CN116396311A - Boron-containing organic compound and organic electroluminescent device prepared from same - Google Patents
Boron-containing organic compound and organic electroluminescent device prepared from same Download PDFInfo
- Publication number
- CN116396311A CN116396311A CN202211631638.6A CN202211631638A CN116396311A CN 116396311 A CN116396311 A CN 116396311A CN 202211631638 A CN202211631638 A CN 202211631638A CN 116396311 A CN116396311 A CN 116396311A
- Authority
- CN
- China
- Prior art keywords
- substituted
- group
- deuterated
- phenyl
- unsubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 75
- -1 methyl-substituted cyclopentyl group Chemical group 0.000 claims description 135
- 239000010410 layer Substances 0.000 claims description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims description 63
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 59
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 50
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 31
- 239000004305 biphenyl Substances 0.000 claims description 28
- 235000010290 biphenyl Nutrition 0.000 claims description 27
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 24
- 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 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 16
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 15
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229910052805 deuterium Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- 150000001975 deuterium Chemical group 0.000 claims description 8
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 229910052722 tritium Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 7
- 125000005561 phenanthryl group Chemical group 0.000 claims description 7
- 125000001544 thienyl group Chemical group 0.000 claims description 7
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 6
- 125000004431 deuterium atom Chemical group 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 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 4
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 239000002346 layers by function Substances 0.000 claims description 4
- 125000005493 quinolyl group Chemical group 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 125000004306 triazinyl group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims 6
- AEIOZWYBDBVCGW-UHFFFAOYSA-N 2-tert-butylaniline Chemical group CC(C)(C)C1=CC=CC=C1N AEIOZWYBDBVCGW-UHFFFAOYSA-N 0.000 claims 2
- 125000001300 boranyl group Chemical group [H]B([H])[*] 0.000 claims 2
- 125000004618 benzofuryl group Chemical class O1C(=CC2=C1C=CC=C2)* 0.000 claims 1
- 125000004987 dibenzofuryl group Chemical class C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 29
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 116
- 238000006243 chemical reaction Methods 0.000 description 95
- 239000002994 raw material Substances 0.000 description 77
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 48
- 238000010898 silica gel chromatography Methods 0.000 description 48
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 48
- 238000005259 measurement Methods 0.000 description 47
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 46
- 238000010992 reflux Methods 0.000 description 43
- 239000012044 organic layer Substances 0.000 description 38
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 229910000027 potassium carbonate Inorganic materials 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 24
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 24
- 229910052802 copper Inorganic materials 0.000 description 24
- 239000010949 copper Substances 0.000 description 24
- 229940117389 dichlorobenzene Drugs 0.000 description 24
- 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 24
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 23
- 239000010408 film Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 238000007740 vapor deposition Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000002178 anthracenyl group Chemical class C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 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 4
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- DEVSOMFAQLZNKR-RJRFIUFISA-N (z)-3-[3-[3,5-bis(trifluoromethyl)phenyl]-1,2,4-triazol-1-yl]-n'-pyrazin-2-ylprop-2-enehydrazide Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(C2=NN(\C=C/C(=O)NNC=3N=CC=NC=3)C=N2)=C1 DEVSOMFAQLZNKR-RJRFIUFISA-N 0.000 description 2
- QTMAZYGAVHCKKX-UHFFFAOYSA-N 2-[(4-amino-5-bromopyrrolo[2,3-d]pyrimidin-7-yl)methoxy]propane-1,3-diol Chemical compound NC1=NC=NC2=C1C(Br)=CN2COC(CO)CO QTMAZYGAVHCKKX-UHFFFAOYSA-N 0.000 description 2
- XASOHFCUIQARJT-UHFFFAOYSA-N 8-methoxy-6-[7-(2-morpholin-4-ylethoxy)imidazo[1,2-a]pyridin-3-yl]-2-(2,2,2-trifluoroethyl)-3,4-dihydroisoquinolin-1-one Chemical compound C(N1C(=O)C2=C(OC)C=C(C=3N4C(=NC=3)C=C(C=C4)OCCN3CCOCC3)C=C2CC1)C(F)(F)F XASOHFCUIQARJT-UHFFFAOYSA-N 0.000 description 2
- CDEASXIPDPAOGW-UHFFFAOYSA-N bis[4-(9,9-dimethylacridin-10-yl)phenyl]methanone Chemical compound C12=CC=CC=C2N(C2=C(C1(C)C)C=CC=C2)C1=CC=C(C(=O)C2=CC=C(N3C4=CC=CC=C4C(C4=C3C=CC=C4)(C)C)C=C2)C=C1 CDEASXIPDPAOGW-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a boron-containing organic compound and an organic electroluminescent device prepared from the same, and belongs to the technical field of semiconductors. The structure of the organic compound is shown as a general formula (1),
the compound has narrow half-peak width, high fluorescence quantum yield, proper luminescent color and proper HOMO and LUMO energy levels, and can be used as a green light doping material of a luminescent layer of an organic electroluminescent device when being used as a doping material in the luminescent layer material of the OLED luminescent device, thereby improving the luminescent color purity and the luminescent efficiency of the device.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a boron-containing organic compound and an organic electroluminescent device prepared from the same.
Background
The traditional fluorescent doping material is limited by early technology, only 25% of singlet excitons formed by electric excitation can be used for emitting light, the internal quantum efficiency of the device is low (25% at maximum), the external quantum efficiency is generally lower than 5%, and the efficiency of the device is quite different from that of a phosphorescent device. The phosphorescent material enhances intersystem crossing due to strong spin-orbit coupling of heavy atom center, and can effectively utilize singlet excitons and triplet excitons formed by electric excitation to emit light, so that the internal quantum efficiency of the device reaches 100%. However, most phosphorescent materials are expensive, the stability of the materials is poor, the color purity is poor, and the problems of serious roll-off of the device efficiency and the like limit the application of the phosphorescent materials in OLED.
