CN106554322B - Phenazine derivative and application thereof in organic electroluminescent device - Google Patents
Phenazine derivative and application thereof in organic electroluminescent device Download PDFInfo
- Publication number
- CN106554322B CN106554322B CN201510640793.8A CN201510640793A CN106554322B CN 106554322 B CN106554322 B CN 106554322B CN 201510640793 A CN201510640793 A CN 201510640793A CN 106554322 B CN106554322 B CN 106554322B
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- formula
- dibromophenazine
- boronic acid
- compound represented
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- 125000001791 phenazinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 title claims abstract 8
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 22
- -1 chrysene -yl Chemical group 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 11
- 230000005525 hole transport Effects 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 6
- 125000005580 triphenylene group Chemical group 0.000 claims description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims description 3
- 125000001725 pyrenyl group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 100
- 238000006243 chemical reaction Methods 0.000 description 90
- 229910052757 nitrogen Inorganic materials 0.000 description 89
- 238000003786 synthesis reaction Methods 0.000 description 74
- 239000003153 chemical reaction reagent Substances 0.000 description 65
- ABVGUWJHWXBGEH-UHFFFAOYSA-N 2,8-dibromophenazine Chemical compound C1=CC(Br)=CC2=NC3=CC(Br)=CC=C3N=C21 ABVGUWJHWXBGEH-UHFFFAOYSA-N 0.000 description 57
- 230000015572 biosynthetic process Effects 0.000 description 52
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 52
- 238000000034 method Methods 0.000 description 49
- 238000004440 column chromatography Methods 0.000 description 46
- 238000000921 elemental analysis Methods 0.000 description 44
- MILNCXRRKCVYAV-UHFFFAOYSA-N 2,7-dibromophenazine Chemical compound C1=C(Br)C=CC2=NC3=CC(Br)=CC=C3N=C21 MILNCXRRKCVYAV-UHFFFAOYSA-N 0.000 description 34
- 239000004327 boric acid Substances 0.000 description 23
- 239000002994 raw material Substances 0.000 description 22
- BQHVXFQXTOIMQM-UHFFFAOYSA-N (4-naphthalen-1-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC2=CC=CC=C12 BQHVXFQXTOIMQM-UHFFFAOYSA-N 0.000 description 18
- RCOAUYBPVRIYBG-UHFFFAOYSA-N [4-(2-phenylbenzimidazol-1-yl)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2N=C1C1=CC=CC=C1 RCOAUYBPVRIYBG-UHFFFAOYSA-N 0.000 description 16
- 238000000926 separation method Methods 0.000 description 15
- 150000002988 phenazines Chemical class 0.000 description 14
- MWEKPLLMFXIZOC-UHFFFAOYSA-N pyren-1-ylboronic acid Chemical compound C1=C2C(B(O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 MWEKPLLMFXIZOC-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- XSQUPVXOENTCJV-UHFFFAOYSA-N (6-phenylpyridin-3-yl)boronic acid Chemical compound N1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XSQUPVXOENTCJV-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- JCDAUYWOHOLVMH-UHFFFAOYSA-N phenanthren-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC3=CC=CC=C3C2=C1 JCDAUYWOHOLVMH-UHFFFAOYSA-N 0.000 description 10
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 8
- RVPCPPWNSMAZKR-UHFFFAOYSA-N (10-phenylanthracen-9-yl)boronic acid Chemical compound C12=CC=CC=C2C(B(O)O)=C2C=CC=CC2=C1C1=CC=CC=C1 RVPCPPWNSMAZKR-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- YNDGEMZBYUVHTH-UHFFFAOYSA-N [4-(10-phenylanthracen-9-yl)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YNDGEMZBYUVHTH-UHFFFAOYSA-N 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 4
- 125000004556 carbazol-9-yl group Chemical group C1=CC=CC=2C3=CC=CC=C3N(C12)* 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ICQAKBYFBIWELX-UHFFFAOYSA-N (4-naphthalen-2-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=C(C=CC=C2)C2=C1 ICQAKBYFBIWELX-UHFFFAOYSA-N 0.000 description 2
- BRMXCUCHGKWTIO-UHFFFAOYSA-N (4-phenanthren-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC2=CC=CC=C2C2=CC=CC=C12 BRMXCUCHGKWTIO-UHFFFAOYSA-N 0.000 description 2
- ISMRPUXCQLIMJL-UHFFFAOYSA-N (4-pyren-1-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=C(C=C2)C3=C4C2=CC=CC4=CC=C13 ISMRPUXCQLIMJL-UHFFFAOYSA-N 0.000 description 2
- CNRNNPZITWDZGC-UHFFFAOYSA-N (7,10-diphenylfluoranthen-3-yl)boronic acid Chemical compound C=12C3=CC=CC=1C(B(O)O)=CC=C2C1=C3C(C=2C=CC=CC=2)=CC=C1C1=CC=CC=C1 CNRNNPZITWDZGC-UHFFFAOYSA-N 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- WDRUBCBSUBXPSW-UHFFFAOYSA-N 2,4-diphenylpyrimidine Chemical compound C1=CC=CC=C1C1=CC=NC(C=2C=CC=CC=2)=N1 WDRUBCBSUBXPSW-UHFFFAOYSA-N 0.000 description 2
- WIHHVKUARKTSBU-UHFFFAOYSA-N 4-bromobenzene-1,2-diamine Chemical compound NC1=CC=C(Br)C=C1N WIHHVKUARKTSBU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003220 pyrenes Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- WFOZWGDQDLFREE-UHFFFAOYSA-N 1,2-dibromophenazine Chemical compound C1=CC=CC2=NC3=C(Br)C(Br)=CC=C3N=C21 WFOZWGDQDLFREE-UHFFFAOYSA-N 0.000 description 1
- PJEGRMFPMZBYJI-UHFFFAOYSA-N 1,2-diphenylfluoranthene Chemical class C1=CC=CC=C1C1=CC2=CC=CC(C=3C4=CC=CC=3)=C2C4=C1C1=CC=CC=C1 PJEGRMFPMZBYJI-UHFFFAOYSA-N 0.000 description 1
- AKJYCUBHAHKANS-UHFFFAOYSA-N 18,19-diphenylpentacyclo[10.7.1.02,11.03,8.016,20]icosa-1(20),2(11),3,5,7,9,12,14,16,18-decaene Chemical class C1=CC=CC=C1C1=CC2=CC=CC(C=3C4=C5C=CC=CC5=CC=3)=C2C4=C1C1=CC=CC=C1 AKJYCUBHAHKANS-UHFFFAOYSA-N 0.000 description 1
- LTHKZYVCVXHKLZ-UHFFFAOYSA-N 4-Bromo-3,5-cyclohexadiene-1,2-dione Chemical compound BrC1=CC(=O)C(=O)C=C1 LTHKZYVCVXHKLZ-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- 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
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- 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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Abstract
The invention relates to a phenazine derivative, and the compound has a structure shown in a formula (1). The phenazine derivatives of the invention are suitable as ETL materials in electroluminescent displays. The use of the material can effectively reduce the working voltage of the organic electroluminescent device and improve the luminous efficiency of the organic electroluminescent device.
Description
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a phenazine derivative, a phenazine derivative intermediate, a preparation method of the phenazine derivative intermediate, and an application of the phenazine derivative and the phenazine intermediate in an electron transport material.
Background
The electron transport material traditionally used in electroluminescent devices is Alq3However, Alq3Has a low electron mobility ratio (approximately at 10)-6cm2Vs). In order to improve the electron transport properties of electroluminescent devices, researchers have made a great deal of exploratory work.
LG chemistry in chinese patent specification CN 101003508A reports a series of pyrene derivatives as electron transporting and injecting materials in electroluminescent devices to improve the luminous efficiency of the devices. FFF-Blm4 (J.Am.chem.Soc.; (Communication); 2008; 130 (11); 3282-. Kodak in U.S. patents (publication nos. US 2006/0204784 and US 2007/0048545) mentioned a hybrid electron transport layer formed by doping one material with a low LUMO level material with another electron transport material with a low device operating voltage and other materials such as metallic materials. Devices based on such hybrid electron transport layers provide improved device efficiency, but increase the complexity of the device fabrication process, which is detrimental to OLED cost reduction. The stable and efficient electron transport material and/or electron injection material are/is developed, so that the device lighting and working voltage is reduced, the device efficiency is improved, the device service life is prolonged, and the method has important practical application value.
Disclosure of Invention
The invention aims to provide a novel phenazine derivative which can be used in the field of organic electroluminescent display. In particular, the compounds can be used as electron transport materials in organic electroluminescent displays.
The use of the material can effectively reduce the working voltage of the organic electroluminescent device and improve the luminous efficiency of the organic electroluminescent device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a phenazine derivative having a structure represented by formula (1):
wherein: ar (Ar)1And Ar2The same or different, are respectively and independently selected from H, halogen and substituted or unsubstituted C4-C30Aryl ring radical of (2), substituted or unsubstituted C4-C30Heteroaryl ring radical, substituted or unsubstituted C4-C30Condensed ring aryl, substituted or unsubstituted C4-C30Fused heterocyclic aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano, arylAromatic secondary amine groups, aliphatic secondary amine groups, substituted or unsubstituted carbazol-9-yl groups, aromatic and aliphatic substituted pyridyl groups, or benzimidazolyl substituted phenyl groups; ar (Ar)1And Ar2Not simultaneously from H.
Preferably, the formula (1) is a structure represented by formula (2) and formula (3):
Ar1and Ar2The same or different, are respectively and independently selected from H, halogen and substituted or unsubstituted C4-C30Aryl ring radical of (2), substituted or unsubstituted C4-C30Heteroaryl ring radical, substituted or unsubstituted C4-C30Condensed ring aryl, substituted or unsubstituted C4-C30Fused heterocyclic aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano, aromatic secondary amine, aliphatic secondary amine, substituted or unsubstituted carbazol-9-yl, aromatic and aliphatic substituted pyridyl, or benzimidazolyl substituted phenyl;
Ar1and Ar2Not simultaneously from H.
The substituent on the aromatic ring group, the heteroaromatic ring group, the condensed ring aryl group and the condensed heterocyclic aryl group is the aromatic ring group, the heteroaromatic ring group, the condensed ring aryl group or the condensed heterocyclic aryl group, substituted or unsubstituted alkyl, naphthenic base, secondary amino, cyano-group and halogen.
The substituted or unsubstituted aromatic hydrocarbon group is phenyl, o-tolyl, p-tolyl or tert-butylphenyl; the substituted or unsubstituted heterocyclic aromatic hydrocarbon group is furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, pyridine, pyrazine, 2.4-methyl-1.3.5 triazine or 4.6 diphenyl pyrimidine and the like; the substituted or unsubstituted condensed ring aromatic hydrocarbon group is naphthyl, phenanthryl, anthryl, pyrenyl,
A fluorenyl, triphenylene, or 9, 9-dimethyl-2-fluorenyl group; the substituted or unsubstituted fused heterocyclic aromatic hydrocarbon group is quinolineIsoquinoline, quinazoline; substituted or unsubstituted alkyl is trifluoromethyl or alkyl.
The formula (1) preferably has a specific structure shown by the following formulae (4) to (47):
the application of the phenazine derivative in an organic electroluminescent device.
The phenazine derivative is useful as an electron transport material.
An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer, and the electron transport material of the electron transport layer is the phenazine derivative as defined in any one of claims 1 to 5.
Compared with the prior art, the phenazine-containing derivative has the advantages that:
the condensed ring aromatic hydrocarbon derivative of the quinoxaline group belongs to a typical electron-deficient system, and has suitable HOMO and LUMO energy levels, so that the condensed ring aromatic hydrocarbon derivative has good electron accepting capacity. The condensed ring aromatic hydrocarbon system which is coplanar in a space structure has good electron transfer capability. Therefore, the benzacridine compound is an excellent electron transport material.
Experiments show that when the condensed ring aromatic hydrocarbon derivative of the quinoxaline group is used as an electron transmission material, compared with Bphen which is used as the electron transmission material, the driving voltage of a device is reduced, the working voltage of the device is effectively reduced, the lumen efficiency is improved, the power consumption of the device is reduced, and the condensed ring aromatic hydrocarbon derivative is an electron transmission material with good performance.
Drawings
FIG. 1 shows a nuclear magnetic spectrum of a compound represented by the formula (9) ((1HNMR)；
FIG. 2 is a nuclear magnetic spectrum of a compound represented by the formula (15) ((1HNMR)；
FIG. 3 is a nuclear magnetic spectrum of a compound represented by the formula (26) ((R))1HNMR)；
FIG. 4 is a nuclear magnetic spectrum of a compound represented by the formula (31) ((1HNMR)；
FIG. 5 is a nuclear magnetic spectrum of a compound represented by the formula (36) ((R))1HNMR)；
FIG. 6 is a nuclear magnetic spectrum of a compound represented by the formula (45) ((1HNMR)。
Detailed Description
Basic raw materials used in the present invention, for example, 4-bromoo-phenylenediamine, 4-bromoo-benzoquinone (4-bromocyclohexane-3, 5-diene-1, 2-dione), various brominated derivatives of anthracene, brominated derivatives of diphenylbenzofluoranthene, brominated derivatives of diphenylfluoranthene, various brominated derivatives of triphenylene, and the like
The bromo-derivative of (A) and various bromo-derivatives of pyrene can be purchased in various chemical raw material markets at home or can be synthesized by a common method in a laboratory.
The various bromides can be prepared into corresponding boric acid compounds by a common method.
A phenazine derivative having a structure represented by formula (1):
wherein: ar (Ar)1And Ar2The same or different, are respectively and independently selected from H, halogen and substituted or unsubstituted C4-C30Aryl ring radical of (2), substituted or unsubstituted C4-C30Heteroaryl ring radical, substituted or unsubstituted C4-C30Condensed ring aryl, substitutedSubstituted or unsubstituted C4-C30Fused heterocyclic aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano, aromatic secondary amine, aliphatic secondary amine, substituted or unsubstituted carbazol-9-yl, aromatic and aliphatic substituted pyridyl, or benzimidazolyl substituted phenyl; ar (Ar)1And Ar2Not simultaneously from H.
Preferably, the formula (1) is a structure represented by formula (2) and formula (3):
Ar1and Ar2The same or different, are respectively and independently selected from H, halogen and substituted or unsubstituted C4-C30Aryl ring radical of (2), substituted or unsubstituted C4-C30Heteroaryl ring radical, substituted or unsubstituted C4-C30Condensed ring aryl, substituted or unsubstituted C4-C30Fused heterocyclic aryl, substituted or unsubstituted alkyl, cycloalkyl, cyano, aromatic secondary amine, aliphatic secondary amine, substituted or unsubstituted carbazol-9-yl, aromatic and aliphatic substituted pyridyl, or benzimidazolyl substituted phenyl;
Ar1and Ar2Not simultaneously from H.
The substituent on the aromatic ring group, the heteroaromatic ring group, the condensed ring aryl group and the condensed heterocyclic aryl group is the aromatic ring group, the heteroaromatic ring group, the condensed ring aryl group or the condensed heterocyclic aryl group, substituted or unsubstituted alkyl, naphthenic base, secondary amino, cyano-group and halogen.
The substituted or unsubstituted aromatic hydrocarbon group is phenyl, o-tolyl, p-tolyl or tert-butylphenyl; the substituted or unsubstituted heterocyclic aromatic hydrocarbon group is furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, pyridine, pyrazine, 2.4-methyl-1.3.5 triazine or 4.6 diphenyl pyrimidine and the like; the substituted or unsubstituted condensed ring aromatic hydrocarbon group is naphthyl, phenanthryl, anthryl, pyrenyl,
A fluorenyl, triphenylene, or 9, 9-dimethyl-2-fluorenyl group; the substituted or unsubstituted fused heterocyclic aromatic hydrocarbon group is quinoline, isoquinoline or quinazoline; substituted or unsubstituted alkyl is trifluoromethyl or alkyl.
The formula (1) preferably has a specific structure shown by the following formulae (4) to (47):
the application of the phenazine derivative in an organic electroluminescent device.
The phenazine derivative is useful as an electron transport material.
An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer, and the electron transport material of the electron transport layer is the phenazine derivative as defined in any one of claims 1 to 5.
Example 1 Synthesis of dibromophenazine
Adding 3.91 g (molecular weight 186, 0.021mol) of 4-bromo o-phenylenediamine, 3.91 g (molecular weight 186, 0.021mol) of 4-bromo o-benzoquinone and 40 ml of ethanol into a 250ml three-neck flask, dropwise adding 0.2 g of concentrated sulfuric acid (concentration 98%) within 3min under the stirring condition, reacting for 4 hours at 65 ℃, cooling to room temperature after the reaction is finished, filtering, washing with water, drying, separating by column chromatography, eluting with ethyl acetate/petroleum ether to obtain 5.82 g (molecular weight 336) of almost equal 2, 7-dibromo phenazine and 2, 8-dibromo phenazine, and the total yield is 82.4%.
Example 2
Synthesis of Compound represented by the formula (4)
A1000 ml three-neck flask is stirred by magnetic force and protected by nitrogen, and 6.72g (molecular weight 336, 0.02mol) of 2, 8-dibromophenazine, 7.4g (molecular weight 172, 0.043mol) of naphthalene-2-boric acid, 2.3g (molecular weight 1154, 0.002mol) of tetrakis (triphenylphosphine) palladium, 100ml of 2M sodium carbonate aqueous solution, 100ml of toluene and 100ml of ethanol are added. After argon displacement, reflux was carried out, the reaction was monitored by Thin Layer Chromatography (TLC), and after 3.5 hours TLC found that the starting bromide reacted completely, leaving only product sites. And (3) cooling, separating an organic layer, evaporating to dryness, performing column chromatography separation, and leaching with ethyl acetate/petroleum ether to obtain 8.1g of the compound shown in the formula (4), wherein the molecular weight is 432, and the yield is 93.8%.
Product MS (m/e): 432, elemental analysis (C)32H20N2): theoretical value C: 88.86%, H: 4.66%, N: 6.48 percent; found value C: 88.83%, H: 4.67%, N: 6.50 percent.
Example 3
Synthesis of Compound represented by the formula (5)
The procedure was as in example 2 except that naphthalene-2-boronic acid was changed to naphthalene-1-boronic acid, and the other reagents were not changed to give a compound represented by the formula (5).
Product MS (m/e): 432, elemental analysis (C)32H20N2): theoretical value C: 88.86%, H: 4.66%, N: 6.48 percent; found value C: 88.88%, H: 4.67%, N: 6.45 percent.
Example 4
Synthesis of Compound represented by the formula (6)
The procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, and the other reagents were not changed to give a compound represented by the formula (6).
Product MS (m/e): 432, elemental analysis (C)32H20N2): theoretical value C: 88.86%, H: 4.66%, N: 6.48 percent; found value C: 88.85%, H: 4.69%, N: 6.46 percent。
Example 5
Synthesis of Compound represented by the formula (7)
The procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to naphthalene-1-boronic acid, and the other reagents were not changed to give a compound represented by formula (7).
Product MS (m/e): 432, elemental analysis (C)32H20N2): theoretical value C: 88.86%, H: 4.66%, N: 6.48 percent; found value C: 88.84%, H: 4.69%, N: 6.47 percent.
Example 6
Synthesis of Compound represented by the formula (8)
The procedure was as in example 2 except that the starting naphthalene-2-boronic acid was changed to p- (naphthalene-1-yl) phenylboronic acid and the other reagents were changed to give a compound represented by the formula (8).
Product MS (m/e): 584, elemental analysis (C)44H28N2): theoretical value C: 90.38%, H: 4.83%, N: 4.79 percent; found value C: 90.34%, H: 4.86%, N: 4.82 percent.
Example 7
Synthesis of Compound represented by the formula (9)
The procedure of synthesis was the same as in example 2 except that the starting material naphthalene-2-boronic acid was changed to p- (naphthalene-2-yl) phenylboronic acid and the other reagents were changed to give a compound represented by formula (9); nuclear magnetic spectrum of (1HNMR) is shown in fig. 1.
Product MS (m/e): 584, elemental analysis (C)44H28N2): theoretical value C: 90.38%, H: 4.83%, N: 4.79 percent; found value C: 90.37%, H: 4.82%, N: 4.81 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 1.
Example 8
Synthesis of Compound represented by the formula (10)
The procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to p- (naphthalene-2-yl) phenylboronic acid, and the other reagents were not changed to give a compound represented by formula (10).
Product MS (m/e): 584, elemental analysis (C)44H28N2): theoretical value C: 90.38%, H: 4.83%, N: 4.79 percent; found value C: 90.33%, H: 4.86%, N: 4.81 percent.
Example 9
Synthesis of Compound represented by the formula (11)
The procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to p- (naphthalene-1-yl) phenylboronic acid, and the other reagents were not changed to give a compound represented by formula (11).
Product MS (m/e): 584, elemental analysis (C)44H28N2): theoretical value C: 90.38%, H: 4.83%, N: 4.79 percent; found value C: 90.37%, H: 4.86%, N: 4.77 percent.
Example 10
Synthesis of Compound represented by the formula (12)
The procedure was as in example 2 except that the starting naphthalene-2-boronic acid was changed to phenanthrene-9-boronic acid and the other reagents were changed to give the compound represented by formula (12).
Product MS (m/e): 532, elemental analysis (C)40H24N2): theoretical value C: 90.20%, H: 4.54%, N: 5.26 percent; found value C: 90.23%, H: 4.55%, N: 5.22 percent.
Example 11
Synthesis of Compound represented by the formula (13)
The synthesis procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to phenanthrene-9-boronic acid, and the other reagents were unchanged to give the compound represented by formula (13).
Product MS (m/e): 532, elemental analysis (C)40H24N2): theoretical value C: 90.20%, H: 4.54%, N: 5.26 percent; found value C: 90.24%, H: 4.52%, N: 5.24 percent.
Example 12
Synthesis of Compound represented by the formula (14)
The procedure was as in example 2 except that the starting naphthalene-2-boronic acid was changed to p- (phenanthren-9-yl) phenylboronic acid and the other reagents were changed to give a compound represented by formula (14).
Product MS (m/e): 684 elemental analysis (C)52H32N2): theoretical value C: 91.20%, H: 4.71%, N: 4.09%; found value C: 91.23%, H: 4.72%, N: 4.05 percent.
Example 13
Synthesis of Compound represented by the formula (15)
The synthesis procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to p- (phenanthrene-9-yl) phenylboronic acid, and the other reagents were unchanged to give the compound represented by formula (15).
Product MS (m/e): 684 elemental analysis (C)52H32N2): theoretical value C: 91.20%, H: 4.71%, N: 4.09%; found value C: 91.22%, H: 4.74%, N: 4.04 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 2.
Example 14
Synthesis of Compound represented by the formula (16)
The procedure was the same as in example 2 except that the starting material naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the other reagents were not changed to obtain a compound represented by formula (16).
Product MS (m/e): 580, elemental analysis (C)44H24N2): theoretical value C: 91.01%, H: 4.17%, N: 4.82%; found value C: 91.03%, H: 4.13%, N: 4.84 percent.
Example 15
Synthesis of Compound represented by the formula (17)
The synthesis procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the other reagents were unchanged to obtain the compound represented by formula (17).
Product MS (m/e): 580, elemental analysis (C)44H24N2): theoretical value C: 91.01%, H: 4.17%, N: 4.82%; found value C: 91.02%, H: 4.15%, N: 4.83 percent.
Example 16
Synthesis of Compound represented by the formula (18)
The procedure was the same as in example 2 except that the starting naphthalene-2-boronic acid was changed to p- (pyrene-1-yl) phenylboronic acid and the other reagents were changed to give a compound represented by formula (18).
Product MS (m/e): 732 elemental analysis (C)56H32N2): theoretical value C: 91.78%, H: 4.40%, N: 3.82 percent; found value C: 91.73%, H: 4.43%, N: 3.84 percent.
Example 17
Synthesis of Compound represented by the formula (19)
The synthesis procedure was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to p- (pyrene-1-yl) phenylboronic acid, and the other reagents were unchanged to give a compound represented by formula (19).
Product MS (m/e): 732 elemental analysis (C)56H32N2): theoretical value C: 91.78%, H: 4.40%, N: 3.82 percent; found value C: 91.74%, H: 4.41%, N: 3.85 percent.
Example 18
Synthesis of Compound represented by the formula (20)
The synthesis reaction is divided into two steps. The first step is the same as example 2, except that naphthalene-2-boronic acid is changed into p- (naphthalene-1-yl) phenylboronic acid, 2, 8-dibromophenazine and p- (naphthalene-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography separation is carried out after reaction to obtain monobromo product;
the second step was the same as example 2 except that the starting material 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, and the other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (20).
Product MS (m/e): 582, elemental analysis (C)44H26N2): theoretical value C: 90.69%, H: 4.50%, N: 4.81 percent; found value C: 90.64%, H: 4.52%, N: 4.84 percent.
Example 19
Synthesis of Compound represented by the formula (21)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into p- (naphthalene-1-yl) phenylboronic acid, 2, 7-dibromophenazine and p- (naphthalene-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained by column chromatography separation after the reaction;
the second step was the same as example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (21).
Product MS (m/e): 582, elemental analysis (C)44H26N2): theoretical value C: 90.69%, H: 4.50%, N: 4.81 percent; found value C: 90.65%, H: 4.53%, N: 4.82 percent.
Example 20
Synthesis of Compound represented by the formula (22)
The procedure was as in example 2 except that the starting naphthalene-2-boronic acid was changed to 9-phenylanthracene-10-boronic acid, and the other reagents were changed to give a compound represented by the formula (22).
Product MS (m/e): 684 elemental analysis (C)52H32N2): theoretical value C: 91.20%, H: 4.71%, N: 4.09%; found value C: 91.23%, H: 4.73%, N: 4.04 percent.
Example 21
Synthesis of Compound represented by the formula (23)
The procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to 9-phenylanthracene-10-boronic acid, and the other reagents were changed to give a compound represented by formula (23).
Product MS (m/e): 684 elemental analysis (C)52H32N2): theoretical value C: 91.20%, H: 4.71%, N: 4.09%; found value C: 91.22%, H: 4.72%, N: 4.06 percent.
Example 22
Synthesis of Compound represented by the formula (24)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material naphthalene-2-boric acid is changed into p- (naphthalene-1-yl) phenylboronic acid, 2, 8-dibromophenazine and p- (naphthalene-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to 9-phenylanthracene-10-boronic acid, and monobromo product obtained in the first step was charged in equimolar amounts with 9-phenylanthracene-10-boronic acid, other reagents and reaction conditions were not changed, and the compound represented by formula (24) was obtained by column chromatography after the reaction.
Product MS (m/e): 634, elemental analysis (C)48H30N2): theoretical value C: 90.82%, H: 4.76%, N: 4.41 percent; found value C: 90.84%, H: 4.72%, N: 4.44 percent.
Example 23
Synthesis of Compound represented by the formula (25)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into p- (naphthalene-1-yl) phenylboronic acid, 2, 7-dibromophenazine and p- (naphthalene-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained by column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to 9-phenylanthracene-10-boronic acid, and monobromo product obtained in the first step was charged in equimolar amounts with 9-phenylanthracene-10-boronic acid, other reagents and reaction conditions were not changed, and the compound represented by formula (25) was obtained by column chromatography after the reaction.
Product MS (m/e): 634, elemental analysis (C)48H30N2): theoretical value C: 90.82%, H: 4.76%, N: 4.41 percent(ii) a Found value C: 90.83%, H: 4.74%, N: 4.43 percent.
Example 24
Synthesis of Compound represented by the formula (26)
The procedure of synthesis was the same as in example 2 except that the starting naphthalene-2-boronic acid was changed to 7, 10-diphenylfluoranthene-3-boronic acid, and the other reagents were not changed to give a compound represented by formula (26).
Product MS (m/e): 884 elemental analysis (C)68H40N2): theoretical value C: 92.28%, H: 4.56%, N: 3.17 percent; found value C: 92.32%, H: 4.54%, N: 3.14 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 3.
Example 25
Synthesis of Compound represented by the formula (27)
The procedure of synthesis was the same as in example 2 except that the starting material 2, 8-dibromophenazine was changed to 2, 7-dibromophenazine, naphthalene-2-boronic acid was changed to 7, 10-diphenylfluoranthene-3-boronic acid, and the other reagents were not changed to give a compound represented by formula (27).
Product MS (m/e): 884 elemental analysis (C)68H40N2): theoretical value C: 92.28%, H: 4.56%, N: 3.17 percent; found value C: 92.30%, H: 4.54%, N: 3.16 percent.
Example 26
Synthesis of Compound represented by the formula (28)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 2-phenylpyridine-5-boric acid, the 2, 7-dibromophenazine and the 2-phenylpyridine-5-boric acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (9-phenylanthracen-10-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was equimolar dosed with p- (9-phenylanthracen-10-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and after the reaction, column chromatography was performed to obtain the compound represented by formula (28).
Product MS (m/e): 661 elemental analysis (C)49H31N3): theoretical value C: 88.93%, H: 4.72%, N: 6.35 percent; found value C: 88.91%, H: 4.76%, N: 6.33 percent.
Example 27
Synthesis of Compound represented by the formula (29)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 2-phenylpyridine-5-boronic acid, the 2, 8-dibromophenazine and the 2-phenylpyridine-5-boronic acid are fed in an equimolar way, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (9-phenylanthracen-10-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was equimolar dosed with p- (9-phenylanthracen-10-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and after the reaction, column chromatography was performed to obtain the compound represented by formula (29).
Product MS (m/e): 661 elemental analysis (C)49H31N3): theoretical value C: 88.93%, H: 4.72%, N: 6.35 percent; found value C: 88.95%, H: 4.73%, N: 6.32 percent.
Example 28
Synthesis of Compound represented by the formula (30)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 2-phenylpyridine-5-boronic acid, the 2, 8-dibromophenazine and the 2-phenylpyridine-5-boronic acid are fed in an equimolar way, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second step was the same as example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (30).
Product MS (m/e): 533, elemental analysis (C)39H23N3): theoretical value C: 87.78%, H: 4.34%, N: 7.87 percent; found value C: 87.81%, H: 4.35%, N: 7.84 percent.
Example 29
Synthesis of Compound represented by the formula (31)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 2-phenylpyridine-5-boric acid, the 2, 7-dibromophenazine and the 2-phenylpyridine-5-boric acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second step was the same as example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (31).
Product MS (m/e): 533, elemental analysis (C)39H23N3): theoretical value C: 87.78%, H: 4.34%, N: 7.87 percent; found value C: 87.82%, H: 4.33%, N: 7.85 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 4.
Example 30
Synthesis of Compound represented by the formula (32)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 2-phenylpyridine-5-boronic acid, the 2, 8-dibromophenazine and the 2-phenylpyridine-5-boronic acid are fed in an equimolar way, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (naphthalen-1-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was charged in equimolar amounts with p- (naphthalen-1-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and the compound represented by formula (32) was obtained by column chromatography after the reaction.
Product MS (m/e): 535, elemental analysis (C)39H25N3): theoretical value C: 87.45%, H: 4.70%, N: 7.84 percent; found value C: 87.43%, H: 4.75%, N: 7.82 percent.
Example 31
Synthesis of Compound represented by the formula (33)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 2-phenylpyridine-5-boric acid, the 2, 7-dibromophenazine and the 2-phenylpyridine-5-boric acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (naphthalen-1-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was charged in equimolar amounts with p- (naphthalen-1-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and the compound represented by formula (33) was obtained by column chromatography after the reaction.
Product MS (m/e): 535, elemental analysis (C)39H25N3): theoretical value C: 87.45%, H: 4.70%, N: 7.84 percent; found value C: 87.41%, H: 4.73%, N: 7.86 percent.
Example 32
Synthesis of Compound represented by the formula (34)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 2-phenylpyridine-5-boronic acid, the 2, 8-dibromophenazine and the 2-phenylpyridine-5-boronic acid are fed in an equimolar way, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second step is the same as example 2 except that 2, 8-dibromophenazine is changed to the monobromo product obtained in the first step, naphthalene-2-boronic acid is changed to phenanthrene-9-boronic acid, the monobromo product obtained in the first step and phenanthrene-9-boronic acid are charged in equimolar amounts, other reagents and reaction conditions are not changed, and after the reaction, column chromatography is performed to obtain the compound represented by formula (34).
Product MS (m/e): 509, elemental analysis (C)37H23N3): theoretical value C: 87.21%, H: 4.55%, N: 8.25 percent; found value C: 87.23%, H: 4.54%, N: 8.23 percent.
Example 33
Synthesis of Compound represented by the formula (35)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 2-phenylpyridine-5-boric acid, the 2, 7-dibromophenazine and the 2-phenylpyridine-5-boric acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second step is the same as example 2 except that 2, 8-dibromophenazine is changed to the monobromo product obtained in the first step, naphthalene-2-boronic acid is changed to phenanthrene-9-boronic acid, the monobromo product obtained in the first step and phenanthrene-9-boronic acid are charged in equimolar amounts, other reagents and reaction conditions are not changed, and after the reaction, column chromatography is performed to separate the compound shown in formula (35).
Product MS (m/e): 509, elemental analysis (C)37H23N3): theoretical value C: 87.21%, H: 4.55%, N: 8.25 percent; found value C: 87.22%, H: 4.51%, N: 8.27 percent.
Example 34
Synthesis of Compound represented by the formula (36)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, and the 2, 7-dibromophenazine and the 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain a monobromo product;
the second step is the same as example 2 except that 2, 8-dibromophenazine is changed to the monobromo product obtained in the first step, naphthalene-2-boronic acid is changed to phenanthrene-9-boronic acid, the monobromo product obtained in the first step and phenanthrene-9-boronic acid are charged in equimolar amounts, other reagents and reaction conditions are not changed, and after the reaction, column chromatography is performed to obtain the compound represented by formula (36).
Product MS (m/e): 624, elemental analysis (C)45H28N4): theoretical value C: 86.51%, H: 4.52%, N: 8.97 percent; found value C: 86.53%, H: 4.54%, N: 8.93 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 5.
Example 35
Synthesis of Compound represented by the formula (37)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, 2, 8-dibromophenazine and 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain monobromo product;
the second step is the same as example 2 except that 2, 8-dibromophenazine is changed to the monobromo product obtained in the first step, naphthalene-2-boronic acid is changed to phenanthrene-9-boronic acid, the monobromo product obtained in the first step and phenanthrene-9-boronic acid are charged in equimolar amounts, other reagents and reaction conditions are not changed, and after the reaction, column chromatography is performed to obtain the compound represented by formula (37).
Product MS (m/e): 624, elemental analysis (C)45H28N4): theoretical value C: 86.51%, H: 4.52%, N: 8.97 percent; found value C: 86.54%, H: 4.52%, N: 8.94 percent.
Example 36
Synthesis of Compound represented by the formula (38)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, 2, 8-dibromophenazine and 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain monobromo product;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (naphthalen-1-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was charged in equimolar amounts with p- (naphthalen-1-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and the compound represented by formula (38) was obtained by column chromatography after the reaction.
Product MS (m/e): 650, elemental analysis (C)47H30N4): theoretical value C: 86.74%, H: 4.65%, N: 8.61 percent; found value C: 86.72%, H: 4.64%, N: 8.64 percent.
Example 37
Synthesis of Compound represented by the formula (39)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, and the 2, 7-dibromophenazine and the 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain a monobromo product;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first procedure herein, naphthalene-2-boronic acid was changed to p- (naphthalen-1-yl) phenylboronic acid, and the monobromo product obtained in the first procedure was charged in equimolar amounts with p- (naphthalen-1-yl) phenylboronic acid, the other reagents and reaction conditions were unchanged, and the compound represented by formula (39) was obtained by column chromatography after the reaction.
Product MS (m/e): 650, elemental analysis (C)47H30N4): theoretical value C: 86.74%, H: 4.65%, N: 8.61 percent; found value C: 86.76%, H: 4.61%, N: 8.63 percent.
Example 38
Synthesis of Compound represented by the formula (40)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, 2, 8-dibromophenazine and 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain monobromo product;
the second step was the same as example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (40).
Product MS (m/e): 648 elemental analysis (C)47H28N4): theoretical value C: 87.01%, H: 4.35%, N: 8.64 percent; found value C: 87.04%, H: 4.34%, N: 8.62 percent.
Example 39
Synthesis of Compound represented by the formula (41)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, and the 2, 7-dibromophenazine and the 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain a monobromo product;
the second step was the same as example 2 except that 2, 8-dibromophenazine was changed to the monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to pyrene-1-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with pyrene-1-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain the compound represented by formula (41).
Product MS (m/e): 648 elemental analysis (C)47H28N4): theoretical value C: 87.01%, H: 4.35%, N: 8.64 percent; found value C: 87.03%, H: 4.36%, N: 8.61 percent.
Example 40
Synthesis of Compound represented by the formula (42)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, 2, 8-dibromophenazine and 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain monobromo product;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to triphenylene-2-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with triphenylene-2-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was carried out to obtain a compound represented by formula (42).
Product MS (m/e): 674, elemental analysis (C)49H30N4): theoretical value C: 87.22%, H: 4.48%, N: 8.30 percent; found value C: 87.24%, H: 4.43%, N: 8.33 percent.
EXAMPLE 41
Synthesis of Compound represented by the formula (43)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid, and the 2, 7-dibromophenazine and the 4- (2-phenyl-1H-benzo [ d ] imidazol-1-yl) phenylboronic acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and column chromatography is carried out after the reaction to obtain a monobromo product;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to triphenylene-2-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with triphenylene-2-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was carried out to obtain a compound represented by formula (43).
Product MS (m/e): 674, elemental analysis (C)49H30N4): theoretical value C: 87.22%, H: 4.48%, N: 8.30 percent; found value C: 87.23%, H: 4.45%, N: 8.32 percent.
Example 42
Synthesis of Compound represented by the formula (44)
The synthesis reaction is divided into two steps.
The first step is the same as example 2, except that the raw material naphthalene-2-boronic acid is changed into 2-phenylpyridine-5-boronic acid, the 2, 8-dibromophenazine and the 2-phenylpyridine-5-boronic acid are fed in an equimolar way, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to triphenylene-2-boronic acid, and the monobromo product obtained in the first step was charged in equimolar amounts with triphenylene-2-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was carried out to obtain a compound represented by formula (44).
Product MS (m/e): 559, elemental analysis (C)41H25N3): theoretical value C: 87.99%, H: 4.50%, N: 7.51 percent; found value C: 87.94%, H: 4.52%, N: 7.54 percent.
Example 43
Synthesis of Compound represented by the formula (45)
The synthesis reaction is divided into two steps.
The first step is the same as the example 2, except that the raw material 2, 8-dibromophenazine is changed into 2, 7-dibromophenazine, naphthalene-2-boric acid is changed into 2-phenylpyridine-5-boric acid, the 2, 7-dibromophenazine and the 2-phenylpyridine-5-boric acid are fed in equimolar amount, other reagents and reaction conditions are not changed, and the monobromo product is obtained after column chromatography separation after the reaction;
the second procedure was the same as in example 2 except that 2, 8-dibromophenazine was changed to monobromo product obtained in the first step herein, naphthalene-2-boronic acid was changed to triphenylene-2-boronic acid, and monobromo product obtained in the first step was charged in equimolar amounts to triphenylene-2-boronic acid, other reagents and reaction conditions were not changed, and after the reaction, column chromatography was performed to obtain a compound represented by formula (45).
Product MS (m/e): 559, elemental analysis (C)41H25N3): theoretical value C: 87.99%, H: 4.50%, N: 7.51 percent; found value C: 87.96%, H: 4.52%, N: 7.52 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 1.
Example 44
Synthesis of Compound represented by the formula (46)
The procedure was as in example 2 except that the starting naphthalene-2-boronic acid was changed to triphenylene-2-boronic acid, and the other reagents were not changed to give a compound represented by the formula (46).
Product MS (m/e): 632, elemental analysis (C)48H28N2): theoretical value C: 91.11%, H: 4.46%, N: 4.43 percent; found value C: 91.14%, H: 4.42%, N: 4.44 percent.
Example 45
Synthesis of Compound represented by the formula (47)
The procedure was the same as in example 2 except that 2, 8-dibromophenazine was used as the starting material, 2, 7-dibromophenazine was used, naphthalene-2-boronic acid was used as the starting material, triphenylene-2-boronic acid was used as the starting material, and the other reagents were not used to obtain a compound represented by formula (47).
Product MS (m/e): 632, elemental analysis (C)48H28N2): theoretical value C: 91.11%, H: 4.46%, N: 4.43 percent; found value C: 91.12%, H: 4.43%, N: 4.45 percent.
The following are examples of the use of the compounds of the invention:
example 46
To facilitate comparison of the transport properties of these electron transport materials, the present inventors designed a simple electroluminescent device using EM1 as the emissive material (EM1 is the host material and not the emissive material in order not to pursue high efficiency but to verify the possibility of these materials being practical) and using the high efficiency electron transport material Bphen as the comparative material. The structures of EM1 and Bphen are:
the structure of the organic electroluminescent device in the embodiment of the invention is as follows:
substrate/anode/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/cathode.
The substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. In the invention, the glass substrate and the ITO are used as anode materials in the manufacture of the organic electroluminescent device.
Various triarylamine-based materials may be used for the hole transport layer. The hole transport material selected for use in the fabrication of the organic electroluminescent device of the present invention is NPB. The NPB structure is:
the cathode can adopt a metal and a mixture structure thereof, such as Mg: ag. Ca: ag, etc., or an electron injection layer/metal layer structure, such as LiF/Al, Li2O/Al and the like. The cathode material selected in the preparation of the organic electroluminescent device is LiF/Al.
The compound in this embodiment is used as an electron transport material in an organic electroluminescent device, and the EML is used as a light emitting layer material, so that a plurality of organic electroluminescent devices are prepared, and the structure of each organic electroluminescent device is as follows: ITO/NPB (40nm)/EM1(30nm)/ETL material (20nm)/LiF (0.5nm)/Al (150 nm);
in one comparative organic electroluminescent device, Bphen was used as the electron transport material, and the materials of the present invention were used for the remaining organic electroluminescent devices.
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an 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 cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, on the anode layer filmPerforming vacuum vapor deposition on NPB as a hole transport layer, wherein the vapor deposition rate is 0.1nm/s, and the vapor deposition film thickness is 40 nm;
vacuum evaporating EM1 on the hole transport layer to serve as a light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
vacuum evaporating a compound represented by a layer (4), a formula (6), a formula (12), a formula (13), a formula (16), a formula (22), a formula (26), a formula (34), a formula (36), a formula (46) or a formula (47) on the luminescent layer to be used as an electron transport layer material of the device, using Bphen as a contrast material of the electron transport layer material of the device, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporated film is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The organic electroluminescent device properties are given in the following table:
| compound numbering | Required luminance cd/m2 | Voltage V | Current efficiency cd/A |
| Bphen | 1000.00 | 6.2 | 6.1 |
| Formula (4) | 1000.00 | 5.7 | 6.8 |
| Formula (6) | 1000.00 | 5.7 | 6.9 |
| Formula (12) | 1000.00 | 5.6 | 6.8 |
| Formula (13) | 1000.00 | 5.5 | 7.1 |
| Formula (16) | 1000.00 | 5.6 | 7.2 |
| Formula (22) | 1000.00 | 5.6 | 7.1 |
| Formula (26) | 1000.00 | 5.7 | 7.1 |
| Formula (34) | 1000.00 | 5.6 | 7.3 |
| Formula (36) | 1000.00 | 5.7 | 7.2 |
| Formula (46) | 1000.00 | 5.6 | 7.3 |
| Formula (47) | 1000.00 | 5.7 | 7.1 |
The results show that the novel organic material is used for the organic electroluminescent device, can effectively reduce the working voltage of the device and improve the current efficiency, and is an electron transport material with good performance.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.
Claims (5)
1. A phenazine derivative having a structure represented by formula (2) and formula (3):
wherein: ar (Ar)1And Ar2Same or different, each is independently selected from substituted or unsubstituted C4-C30A fused ring aryl group;
the substituted or unsubstituted condensed ring aryl is naphthyl, phenanthryl, anthryl, pyrenyl, chrysene -yl, fluorenyl, triphenylene or 9, 9-dimethyl-2-fluorenyl.
2. A phenazine derivative having a structure represented by formula (2) and formula (3):
wherein: ar (Ar)1And Ar2Identical or different, each independently selected from benzimidazolyl-substituted phenyl groups.
3. A phenazine derivative having a specific structure represented by the following formulae (4) to (47):
4. use of a phenazine derivative according to any one of claims 1 to 3 as an electron transport material in an organic electroluminescent device.
5. An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer, and is characterized in that:
the electron transport material of the electron transport layer is the phenazine derivative according to any one of claims 1 to 3.
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| KR101612903B1 (en) * | 2013-04-09 | 2016-04-19 | 희성소재 (주) | Phenazine-based compound and organic light emitting device comprising the same |
| KR102268119B1 (en) * | 2013-08-30 | 2021-06-21 | 엘지디스플레이 주식회사 | Pyrene compound and organic light emitting diode device comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998617A (en) * | 1997-04-02 | 1999-12-07 | Gentex Corporation | Electrochromic compounds |
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