CN115521253B - Bibiquinoline derivative compound and application thereof - Google Patents
Bibiquinoline derivative compound and application thereof Download PDFInfo
- Publication number
- CN115521253B CN115521253B CN202211496606.XA CN202211496606A CN115521253B CN 115521253 B CN115521253 B CN 115521253B CN 202211496606 A CN202211496606 A CN 202211496606A CN 115521253 B CN115521253 B CN 115521253B
- Authority
- CN
- China
- Prior art keywords
- reaction
- added
- water
- pph
- 1mol
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 80
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 105
- 238000006243 chemical reaction Methods 0.000 description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 89
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 84
- 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 62
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 62
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 42
- 238000002347 injection Methods 0.000 description 35
- 239000007924 injection Substances 0.000 description 35
- 239000000843 powder Substances 0.000 description 32
- 239000007787 solid Substances 0.000 description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
- 229910000027 potassium carbonate Inorganic materials 0.000 description 31
- 239000011541 reaction mixture Substances 0.000 description 24
- 238000001953 recrystallisation Methods 0.000 description 24
- 238000001704 evaporation Methods 0.000 description 22
- 230000005525 hole transport Effects 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 230000008020 evaporation Effects 0.000 description 17
- 239000002019 doping agent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- SUXIPCHEUMEUSV-UHFFFAOYSA-N 4-bromoquinoline Chemical compound C1=CC=C2C(Br)=CC=NC2=C1 SUXIPCHEUMEUSV-UHFFFAOYSA-N 0.000 description 10
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- IBGUDZMIAZLJNY-UHFFFAOYSA-N 1,4-dibromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=C(Br)C2=C1 IBGUDZMIAZLJNY-UHFFFAOYSA-N 0.000 description 4
- PIWNKSHCLTZKSZ-UHFFFAOYSA-N 8-bromoquinoline Chemical compound C1=CN=C2C(Br)=CC=CC2=C1 PIWNKSHCLTZKSZ-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- FNKCOUREFBNNHG-UHFFFAOYSA-N 1,3-dibromo-5-chlorobenzene Chemical compound ClC1=CC(Br)=CC(Br)=C1 FNKCOUREFBNNHG-UHFFFAOYSA-N 0.000 description 2
- SEQGFOQDPHXWPY-UHFFFAOYSA-N 1,6-dibromophenanthrene Chemical compound C1=CC=C2C3=CC(Br)=CC=C3C=CC2=C1Br SEQGFOQDPHXWPY-UHFFFAOYSA-N 0.000 description 2
- TUQSVSYUEBNNKQ-UHFFFAOYSA-N 2,4-dichloroquinazoline Chemical compound C1=CC=CC2=NC(Cl)=NC(Cl)=C21 TUQSVSYUEBNNKQ-UHFFFAOYSA-N 0.000 description 2
- IAKIEFRRBKQXIW-UHFFFAOYSA-N 4-bromo-2-phenylquinoline Chemical compound N=1C2=CC=CC=C2C(Br)=CC=1C1=CC=CC=C1 IAKIEFRRBKQXIW-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- IFIHYLCUKYCKRH-UHFFFAOYSA-N 6-bromoquinoline Chemical compound N1=CC=CC2=CC(Br)=CC=C21 IFIHYLCUKYCKRH-UHFFFAOYSA-N 0.000 description 2
- DAHYJSFUKJLEEJ-UHFFFAOYSA-N 8-bromo-4-chloroquinoline Chemical compound C1=CC=C2C(Cl)=CC=NC2=C1Br DAHYJSFUKJLEEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000005549 heteroarylene group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- KOFLVDBWRHFSAB-UHFFFAOYSA-N 1,2,4,5-tetrahydro-1-(phenylmethyl)-5,9b(1',2')-benzeno-9bh-benz(g)indol-3(3ah)-one Chemical compound C1C(C=2C3=CC=CC=2)C2=CC=CC=C2C23C1C(=O)CN2CC1=CC=CC=C1 KOFLVDBWRHFSAB-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- PJZDEYKZSZWFPX-UHFFFAOYSA-N 2,6-dibromonaphthalene Chemical compound C1=C(Br)C=CC2=CC(Br)=CC=C21 PJZDEYKZSZWFPX-UHFFFAOYSA-N 0.000 description 1
- HTFNVAVTYILUCF-UHFFFAOYSA-N 2-[2-ethoxy-4-[4-(4-methylpiperazin-1-yl)piperidine-1-carbonyl]anilino]-5-methyl-11-methylsulfonylpyrimido[4,5-b][1,4]benzodiazepin-6-one Chemical compound CCOc1cc(ccc1Nc1ncc2N(C)C(=O)c3ccccc3N(c2n1)S(C)(=O)=O)C(=O)N1CCC(CC1)N1CCN(C)CC1 HTFNVAVTYILUCF-UHFFFAOYSA-N 0.000 description 1