With the advent of the 5G age, higher requirements are put on the color development standard, and besides high efficiency and stability, the luminescent material also needs narrower half-peak width to improve the luminescent color purity of the device. The fluorescent doping material can realize high fluorescence quanta and narrow half-peak width through molecular engineering, the blue fluorescent doping material has obtained a staged breakthrough, and the half-peak width of the boron material can be reduced to below 30 nm; in the green light region where human eyes are more sensitive, research is mainly focused on phosphorescent doped materials, but the luminescence peak shape is difficult to narrow by a simple method, so that the research on efficient green fluorescent doped materials with narrow half-peak width is of great significance for meeting higher color development standards.
In addition, the TADF sensitized fluorescence Technology (TSF) combines the TADF material with the fluorescence doped material, the TADF material is used as an exciton sensitization medium, the triplet state exciton formed by electric excitation is converted into the singlet state exciton, and the energy is transferred to the fluorescence doped material through the long-range energy transfer of the singlet state exciton, so that the device internal quantum efficiency of 100% can be achieved, the defect of insufficient utilization rate of the exciton of the fluorescence doped material can be overcome, the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of the fluorescence doped material can be effectively exerted, and the technology has wide prospect in the application of OLEDs.
The boron compound with a resonance structure can easily realize narrow half-peak width luminescence, and the material is applied to the TADF sensitized fluorescent technology, so that the device preparation with high efficiency and narrow half-peak width emission can be realized. As in CN 107507921A and CN 110492006A, disclosed is a light emitting layer composition technology in which TADF materials with the lowest singlet and lowest triplet energy level difference of 0.2eV or less are used as the main body and boron-containing materials are used as the doping materials; CN110492005a and CN 110492009A disclose a luminescent layer composition scheme with exciplex as main body and boron-containing material as doping; can realize efficiency comparable to phosphorescence and relatively narrow half-width. Therefore, the development of the TADF sensitized fluorescence technology based on the narrow half-peak width boron luminescent material has unique advantages and strong potential on the index display facing BT.2020.
Disclosure of Invention
In view of the above problems in the prior art, the present application provides a boron-containing organic compound and an organic electroluminescent device prepared from the same. The compound can be used as a green light doping material of a luminescent layer of an organic electroluminescent device, thereby improving the luminescent color purity and the service life of the device.
The technical scheme of the invention is as follows: a boron-containing organic compound, the structure of which is shown as a general formula (1):
In the general formula (1), Z is represented by C-R, which are identical or different at each occurrence 1 ；
R is represented by substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
x is O, S, se, N (R) 2 )、C(R 3 )(R 4 ) Or Si (R) 5 )(R 6 )；
Z 1 Represented by C-R 7 ；
R 1 、R 7 Each independently represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy, substituted or unsubstituted arylamino, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
R 2 -R 6 respectively and independently represented as substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of heteroaryl groups, and adjacent R 1 May also be linked into a ring; adjacent R 7 May also be linked into a ring; r is R 2 -R 6 May also be adjacent to R 7 Connected into a ring;
the substituents for the substituents are optionally selected from deuterium atoms, tritium atoms, halogen atoms, C 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl, C 6 ～C 30 Aryl, C 2 ～C 30 One or more of heteroaryl;
the hetero atom in the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen atoms.
Preferably, the structure of the organic compound is shown as a general formula (2) or a general formula (3):
z, X, R, Z in the general formulae (2) and (3) 1 Is as defined above.
Further preferably, the structure of the organic compound is represented by any one of the general formulas (4) to (15):
z, Z in the general formulae (4) to (15) 1 、R、R 2 -R 6 Is as defined above.
Preferably, the structure of the organic compound is shown as any one of the general formulas (1-1) to (1-2):
in the general formulae (1-1) to (1-2), Y 1 -Y 14 Are each independently represented by C-H or C-R a ；
R a Represented by deuterium atoms, tritium atoms, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
r is represented by substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstitutedC 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
x is O, S, se, N (R) 2 )、C(R 3 )(R 4 ) Or Si (R) 5 )(R 6 )；
R 2 -R 6 Respectively and independently represented as substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
the substituents for the substituents are optionally selected from deuterium atoms, tritium atoms, halogen atoms, C 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl, C 6 ～C 30 Aryl, C 2 ～C 30 One or more of heteroaryl;
the hetero atom in the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen atoms.
Preferably, the structure of the organic compound is shown as any one of the general formulas (1-3) to (1-4):
in the general formulae (1-3) to (1-4), R a1 ～R a12 Each independently represents a hydrogen atom, a deuterium atom, a tritium atom, a substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
r is represented by substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
x is O, S, se, N (R) 2 )、C(R 3 )(R 4 ) Or Si (R) 5 )(R 6 )；
R 2 -R 6 Respectively and independently represented as substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
Ar 1 、Ar 2 represented independently as hydrogen atoms, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
the substituents for the substituents are optionally selected from deuterium atoms, tritium atoms, halogen atoms, C 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl, C 6 ～C 30 Aryl, C 2 ～C 30 One or more of heteroaryl;
the hetero atom in the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen atoms.
Preferably, the Ar 1 、Ar 2 Independently of each other, are represented by hydrogen atom, deuterium atom, methyl, phenyl, tert-butyl substituted phenyl, CD 3 One of them.
Preferably, the R a1 ～R a12 Each independently represents a hydrogen atom, a deuterium atom, a tritium atom, a cyano group, a halogen atom, an adamantyl group, a methyl group, a deuteromethyl group, a tritium methyl group, a trifluoromethyl group, an ethyl group, a deuteroethyl groupTritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritiated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furyl, thienyl, benzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted borane, methoxy, tert-butoxy;
Preferably, the substituents for the substituents are optionally selected from one or more of deuterium, chlorine, fluorine, trifluoromethyl, adamantyl, cyano, methyl, ethyl, propyl, isopropyl, tert-amyl, tert-butyl, methoxy, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, quinolinyl, isoquinolinyl, furanyl, thienyl, indolyl, pyrrolyl, dibenzofuranyl, dibenzothiophenyl, 9-dimethylfluorenyl, spirofluorenyl, carbazolyl, N-phenylcarbazolyl, carbazolyl, azaphenanthryl.
Preferred embodiments, provided thatThe R is a1 ～R a12 Each independently represented by the structure shown below:
a hydrogen atom,
Preferably, the R is represented by the following structure:
Preferably, adjacent R 7 Can be connected into the following structure:
preferably, the R a Represented by any one of the following structures:
Preferably, the R 1 、R 7 Are respectively and independently represented by hydrogen atom, deuterium atomTritium atom, halogen atom, adamantyl, methyl, deuteromethyl, tritiated methyl, trifluoromethyl, ethyl, deuteroethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritiated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridinyl, phenyl-substituted pyridinyl, quinolinyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, t-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, t-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated t-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated t-butyl-substituted biphenyl, phenyl-substituted amino, t-butylbenzene-substituted amino, t-butyl-substituted dibenzofuranyl, phenyl-substituted t-butyl, xanthonyl, phenyl-substituted triazinyl, phenyl-substituted boranyl, methoxy, t-butoxy.
Said R, R 2 、R 3 、R 4 、R 5 、R 6 Are each independently represented by phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridinyl, phenyl-substituted pyridinyl, quinolinyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenylPhenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl;
Preferably, the R a Represented by hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl, methyl, deuterated methyl, tritiated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritiated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furyl, thienyl, benzofuryl dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, t-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, t-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated t-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated t-butyl-substituted biphenyl, phenyl-substituted amino, t-butylbenzene-substituted amino Butyl substituted dibenzofuranyl, phenyl substituted tert-butyl, xanthone, phenyl substituted triazinyl, phenyl substituted borane, methoxy, tert-butoxy.
Preferably, the specific structure of the boron-containing organic compound is any one of the following structures:
an organic electroluminescent device comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, the organic light-emitting functional layer comprising a light-emitting layer containing the boron-containing organic compound.
Preferably, the light emitting layer comprises a host material and a doping material, and the doping material contains the boron-containing organic compound.
Preferably, the light-emitting layer comprises a first host material, a second host material and a doping material, at least one of the first host material and the second host material is a TADF material, and the doping material is the boron-containing organic compound.
The beneficial technical effects of the invention are as follows:
(1) The compound disclosed by the invention is applied to an OLED device, can be used as a doping material of a luminescent layer material, can emit green fluorescence under the action of an electric field, and can be applied to the field of OLED illumination or OLED display;
(2) The compound provided by the invention has higher fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;
(3) The compound is used as a doping material, and the TADF sensitizer is introduced as a second main body, so that the efficiency of the device can be effectively improved;
(4) The spectrum FWHM of the compound is narrower, the color gamut of the device can be effectively improved, and the luminous efficiency of the device is improved;
(5) The compound has higher vapor deposition decomposition temperature, can inhibit vapor deposition decomposition of materials and effectively prolongs the service life of devices.
Drawings
FIG. 1 is a schematic diagram of the structure of an OLED device using the materials of the present invention;
wherein 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the embodiments of the present invention and features in the embodiments of the present invention may be combined with each other without conflict. The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting.
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
The starting materials involved in the synthetic examples of the present invention are all commercially available or are prepared by methods conventional in the art;
example 1 synthesis of compound 67:
33.4mmol of raw material A-1, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-1.LC-MS: measurement value: 312.09 ([ M+H)] + ) Theoretical value: 311.03.
33.4mmol of raw material C-1, 33.4mmol of raw material D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-1.LC-MS: measurement value: 210.16 ([ M+H)] + ) Theoretical value: 209.08.
69mmol of intermediate a-1, 69mmol of intermediate b-1, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then subjected to silica gel column chromatography Purification gives intermediate c-1.LC-MS: measurement value: 485.01 ([ M+H)] + ) Theoretical value: 484.13.
47mmol of intermediate c-1 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 67. 1 H NMR(400MHz,Chloroform-d)δ9.09–8.96(m,1H),8.04–7.80(m,2H),7.65–6.89(m,15H),6.71(dd,1H)。
Example 2 synthesis of compound 70:
26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added into a three-necked flask under the protection of nitrogen, and the mixture is heated to reflux for reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-2.LC-MS: measurement value: 464.21 ([ M+H)] + ) Theoretical value: 463.09.
33.4mmol of raw material C-1, 33.4mmol of raw material D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours.After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-1.LC-MS: measurement value: 210.16 ([ M+H)] + ) Theoretical value: 209.08.
69mmol of intermediate a-2, 69mmol of intermediate b-1, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-2.LC-MS: measurement value: 637.10 ([ M+H)] + ) Theoretical value: 636.20.
47mmol of intermediate c-2 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 70. 1 H NMR(400MHz,Chloroform-d)δ8.66(d,1H),8.00–7.78(m,2H),7.64–6.90(m,24H)。
Example 3 synthesis of compound 88:
26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added into a three-necked flask under the protection of nitrogen, and the mixture is heated to reflux for reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 10.3mmol of copper and 6.9mmol of 18 are introduced under the protection of nitrogenCrown-6 and 70mL dichlorobenzene were added to a three-necked flask and reacted under reflux for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-2.LC-MS: measurement value: 464.21 ([ M+H)] + ) Theoretical value: 463.09.
33.4mmol of raw material C-1, 33.4mmol of raw material D-3, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-3.LC-MS: measurement value: 266.31 ([ M+H)] + ) Theoretical value: 265.15.
69mmol of intermediate a-2, 69mmol of intermediate b-3, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-3.LC-MS: measurement value: 693.38 ([ M+H)] + ) Theoretical value: 692.26.
47mmol of intermediate c-3 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 88. 1 HNMR(400MHz,Chloroform-d)δ8.64(d,1H),7.96–7.82(m,2H),7.60–6.95(m,23H),1.34–1.26(s,9H)。
Example 4 synthesis of compound 113:
in a three-mouth bottle, nitrogen is introduced26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added under the protection of gas, and the mixture is heated to reflux reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H) ] + ) Theoretical value: 319.14.
15mmol of raw material G-4, 40mmol of raw material H-4, 50mmol of potassium carbonate, 0.5mmol of tetra (triphenylphosphine) palladium, 100mL of tetrahydrofuran and 10mL of water are added into a three-necked flask under the protection of nitrogen, stirred at 75 ℃ for reaction for 12 hours, and cooled to room temperature after the reaction. Saturated saline was added, extracted 3 times with ethyl acetate, and then the organic phase was dried over anhydrous sodium sulfate, concentrated and separated by column chromatography to give raw material B-4.LC-MS: measurement value: 455.82 ([ M+H)] + ) Theoretical value: 454.96.
33.4mmol of raw material A-2, 33.4mmol of raw material B-4, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-4.LC-MS: measurement value: 695.09 ([ M+H)] + ) Theoretical value: 694.17.
33.4mmol of raw material C-1, 33.4mmol of raw material D-4, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-4.LC-MS: measurement value: 342.10 ([ M+H) ] + ) Theoretical value: 341.18.
69mmol of intermediate a-4, 69mmol of intermediate b-4, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-4.LC-MS: measurement value: 1000.21 ([ M+H)] + ) Theoretical value: 999.37.
under nitrogen, 47mmol of intermediate c-4 was added to a reactor containing 200ml t-butylbenzene three-necked flask and cooled to-30℃95mmol of t-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 113. 1 H NMR(400MHz,Chloroform-d)δ8.69–8.50(m,5H),8.24(dd,1H),7.97–7.80(m,3H),7.63–7.11(m,29H),7.03(d,1H),1.34–1.27(s,9H)。
Example 5 synthesis of compound 155:
15mmol of raw material G-4, 40mmol of raw material H-4, 50mmol of potassium carbonate, 0.5mmol of tetra (triphenylphosphine) palladium, 100mL of tetrahydrofuran and 10mL of water are added into a three-necked flask under the protection of nitrogen, stirred at 75 ℃ for reaction for 12 hours, and cooled to room temperature after the reaction. Saturated saline was added, extracted 3 times with ethyl acetate, and then the organic phase was dried over anhydrous sodium sulfate, concentrated and separated by column chromatography to give raw material B-4.LC-MS: measurement value: 455.82 ([ M+H) ] + ) Theoretical value: 454.96.
33.4mmol of raw material A-1, 33.4mmol of raw material B-4, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-5.LC-MS: measurement value: 543.15 ([ M+H)] + ) Theoretical value: 542.11.
33.4mmol of raw material C-5, 33.4mmol of raw material D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction is finished, the pressure is reduced, the organic layer is concentrated, and then the organic layer is purified by silica gel column chromatography,intermediate b-5 is obtained. LC-MS: measurement value: 256.12 ([ M+H)] + ) Theoretical value: 255.06.
69mmol of intermediate a-5, 69mmol of intermediate b-5, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-5.LC-MS: measurement value: 732.01 ([ M+H)] + ) Theoretical value: 731.19.
47mmol of intermediate c-5 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 155. 1 H NMR(400MHz,Chloroform-d)δ6.94(2H,m),7.02(1H,m),7.13–7.40(5H,m),7.48–7.74(8H,m),7.81–8.01(3H,m),8.17–8.32(6H,m),8.44–8.50(2H,m),8.69(1H,m)。
Example 6 synthesis of compound 165:
26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added into a three-necked flask under the protection of nitrogen, and the mixture is heated to reflux for reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 10.3mmol of copper and 6.9mmol of the raw material B are stirred under the protection of nitrogen 18-crown-6 and 70mL dichlorobenzene were added to a three-necked flask and reacted under reflux for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-2.LC-MS: measurement value: 464.21 ([ M+H)] + ) Theoretical value: 463.09.
33.4mmol of C-6, 33.4mmol of D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are introduced under nitrogen protection and reacted for 48 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-6.LC-MS: measurement value: 226.02 ([ M+H)] + ) Theoretical value: 225.06.
69mmol of intermediate a-2, 69mmol of intermediate b-6, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-6.LC-MS: measurement value: 653.25 ([ M+H)] + ) Theoretical value: 652.17.
47mmol of intermediate c-6 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 165. 1 H NMR(400MHz,Chloroform-d)δ7.14–7.83(20H,m),7.88–8.06(4H,m),8.22(1H,m),8.80–9.08(2H,m)。
Example 7 synthesis of compound 178:
in the three-mouth bottle, lead to26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added under the protection of nitrogen, and the mixture is heated to reflux reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-7, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate a-7.LC-MS: measurement value: 520.31 ([ M+H)] + ) Theoretical value: 519.15.
33.4mmol of C-6, 33.4mmol of D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are introduced under nitrogen protection and reacted for 48 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-6.LC-MS: measurement value: 226.02 ([ M+H)] + ) Theoretical value: 225.06.
69mmol of intermediate a-7, 69mmol of intermediate b-6, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-7.LC-MS: measurement value: 709.28 ([ M+H)] + ) Theoretical value: 708.24.
47mmol of intermediate c-7 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, t-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and then passed throughPurifying by silica gel column chromatography to obtain compound 178. 1 HNMR(400MHz,Chloroform-d)δ8.65(d,1H),7.97–7.80(m,2H),7.79–7.62(m,2H),7.59–6.86(m,21H),1.33–1.25(s,9H)。
Example 8 synthesis of compound 183:
15mmol of raw material G-4, 40mmol of raw material H-4, 50mmol of potassium carbonate, 0.5mmol of tetra (triphenylphosphine) palladium, 100mL of tetrahydrofuran and 10mL of water are added into a three-necked flask under the protection of nitrogen, stirred at 75 ℃ for reaction for 12 hours, and cooled to room temperature after the reaction. Saturated saline was added, extracted 3 times with ethyl acetate, and then the organic phase was dried over anhydrous sodium sulfate, concentrated and separated by column chromatography to give raw material B-4.LC-MS: measurement value: 455.82 ([ M+H ] +) theoretical value: 454.96.
33.4mmol of raw material A-1, 33.4mmol of raw material B-4, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-5.LC-MS: measurement value: 543.15 ([ M+H)] + ) Theoretical value: 542.11.
33.4mmol of C-6, 33.4mmol of D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are introduced under nitrogen protection and reacted for 48 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-6.LC-MS: measurement value: 226.02 ([ M+H)] + ) Theoretical value: 225.06.
69mmol of intermediate a-5, 69mmol of intermediate b-6, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-8.LC-MS: measurement value: 732.25 ([ M+H)] + ) Theoretical value: 731.19。
47mmol of intermediate c-8 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the completion of the reaction, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 183. 1 HNMR(400MHz,Chloroform-d)δ9.10–8.94(m,1H),8.71–8.50(m,4H),8.00–6.89(m,22H),6.70(dd,1H)。
Example 9 synthesis of compound 215:
26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added into a three-necked flask under the protection of nitrogen, and the mixture is heated to reflux for reaction at 90 ℃. After the reaction was completed, the reaction was precipitated with about 5 times of ice water and filtered, and then the resultant product was recrystallized (water: ethanol=1:2) to obtain raw material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-2.LC-MS: measurement value: 464.21 ([ M+H)] + ) Theoretical value: 463.09.
33.4mmol of raw material G-9, 33.4mmol of raw material H-9, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give raw material C-9.L (L)C-MS: measurement value: 228.17 ([ M+H)] + ) Theoretical value: 227.05.
33.4mmol of raw material C-9, 33.4mmol of raw material D-1, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate b-9.LC-MS: measurement value: 285.11 ([ M+H)] + ) Theoretical value: 284.13.
69mmol of intermediate a-2, 69mmol of intermediate b-9, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-9.LC-MS: measurement value: 712.30 ([ M+H)] + ) Theoretical value: 711.24.
47mmol of intermediate c-9 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 215. 1 H NMR(400MHz,Chloroform-d)δ7.11-7.72(21H,m),7.84(2H,m),7.88-8.19(6H,m),8.30(1H,m),8.67(1H,m),8.93(1H,m)。
Example 10 synthesis of compound 239:
26mmol of raw material E-2, 26mmol of raw material F-2, 52mmol of concentrated sulfuric acid and 100ml of ethanol are added into a three-necked flask under the protection of nitrogen, and the mixture is heated to reflux for reaction at 90 ℃. After the reaction is completed, the reactants are usedIce water precipitation 5 times and filtration, and then recrystallization of the resulting product (water: ethanol=1:2) gave starting material a-2.LC-MS: measurement value: 320.02 ([ M+H)] + ) Theoretical value: 319.14.
33.4mmol of raw material A-2, 33.4mmol of raw material B-1, 172mmol of potassium carbonate, 103mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate a-2.LC-MS: measurement value: 464.21 ([ M+H)] + ) Theoretical value: 463.09.
33.4mmol of raw material G-10, 66.8mmol of raw material H-9, 172mmol of potassium carbonate, 103mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure is reduced and the organic layer is concentrated, and then the organic layer is purified by silica gel column chromatography to obtain the raw material C-10.LC-MS: measurement value: 319.22 ([ M+H)] + ) Theoretical value: 318.06.
33.4mmol of raw material C-10, 33.4mmol of raw material D-1, 172mmol of potassium carbonate, 103mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the pressure was reduced and the organic layer was concentrated, followed by purification by silica gel column chromatography to give intermediate b-10.LC-MS: measurement value: 376.22 ([ M+H)] + ) Theoretical value: 375.14.
69mmol of intermediate a-2, 69mmol of intermediate b-10, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-10.LC-MS: measurement value: 803.18 ([ M+H)] + ) Theoretical value: 802.26.
47mmol of intermediate c-10 was added to a three-necked flask containing 200ml of t-butylbenzene under nitrogen and cooled to-30℃and 95mmol of t-butyllithium pentane solution (1.7M) was slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooling to-50 ℃, adding 95mmol of boron tribromide dropwise, heating to room temperature andstirring is carried out for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 239. 1 HNMR(400MHz,Chloroform-d)δ8.65(d,1H),8.00–7.80(m,2H),7.73–6.90(m,34H)。
Synthesis of Compound 250 from example 11:
33.4mmol of raw material C-11, 33.4mmol of raw material D-11, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 12 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate b-11.LC-MS: measurement value: 470.33 ([ M+H)] + ) Theoretical value: 469.28.
69mmol of intermediate a-7, 69mmol of intermediate b-11, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-11.LC-MS: measurement value: 953.55 ([ M+H)] + ) Theoretical value: 952.46.
47mmol of intermediate c-11 was introduced under nitrogen into a sealed pressure-resistant tube containing 200ml of tert-butylbenzene and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 250.
Example 12 synthesis of compound 251:
15mmol of raw material G-4, 40mmol of raw material H-12, 50mmol of potassium carbonate, 0.5mmol of tetra (triphenylphosphine) palladium, 100mL of tetrahydrofuran and 10mL of water are added into a three-necked flask under the protection of nitrogen, stirred at 75 ℃ for reaction for 12 hours, and cooled to room temperature after the reaction. Saturated saline was added, extraction was performed 3 times with ethyl acetate, and then the organic phase was dried over anhydrous sodium sulfate, concentrated and separated by column chromatography to obtain raw material B-12.LC-MS: measurement value: 344.90 ([ M+H)] + ) Theoretical value: 343.86.
33.4mmol of raw material A-2, 33.4mmol of raw material B-12, 172mmol of potassium carbonate, 10.3mmol of copper, 6.9mmol of 18-crown-6 and 70mL of dichlorobenzene are added to a three-necked flask under the protection of nitrogen, and reflux reaction is carried out for 48 hours. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate a-12.LC-MS: measurement value: 584.15 ([ M+H)] + ) Theoretical value: 583.07.
69mmol of intermediate a-7, 69mmol of intermediate b-11, 1.4mmol of dibenzylideneacetone dipalladium, 3mmol of tri-tert-butylphosphine, 103mmol of tert-butyl alcohol and 200ml of toluene are added to the flask under the protection of nitrogen and are reacted for 6 hours under reflux. After the reaction, the organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography to give intermediate c-12.LC-MS: measurement value: 973.36 ([ M+H) ] + ) Theoretical value: 972.42.
47mmol of intermediate c-12 was added to a three-necked flask containing 200ml of tert-butylbenzene under nitrogen and cooled to-30℃and 95mmol of tert-butyllithium pentane solution (1.7M) were slowly added dropwise. After the completion of the dropwise addition, the temperature was raised to 60℃and stirred for 3 hours, and then pentane was distilled off. Then cooled again to-50℃and 95mmol of boron tribromide were added dropwise, warmed to room temperature and stirred for 1 hour. After cooling to 0℃again, 95mmol of N, N-diisopropylethylamine was added and stirred at 120℃for 3 hours. After the reaction was completed, tert-butylbenzene was removed by distillation under reduced pressure, extracted with water and ethyl acetate, concentrated, and purified by silica gel column chromatography to give compound 251.
The structural characterization of the compounds obtained in each example is shown in Table 1
TABLE 1
The compound of the invention is used in a light-emitting device and can be used as a doping material of a light-emitting layer. The compounds prepared in the above examples of the present invention were tested for physicochemical properties, and the test results are shown in table 2:
TABLE 2
Note that: PLQY (fluorescence quantum yield) and FWHM (full width at half maximum) were measured in a thin film state by a fluorescent-3 series fluorescence spectrometer of Horiba. Tau (transient) is measured in the thin film state by Fluorolog-3 series fluorescence spectrometer of Horiba, k r (radiation transition rate) =1/τ.
As can be seen from the data in the table 2, the compound of the invention has higher fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%; meanwhile, the spectrum FWHM of the material is narrower, the color gamut of the device can be effectively improved, and the luminous efficiency of the device is improved; finally, the vapor deposition decomposition temperature of the material is higher, the vapor deposition decomposition of the material can be restrained, the radiation transition rate of the material is higher, and the service life of the device can be effectively prolonged.
The effect of the OLED materials synthesized according to the present invention in the device will be described in detail below with reference to device examples 1 to 12 and device comparative examples 1 to 5. The device examples 2 to 12 and the device comparative examples 1 to 5 of the present invention were identical in the manufacturing process of the device as compared with the device example 1, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept uniform, except that the light-emitting layer material in the device was replaced. The layer structure and test results for each device example are shown in tables 3 and 4, respectively.
Device example 1
As shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness 150 nm) is washed, that is, washed with a cleaning agent (semiconductor M-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the transparent ITO surface. On the ITO anode layer 2 after the above washing, HT-1 and HI-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 to HI-1 was 97:3. Next, HT-1 was evaporated to a thickness of 60nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 30nm as an electron blocking layer 5. After the electron blocking material was evaporated, a light emitting layer 6 of an OLED light emitting device was fabricated, using CBP as a host material, compound 67 as a dopant material, and the mass ratio of CBP to compound 67 was 97:3, with a light emitting layer film thickness of 30nm. After the light-emitting layer 6 was deposited, vacuum deposition of HB-1 was continued to give a film thickness of 5nm, and this layer was a hole blocking layer 7. After the hole blocking layer 7, vacuum evaporation is continued to be carried out on ET-1 and Liq, the mass ratio of ET-1 to Liq is 1:1, the film thickness is 30nm, and the electron transport layer 8 is formed. On the electron transport layer 8, a LiF layer having a film thickness of 1nm, which is an electron injection layer 9, was formed by a vacuum vapor deposition apparatus. On the electron injection layer 9, mg having a film thickness of 80nm was produced by a vacuum vapor deposition apparatus: the mass ratio of Mg to Ag in the Ag electrode layer is 1:9, and the Ag electrode layer is used as the cathode layer 10.
The effect of the OLED materials synthesized according to the present invention in the device will be described in detail below with reference to device examples 13 to 24 and device comparative examples 6 to 10. The device of the invention of examples 14-24 and device of comparative examples 6-10 were identical in the fabrication process to the device of example 13, and the same substrate materials and electrode materials were used, and the film thickness of the electrode materials was also kept uniform, except that the luminescent layer materials in the device were replaced. The layer structure and test results for each device example are shown in tables 3 and 4, respectively.
Device example 13
The transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150 nm) is washed, namely, washing with a cleaning agent (semiconductor M-L20), washing with pure water, drying, and ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, HT-1 and HI-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 to HI-1 was 97:3. Next, HT-1 was evaporated to a thickness of 60nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 30nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, a luminescent layer 6 of the OLED luminescent device is manufactured, CBP and DMAC-BP are used as double main materials, a compound 67 is used as a doping material, the mass ratio of the CBP, the DMAC-BP and the compound 67 is 67:30:3, and the thickness of the luminescent layer is 30nm. After the light-emitting layer 6 was deposited, vacuum deposition of HB-1 was continued to give a film thickness of 5nm, and this layer was a hole blocking layer 7. After the hole blocking layer 7, vacuum evaporation is continued to be carried out on ET-1 and Liq, the mass ratio of ET-1 to Liq is 1:1, the film thickness is 30nm, and the electron transport layer 8 is formed. On the electron transport layer 8, a LiF layer having a film thickness of 1nm, which is an electron injection layer 9, was formed by a vacuum vapor deposition apparatus. On the electron injection layer 9, mg having a film thickness of 80nm was produced by a vacuum vapor deposition apparatus: the mass ratio of Mg to Ag in the Ag electrode layer is 1:9, and the Ag electrode layer is used as the cathode layer 10.
The molecular structural formula of the related material is shown as follows:
after completing the OLED light emitting device as described above, the anode and cathode were connected by a well-known driving circuit, and the current efficiency, external quantum efficiency and lifetime of the device were measured. Examples of devices prepared in the same manner and comparative examples are shown in table 3; the test results of the current efficiency, external quantum efficiency and lifetime of the obtained device are shown in table 4.
TABLE 3 Table 3
TABLE 4 Table 4
Note that: voltage, current efficiency, luminescence peak using an IVL (current-voltage-brightness) test system (fresco scientific instruments, su-state); the life test system is an EAS-62C OLED device life tester of Japanese system technical research company; LT95 refers to the time taken for the device brightness to decay to 95%; all data were at 10mA/cm 2 And (5) testing.
As can be seen from the device data results of table 4, the current efficiency and device lifetime of the compounds of the present invention in the single host system devices are higher as compared to the device comparative examples 1 to 10; in a double-main-body system device, the device efficiency also shows a better effect, and the boron-nitrogen condensed ring parent nucleus can enhance the resonance intensity and improve the device efficiency; compared with the device comparative examples 1-10, the compound of the invention has larger improvement on the current efficiency and the service life of the device in the single-body system device and the double-body system device, which are all OLED devices made of known materials.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, but any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The boron-containing organic compound is characterized by having a structure shown in a general formula (1):
in the general formula (1), Z is represented by C-R, which are identical or different at each occurrence 1 ；
R is represented by substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
x is O, S, se, N (R) 2 )、C(R 3 )(R 4 ) Or Si (R) 5 )(R 6 )；
Z 1 Represented by C-R 7 ；
R 1 、R 7 Each independently represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy, substituted or unsubstituted arylamino, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
R 2 -R 6 respectively and independently represented as substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of heteroaryl groups, and adjacent R 1 May also be linked into a ring; adjacent R 7 May also be linked into a ring; r is R 2 -R 6 May also be adjacent to R 7 Connected into a ring;
the substituents for the substituents are optionally selected from deuterium atoms, tritium atoms, halogen atoms, C 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl, C 6 ～C 30 Aryl, C 2 ～C 30 One or more of heteroaryl;
the hetero atom in the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen atoms.
2. The boron-containing organic compound according to claim 1, wherein the structure of the organic compound is represented by general formula (2) or general formula (3):
z, X, R, Z in the general formulae (2) and (3) 1 Is as defined in claim 1.
3. The boron-containing organic compound according to claim 1, wherein the structure of the organic compound is represented by any one of the general formulae (4) to (15):
z, Z in the general formulae (4) to (15) 1 、R、R 2 -R 6 Is as defined in claim 1.
4. The boron-containing organic compound according to claim 1, wherein the structure of the organic compound is represented by any one of the general formulae (1-1) to (1-2):
In the general formulae (1-1) to (1-2), Y 1 -Y 14 Are each independently represented by C-H or C-R a ；
R a Represented by deuterium atomsTritium atom, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
r is represented by substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
x is O, S, se, N (R) 2 )、C(R 3 )(R 4 ) Or Si (R) 5 )(R 6 )；
R 2 -R 6 Respectively and independently represented as substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 10 Aryloxy, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 One of the heteroaryl groups;
the substituents for the substituents are optionally selected from deuterium atoms, tritium atoms, halogen atoms, C 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl, C 6 ～C 30 Aryl, C 2 ～C 30 One or more of heteroaryl;
the hetero atom in the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen atoms.
5. The boron-containing organic compound according to claim 1, wherein adjacent R 7 Can be connected into the following structure:
6. The boron-containing organic compound according to claim 4, wherein said R a Represented by any one of the following structures:
and (3) tert-butyl.
7. The boron-containing organic compound according to claim 1 or 4, wherein said R 1 、R 7 Each independently represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, an adamantyl group, a methyl group, a deuteromethyl group, a tritiated methyl group, a trifluoromethyl group, an ethyl group, a deuteroethyl group, a tritiated ethyl group, an isopropyl group, a deuterated isopropyl group, a tritiated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a tritiated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a tritiated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a tritiated phenyl group, a biphenyl group, a deuterated biphenyl group, a tritiated biphenyl group, a terphenyl group, a deuterated terphenyl group, a tritiated terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthryl group, a phenanthryl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furyl group, a dibenzothienyl group, a carbazolyl group N-phenylcarbazolyl, 9-dimethylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, methyl substituted biphenyl, ethyl substituted biphenyl, isopropyl substituted biphenyl, tert-butyl substituted biphenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl, deuterated tert-butyl substituted phenyl, deuterated methyl substituted biphenyl, deuterated ethyl substituted biphenyl, deuterated isopropyl substituted biphenyl, deuterated tert-butyl substituted biphenyl, phenyl substituted amino, tert-butylbenzene substituted amino, tert-butyl substituted dibenzofuranyl, phenyl substituted tert-butyl, xanthone, phenyl substituted triazinyl, phenyl substituted boranyl, One of methoxy and tert-butoxy;
said R, R 2 、R 3 、R 4 、R 5 、R 6 Examples of the substituent include, but are not limited to, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, terphenyl, deuterated terphenyl, tritiated terphenyl, naphthyl, anthryl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butyl-substituted benzofuranyl, tert-butyl-substituted biphenyl, tert-butyl-substituted benzofuranyl, and monooxo-substituted triazine;
The R is a Represented by hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl group, methyl group, deuterated methyl group, tritiated methyl group, trifluoromethyl group, ethyl group, deuterated ethyl group, tritiated ethyl group, isopropyl group, deuterated isopropyl group, tritiated isopropyl group, tert-butyl group, deuterated tert-butyl group, tritiated tert-butyl group, cyclopentyl group, deuterated cyclopentyl group, tritiated cyclopentyl group, methyl-substituted cyclopentyl group, cyclohexyl group, phenyl group, deuterated phenyl group, tritiated phenyl group, biphenyl group, deuterated biphenyl group, tritiated biphenyl group, terphenyl group, deuterated terphenyl group, tritiated terphenyl group, diphenyl ether group, methyl-substituted diphenyl ether group, naphthyl group, anthryl group, phenanthryl group, pyridyl group, phenyl-substituted pyridyl group, quinolyl group, furyl group, thienyl group, benzofuryl group, dibenzofuryl group, dibenzothienyl group, carbazolyl group, N-phenylcarbazolyl group, 9-diphenyl groupMethyl fluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, t-butyl substituted phenyl, methyl substituted biphenyl, ethyl substituted biphenyl, isopropyl substituted biphenyl, t-butyl substituted biphenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl, deuterated t-butyl substituted phenyl, deuterated methyl substituted biphenyl, deuterated ethyl substituted biphenyl, deuterated isopropyl substituted biphenyl, deuterated t-butyl substituted biphenyl, phenyl substituted amino, t-butylbenzene substituted amino, t-butyl substituted dibenzofuranyl, phenyl substituted t-butyl, xanthone, phenyl substituted triazinyl, phenyl substituted boranyl, methoxy, t-butoxy.
8. The boron-containing organic compound according to claim 1, wherein the specific structure of the organic compound is any one of the following structures:
9. an organic electroluminescent device comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, the organic light-emitting functional layer comprising a light-emitting layer, characterized in that the light-emitting layer contains the boron-containing organic compound according to any one of claims 1 to 8.
Preferably, the light-emitting layer comprises a host material and a doping material, the doping material comprising the boron-containing organic compound of any one of claims 1 to 8.
10. The organic electroluminescent device according to claim 9, wherein the light-emitting layer comprises a first host material, a second host material, and a doping material, wherein at least one of the first host material and the second host material is a TADF material, and wherein the doping material is the boron-containing organic compound according to any one of claims 1 to 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111600627 | 2021-12-24 | ||
| CN2021116006277 | 2021-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116396311A true CN116396311A (en) | 2023-07-07 |
Family
ID=87018526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211631638.6A Pending CN116396311A (en) | 2021-12-24 | 2022-12-19 | Boron-containing organic compound and organic electroluminescent device prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116396311A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440204A (en) * | 2018-12-29 | 2020-07-24 | 江苏三月科技股份有限公司 | Organic electroluminescent material containing boron and application thereof in organic electroluminescent device |
| CN111933810A (en) * | 2019-07-29 | 2020-11-13 | Sfc株式会社 | Organic light-emitting element comprising boron compound |
| CN112898323A (en) * | 2019-12-03 | 2021-06-04 | 北京鼎材科技有限公司 | Compound, application thereof and organic electroluminescent device comprising compound |
| KR20210067948A (en) * | 2019-11-29 | 2021-06-08 | 주식회사 엘지화학 | Organic light emitting device |
| CN112961174A (en) * | 2021-02-05 | 2021-06-15 | 吉林奥来德光电材料股份有限公司 | Polycyclic aromatic compound and preparation method and application thereof |
| CN113072925A (en) * | 2020-01-03 | 2021-07-06 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent materials and organic electroluminescent device comprising the same |
| CN113366002A (en) * | 2019-11-29 | 2021-09-07 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| CN113493475A (en) * | 2020-04-07 | 2021-10-12 | 材料科学有限公司 | Organic compound and organic electroluminescent element comprising same |
| CN113527342A (en) * | 2020-04-14 | 2021-10-22 | 材料科学有限公司 | Organic compound and organic electroluminescent element comprising same |
| WO2021230653A1 (en) * | 2020-05-12 | 2021-11-18 | 에스에프씨 주식회사 | Organic light-emitting compound and organic light-emitting device comprising same |
| CN113812015A (en) * | 2019-11-29 | 2021-12-17 | 株式会社Lg化学 | Organic light emitting device |
-
2022
- 2022-12-19 CN CN202211631638.6A patent/CN116396311A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440204A (en) * | 2018-12-29 | 2020-07-24 | 江苏三月科技股份有限公司 | Organic electroluminescent material containing boron and application thereof in organic electroluminescent device |
| CN111933810A (en) * | 2019-07-29 | 2020-11-13 | Sfc株式会社 | Organic light-emitting element comprising boron compound |
| KR20210067948A (en) * | 2019-11-29 | 2021-06-08 | 주식회사 엘지화학 | Organic light emitting device |
| CN113366002A (en) * | 2019-11-29 | 2021-09-07 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| CN113812015A (en) * | 2019-11-29 | 2021-12-17 | 株式会社Lg化学 | Organic light emitting device |
| CN113853377A (en) * | 2019-11-29 | 2021-12-28 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting device comprising same |
| CN112898323A (en) * | 2019-12-03 | 2021-06-04 | 北京鼎材科技有限公司 | Compound, application thereof and organic electroluminescent device comprising compound |
| CN113072925A (en) * | 2020-01-03 | 2021-07-06 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent materials and organic electroluminescent device comprising the same |
| CN113493475A (en) * | 2020-04-07 | 2021-10-12 | 材料科学有限公司 | Organic compound and organic electroluminescent element comprising same |
| CN113527342A (en) * | 2020-04-14 | 2021-10-22 | 材料科学有限公司 | Organic compound and organic electroluminescent element comprising same |
| WO2021230653A1 (en) * | 2020-05-12 | 2021-11-18 | 에스에프씨 주식회사 | Organic light-emitting compound and organic light-emitting device comprising same |
| CN112961174A (en) * | 2021-02-05 | 2021-06-15 | 吉林奥来德光电材料股份有限公司 | Polycyclic aromatic compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113929709A (en) | Boron-nitrogen-containing organic compound and organic electroluminescent device comprising same | |
| CN115197184A (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN114315876A (en) | Boron-containing organic compound as OLED (organic light emitting diode) doping material and organic light emitting device | |
| CN113929708A (en) | Boron-containing compound and application thereof in organic electroluminescent device | |
| CN114105868B (en) | Organic compound with 4-cyanopyridine as core and organic electroluminescent device comprising same | |
| CN114105956B (en) | Compound taking triazine derivative as core and organic electroluminescent device comprising compound | |
| CN113072568B (en) | Organic electroluminescent material containing diboron and application thereof | |
| CN114106023A (en) | Boron-nitrogen organic compound and organic light-emitting device comprising same | |
| CN114276337A (en) | TADF material and organic electroluminescent device comprising same | |
| WO2022063107A1 (en) | Boron-containing organic compound serving as oled dopant material, and application thereof | |
| CN113121500B (en) | Phosphorescent platinum complex serving as OLED (organic light emitting diode) doping material and application thereof | |
| CN114276372A (en) | Boron-containing condensed ring compound for OLED light-emitting layer and application thereof | |
| CN114075229A (en) | Boron-containing organic compound and application thereof in organic electroluminescent device | |
| CN114276374A (en) | Boron-containing organic compound as doping material and organic light-emitting device comprising same | |
| CN116396311A (en) | Boron-containing organic compound and organic electroluminescent device prepared from same | |
| CN114621203B (en) | Ketone-containing TADF organic compound and its application | |
| CN114507224B (en) | Ketone-containing organic compound and application thereof | |
| WO2023155913A1 (en) | Boron-containing compound, light-emitting device and display apparatus | |
| CN114456155B (en) | Compound with azabenzene as core and application thereof | |
| CN113121508B (en) | Organic electroluminescent material containing metal platinum and application thereof | |
| CN114805319B (en) | Compound taking triazine derivative as core and organic electroluminescent device comprising same | |
| CN114685465B (en) | Ketone-containing organic compound and organic electroluminescent device comprising same | |
| CN116789685A (en) | Boron-containing organic compound and organic electroluminescent device prepared from same | |
| CN116925114A (en) | Boron-containing organic compound and organic electroluminescent device prepared from same | |
| CN116606309A (en) | Boron-containing organic compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |