和碘0.46mmol加入到步骤(1)纯化的500ml有机溶剂苯中,边溶解边搅拌,完全溶解后,通惰性气体30分钟;
(3)在持续搅拌情况下,将18ml环氧丙烷加入步骤(2)所得的溶液中,使溶液中环氧丙烷的浓度为0.51摩尔/升;
(4)用500W的高压汞灯透过石英玻璃照射步骤(3)所得的溶液0.5-1小时至反应结束得粗产物;
(5)真空旋蒸出溶剂,将所得的粗产物溶解在三氯甲烷中,依次用质量分数为15%的Na2S2O3溶液和蒸馏水洗涤得有机滤液;
(6)对步骤(5)的有机滤液进行萃取、洗涤、干燥、旋干、硅胶柱层析、重结晶分离提纯后,得到5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)。
本发明合成方法中原料反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑衍生物(Ⅱ)的合成方法,化合物Ⅱ母核结构的化合物合成参见文献报道,通过文献Hua,W.;Liu,Z.;Duan,L.;etal,RSCAdvances2015,5(1),75.的合成方法我们获得了化合物Ⅱ。
本发明采取通过增加引入功能团的活性位点合成功能性芳香稠环衍生物,通过引入特定的合适功能基团,不仅可以有效改善有机分子的溶解性而且还可以调控分子的物化性能。此前尚未见此类化合物及其应用的报道。
3.基于芴与咔唑的高稠环一氮杂[7]螺烯化合物(Ⅰ)的应用
本发明还将基于芴与咔唑的高稠环一氮杂[7]螺烯化合物(Ⅰ)作为发光材料应用于制备有机发光二极管中;尤其是化合物5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)作为发光层材料应用于制备有机发光二极管中,该器件发出亮度达到2700cdm-2的蓝紫色光,其CIE坐标为(0.157,0.078)。
以上所述的应用,本发明式I的基于芴与咔唑的高稠环一氮杂[7]螺烯化合物按1:9质量比与9,9'-(1,3-苯基)二-9H-咔唑(mCP)混合作为有机发光二极管器件的客体与主体发光材料。
优选的,有机发光二极管器件结构如图11所示,各层由下往上依次ITO玻璃、氧化铟锡、4,4‘-双[氮-(1-萘基)-氮-苯氨基]联苯(NPB)、5,11,11‐三己基一氮杂[7]螺烯I(a)和9,9'-(1,3-苯基)二-9H-咔唑(mCP)按照质量比1:9的混合材料、4,7-二苯基-1,10-菲咯啉(Bphen)、镁银合金、银。
本发明的优良效果如下:
与现有的螺烯衍生物相比,本发明以廉价芴和咔唑衍生物为原料,在较短的时间内就以很高的产率得到一类溶解性良好的高稠环一氮杂[7]螺烯化合物。反应操作简单,避免使用昂贵的试剂,降低制备的成本,易于推广应用。本发明基于芴与咔唑的高稠环一氮杂[7]螺烯类化合物可在有机电致发光、有机场效应管、有机二阶非线性、手性液晶以及生物医药等领域得到广泛应用。
附图说明
图1为反-9,9-二己基-2-(2-咔唑乙烯基)芴Ⅱ(a)的氢谱图;横坐标为化学位移δ,单位:ppm。
图2为反-9,9-二己基-2-(2-咔唑乙烯基)芴Ⅱ(a)的碳谱图;横坐标为化学位移δ,单位:ppm。
图3为反-9,9-二己基-2-(2-咔唑乙烯基)芴Ⅱ(a)的质谱图;横坐标为质荷比m/z;纵坐标为相对强度,单位:%。
图4为反-9,9-二己基-2-(2-咔唑乙烯基)芴Ⅱ(a)的电离飞行时间质谱(MALDI-TOFMS)图;横坐标为质荷比m/z;纵坐标为相对强度,单位:%。
图5为5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的氢谱图;横坐标为δ,单位:ppm。
图6为5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的碳谱图;横坐标为δ,单位:ppm。
图7为5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的质谱图;横坐标为质荷比m/z;纵坐标为相对强度,单位:%。
图8为5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的电离飞行时间质谱(MALDI-TOFMS)图;横坐标为质荷比m/z;纵坐标为相对强度,单位:%。
图9为Ⅰ(a)晶体的一个不对称单位。
图10为Ⅰ(a)晶体沿b轴堆积图,为清晰起见氢原子被省略。
图11为有机发光二极管器件结构图;图中:Bphen:4,7-二苯基-1,10-菲咯啉;mCP:9,9'-(1,3-苯基)二-9H-咔唑;NPB:4,4‘-双[氮-(1-萘基)-氮-苯氨基]联苯。
图12为有机发光二极管光谱电压图。
图13为有机发光二极管电压电流密度亮度图。
图14为有机发光二极管电流密度电流效率流明效率图。
具体实施方式
下面结合实施例对本发明做进一步的说明,但不限于此。仪器与试剂说明如下:
高压汞灯(北京中教金源科技有限公司有售),苯用常压蒸馏的方法进行纯化,其余试剂均为化学纯。
关于原料,以下以实施例1的原料Ⅱ(a)的制备方法为例,反应式如下:
制备步骤如下:
9-正己基咔唑Ⅴ(a):在500ml单口圆底烧瓶中加入四丁基溴化铵3g(5mol%)(TBAB,(n-C4H9)4BrN)、咔唑33.4g(0.2mol),然后将NaOH12.0g(0.3mol),140ml的丙酮加入到上述溶液中。加热回流反应3h,冷却至室温。通过恒压滴液漏斗缓慢滴加溴代正己烷(C6H13Br)42.6ml(0.3mol)与60ml丙酮的混合液滴加完毕,加热回流反应24h。反应结束后将丙酮旋蒸出,冷却,0℃低温浴下将剩余混合物倒入300ml的冰水中,剧烈搅拌1h。充分搅拌后,抽滤。滤饼用蒸馏水洗涤3次。用分液漏斗将水相的油状物分离,水相用二氯甲烷萃取,富集,旋蒸,用无水乙醇重结晶。产物为白色针状晶体,重40g,产率79%。1H(300MHz,CDCl3,δ):8.11(s,1H),8.08(s,1H),7.48-7.38(m,4H),7.24-7.19(m,2H),4.28(t,J=7.2Hz,2H),1.91-1.81(m,2H),1.43-1.22(m,6H),0.86(t,J=6.9Hz,3H).13C(75MHz,CDCl3,δ):140.45,125.56,122.84,120.33,118.69,108.65,43.10,31.60,28.95,26.99,22.55,14.01.HRMS(m/z):252.1736[M+H]+(calcdforC18H21N+H:252.1747).
3-甲酰基-9-己基咔唑Ⅳ(a):0℃氩气保护、快速搅拌下,将三氯氧磷(POCl3)1.17ml(12.55mmol)逐滴滴加到盛有N,N-二甲基甲酰胺(DMF)(1.13ml,14.60mmol)的三口瓶中。滴毕,向反应体系滴加9-正己基咔唑3.145g(12.50mmol)的三氯甲烷(15ml)溶液,继续反应回流16h后冷却到室温。然后,将反应混合物300ml冰水混合物中,并用饱和的NaHCO3溶液调节pH至8,剧烈搅拌3h。混合体系用三氯甲烷萃取几次。将富集的三氯甲烷溶液用去离子水洗涤几次后,用无水硫酸钠干燥。1h后,将溶液过滤去除无水硫酸钠,真空旋蒸得到粗产物,柱层析(硅胶,石油醚/乙酸乙酯,25/1,v/v)分离得到纯净产物(2.551g,73.0%)。1H(300MHz,CDCl3,δ)10.09(s,1H),8.61(d,J=1.2Hz,1H),8.15(d,J=7.8Hz,1H),8.00(dd,J=8.7Hz,1H),7.56-7.44(m,3H),7.35-7.25(m,1H),4.33(t,J=7.2Hz,2H),1.94-1.84(m,2H),1.42-1.28(m,6H),0.86(t,J=6.9Hz,3H).13C(75MHz,CDCl3,δ)191.71,144.08,141.19,128.54,127.14,126.68,123.96,123.08,123.01,120.73,120.27,109.37,108.92,43.44,31.49,28.88,26.90,22.49,13.94.HRMS(m/z):280.1652[M+H]+(calcdforC19H21NO+H:280.1652).
9-己基-3-乙烯基-咔唑Ⅲ(a):0℃的低温氩气保护下,向快速搅拌的甲基三苯基碘化膦2.9g(7.2mmol)的THF(20ml)悬浊液中加入叔丁醇钾(KotBu)1.06g(10.8mmol),10分钟后加入THF(20ml)溶解的3-甲酰基-9正己基咔唑(2.0g,7.2mmol)。继续反应10分钟后,向容器中加入5ml的水,使反应淬灭。将反应液抽滤,抽滤后得到的固体用石油醚洗三遍,滤液用二氯甲烷萃取三次。将萃取液依次用去离子水、饱和食盐水洗涤三次后,用无水硫酸镁干燥1h。最后将萃取液旋蒸得到粗产物,柱层析(硅胶,石油醚/乙酸乙酯,40/1,v/v)分离得到纯净产物。最终得到无色液体1.6g,产率80%。HRMS(m/z):278.1874[M+H]+(calcforC20H23N+H:278.1903).
2‐溴芴IV(b)常温下,将干燥好的250ml三口烧瓶,导气管,三通连接好,放入磁子,加入芴5g(30mmol),三氯化铁(FeCl3)0.26g(4.4mmol)抽真空通氩气,反复3次。加入无水N,N-二甲基甲酰胺50ml,搅拌。取9gNBS(50mmol)与50ml无水N,N-二甲基甲酰胺配成溶液,用恒压漏斗逐滴在黑暗处加入。搅拌反应24h。将所得溶液用HCl(0.1M,10ml)处理,并用NaHCO3(84mg)中和HCl萃取并旋蒸,用正己烷重结晶,得白色固体5.88g,产率80%。1H(300MHz,CDCl3,δ):7.81-7.75(m,1H),7.68-7.59(m,2H),7.55-7.48(m,2H),7.41-7.28(m,2H),3.89(s,2H).
9,9-二己基-2-溴芴IV(b)常温下,将干燥好的250ml三口烧瓶,导气管,三通连接好,放入磁子,取2‐溴芴1.6g(6.5mmol),加入二甲基亚砜35ml,抽真空通氩气,反复3次。加入溴代正己烷(C6H13Br)2ml(14mmol)与苄基三乙基氯化铵(TEBAC)73mg(20mmol),然后加入10ml50%氢氧化钠(NaOH)7.58g,在N2的保护下搅拌。溶液颜色会逐渐变成橙色、红色、紫色。常温反应20h。用乙醚萃取并旋蒸,用石油醚过层析柱得到浅黄色油状物2.49g,产率93%。1H(300MHz,CDCl3,δ):7.68-7.64(m,1H),7.56-7.54(m,1H),7.45-7.42(m,2H),7.34-7.31(m,3H),2.01-1.85(m,4H),1.14-1.02(m,12H),0.76(t,J=6.9Hz,6H),0.59(t,J=6.9Hz,4H).13C(75MHz,CDCl3,δ):151.93,149.27,139.10,138.98,128.82,126.41,125.87,125.08,121.83,119.98,119.90,118.69,54.33,39.26,30.44,28.61,22.63,21.54,12.96.
反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑Ⅲ(b):在氩气保护下,依次向干燥的三口烧瓶中加入9-己基-3-乙烯基-咔唑(1.39g,5mmol),醋酸钯(0.112g,0.5mmol),三苯基膦(1.36g,5mmol),碳酸钾(0.69g,5mmol),9,9-二己基-2-溴芴(2.06g,5mmol),40ml分子筛除水的N,N-二甲基甲酰胺.100℃下加热反应48个小时。反应结束以后,将反应液倾倒于水中。将水相用二氯甲烷萃取三次。萃取液依次用去离子水、饱和食盐水洗涤三次以后,用无水硫酸镁干燥1小时。最后将萃取液真空旋蒸得到粗产物,柱层析(硅胶,石油醚/二氯甲烷,25/1,v/v)分离得到无色油状产物1.53g,产率50.3%。1H(300MHz,CDCl3,δ):8.27-8.23(m,1H),8.13(d,J=7.5Hz,1H),7.73-7.65(m,3H),7.57-7.50(m,2H),7.47-7.45(m,1H),7.42-7.26(m,7H),7.23-7.12(m,1H),4.32-4.27(m,,2H),2.03-1.97(m,3H),1.93-1.83(m,2H),1.40-1.25(m,9H),1.18-1.06(m,10H),0.89-0.85(m,4H),0.78-0.74(m,6H),0.70-0.63(m,3H).13C(75MHz,CDCl3,δ):150.18,149.89,139.93,139.80,139.31,139.15,135.87,127.85,127.67,125.78,125.69,125.64,124.73,124.19,123.34,122.17,121.85,121.78,119.37,118.80,118.51,117.92,117.55,107.86,107.82,53.94,42.18,39.51,30.55,30.49,28.74,28.68,27.96,25.95,22.72,21.58,21.53,12.99.MALDI-TOFMS(m/z):609.39(calcdforC45H55N:609.43);HRMS(m/z):609.4460(calcdforC45H55N:609.4335)。
实施例1:5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的制备
具体步骤如下:
(1)将有机溶剂苯用常压蒸馏的方法进行纯化,在惰性气氛下保存待用;
(2)将反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑Ⅱ(a)(0.45mmol)和碘(I2,0.46mmol)加入到步骤(1)纯化的500ml有机溶剂苯中,边溶解边快速搅拌,完全溶解后,通惰性气体30分钟;
(3)在持续搅拌情况下,将18ml环氧丙烷加入步骤(2)所得的溶液中,使溶液中环氧丙烷的浓度为0.51摩尔/升;
(4)用500W的高压汞灯透过石英玻璃照射步骤(3)所得的溶液15分钟至反应结束,得粗产物;
(5)真空旋蒸出溶剂,将所得的粗产物溶解在三氯甲烷中,依次用质量分数为15%的Na2S2O3溶液和蒸馏水洗涤;
(6)对有机滤液进行萃取、洗涤、干燥、旋干、硅胶柱层析、重结晶分离提纯后,得到5,11,11-三己基一氮杂[7]螺烯Ⅰ(a),产量0.090g,产率33.3%。
现将5,11,11-三己基一氮杂[7]螺烯的波谱分析如下:
1H(300MHz,CDCl3,δ):9.80(s,1H),8.97(d,J=8.1,1H),7.92-7.76(m,5H),7.68-7.66(m,1H),7.61-7.51(m,2H),7.43-7.28(m,4H),4.48(t,J=7.2,2H),2.18-2.04(m,4H),2.02-1.92(m,2H),1.49-1.41(m,2H),1.38-1.27(m,4H),1.11-1.07(m,12H),0.88(t,J=6.9,3H),0.83-0.72(m,10H).
13C(75MHz,CDCl3,δ):151.27,149.65,141.23,140.22,140.11,138.58,132.82,129.00,128.49,127.41,127.12,127.00,126.94,126.92,124.79,124.35,123.86,123.26,123.17,121.42,119.86,118.65,118.29,116.65,109.76,109.22,54.95,43.23,40.89,31.61,31.52,29.81,29.19,27.01,24.00,22.61,22.57,14.03,14.00.
MALDI-TOFMS(m/z):607.33(calcdforC45H53N:607.42);
HRMS(m/z):608.4476[M+H]+(calcdforC45H53N+H:608.4212).
原料反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑和产物5,11,11-三己基一氮杂[7]螺烯的核磁共振谱、质谱如附图所示。
5,11,11-三己基一氮杂[7]螺烯的单晶培养及解析:室温下在饱和的5,11,11-三己基一氮杂[7]螺烯二氯甲烷溶液中加入适量的乙醇,混合均匀,缓慢挥发,得到片状单晶。正交晶系,空间群Pbca,晶胞参数
5,11,11-三己基一氮杂[7]螺烯作为发光材料应用在有机发光二极管中,有机发光二极管器件结构如图11所示,各层由下往上依次ITO玻璃、氧化铟锡、4,4‘-双[氮-(1-萘基)-氮-苯氨基]联苯(NPB)、5,11,11‐三己基一氮杂[7]螺烯I(a)和9,9'-(1,3-苯基)二-9H-咔唑(mCP)按照质量比10:90的混合材料、4,7-二苯基-1,10-菲咯啉(Bphen)、镁银合金、银。电致发光性能见图12-14,该器件发出亮度达到2700cdm-2的蓝紫色光,其CIE坐标为(0.157,0.078)。
实施例2:13‐溴‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(b)的制备
化学反应式如下:
实施例3:13-二(三甲苯基)硼基-5,11,11-三己基一氮杂[7]螺烯Ⅰ(c)的制备
化学反应式如下:
实施例4:13-吡啶-5,11,11-三己基一氮杂[7]螺烯Ⅰ(d)
化学反应式如下:
实施例5:5,11,11-三吡啶一氮杂[7]螺烯Ⅰ(e)
化学反应式如下:
Claims (9)
1.一种基于芴与咔唑的高稠环一氮杂[7]螺烯化合物,其特征在于,具有式Ⅰ所示的结构:
其中,取代基R2、R5、R9、R10、R12各自独立的为C1-C6的烷基、Cl、Br、苯、二(三甲苯基)硼或吡啶;R1、R3-R4、R6-R8、R11、R13-R15为H。
2.如权利要求1所述的化合物,其特征在于,化合物是下列之一:
5,11,11‐三己基一氮杂[7]螺烯Ⅰ(a)
2,13‐二溴‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(b)
13‐二(三甲苯基)硼基‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(c)
13‐吡啶‐5,11,11‐三己基一氮杂[7]螺烯Ⅰ(d)
5,11,11‐三吡啶一氮杂[7]螺烯Ⅰ(e)
3.如权利要求1所述的化合物的合成方法,以反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑衍生物为原料,通过光催化闭环反应制备而得;具体步骤如下:
(1)将有机溶剂用蒸馏法纯化,在惰性气氛下保存待用;
(2)将反-9-己基-3-(9,9-二己基-2-芴-乙烯基)咔唑衍生物和化学计量比的碘加入到步骤(1)纯化的有机溶剂中,边溶解边搅拌,完全溶解后使溶液中溶质的浓度均为0.01-1摩尔/升,通惰性气体30-60分钟;
(3)在持续搅拌情况下,将环氧丙烷加入步骤(2)所得的溶液中,使溶液中环氧丙烷的浓度为0.1-2.5摩尔/升;
(4)用250-500W的高压汞灯透过石英玻璃照射步骤(3)所得的溶液5-50分钟至反应结束,得到粗产物;
(5)真空旋蒸出溶剂,将所得的粗产物溶解在二氯甲烷中,依次用质量分数为10-35%的Na2S2O3溶液和蒸馏水洗涤得有机滤液;
(6)对步骤(5)的有机滤液进行分离提纯得到产物。
4.如权利要求3所述的化合物的合成方法,其特征在于,步骤(1)中所述的有机溶剂选自苯、甲苯、正己烷、四氢呋喃或二氯甲烷中的一种。
5.如权利要求3所述的化合物的合成方法,其特征在于,步骤(6)中的分离提纯是指对有机滤液进行萃取、洗涤、干燥、旋干、硅胶柱层析、重结晶分离后得产物。
6.如权利要求2所述的化合物的合成方法,其特征在于,其中5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)的合成方法,包括如下步骤:
(1)将有机溶剂苯用常压蒸馏的方法进行纯化,在惰性气氛下保存待用;
(2)将反-9,9-二己基-2-(2-咔唑乙烯基)芴0.45mmol和碘0.46mmol加入到步骤(1)纯化的500ml有机溶剂苯中,边溶解边快速搅拌,完全溶解后,通惰性气体30分钟;
(3)在持续搅拌情况下,将18ml环氧丙烷加入步骤(2)所得的溶液中,使溶液中环氧丙烷的浓度为0.51摩尔/升;
(4)用500W的高压汞灯透过石英玻璃照射步骤(3)所得的溶液15分钟至反应结束得粗产物;
(5)真空旋蒸出溶剂,将所得的粗产物溶解在三氯甲烷中,依次用质量分数为15%的Na2S2O3溶液和蒸馏水洗涤;
(6)对有机滤液进行萃取、洗涤、干燥、旋干、硅胶柱层析、重结晶分离提纯后,得到5,11,11-三己基一氮杂[7]螺烯Ⅰ(a)。
7.权利要求1或2所述的化合物作为发光材料在制备有机发光二极管中的应用。
8.如权利要求7所述的应用,其特征在于,权利要求1或2所述的化合物按10:90质量比与9,9'-(1,3-苯基)二-9H-咔唑混合作为有机发光二极管器件的客体与主体发光材料。
9.一种有机发光二极管器件,其特征在于,各层由下往上依次ITO玻璃、氧化铟锡、4,4‘-双[氮-(1-萘基)-氮-苯氨基]联苯(NPB)、5,11,11‐三己基一氮杂[7]螺烯I(a)和9,9'-(1,3-苯基)二-9H-咔唑(mCP)按照质量比1:9的混合材料、4,7-二苯基-1,10-菲咯啉(Bphen)、镁银合金、银。
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