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- KPGPIQKEKAEAHM-UHFFFAOYSA-N 2-chloro-3-phenylquinoxaline Chemical compound ClC1=NC2=CC=CC=C2N=C1C1=CC=CC=C1 KPGPIQKEKAEAHM-UHFFFAOYSA-N 0.000 description 1
- QWNCDHYYJATYOG-UHFFFAOYSA-N 2-phenylquinoxaline Chemical compound C1=CC=CC=C1C1=CN=C(C=CC=C2)C2=N1 QWNCDHYYJATYOG-UHFFFAOYSA-N 0.000 description 1
- GYCPLYCTMDTEPU-UHFFFAOYSA-N 5-bromopyrimidine Chemical compound BrC1=CN=CN=C1 GYCPLYCTMDTEPU-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- -1 quinoline derivative compound Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- 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
- C07D401/10—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 linked by a carbon chain containing aromatic rings
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of organic light-emitting display, and relates to a bisquinoline derivative compound and application thereof. When the organic electroluminescent material is used as an electron transport material, the organic electroluminescent device can effectively reduce the driving voltage, improve the luminous efficiency and prolong the service life. The invention also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
（I）。
Description
Technical Field
The invention relates to the technical field of organic light-emitting display, in particular to a bisquinoline derivative compound and application thereof.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which brings great opportunities and challenges for the design and development of functional materials with various structures for technicians in the field.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, flexible display and large-area display can be realized, the optical performance, the electrical performance, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (including host materials and guest materials), and the like. At present, as an important functional material, an electron transport material has a direct influence on the mobility of electrons, and ultimately influences the luminous efficiency of an OLED. At present, the problem of low mobility of commercial electron transport materials is an important limiting factor in the development of device performance, and more researches are worth to be made for developing materials with higher mobility.
Disclosure of Invention
In view of the above deficiencies of the prior art, it is an object of the present invention to provide a compound which, when used as an electron transport material, enables an improvement in the operating efficiency and an extension in the lifetime of an organic electroluminescent device.
The invention aims at providing a duplex quinoline derivative compound which has a structure shown as a formula (I):
（I）
wherein,
L 1 、L 2 、L 3 each independently selected from hydrogen, C unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted by Rc 3 -C 40 A heteroarylene group;
X 1 -X 8 、Y 1 -Y 8 each independently selected from C or N, and at least one X and at least one Y are N;
the heteroatoms on the arylene and heteroarylene groups are each independently selected from O, S, or N;
further, each Rc is independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Further, L is 1 、L 2 、L 3 Each independently selected from the following subunits of compounds unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene, fluorene, pyrimidine, quinoline, isoquinoline, quinazoline, quinoxaline, naphthyridine, dibenzofuran, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene.
Still further, the bisquinoline derivative compound is selected from compounds represented by the following A1 to a 25:
it is an object of a second aspect of the present invention to provide an electron transport material comprising at least one of the compounds provided by the first aspect of the present invention.
It is an object of a third aspect of the present invention to provide an organic electroluminescent device comprising at least one of the electron transport materials provided by the second aspect of the present invention.
