CN115974702A - Spiro compound and application thereof - Google Patents
Spiro compound and application thereof Download PDFInfo
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- CN115974702A CN115974702A CN202310114497.9A CN202310114497A CN115974702A CN 115974702 A CN115974702 A CN 115974702A CN 202310114497 A CN202310114497 A CN 202310114497A CN 115974702 A CN115974702 A CN 115974702A
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- 150000003413 spiro compounds Chemical class 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- -1 cyano, hydroxyl Chemical group 0.000 claims description 20
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 9
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 9
- 229910052805 deuterium Inorganic materials 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 8
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 6
- 125000005104 aryl silyl group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 4
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- NHFDIUPJVYYTLG-UHFFFAOYSA-N carbononitridic isocyanide Chemical compound [C-]#[N+]C#N NHFDIUPJVYYTLG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 3
- 235000021003 saturated fats Nutrition 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 45
- 238000000859 sublimation Methods 0.000 abstract description 20
- 230000008022 sublimation Effects 0.000 abstract description 20
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 229920001621 AMOLED Polymers 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 45
- 238000003786 synthesis reaction Methods 0.000 description 45
- 238000000746 purification Methods 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 101100457453 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MNL1 gene Proteins 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 101100451713 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) HTL1 gene Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical class C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004134 1-norbornyl group Chemical group [H]C1([H])C([H])([H])C2(*)C([H])([H])C([H])([H])C1([H])C2([H])[H] 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- KJRJBBVVHYGROV-UHFFFAOYSA-N ClP(C1=CC=C(C=C1)N(C)C)(C(C)(C)C)(C(C)(C)C)Cl Chemical compound ClP(C1=CC=C(C=C1)N(C)C)(C(C)(C)C)(C(C)(C)C)Cl KJRJBBVVHYGROV-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical group CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
-
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The spiro compound of the present invention has a structure represented by formula (1). The spiro compound provided by the invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of devices and the like, and can be used for organicIn an electroluminescent device. Meanwhile, the material has a lower melting point, and is favorable for the evaporation stability of the material when being used as a melting type material. The compound is used as a hole injection and transport material and has the possibility of being applied to the AMOLED industry.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material suitable for an organic electroluminescent device, and particularly relates to a spiro compound and application thereof.
Background
At present, organic electroluminescent devices (OLEDs), which are a new generation of display technology, are receiving more and more attention in display and lighting technologies, and have a wide application prospect. However, the performance of OLED devices, such as light emission efficiency, driving voltage, and lifetime, is still in need of further enhancement and improvement compared to market application requirements.
Generally, the OLED device has a basic structure in which various organic functional material thin films with different functions are sandwiched between metal electrodes, as a sandwich structure, and holes and electrons are respectively injected from a cathode and an anode under the driving of current, and after the holes and the electrons move for a certain distance, they are recombined in a light emitting layer and released in the form of light or heat, thereby generating light emission of the OLED. However, the organic functional material is a core component of the organic electroluminescent device, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film forming stability, crystallinity, color saturation and the like of the material are main factors influencing the performance of the device.
In order to obtain an organic light emitting device with excellent performance, the selection of materials is important, and the materials not only comprise an emitter material which plays a role in light emission, but also comprise functional materials such as a hole injection material, a hole transport material, a host material, an electron transport material, an electron injection material and the like which are mainly used for carrier injection and transport in the device, and the selection and optimization of the materials can improve the transport efficiency of holes and electrons, balance the holes and the electrons in the device, and further improve the voltage, the light emitting efficiency and the service life of the device.
Patent document 1 (CN 103108859B) describes
The spirofluorene arylamine structure is used as a hole transport material, the material provides better device performance, but the service life of the device, particularly the service life of a blue light-emitting device, is required to be further improved, and the transverse hole mobility of the material is required to be further improved so as to provide better low gray scale color purity of an OLED product; patent document 2 (CN 103641726B) describes->
The spirofluorene arylamine structure is used as a second hole transport material, and the device performance of the material needs to be greatly improved, particularly the device efficiency; patent document 3 (CN 111548278A) describes->
The arylamine of the spirofluorene arylamine contains substituent groups such as alkyl, deuterium, cycloalkyl and other structures which are used as hole transport materials, the device performance of the materials is to be further improved, and particularly the service life of the devices is prolonged; patent document 4 (CN 114835591A) describes->
The device performance of the arylamine hole transport material containing the unilateral cycloalkyl substituted diphenylfluorene is to be further improved, particularly the device efficiency, and meanwhile, the reported compound has higher melting point and is not suitable for being applied to the industry as a molten material. Patent document 5 (CN 112110825B) describes
The structure takes adamantyl fluorene as a core structure, and does not have the core spirofluorene structureThe same is true. Patent document 6 (CN 107459466B) describes & -bamboo>
The diphenylfluorene structure, also in terms of efficiency and lifetime, is yet to be improved.
Disclosure of Invention
The present invention has been made to solve the above-mentioned drawbacks, and an object of the present invention is to provide a high-performance organic electroluminescent device and a spiro compound material that can realize such an organic electroluminescent device.
The spiro compound of the present invention has a structure represented by formula (1). The spiro compound provided by the invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of devices and the like, and can be used in organic electroluminescent devices. Meanwhile, the material has a lower melting point, and is favorable for the evaporation stability of the material when being used as a melting type material. The compound is used as a hole injection and transport material and has the possibility of being applied to the AMOLED industry.
A spiro compound having a structure represented by the formula (1),
wherein, R is 1 ，R 2 Is substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
wherein, the ring A is selected from substituted or unsubstituted C3-C20 saturated fat rings
Wherein R is a -R d Is a substituent on the benzene ring independently selected from deuterium, halogen, cyano, hydroxyl, mercapto, amine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, mercapto, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, mercapto, or a pharmaceutically acceptable salt thereof,Substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl-mono-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyl-di-C6-C30 arylsilyl, or two adjacent groups may be connected to each other to form an aliphatic ring or an aromatic ring structure;
wherein L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene;
wherein Ar is independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
wherein m, n, p, q are independently selected from 0 or an integer of 1-4;
wherein at least one of the heteroalkyl, heterocycloalkyl, and heteroaryl groups contains a O, N or S heteroatom;
the substitution is by deuterium, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C1-C4 alkyl substituted C6-C10 aryl, C1-C6 alkyl substituted amino, cyano, isonitrile, or phosphino, wherein the number of substitutions is from mono to maximum number of substitutions.
As a preferred spiro compound, which is one of the structures represented by the formulae (2) to (5),
wherein the definitions of the rest symbols are the same as the above.
A preferred spiro compound is a compound having a structure represented by the formula (2) or (3), R 1 And R 2 The same or different.
As preferred spiro compounds, L is represented by the following formula (2) to formula (5) 1 、L 2 、L 3 Preferably a single bond.
Preferred spiro compounds are those having the structures represented by formulas (6) to (9):
as preferred spirocyclic compounds, wherein ring a in said spirocyclic compound is one of the following aliphatic rings:
as preferred spiro compounds, R 1 And R 2 And Ar is selected from substituted or unsubstituted phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl or carbazolyl, wherein the substitution is by deuterium, F, cl, br, C6-C10 aryl, C1-C6 alkyl, C3-C6 cycloalkyl.
Said R is 1 ，R 2 Is substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl.
Preferred spiro compounds are those of one of the formulae below, or the corresponding partially or completely deuterated or fluorinated,
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the invention also relates to the use of the spiro compounds in organic electroluminescent devices.
It is another object of the present invention to provide the spiro compound as a hole injection layer and/or a hole transport layer of an organic electroluminescent device.
The material of the invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of the device and the like, and can be used in organic electroluminescent devices. In particular, the material can be used as a hole injection and transport material in the AMOLED industry.
Drawings
FIG. 1 shows the reaction of compound CPD004 of the present invention in deuterated chloroform solution 1 An HNMR spectrogram,
FIG. 1 shows the reaction of the compound CPD017 of the present invention in deuterated chloroform solution 1 HNMR spectrogram
Detailed Description
The compound of the present invention, a spiro compound, has a structure represented by formula (1),
wherein, R is 1 ，R 2 Is substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
wherein, the ring A is selected from substituted or unsubstituted C3-C20 saturated fat rings
Wherein R is a -R d Independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxyl, mercapto, amine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilylA silyl group, a substituted or unsubstituted diC 1-C10 alkyl-mono C6-C30 arylsilyl group, a substituted or unsubstituted mono C1-C10 alkyl-di C6-C30 arylsilyl group, or two adjacent groups may be linked to each other to form an aliphatic or aromatic cyclic structure;
wherein L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene;
wherein Ar is independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
wherein m, n, p, q are independently selected from 0 or an integer of 1-4;
wherein the heteroalkyl and heteroaryl groups contain at least one O, N or S heteroatom;
the substitution is by deuterium, F, cl, br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, cyano, isonitrile or phosphino, wherein the number of substitutions is from mono-to maximum number of substitutions.
Examples of the groups of the compound represented by the formula (1) will be described below.
In the present specification, "carbon number a to b" in the expression "X group having a to b carbon number which is substituted or unsubstituted" indicates the carbon number in the case where the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.
The alkyl group having 1 to 10 carbon atoms is a linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and isomers thereof, an n-hexyl group and isomers thereof, an n-heptyl group and isomers thereof, an n-octyl group and isomers thereof, an n-nonyl group and isomers thereof, an n-decyl group and isomers thereof, etc., preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and more preferably a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the C3-C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like, and cyclopentyl and cyclohexyl are preferred.
Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, an allyl group, a 1-butadienyl group, a 2-butadienyl group, a 1-hexatrienyl group, a 2-hexatrienyl group, and a 3-hexatrienyl group, and a propenyl group and an allyl group are preferable.
The C1-C10 heteroalkyl group is a linear or branched alkyl group or cycloalkyl group containing an atom other than carbon and hydrogen, and examples thereof include mercaptomethylmethane group, methoxymethane group, ethoxymethane group, tert-butoxymethane group, N-dimethylmethane group, epoxybutane group, epoxypentane group, epoxyhexane group and the like, with methoxymethane group and epoxypentane group being preferred.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a tetracenyl group, a pyrenyl group, a chrysenyl group, a benzo [ c ] phenanthryl group, a benzo [ g ] chrysyl group, a fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a fluoranthenyl group and the like, and a phenyl group and a naphthyl group are preferable.
Specific examples of the heteroaryl group include a pyrrolyl group, a pyrazinyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, an indolyl group, an isoindolyl group, an imidazolyl group, a furyl group, a benzofuryl group, an isobenzofuryl group, a dibenzofuryl group, a dibenzothienyl group, an azabenzofuryl group, an azabenzothienyl group, a diazdibenzofuryl group, a diazdibenzothienyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a carbazolyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a phenazinyl group, a phenothiazinyl group, a phenoxazinyl group, an oxazolinyl group, an oxadiazolyl group, a furazanyl group, a thienyl group, a benzothienyl group, a dihydroacridinyl group, an azacarbazolyl group, a diazacarbozolyl group, and the like, and preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzofuryl group, a dibenzothienyl group, an azabenzofuranyl group, a diazabenzodibenzothienyl group, a carbazolyl group, an azacarbazolyl group and the like.
The following examples are merely for the convenience of understanding the technical invention and should not be construed as specifically limiting the invention.
The raw materials and solvents involved in the synthesis of the compounds of the present invention are commercially available from suppliers well known to those skilled in the art, such as Alfa, acros, and the like.
EXAMPLE 1 Synthesis of Compound CPD003
Synthesis of Compound CPD003-3
Compounds CPD003-1 (20.00g, 66.84mmol), CPD003-2 (12.44g, 73.53mmol), tris (dibenzylideneacetone) dipalladium (1.84g, 2.01mmol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (6.37g, 13.37mmol), sodium tert-butoxide (9.63g, 100.26mmol) and dry toluene (300 ml) were placed in a 1000ml three-necked round-bottomed flask, purged with nitrogen three times, warmed to 100 ℃ and reacted for 3 hours. TLC (ethyl acetate: n-hexane =1 = 20 as developing solvent) monitored the complete consumption of the starting material CPD 003-1.
After cooling to room temperature, toluene (400 ml) was added, washed with deionized water (3 × 200ml), separated, purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane =1, 25 as eluent), and after elution, concentrated at 60 ℃ under reduced pressure to obtain CPD003-3 as a white solid (22.03 g, purity: 99.77%, yield: 85.06%), mass spectrum: 388.22 (M + H).
Synthesis of Compound CPD003
CPD003-4 (23.00g, 45.31mmol), CPD003-3 (17.91g, 46.22mmol), tris (dibenzylideneacetone) dipalladium (0.83g, 0.91mmol), 50% by mass of a toluene solution of tri-tert-butylphosphine (3.67g, 9.06mmol), sodium tert-butoxide (6.53g, 67.97mmol) and dry toluene (350 ml) were charged in a 1000ml three-necked round-bottomed flask, nitrogen was replaced three times with stirring at room temperature, followed by heating to 110 ℃ for 4 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane =1 20 as a developing agent) and the starting material CPD003-4 was consumed.
Cooling to room temperature, adding toluene (400 ml), washing with deionized water (3 × 300ml), separating, purifying by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane =1:15 as eluent), eluting, and concentrating under reduced pressure at 70 ℃ to obtain a white solid; 150ml of methanol was added, slurried at 65 ℃ for 1 hour, filtered, the cake was rinsed with 50ml of methanol, and dried under vacuum at 90 ℃ for 8 hours to give CPD003 (27.79 g, purity: 99.90%, yield: 75.34%) as a white solid. Sublimation purification of 27.79g of crude CPD003 afforded sublimation pure CPD003 (22.51 g, purity: 99.95%, yield: 81.00%), ms spectrum: 814.24 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.67(m,1H),7.55-7.47(m,3H),7.44(d,J＝10.0Hz,2H),7.39(s,1H),7.24(d,J＝3.1Hz,2H),7.15-7.11(m,1H),7.07-6.90(m,13H),6.86-6.80(m,2H),6.76-6.65(m,3H),6.63-6.59(m,1H),1.87-1.78(m,2H),1.67-1.59(m,2H),1.42-1.38(m,4H),1.20(s,18H).
EXAMPLE 2 Synthesis of Compound CPD004
Synthesis of Compound CPD004-2
Referring to the synthesis and purification method of the compound CPD003-3, the target compound CPD004-2 (23.24 g, purity: 99.71%, yield: 81.01%) can be obtained by changing the corresponding raw material: 402.22 (M + H).
Synthesis of Compound CPD004
Referring to the synthesis and purification method of the compound CPD003, the white solid was the objective compound CPD004 (16.34 g, purity: 99.92%, yield: 75.63%) by changing the corresponding starting material. Sublimation purification of 16.34g of crude CPD004 yielded sublimed pure CPD004 (12.51 g, purity: 99.93%, yield: 76.56%), ms spectrum: 828.46 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.72(d,J＝7.5Hz,1H),7.60-7.53(m,4H),7.49(d,J＝7.5Hz,1H),7.33-7.13(m,10H),7.03-6.92(m,7H),6.79(s,1H),6.73(s,2H),6.63(d,J＝7.5Hz,1H),6.57(d,J＝8.4Hz,1H),6.44(s,1H),1.74-1.57(m,5H),1.49-1.38(m,5H),1.21(s,18H).
EXAMPLE 3 Synthesis of Compound CPD014
Synthesis of Compound CPD014
According to the synthesis and purification method of the compound CPD003, the desired compound CPD014 (18.05 g, purity: 99.92%, yield: 73.06%) was obtained as a white solid by simply changing the corresponding starting material. Sublimation purification of 18.05g of crude CPD014 yielded sublimed pure CPD014 (14.44 g, purity: 99.92%, yield: 80.00%), ms spectrum: 838.16 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.73-7.69(m,1H),7.53-7.52(m,2H),7.50-7.46(m,9.1Hz,3H),7.16(d,J＝3.1Hz,2H),7.11-6.91(m,13H),6.89-6.86(m,5H),6.79-6.65(m,3H),2.58-2.32(m,2H),2.04-1.69(m,4H),1.69-1.46(m,4H),1.45-1.26(m,16H).
EXAMPLE 4 Synthesis of the Compound CPD017
Synthesis of Compound CPD017
Referring to the synthesis and purification method of the compound CPD003, only the corresponding raw materials were changed to obtain the desired compound CPD017 as a white solid (14.21 g, purity: 99.93%, yield: 76.06%). Sublimation and purification of 14.21g of crude CPD017 product gave pure CPD017 (10.13 g, purity: 99.94%, yield: 71.28%) by mass spectrometry: 854.26 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.69(d,J＝7.5Hz,1H),7.57-7.48(m,5H),7.30-6.86(m,18H),6.62-6.57(m,4H),6.42(s,1H),1.98(m,4H),1.73-1.26(m,22H).
EXAMPLE 5 Synthesis of Compound CPD029
Synthesis of Compound CPD029-2
Referring to the synthesis and purification method of the compound CPD003-3, only the corresponding raw materials need to be changed, and the target compound CPD029-2 (20.87 g, purity: 99.88%, yield: 74.41%) is obtained, and mass spectrum: 402.22 (M + H).
Synthesis of Compound CPD029
Referring to the synthesis and purification method of the compound CPD003, the white solid was the objective compound CPD029 (17.86 g, purity: 99.91%, yield: 70.11%) by changing the corresponding raw material. Sublimation purification of 17.86g crude CPD029 gave pure CPD029 (14.55 g, purity: 99.92%, yield: 81.46%) as mass spec: 828.14 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.70-7.65(m,1H),7.51-7.44(m,3H),7.44-7.36(m,3H),7.23(d,J＝3.1Hz,2H),7.13-7.05(m,3H),7.03-6.87(m,8H),6.86-6.78(m,3H),6.78-6.68(m,4H),6.63-6.59(m,1H),2.34(s,3H),1.88-1.74(m,4H),1.63-1.58(m,4H),1.27(s,18H).
EXAMPLE 6 Synthesis of Compound CPD038
Synthesis of Compound CPD038-2
According to the synthesis and purification method of the compound CPD003-3, the target compound CPD038-2 (20.87 g, purity: 99.73%, yield: 70.51%) can be obtained by only changing the corresponding raw material: 428.23 (M + H).
Synthesis of Compound CPD038
Referring to the synthesis and purification method of the compound CPD003, the desired compound CPD038 (14.16 g, purity: 99.92%, yield: 70.01%) was obtained as a white solid by simply changing the corresponding starting material. Sublimation purification of 14.16g of crude CPD038 gave sublimation-purified CPD038 (11.03 g, purity: 99.93%, yield: 77.89%), ms: 878.26 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.62(m,8H),7.41(d,J＝2.9Hz,2H),7.36-7.21(m,6H),7.18-7.08(m,4H),7.08-6.94(m,7H),2.56(s,2H),2.24-1.68(m,8H),1.64-1.32(m,16H),1.00(s,6H).
EXAMPLE 7 Synthesis of Compound CPD048
Synthesis of Compound CPD048
Referring to the synthesis and purification method of the compound CPD003, the white solid was obtained as the objective compound CPD048 (20.55 g, purity: 99.94%, yield: 77.41%) by changing the corresponding raw material. Sublimation purification of 20.55g of crude CPD048 gave pure CPD048 (14.58 g, purity: 99.94%, yield: 70.94%), MS: 856.16 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.72-7.66(m,1H),7.53-7.45(m,3H),7.45-7.37(m,3H),7.21(s,2H),7.11-6.88(m,13H),6.88-6.62(m,7H),1.73-1.54(m,9H),1.49-1.36(m,5H)1.12(s,18H).
EXAMPLE 8 Synthesis of Compound CPD050
Synthesis of Compound CPD050
Referring to the synthesis and purification method of the compound CPD003, the white solid was obtained as the objective compound CPD050 (17.63 g, purity: 99.91%, yield: 69.83%) by changing the corresponding raw materials. 17.63g crude CPD050 was purified by sublimation to give pure sublimated CPD050 (13.03 g, purity: 99.93%, yield: 73.90%), ms spectrum: 828.46 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.73-7.64(m,1H),7.51(d,J＝3.2Hz,1H),7.49-7.37(m,4H),7.25-7.14(m,4H),7.07-6.89(m,10H),6.89-6.60(m,9H),1.74-1.53(m,2H),1.48-1.46(m,3H),1.41-1.36(m,5H),1.20(s,18H).
EXAMPLE 9 Synthesis of Compound CPD059
Synthesis of Compound CPD059-2
Referring to the synthesis and purification method of the compound CPD003-3, the target compound CPD059-2 (18.01 g, purity: 99.59%, yield: 80.00%) was obtained by changing the corresponding raw material: 484.22 (M + H).
Synthesis of Compound CPD059
Referring to the synthesis and purification method of the compound CPD003, the desired compound CPD059 (17.56 g, purity: 99.91%, yield: 79.77%) was obtained as a white solid by simply changing the corresponding starting materials. Sublimation purification of 17.56g of crude CPD059 yielded sublimed pure CPD059 (12.97 g, purity: 99.93%, yield: 73.86%) as mass spectrum: 910.23 (M + H).
1 H NMR(400MHz,CDCl 3 )7.71-7.64(m,1H),7.52-7.44(m,3H),7.44-7.36(m,3H),7.25(d,J＝2.9Hz,2H),7.18-7.07(m,6H),7.06-6.88(m,8H),6.88-6.78(m,3H),6.78-6.64(m,2H),2.53-2.50(m,1H),1.71-1.49(m,10H),1.49-1.38(m,10H),1.22(s,18H).
EXAMPLE 10 Synthesis of Compound CPD071
Synthesis of Compound CPD071-2
According to the synthesis and purification method of the reference compound CPD003-3, only the corresponding raw materials are changed to obtain the target compound CPD071-2 (17.77 g, purity: 99.81%, yield: 80.20%), and mass spectrum: 491.20 (M + H).
Synthesis of Compound CPD071
Referring to the synthesis and purification method of the compound CPD003, the white solid was the objective compound CPD071 (16.58 g, purity: 99.92%, yield: 77.63%) by changing the corresponding raw material. Sublimation purification of 16.58g of crude CPD071 yielded sublimed pure CPD071 (11.58 g, purity: 99.93%, yield: 69.84%), ms spectrum: 917.42 (M + H).
1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝7.7Hz,2H),7.72(d,J＝3.3Hz,1H),7.43-7.39(m,2H),7.39-7.30(m,3H),7.20(d,J＝3.1Hz,2H),7.19-6.95(m,11H),6.94-6.84(m,4H),6.82-6.71(m,5H),6.70-6.62(m,2H),1.71-1.56(m,4H),1.47-1.40(m,6H),1.20(s,18H).
Example 11 Synthesis of Compound CPD075
Synthesis of Compound CPD075-2
The compounds CPD003-4 (20.00g, 39.41mmol), CPD075-1 (6.78g, 43.35mmol), dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphorus palladium (II) (0.56g, 0.79mmol), potassium carbonate (10.89g, 78.82mmol), tetrahydrofuran (300 ml) and deionized water (100 ml) were charged into a 1000ml three-necked round bottom flask, purged with nitrogen three times, warmed to 65 ℃ and reacted for 4 hours. TLC (ethyl acetate: n-hexane =1 = 20 as developing solvent) monitored the complete consumption of the starting material CPD 003-4.
The temperature was reduced to 50 ℃, tetrahydrofuran was removed by concentration under reduced pressure, ethyl acetate (800 ml) was added, washed with deionized water (3 × 350ml), the liquid was separated, purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane =1:30 as eluent), and after elution, concentrated under reduced pressure at 60 ℃ to give CPD075-2 as a white solid (16.75 g, purity: 99.61%, yield: 78.85%), mass spectrum: 539.12 (M + H).
Synthesis of Compound CPD075
Referring to the synthesis and purification method of the compound CPD003, the reaction was carried out at 130 ℃ for 5 hours with the corresponding raw material changed to xylene as a reaction solvent, to obtain the desired compound CPD075 as a white solid (13.05 g, purity: 99.94%, yield: 74.22%). Sublimation purification of 13.05g of crude CPD075 product gave pure CPD075 (10.01 g, purity: 99.94%, yield: 76.70%) as mass spectrum: 890.20 (M + H).
1 H NMR(400MHz,CDCl 3 )δ7.72 -7.67(m,2H),7.58(d,J＝2.9Hz,1H),7.54-7.44(m,3H),7.43-7.34(m,3H),7.21(d,J＝3.1Hz,2H),7.19-7.11(m,2H),7.07-6.89(m,10H),6.89-6.71(m,8H),6.68-6.66(m,2H),1.82-1.75(m,2H),1.68-1.60(m,2H),1.49-1.41(m,4H),1.21(s,18H).
Application example: fabrication of organic electroluminescent devices
A 50mm x 1.0mm glass substrate with an ITO (100 nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees and then subjected to N2 Plasma treatment for 30 minutes. The washed glass substrate was mounted on a substrate holder of a vacuum evaporation apparatus, and first, a compound HATCN was evaporated on the surface on the side of the transparent electrode line so as to cover the transparent electrode, thereby forming a thin film having a thickness of 5nm, then, an HTM1 was evaporated, thereby forming a thin film having a thickness of 60nm as an HTL1, and then, an HTM2 was evaporated on the HTM1 thin film, thereby forming a thin film having a thickness of 10nm as an HTL2, and then, a host material and a dopant material were evaporated on the HTM2 thin film in a co-evaporation mode (ratio 98%: 2%) to form a thin film having a thickness of 25nm. On the light-emitting layer, HBL (5 nm) as a hole blocking layer material and ETL (30 nm) as an electron transport material were sequentially evaporated according to the following formulation, and then LiQ (1 nm) as an electron injection material was evaporated on the electron transport material layer, and then Mg/Ag (100nm, 1).
Evaluation:
the devices were subjected to device performance tests, and the compounds of examples of the present invention and comparative examples 1 to 3 were compared as HTL layers, respectively, and the luminescence spectrum was tested using a system of both spectral radiation (CS 2000) using a constant current power supply (Keithley 2400) and a fixed current density flowing through the light emitting element. At the same time, the current density is 20mA/cm 2 Next, the device voltage value, the current efficiency, and the time (LT 90) at which the test luminance was 90% of the initial luminance were measured. The results are as followsTable 1:
comparison of sublimation temperature: the sublimation temperature is defined as: the evaporation rate was 1 angstrom per second at a temperature corresponding to a degree of vacuum of 10-7 Torr. The test results were as follows:
| material | Sublimation temperature/. Degree.C |
| CPD003 | 264 |
| CPD014 | 263 |
| CPD017 | 266 |
| CPD029 | 265 |
| CPD050 | 267 |
| Comparative Compound 1 | 268 |
| Comparative Compound 2 | 268 |
| Comparative Compound 3 | 265 |
| Comparative Compound 4 | 275 |
| HTM1 | 380 |
| HTM2 | 275 |
As can be seen from the comparison of the data in the above table, the hole transport material of the present invention has a lower sublimation temperature, which is advantageous for industrial applications.
Comparison of carrier lateral mobility:
a 50mm x 1.0mm glass substrate is transformed into a glass substrate with ITO (100 nm) transparent electrodes and Mg/Ag (100nm, 1 2 Plasma treatment for 30 min. The washed glass substrate was mounted on a substrate holder of a vacuum evaporation apparatus, and first, an HTL1 layer having a thickness of 10nm was evaporated on a surface having a transparent electrode in such a manner as to cover the transparent electrode (3% HATCN was doped in CPD014, CPD017, comparative 1-3 compounds, and HTM1, respectively), and then an HTL2 layer having a thickness of 100nm was evaporated (CPD 014, CPD017, comparative 1-3 compounds, and HTM1, respectively), and voltage-current curves thereof were measured after encapsulation to obtain transverse transmission current data, and transverse resistance values ratios of the respective materials were obtained by calculation (calculated with comparative compound 1 as 100%). It can be observed that when the test voltage is 15v, the lateral resistance values of CPD014 and CPD017 are higher, both higher than those of comparative compounds 1-3 and HTM1, indicating that the lateral mobility of the carriers is small, the lateral crosstalk current is small, and the good low gray scale color purity is facilitated.
| HTL1 | HTL2 | Transverse resistance ratio (%) |
| 3％HATCN：97％CPD014 | CPD014 | 355％ |
| 3％HATCN：97％CPD017 | CPD017 | 271％ |
| 3% of HATCN:97% comparison 1 | Comparative example 1 | 100％ |
| 3% of HATCN:97% comparison 2 | Comparative example 2 | 97％ |
| 3% of HATCN:97% comparison 3 | Comparison No. 3 | 99％ |
| 3% of HATCN:97% comparison 4 | Comparative example 4 | 95％ |
| 3％HATCN：97％HTM1 | HTM1 | 69％ |
The material of the invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, small carrier transverse mobility, high luminous efficiency, long service life of the device and the like, and can be used in organic electroluminescent devices. In particular, the material can be used as a hole injection and transport material in the AMOLED industry.
Claims (11)
1. A spiro compound having a structure represented by the formula (1),
wherein, R is 1 ，R 2 Is substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
wherein, the ring A is selected from substituted or unsubstituted saturated fat rings of C3-C20;
wherein R is a -R d Is a substituent on the benzene ring, independently selected from deuterium, halogen, cyano, hydroxyl, mercapto, amine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri C1-C10 alkylsilyl, substituted or unsubstituted tri C6-C12 arylsilyl, substituted or unsubstituted di C1-C10 alkyl-C6-C30 arylsilyl, substituted or unsubstituted mono C1-C10 alkyl-di C6-C30 arylsilyl, or two adjacent groups may be linked to each other to form an aliphatic or aromatic ring structure;
wherein L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene;
wherein Ar is independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
wherein m, n, p, q are independently selected from 0 or an integer of 1-4;
wherein the heteroalkyl, heterocycloalkyl, and heteroaryl contain at least one O, N or S heteroatom;
the substitution is by deuterium, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, C6-C10 aryl, C1-C4 alkyl substituted C6-C10 aryl, cyano, isonitrile or phosphino, wherein the number of substitutions is from mono-to maximum number of substitutions.
2. The spiro compound according to claim 1, which is one of structures represented by formula (2) to formula (5),
wherein the definitions of the rest symbols are the same as the above.
3. The spiro compound according to claim 2, which has a structure represented by formula (2) or formula (3), R 1 And R 2 The same or different.
4. The spiro compound according to claim 2, wherein L is represented by formula (2) to formula (5) 1 、L 2 、L 3 Is a single bond.
5. The spiro compound according to claim 4, which has one of the structures shown in formulas (6) to (9):
6. the spirocyclic compound according to claim 2, wherein ring a in said spirocyclic compound is one of the following aliphatic rings:
7. spirocyclic compound according to any of claims 1 to 6, R 1 And R 2 And Ar is selected from substituted or unsubstituted phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl or carbazolyl, wherein the substitution is by deuterium, F, cl, br, C6-C10 aryl, C1-C6 alkyl, C3-C6 cycloalkyl.
8. The spiro compound of claim 7, R 1 ，R 2 Is substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl.
9. The spiro compound according to claim 1, being one of the following structural formulae, or the corresponding partially or fully deuterated or fluorinated:
10. use of the spiro compound according to any one of claims 1 to 9 in an organic electroluminescent device.
11. Use according to claim 10 of a spiro compound according to any of claims 1 to 9 as a hole injection layer and/or a hole transport layer in an organic electroluminescent device.
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