It is an object of the fourth aspect of the present invention to provide a display apparatus comprising the organic electroluminescent device provided by the third aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the compound provided by the invention has a parent structure of ortho-disubstituted pyridine fragments, has high bond energy among atoms, has good thermal stability, is favorable for intermolecular solid-state accumulation, has a simple and easy preparation process and easily-obtained raw materials, and is suitable for industrial production. When the material is used as an electron transport material, the material has a proper energy level with the adjacent layers, so that the injection and the migration of excitons are facilitated, the driving voltage can be effectively reduced, the LUMO energy level distribution of the material is high in delocalization, the electron transfer rate is high, and the good luminous efficiency and the service life can be realized in an organic electroluminescent device. The compound of the invention has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and can prolong the service life when being used in an organic electroluminescent device. The organic electroluminescent device comprises the compound as an electron transport material, so that the driving voltage can be effectively reduced, the luminous efficiency is improved, and the service life of the organic electroluminescent device is prolonged. The display device provided by the invention has excellent display effect.
Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other embodiments can be obtained by referring to the drawings.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device. Each part is as follows:
1. a substrate; 2. a reflective anode electrode; 3. a hole injection layer; 4. a hole transport layer; 5. a light emitting layer; 6. an electron transport layer; 7. an electron injection layer; 8. and a cathode electrode.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention. All other embodiments that can be derived by one of ordinary skill in the art from the disclosure are intended to be within the scope of the disclosure.
In the present invention, there is no particular limitation on the kind and structure of the organic electroluminescent device, and there may be different types and structures of organic electroluminescent devices known in the art as long as the electron transport material provided by the present invention can be used.
The organic electroluminescent device of the present invention may be a light emitting device of a top emission structure, and may sequentially include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode on a substrate.
The organic electroluminescent device of the present invention may also be a light-emitting device of a bottom light-emitting structure, and may sequentially include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode structure on a substrate.
The organic electroluminescent device of the present invention may also be a light-emitting device of a double-sided light-emitting structure, and may sequentially include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode structure on a substrate.
In addition, an electron blocking layer may be provided between the hole transport layer and the light emitting layer, a hole blocking layer may be provided between the light emitting layer and the electron transport layer, and a light extraction layer may be provided on the transparent electrode on the light outgoing side. However, the structure of the organic electroluminescent device of the present invention is not limited to the above-described specific structure, and the above-described layers may be omitted or added if necessary. The present invention is not particularly limited in the thickness of each layer as long as the object of the present invention can be achieved. For example, the organic electroluminescent device may include an anode made of a metal, a hole injection layer (5 nm to 20 nm), a hole transport layer (80 nm to 140 nm), an electron blocking layer (5 nm to 20 nm), a light emitting layer (150 nm to 400 nm), a hole blocking layer (5 nm to 20 nm), an electron transport layer (300 nm to 800 nm), an electron injection layer (5 nm to 20 nm), a transparent or semitransparent cathode, and a light extraction layer (50 nm to 90 nm) in this order on a substrate.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not meant to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present invention are within the scope of the present invention.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically shows only the structure of a typical organic electroluminescent device, the present invention is not limited to this structure, and the electron transport material of the present invention may be used for any type of organic electroluminescent device.
In the present invention, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass, polymer materials, and glass and polymer materials with Thin Film Transistor (TFT) components, etc. may be used.
In the present invention, the reflective anode material 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art 2 ) The transparent conductive material such as zinc oxide (ZnO) may be selected from a metal material such as silver and an alloy thereof, aluminum and an alloy thereof, an organic conductive material such as poly-3, 4-ethylenedioxythiophene (PEDOT), a multilayer structure of the above materials, and the like.
In the present invention, the material of the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art. For example, at least one of known Hole Transport Materials (HTM) is selected as the hole injection material.
In the present invention, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be used. For example, the p-type dopant may be selected from, but is not limited to, at least one of the following p-1 to p-3 compounds:
in the present invention, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present invention, the material of the hole transport layer 4 is not particularly limited, and a Hole Transport Material (HTM) known in the art may be used. The number of layers of the hole transport layer 4 is not particularly limited, and may be adjusted as needed as long as the object of the present invention is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, the HTM for the hole injection layer 3 material and the HTM for the hole transport layer 4 material may be selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:
in the present invention, the light emitting layer 5 may include a blue light emitting layer, a green light emitting layer, or a red light emitting layer, the light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, the material of the light emitting layer 5 may include a host material and a guest material.
In the present invention, the host material may be selected from, but is not limited to, at least one of the following BH-1 to BH-10 compounds:
in the present invention, the guest material is not particularly limited, and at least one of guest materials of a light emitting layer known in the art may be used. For example, the guest material of the light-emitting layer 5 may be selected from, but not limited to, at least one of the following BD-1 to BD-9 compounds:
in the present invention, the amount of the guest material of the light-emitting layer 5 is not particularly limited, and may be an amount known to those skilled in the art.
In the present invention, the electron transport layer 6 contains at least one of the electron transport materials of the present invention, and the electron transport layer 6 may also contain a combination of at least one of the electron transport materials of the present invention and at least one of the known electron transport materials. The number of the electron transport layers 6 is not particularly limited, and may be adjusted according to actual needs as long as the object of the present invention is satisfied, for example, 1, 2, 3,4 or more layers.
For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:
in the present invention, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be used, for example, the following n-type dopants may be used:
n-1。
in the present invention, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present invention, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of BaO, na, li, ca and the like.
In the present invention, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, magnesium silver mixture, metal such as LiF/Al, ITO, al, and the like, oxide, and the like.
The object of the fourth aspect of the invention is to provide a display device comprising the organic electroluminescent device provided by the third aspect of the invention. The display device includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.
The method for preparing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art may be used, for example, the present invention may be prepared by the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively performing steps of medicine washing, water washing, hair brushing, high-pressure water washing, air knife and the like in a cleaning machine, and then performing heat treatment;
(2) Vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3;
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) A luminescent layer 5 is evaporated on the hole transport layer 4 in vacuum, wherein the luminescent layer 5 comprises a host material and a guest material;
(5) Vacuum evaporating an electron transport material on the luminescent layer 5 to form an electron transport layer 6;
(6) Vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;
(7) A cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The above description is made only for the structure of a typical organic electroluminescent device and a method for fabricating the same, and it is to be understood that the present invention is not limited to this structure. The electron transport material of the present invention can be used for an organic electroluminescent device of any structure, and the organic electroluminescent device can be prepared by any preparation method known in the art.
The method for synthesizing the compound of the present invention is not particularly limited, and the synthesis can be carried out by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present invention.
Synthesis example 1 Synthesis of Compound A2:
into a reaction flask were charged 100mmol of 8-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting for 12h at 60 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on 8-bromoquinoline.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of toluene, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
Into a reaction flask were added 100mmol of 1, 4-dibromonaphthalene, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A2. Wherein, pd (PPh) 3 ) 4 The amount of (2) added is 2mol% of 1, 4-dibromonaphthalene.
The hydrogen spectrum characterization of A2 resulted in:
1 H NMR (400 MHz, CDCl 3 )8.83- 8.62 (m, 4H), 7.74 (s, 2H), 7.67 (d, J = 10.0 Hz, 4H), 7.57-7.46 (m, 8H), 7.29-7.10 (m, 8H).
mass spectrometry data: theoretical, 534.2 experimental, 534.1.
Synthesis example 2 Synthesis of Compound A4:
into a reaction flask were charged 100mmol of 6-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on 6-bromoquinoline.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of toluene, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
Into a reaction flask were charged 100mmol of 1, 4-dibromonaphthalene, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized from toluene to purify it to obtain white powder A4. Wherein, pd (PPh) 3 ) 4 The amount of (A) added was 2mol% of 1, 4-dibromonaphthalene.
The hydrogen spectrum of A4 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )8.38 (s, 2H), 8.09 (d, J = 11.4 Hz, 4H), 7.75-7.58 (m, 6H), 7.47-7.33 (m, 8H), 7.26 (d, J = 10.0 Hz, 6H).
mass spectrometry data: theoretical, 534.2 experimental, 534.0.
Synthesis example 3 Synthesis of Compound A8:
into a reaction flask were charged 100mmol of 4-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on the 4-bromoquinoline.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of toluene, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
Into a reaction flask were charged 100mmol of 3, 8-dibromophenanthrene, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder A8. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 2mol% based on the 3, 8-dibromophenanthrene.
The hydrogen spectrum of A8 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )8.43 (d, J =9.6 Hz, 4H), 8.17 - 7.92 (m, 4H), 7.80 -7.64(m, 6H), 7.57 (d, J = 7.6 Hz, 6H), 7.48- 7.25 (m, 8H).
mass spectrometry data: theoretical, experimental 584.2, 584.7.
Synthesis example 4 Synthesis of Compound A10:
into a reaction flask were charged 100mmol of 4-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on the 4-bromoquinoline.
Into a reaction flask were charged 100mmol of 3, 5-dibromochlorobenzene, 200mmol of pinacol diboron diboride, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 2mol% based on the 3, 5-dibromochlorobenzene.
Into a reaction flask were added 100mmol of M2, 200mmol of M1, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol diborate, 41.4g of potassium carbonate (300 mmol), and 800mlAnd 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder M4. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M3.
Into a reaction flask were charged 100mmol of M4, 100mmol of 5-bromopyrimidine, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting for 12h at 60 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder a10. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M4.
The hydrogen spectrum characterization results for a10 are as follows:
1 H NMR (400 MHz, CDCl 3 )9.62 (s, 1H), 9.12 (s, 1H), 8.87 (s, 1H), 8.28-8.04 (m, 3H), 7.80 (s, 1H), 7.71-7.55 (m, 8H), 7.45 (d, J = 7.2 Hz, 6H), 7.25-7.16 (m, 4H).
mass spectrometry data: theoretical, 562.2 experimental, 561.9.
Synthesis example 5 Synthesis of Compound A12:
into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized from toluene to purify it to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 2-chloro-31mol% of phenylquinoxaline.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
To a reaction flask were added 100mmol of 8-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on 8-bromoquinoline.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting for 12h at 100 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder M4. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M3.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2, 6-dibromonaphthalene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting for 12h at 60 ℃. After the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, pd (PPh) 3 ) 4 Is added withThe amount of addition was 1mol% of M4.
Into a reaction flask were charged 100mmol of M2, 100mmol of M5, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a12. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M2.
The hydrogen spectrum of a12 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )8.84 (d, J = 10.0 Hz, 4H), 8.17 (d, J = 9.2 Hz, 2H), 8.05 (t, J = 8.0 Hz, 4H), 7.89 (s, 1H), 7.69-7.56 (m, 7H), 7.46-7.30 (m, 7H), 7.25-7.10(m, 4H).
mass spectrometry data: theoretical, 611.2 experimental, 611.5.
Synthesis example 6 Synthesis of Compound A15:
into a reaction flask were charged 100mmol of 4-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on the 4-bromoquinoline.
Into a reaction flask were charged 100mmol of M1, 200mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. Stopping the reaction after the reaction is finished, and cooling the reactantsCooling to room temperature, adding water, filtering, washing with water, and recrystallizing the obtained solid with toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
Into a reaction flask were charged 100mmol of 2, 4-dichloroquinazoline, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a15. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 2mol% based on the amount of 2, 4-dichloroquinazoline.
The hydrogen spectrum of a15 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )8.44-8.22 (m, 4H), 8.08 (d, J = 9.2 Hz, 4H), 7.96-7.79 (m, 6H), 7.56 (d, J =10.4 Hz, 4H), 7.48-7.25 (m, 6H).
mass spectrometry data: theoretical, 536.2 experimental, 535.8.
Synthesis example 7 Synthesis of Compound A19:
into a reaction flask were charged 100mmol of 2-phenyl-4-bromoquinoline, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on the 2-phenyl-4-bromoquinoline.
100mmol of M1, 100mmol of NBS and 800ml of chloroform were put into a reaction flask and reacted at room temperature for 8 hours. After the reaction was completed, the reaction was stopped, water was added, filtered, washed with water, and the obtained solid was recrystallized from toluene to obtain white powder M2.
Into a reaction flask were charged 100mmol of 4-bromoquinoline, 200mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 2mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 2mol% based on the 4-bromoquinoline.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol diboride, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting at 100 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder M4. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M3.
Into a reaction flask were added 100mmol of M2, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting for 12h at 60 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder a19. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M2. The hydrogen spectrum of a19 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )8.83 (s, 1H), 8.42-8.17 (m, 5H), 7.88 (d, J = 10.0 Hz, 4H), 7.78-7.68(m, 5H), 7.58 (d, J = 10.0 Hz, 2H), 7.50-7.37 (m, 7H), 7.26 (d, J = 8.4 Hz, 4H).
mass spectrometry data: theoretical, 584.2 experimental, 583.6.
Synthesis example 8 Synthesis of Compound A21:
into a reaction flask were charged 100mmol of 4-bromoquinoline, 100mmol of p-chlorobenzoic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting at 60 ℃ for 12h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on the 4-bromoquinoline.
Into a reaction flask were charged 100mmol of M1, 200mmol of pinacol diboron, 41.4g of potassium carbonate (300 mmol), 800ml of dioxane, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And reacting for 12h at 100 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M1.
Into a reaction flask were added 100mmol of 4-chloro-8-bromoquinoline, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) And reacting for 12h at 60 ℃. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on 4-chloro-8-bromoquinoline.
Into a reaction flask were charged 100mmol of M3, 200mmol of M2, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added 3 ) 4 ) At 60 ℃ CThe reaction is carried out for 12 hours. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a21. Wherein, pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M3.
The hydrogen spectrum of a21 is characterized as follows:
1 H NMR (400 MHz, CDCl 3 )9.00-8.65 (m, 3H), 8.16 (d, J = 10.0 Hz, 4H), 7.80 (s, 1H), 7.69 (d, J = 10.4 Hz, 4H), 7.50 (d, J = 8.8 Hz, 4H), 7.36-7.21 (m, 6H), 7.26 (d, J = 8.0 Hz, 4H).
mass spectrometry data: theoretical, 535.2 experimental, 535.4.
The other compounds of the present invention can be synthesized by selecting suitable raw materials according to the ideas of the above synthesis examples 1 to 8, and can also be synthesized by selecting any other suitable methods and raw materials.
Example 1
Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
then, the glass substrate with the anode is placed in a vacuum chamber and is vacuumized to be less than 10 DEG -5 Performing vacuum evaporation on the anode layer film by using a torr, wherein the material of the hole injection layer comprises a hole injection layer material HT-11 and a p-type dopant p-1, and evaporation is performed by using a multi-source co-evaporation method, the evaporation rate of the hole injection layer material HT-11 is adjusted to be 0.1nm/s, the evaporation rate of the p-type dopant p-1 is 3% of the evaporation rate of the hole injection layer material HT-11, and the evaporation film thickness is 10nm; the hole injection layer material HT-11 and the p-type dopant p-1 are as follows:
and then, vacuum evaporating a hole transport material HT-7 as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport material HT-7 is as follows:
HT-7；
then, a light-emitting layer is evaporated on the hole transport layer in vacuum, the light-emitting layer comprises a main material BH-4 and a fluorescent dopant BD-1, evaporation is carried out by a multi-source co-evaporation method, wherein the evaporation rate of the main material BH-4 is adjusted to be 0.1nm/s, the evaporation rate of the fluorescent dopant BD-1 is 3% of the evaporation rate of the main material BH-4, and the thickness of the evaporation film is 30nm; the host material BH-4 and the fluorescent dopant BD-1 are as follows:
then, an electron transport layer is vacuum-evaporated on the luminescent layer, wherein the electron transport material is a compound A2, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30nm; the electron transport material A2 was as follows:
then, carrying out vacuum evaporation on LiF with the thickness of 5nm on the electron transport layer to serve as an electron injection layer, wherein the evaporation rate is 0.1nm/s;
and finally, performing vacuum evaporation on the A2 layer with the thickness of 150nm on the electron injection layer to serve as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 0.1nm/s.
Examples 2 to 8
The same as example 1 except that A4, A8, a10, a12, a15, a19, and a21 were used instead of A2 for the electron transporting material.
Comparative example 1
The same as example 1 except that ET-19 was used as the electron transporting material; the ET-19 structure is as follows:
comparative example 2
The same as example 1 except that R was used as an electron transporting material; the structure of R is as follows:
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage, current efficiency and lifetime of the organic electroluminescent devices prepared in examples 1 to 8 and comparative examples 1 and 2 were measured at the same luminance using a digital source meter and a luminance meter, and specifically, the luminance of the organic electroluminescent device was measured to reach 1000cd/m at a rate of 0.1V/sec by increasing the voltage 2 The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; life test of LT95 is as follows: using a luminance meter at 1000cd/m 2 The luminance drop of the organic electroluminescent device was measured to 950cd/m by maintaining a constant current at luminance 2 Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance results
It can be seen from table 1 that the compounds A2, A4, A8, a10, a12, a15, a19, and a21 prepared by the present invention are used as electron transport materials for organic electroluminescent devices, and can effectively reduce driving voltage, improve current efficiency, and prolong the service life of the devices.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (4)
1. A bisquinoline derivative compound selected from the group consisting of:
2. an electron transport material comprising at least one compound of claim 1.
3. An organic electroluminescent device, characterized in that it comprises at least one of the electron transport materials according to claim 2.
4. A display device comprising the organic electroluminescent element according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211496606.XA CN115521253B (en) | 2022-11-28 | 2022-11-28 | Bibiquinoline derivative compound and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211496606.XA CN115521253B (en) | 2022-11-28 | 2022-11-28 | Bibiquinoline derivative compound and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115521253A CN115521253A (en) | 2022-12-27 |
| CN115521253B true CN115521253B (en) | 2023-04-07 |
Family
ID=84705377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211496606.XA Active CN115521253B (en) | 2022-11-28 | 2022-11-28 | Bibiquinoline derivative compound and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115521253B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445422B (en) * | 2008-12-31 | 2013-06-12 | 清华大学 | Organic electroluminescent material and application thereof |
| CN101597259B (en) * | 2009-07-07 | 2012-11-07 | 清华大学 | Organic material and application thereof in organic electroluminescence device (OELD) |
| KR101531615B1 (en) * | 2012-04-24 | 2015-07-02 | 제일모직 주식회사 | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode |
| JP6638517B2 (en) * | 2016-03-30 | 2020-01-29 | Jnc株式会社 | Self-organizing polycyclic aromatic compound and organic EL device using the same |
| CN108807697B (en) * | 2017-04-26 | 2022-02-22 | 固安鼎材科技有限公司 | Organic electroluminescent device and phenanthrene derivative |
| CN111269219B (en) * | 2020-03-25 | 2023-05-30 | 烟台显华化工科技有限公司 | Organic luminescent material and organic electroluminescent device |
-
2022
- 2022-11-28 CN CN202211496606.XA patent/CN115521253B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115521253A (en) | 2022-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110526901A (en) | A kind of luminous organic material and its application for preparing organic electroluminescence device | |
| CN113264911A (en) | Compound, organic light-emitting material and organic electroluminescent device | |
| CN112321521B (en) | Electron transport material, organic electroluminescent device and display device | |
| CN110818675A (en) | Organic compound and application thereof | |
| CN112174918B (en) | Compound, hole transport material, organic electroluminescent device and display device | |
| CN112159361A (en) | Electron transport material, organic electroluminescent device and display device | |
| CN111233764B (en) | Organic compound with acridine derived triarylamine structure and application thereof | |
| CN110734446A (en) | organic compound and application thereof | |
| CN109503576B (en) | Organic compound, display panel, and display device | |
| CN112125813B (en) | Compound, hole transport material and organic electroluminescent device | |
| CN112125892B (en) | Compound, electron transport material and organic electroluminescent device | |
| CN112159326A (en) | Compound, luminescent layer dye material and organic electroluminescent device | |
| CN115636755A (en) | Naphthyl substituted diarylamine compound and application thereof | |
| CN113321649B (en) | Compound, electron transport material and organic electroluminescent device | |
| CN112110885B (en) | Hole transport material, organic electroluminescent device and display device | |
| CN115521253B (en) | Bibiquinoline derivative compound and application thereof | |
| CN117143030A (en) | Naphthyl substituted electricity-absorbing fragment compound, electron transport material and application | |
| CN115991699A (en) | Naphthalene bridging double-suction fragment compound | |
| CN115521292B (en) | Quinoline substituted pyridine compound and application thereof | |
| CN115611891B (en) | Quinoline-substituted phenanthroline compound and application thereof | |
| CN113024512A (en) | Aromatic heterocyclic compound used as electron transport material and application thereof | |
| CN112125861A (en) | Compound, electron transport material and organic electroluminescent device | |
| CN115594599B (en) | Bis-naphthalene compound and application thereof | |
| CN117069597B (en) | Compound and application thereof | |
| CN113307764B (en) | Compound, electron transport material, organic electroluminescent device and display device |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |