CN110835304A - Compound with spirofluorene structure as core, preparation method and application thereof - Google Patents
Compound with spirofluorene structure as core, preparation method and application thereof Download PDFInfo
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- CN110835304A CN110835304A CN201810940410.2A CN201810940410A CN110835304A CN 110835304 A CN110835304 A CN 110835304A CN 201810940410 A CN201810940410 A CN 201810940410A CN 110835304 A CN110835304 A CN 110835304A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 65
- 230000000903 blocking effect Effects 0.000 claims abstract description 19
- 239000002346 layers by function Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000000376 reactant Substances 0.000 claims description 36
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Substances [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000004076 pyridyl group Chemical group 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052705 radium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000005549 heteroarylene group Chemical group 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims 4
- 125000000732 arylene group Chemical group 0.000 claims 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 81
- 238000002347 injection Methods 0.000 abstract description 20
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- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
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- 239000000543 intermediate Substances 0.000 description 78
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- 229940125904 compound 1 Drugs 0.000 description 24
- 239000007858 starting material Substances 0.000 description 23
- 238000010189 synthetic method Methods 0.000 description 21
- 239000002994 raw material Substances 0.000 description 16
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- 230000005525 hole transport Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008204 material by function Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 3
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 235000011056 potassium acetate Nutrition 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZYZCALPXKGUGJI-DDVDASKDSA-M (e,3r,5s)-7-[3-(4-fluorophenyl)-2-phenyl-5-propan-2-ylimidazol-4-yl]-3,5-dihydroxyhept-6-enoate Chemical compound C=1C=C(F)C=CC=1N1C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C(C)C)N=C1C1=CC=CC=C1 ZYZCALPXKGUGJI-DDVDASKDSA-M 0.000 description 1
- 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 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- ZMYKITJYWFYRFJ-UHFFFAOYSA-N 4-oxo-4-(2-phenylethylamino)butanoic acid Chemical compound OC(=O)CCC(=O)NCCC1=CC=CC=C1 ZMYKITJYWFYRFJ-UHFFFAOYSA-N 0.000 description 1
- NJIAKNWTIVDSDA-FQEVSTJZSA-N 7-[4-(1-methylsulfonylpiperidin-4-yl)phenyl]-n-[[(2s)-morpholin-2-yl]methyl]pyrido[3,4-b]pyrazin-5-amine Chemical compound C1CN(S(=O)(=O)C)CCC1C1=CC=C(C=2N=C(NC[C@H]3OCCNC3)C3=NC=CN=C3C=2)C=C1 NJIAKNWTIVDSDA-FQEVSTJZSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- UVNCQVZNWDINJX-FQEVSTJZSA-N N-[3-[(4S)-2-amino-4-methyl-6-propan-2-yl-1,3-thiazin-4-yl]-4-fluorophenyl]-5-methoxypyrazine-2-carboxamide Chemical compound COc1cnc(cn1)C(=O)Nc1ccc(F)c(c1)[C@]1(C)C=C(SC(N)=N1)C(C)C UVNCQVZNWDINJX-FQEVSTJZSA-N 0.000 description 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 1
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- IHCHOVVAJBADAH-UHFFFAOYSA-N n-[2-hydroxy-4-(1h-pyrazol-4-yl)phenyl]-6-methoxy-3,4-dihydro-2h-chromene-3-carboxamide Chemical compound C1C2=CC(OC)=CC=C2OCC1C(=O)NC(C(=C1)O)=CC=C1C=1C=NNC=1 IHCHOVVAJBADAH-UHFFFAOYSA-N 0.000 description 1
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- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical compound COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
The invention discloses a compound taking a spirofluorene structure as a core, a preparation method and application thereof, wherein the structure of the compound is shown as a general formula (1). The compound provided by the invention has stronger hole transmission capability, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the organic light emitting diode is used as a light emitting functional layer material of an OLED light emitting device, the exciton utilization rate and the radiation efficiency can be effectively improved by matching the branched chain in the range of the invention.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound containing spirofluorene, a preparation method thereof and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides a compound with a spirofluorene structure as a core and an application thereof in an organic electroluminescent device. The compound contains a spirofluorene structure, is not easy to crystallize, has good film-forming property, thermal stability and higher glass transition temperature, simultaneously has proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a compound taking a spirofluorene structure as a core is disclosed, and the structure of the compound is shown as a general formula (1):
wherein R is1、R2、R3、R4Each independently represents cyano, halogen, C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or a structure represented by the general formula (2); r1、R2、R3、R4Are the same or different, and R1、R2、R3、R4At least one of them is represented by the general formula (2);
in the general formula (2), the L, L1、L2Each independently represents a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted 5 to 5 containing one or more heteroatomsOne of 30-membered heteroarylene;
the R is5、R6Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, and a structure shown in a general formula (3) or a general formula (4); when R is5When represented by the structure of the general formula (4), L1Is not a single bond; when R is6When represented by the structure of the general formula (4), L2Is not a single bond; when L is1、L2When represents a single bond, R5、R6Is not phenyl at the same time;
in the general formulas (3) and (4), X is1Represented by-O-, -S-, -C (R)7)(R8) -or-Si (R)9)(R10)-；X2、X3Each independently represents a single bond, -O-, -S-, -C (R)7)(R8) -or-Si (R)9)(R10)-；
Z1 represents, identically or differently on each occurrence, a nitrogen atom or C-R11；
At L1Or L2In the case of bonding to Z1, Z1Can only be represented as C;
the R is7～R10Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a 5-to 30-membered heteroaryl group substituted or unsubstituted with one or more heteroatoms; r7And R8、R9And R10Can be connected with each other to form a ring;
the R is11Represented by hydrogen atom, cyano group, halogen, C1-20Alkyl of (C)2-20Alkenyl of (a), substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R12Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from halogen, cyano, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
In a preferred embodiment, the R group1、R2、R3、R4Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a furyl group, or a structure represented by general formula (2);
the L, L1、L2Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group and a substituted or unsubstituted benzothiophenyl group;
the R is7～R10Each independently represents one of methyl, ethyl, propyl, isopropyl, tertiary butyl, amyl, phenyl, naphthyl, biphenyl or pyridyl; r7And R8、R9And R10Can also be connected with each other to form a ring;
the R is12Represented by a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group or a pyridyl group; two or more adjacent R12Can be bonded to each other to form a ring;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group or furyl group.
Preferably, the structure of the compound is shown in any one of general formula (5) to general formula (9):
preferably, the general formula (1) can be represented by the following structure, but is not limited thereto: r occurring in the structure1、R2And R3Is the structure described in the general formula (2);
preferably, the general formula (2) may be represented by, but not limited to, the following structure:
the preferable specific structure of the compound taking the spirofluorene structure as the core is as follows:
A preparation method of a compound taking a spirofluorene structure as a core comprises the following two conditions:
(1) when L in the general formula (2) represents a single bond, the compound represented by the general formula (1) is prepared by the following method:
in the above formula, Ra、Rb、Rc、RdEach independently represents F, Cl, Br or H, and Ra、Rb、Rc、RdAt least one of which is selected from F, Cl or Br; intermediate B is selected from R1-H、R2-H、R3-H or R4-H；
The preparation method comprises the following steps: weighing a reactant A and an intermediate B, and dissolving the reactant A and the intermediate B by using toluene; then adding Pd2(dba)3、P(t-Bu)3T isSodium butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate B is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the reactant A to the reactant A is 0.006-0.02:1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the reactant A is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the reactant A is 1.0-3.0: 1;
the preparation method of the intermediate B comprises the following steps:
in the above reaction, intermediate B represents R1-H、R2-H、R3-H or R4-H；
The specific preparation method of the reaction comprises the following steps: weighing raw materials 1 and 2, dissolving with toluene, and adding Pd2(dba)3、P(t-Bu)3And sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate B; the molar ratio of the raw material 1 to the raw material 2 is 1: 1.2-3.0; pd2(dba)3The molar ratio of the sodium tert-butoxide to the raw material 1 is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the raw material 1 is 1.0-3.0: 1; p (t-Bu)3The molar ratio of the raw material to the raw material 1 is 0.006-0.02: 1;
the reaction mainly utilizes the substitution reaction between the amino compound and the halogen atom, the dosage of each substance is the dosage of one-time substitution reaction, when multiple substitution reactions exist, the structure of the amino compound is changed according to one-time substitution reaction, and the one-time substitution reaction is repeated for multiple times;
(2) when L in the general formula (2) is not a single bond, the compound represented by the general formula (1) is prepared by:
the upper typeIn the above formula, Ra、Rb、Rc、RdEach independently represents F, Cl, Br or H, and Ra、Rb、Rc、RdAt least one of which is selected from F, Cl or Br; intermediate C is selected from
The preparation method comprises the following steps: weighing a reactant A and an intermediate C, and dissolving the reactant A and the intermediate C in a mixed solvent of toluene, ethanol and water in a volume ratio of 2:1: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate C is 1: 1.0-2.0; na in aqueous solution2CO3The molar ratio of the reactant A to the reactant A is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the reactant A to the reactant A is 0.006-0.02: 1;
the preparation method of the intermediate C comprises the following steps:
intermediate C in the above reaction represents
The specific preparation method of the reaction comprises the following steps: weighing the intermediate B and the raw material 3, and dissolving with toluene; then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate X; the molar ratio of the intermediate B to the raw material 3 is 1:1.2-3.0, Pd2(dba)3Molar ratio to intermediate BIs 0.006-0.02:1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the intermediate B is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the intermediate B is 1.0-3.0: 1;
weighing intermediate X, bis (pinacolato) diboron and Pd (dppf) Cl in the atmosphere of nitrogen2Dissolving potassium acetate in toluene, reacting at the temperature of 100-120 ℃ for 12-24 hours, sampling a sample point plate, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate C; the molar ratio of the intermediate X to the bis (pinacolato) diboron is 2:1-1.5, and the intermediate X is in contact with Pd (dppf) Cl2The molar ratio of the intermediate X to the potassium acetate is 1: 2-2.5;
the reaction formula mainly utilizes the coupling reaction between the boric acid compound and the halogen atom, the dosage of each substance is the dosage of one-time coupling reaction, and when multiple coupling reactions exist, the structure of the boric acid compound is changed according to one-time coupling reaction, and the one-time coupling reaction is repeated for multiple times.
At least one functional layer of the organic electroluminescent device contains a compound with a spirofluorene structure as a core.
An organic electroluminescent device is characterized in that an electron blocking layer or a hole transport layer material of the organic electroluminescent device contains a compound with a spirofluorene structure as a core.
A lighting or display element comprising the organic electroluminescent device.
The beneficial effect of above-mentioned scheme is:
the pi conjugated effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the asymmetric triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules and enhance the rigidity of the molecules, thereby improving the thermal stability of the molecules; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons and improves the recombination efficiency of excitons in the light-emitting layer.
After the parent nucleus of the compound is substituted by the branched chain, the distance between molecules is increased, the interaction force between molecules is weakened, and therefore the compound has lower evaporation temperature, and the industrial processing window of the material is widened.
When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, and the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved. The compound has good application effect and industrialization prospect in OLED luminescent devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
FIG. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a comparative device.
In the drawings: 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is hole transport, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is an electron transport or hole blocking layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1: synthesis of intermediate B1:
adding 0.01mol of raw material 1-1, 0.012mol of raw material 2-1, 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10-5mol of Pd2(dba)3，5×10-5mol P(t-Bu)3Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target productAn intermediate B1; HPLC purity 99.37%, yield 73.4%; elemental analysis Structure (molecular formula C)24H19N): theoretical value C, 89.68; h, 5.96; n, 4.36; test values are: c, 89.65; h, 5.99; n, 4.37. ESI-MS (M/z) (M +): theoretical value is 321.42, found 321.58.
Example 2: synthesis of intermediate C1:
adding 0.01mol of intermediate B16, 0.012mol of raw material 3-1, 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10-5mol Pd2(dba)3，5×10-5mol P(t-Bu)3Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate X1;
weighing 0.02mol of intermediate X1, 0.012mol of bis (pinacolato) diboron and 0.0002mol of Pd (dppf) Cl under the atmosphere of nitrogen2Dissolving 0.05mol of potassium acetate in toluene, reacting at the temperature of 100-120 ℃ for 12-24 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate C1; HPLC purity 98.99%, yield 73.5%; elemental analysis Structure (molecular formula C)36H32BNO2): theoretical value C, 82.92; h, 6.19; b, 2.07; n, 2.69; o, 6.14; test values are: c, 82.95; h, 6.16; b, 2.05; n, 2.68; and O, 6.17. ESI-MS (M/z) (M +): theoretical value is 521.47, found 521.62.
The synthesis starting materials for intermediates B and C required in the examples are shown in table 1:
TABLE 1
Example 3: synthesis of Compound 1:
adding 0.01mol of raw material A1, 0.012mol of intermediate B1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10-5molPd2(dba)3，5×10-5mol P(t-Bu)3Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, rotatably evaporating the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product with the HPLC purity of 99.63 percent and the yield of 69.8 percent. Elemental analysis Structure (molecular formula C)50H33N): theoretical value C, 92.70; h, 5.13; n, 2.16; test value C, 92.66; h, 5.22; and N, 2.12. HPLC-MS: the molecular weight of the material is 647.82, and the measured molecular weight is 647.35.
Example 4: synthesis of compound 35:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B2 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)53H37N): theoretical C, 92.54; h, 5.42; n, 2.04; test values are: c, 92.58; h, 5.51; and N, 1.91. HPLC-MS: the molecular weight of the material is 687.89, and the measured molecular weight is 688.02.
Example 5: synthesis of compound 38:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B3 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)53H37N): theoretical C, 92.54; h, 5.42; n, 2.04; test values are: c, 92.56; h, 5.52; n, 1.92. HPLC-MS: the molecular weight of the material is 687.89, and the measured molecular weight is 688.04.
Example 6 Synthesis of Compound 54:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B4 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)56H36N2): theoretical value C, 91.27; h, 4.92; n, 3.80; test values are: c, 91.24; h, 4.92; and N, 3.81. HPLC-MS: the molecular weight of the material is 736.92, and the measured molecular weight is 736.76.
Example 7: synthesis of compound 18:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B5 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)56H37N): theoretical value: c, 92.91; h, 5.15; n, 1.93; test values are: c, 92.89; h, 5.16; and N, 1.95. HPLC-MS: the molecular weight of the material is 723.92, and the measured molecular weight is 723.11.
Example 8: synthesis of compound 13:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B6 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)56H37N): theoretical value: c, 92.91; h, 5.15; n, 1.93; test values are: c, 92.90; h, 5.13; and N, 1.97. HPLC-MS: the molecular weight of the material is 723.92, and the molecular weight is measuredAmount 724.11.
Example 9: synthesis of compound 70:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B7 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)63H41N): theoretical value C, 93.19; h, 5.09; n, 1.72; test values are: c, 93.18; h, 5.11; n, 1.71. HPLC-MS: the molecular weight of the material is 812.03, and the measured molecular weight is 811.85.
Example 10: synthesis of compound 159:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B8 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)57H37NO): theoretical value C, 91.05; h, 4.96; n, 1.86; o, 2.13; test values are: c, 91.08; h, 4.95; n, 1.87; o, 2.10. HPLC-MS: the molecular weight of the material is 751.93, and the measured molecular weight is 751.87.
Example 11: synthesis of compound 200:
prepared according to the synthetic method of compound 1 in example 3, except that starting material a2 is substituted for starting material a1 and intermediate B2 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)61H53N): theoretical value C, 91.57; h, 6.68; n, 1.75; test values are: c, 91.58; h, 6.69; n, 1.73. HPLC-MS: the molecular weight of the material is 800.10, and the measured molecular weight is 799.95.
Example 12: synthesis of compound 196:
prepared according to the synthetic method of compound 1 in example 3, except that starting material a2 is substituted for starting material a1 and intermediate B3 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)61H53N): theoretical value C, 91.57; h, 6.68; n, 1.75; test values are: c, 91.60; h, 6.67; n, 1.73. HPLC-MS: the molecular weight of the material is 800.10, and the measured molecular weight is 800.21.
Example 13: synthesis of compound 175:
prepared according to the synthetic method of compound 1 in example 3, except that starting material A3 is substituted for starting material a1 and intermediate B9 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)60H44N2): a theoretical value; c, 90.87; h, 5.59; n, 3.53; test values are: c, 90.85; 5.60; and N, 3.55. HPLC-MS: the molecular weight of the material is 793.03, and the measured molecular weight is 793.18.
Example 14: synthesis of compound 188:
prepared according to the synthetic method of compound 1 in example 3, except that starting material a4 is substituted for starting material a1 and intermediate B10 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)58H41N3): theoretical value C, 89.31; h, 5.30; n, 5.39; test values are: c, 89.30; h, 5.32; n, 5.38. HPLC-MS: the molecular weight of the material is 779.99, and the measured molecular weight is 779.63.
Example 15: synthesis of Compound 5:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B11 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)50H33N): theoretical value C, 92.70; h, 5.13; n is added to the reaction solution to form a reaction solution,2.16; test values are: c, 92.69; h, 5.16; and N, 2.15. HPLC-MS: the molecular weight of the material is 647.82, and the measured molecular weight is 647.93.
Example 16: synthesis of compound 146:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B12 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)56H41NO2): theoretical value C, 88.51; h, 5.44; n, 1.84; o, 4.21; test values are: c, 88.54; h, 5.45; n, 1.82; and O, 4.19. HPLC-MS: the molecular weight of the material is 759.95, and the measured molecular weight is 759.84.
Example 17: synthesis of compound 181:
prepared according to the synthetic method of compound 1 in example 3, except that starting material A3 is substituted for starting material a1 and intermediate B13 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)52H39N): theoretical value C, 92.13; h, 5.80; n, 2.07; test values are: c, 92.16; h, 5.83; and N, 2.08. HPLC-MS: the molecular weight of the material is 677.89, and the measured molecular weight is 678.03.
Example 18: synthesis of compound 243:
prepared according to the synthetic method of compound 1 in example 3, except that starting material a5 is substituted for starting material a1 and intermediate B14 is substituted for intermediate B1; elemental analysis Structure (molecular formula C)56H36FNO): theoretical value C, 88.18; h, 5.03; n, 1.94; o, 2.22; test values are: c, 88.19; h, 5.02; n, 1.96; o, 2.21. HPLC-MS: the molecular weight of the material is 721.88, and the measured molecular weight is 721.93.
Example 19: synthesis of compound 247:
prepared according to the synthetic method of compound 1 in example 3, except that the starting material a6 is used instead of the starting material a1, and the intermediate B15 is used instead of the intermediate B1; elemental analysis Structure (molecular formula C)51H32N2): theoretical value C, 91.04; h, 4.79; n, 4.16; test values are: c, 91.01; h, 4.81; and N, 4.18. HPLC-MS: the molecular weight of the material is 672.83, and the measured molecular weight is 672.99.
Example 20: synthesis of compound 259:
prepared according to the synthetic method of compound 1 in example 3, except that the starting material A3 is used instead of the starting material a1, and the intermediate B16 is used instead of the intermediate B1; elemental analysis Structure (molecular formula C)60H49N): theoretical value C, 91.91; h, 6.30; n, 1.79; test values are: c, 91.89; h, 6.29; n, 1.82. HPLC-MS: the molecular weight of the material is 784.06, and the measured molecular weight is 784.18.
Example 21: synthesis of compound 225:
prepared according to the synthetic method of compound 1 in example 3, except that the starting material a7 is used instead of the starting material a1, and the intermediate B17 is used instead of the intermediate B1; elemental analysis Structure (molecular formula C)64H53N): theoretical value C, 91.94; h, 6.39; n, 1.68; test values are: c, 91.95; h, 6.40; n, 1.66. HPLC-MS: the molecular weight of the material is 836.13, and the measured molecular weight is 836.02.
Example 22: synthesis of compound 215:
synthesis of Compound 1 as in example 3The preparation is different in that the raw material A8 is used for replacing the raw material A1, and the intermediate B2 is used for replacing the intermediate B1; elemental analysis Structure (molecular formula C)53H37N): theoretical C, 92.54; h, 5.42; n, 2.04; test values are: c, 92.57; h, 5.40; and N, 2.03. HPLC-MS: the molecular weight of the material is 687.89, and the measured molecular weight is 688.05.
Example 23: synthesis of compound 127:
prepared according to the synthetic method for compound 1 in example 3, except that intermediate B19 is used instead of intermediate B1; elemental analysis Structure (molecular formula C)59H40N2O): theoretical value C, 89.37; h, 5.08; n, 3.53; o, 2.02; test values are: c, 89.36; h, 5.10; n, 3.51; and O, 2.03. HPLC-MS: the molecular weight of the material is 792.98, and the measured molecular weight is 792.91.
Example 24: synthesis of compound 261:
adding 0.01mol of raw material A8 and 0.015mol of intermediate C1 into a 250ml three-necked bottle, and dissolving the mixture by using a mixed solvent of toluene and ethanol with the volume ratio of 2: 1; under inert atmosphere, 0.02mol of Na is added2CO3Aqueous solution (2M), 0.0001molPd (PPh)3)4(ii) a And (3) reacting the mixed solution of the reactants for 24 hours at the reaction temperature of 100 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain the target product with the HPLC purity of 99.27% and the yield of 73.6%. Elemental analysis Structure (molecular formula C)62H45N): theoretical value: c, 92.62; h, 5.64; n, 1.74; test value C, 92.63; h, 5.62; n, 1.75. HPLC-MS: the molecular weight of the material is 804.05, and the measured molecular weight is 804.22.
Example 25: synthesis of compound 222:
adding 0.01mol of intermediate A1 and 0.015mol of intermediate C2 into a 250ml three-necked bottle, and dissolving the mixture by using a mixed solvent of toluene and ethanol with the volume ratio of 2: 1; under inert atmosphere, 0.02mol of Na is added2CO3Aqueous solution (2M), 0.0001mol Pd (PPh)3)4(ii) a And (3) reacting the mixed solution of the reactants for 24 hours at the reaction temperature of 100 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain the target product with the HPLC purity of 99.16% and the yield of 64.2%. Elemental analysis Structure (molecular formula C)56H35NO): theoretical value: c, 91.15; h, 4.78; n, 1.90; o, 2.17; test value C, 91.16; h, 4.79; n, 1.89; o, 2.16. HPLC-MS: the molecular weight of the material is 737.90, and the measured molecular weight is 737.85.
Example 26: synthesis of compound 217:
prepared according to the synthetic method of compound 1 in example 3, except that the starting material A8 is used instead of the starting material a1, and the intermediate B20 is used instead of the intermediate B1; elemental analysis Structure (molecular formula C)56H37N): theoretical value C, 92.91; h, 5.15; n, 1.93; test values are: c, 92.90; h, 5.14; and N, 1.95. HPLC-MS: the molecular weight of the material is 723.92, and the measured molecular weight is 724.03.
Example 27: synthesis of compound 209:
prepared according to the synthetic method of compound 1 in example 3, except that the starting material a9 was used in place of the starting material a 1; elemental analysis Structure (molecular formula C)58H49N): theoretical value C, 91.66; h, 6.50; n, 1.84; test values are: c, 91.64; h, 6.53; n, 1.83. HPLC-MS: the molecular weight of the material is 760.04, and the measured molecular weight is 759.81.
The compound of the invention is used in a luminescent device, can be used as an electron blocking layer material, and can also be used as a hole transport layer material. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 2:
TABLE 2
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); the highest occupied molecular orbital HOMO energy level was tested by a photoelectron emission spectrometer (AC-2 type PESA) in an atmospheric environment.
The data in the table show that the organic compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the high T1 energy level can block the energy loss of the light-emitting layer, thereby improving the light-emitting efficiency of the device; the appropriate HOMO energy level can solve the problem of carrier injection and can reduce the voltage of the device. Therefore, after the organic compound containing the spirofluorene is used for different functional layers of an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
The application effect of the synthesized OLED material of the present invention in the device is detailed by device examples 1-25 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 25 and the device comparative example 1 of the present invention have the same device manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the hole transport layer material or the electron blocking layer material in the device is replaced. The compositions of the layers of the devices obtained in the examples are shown in table 3.
Device example 1
As shown in fig. 1, an organic electroluminescent device is prepared by the steps of: a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport material compound 1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material compound is 60nm, and the hole transport layer is a hole transport layer 4; d) evaporating an electron blocking material EB-1 on the hole transmission layer 4 in a vacuum evaporation mode, wherein the thickness of the electron blocking material EB-1 is 20nm, and the electron blocking layer 5 is formed on the hole transmission layer; e) a light-emitting layer 6 is evaporated on the electron blocking layer 5, the host material is a compound GH-2 and a compound GH-1, the doping material is GD-1, the mass ratio of the compounds GH-2, GH-1 and GD-1 is 45:45:10, and the thickness is 30 nm; f) evaporating electron transport materials ET-1 and Liq on the light emitting layer 6 in a vacuum evaporation mode, wherein the mass ratio of ET-1 to Liq is 1:1, the thickness is 40nm, and the organic material of the layer is used as a hole blocking/electron transport layer 7; g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8; h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9; after the electroluminescent device was fabricated according to the above procedure, the lifetime and current efficiency of the device were measured, and the results are shown in table 4. The molecular mechanism formula of the related material is as follows:
TABLE 3
TABLE 4
From the results in table 4, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the efficiency and lifetime of the organic compound are greatly improved compared with those of the known OLED materials, especially the lifetime of the organic compound is greatly prolonged.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 3, 11 and 24 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 5 and the figure 2.
TABLE 5
As can be seen from the data in table 5 and fig. 2, device examples 3, 11 and 24 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased in the temperature increasing process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A compound with a spirofluorene structure as a core is characterized in that the structure of the compound is shown as a general formula (1):
wherein，R1、R2、R3、R4Each independently represents a hydrogen atom, a cyano group, a halogen atom, C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms, or a structure represented by the general formula (2); r1、R2、R3、R4Are the same or different, and R1、R2、R3、R4At least one of them is represented by the general formula (2);
in the general formula (2), the L, L1、L2Each independently represents a single bond, substituted or unsubstituted C6-30One of arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
the R is5、R6Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, and a structure shown in a general formula (3) or a general formula (4); when R is5When represented by the structure of the general formula (4), L1Is not a single bond; when R is6When represented by the structure of the general formula (4), L2Is not a single bond; when L is1、L2When represents a single bond, R5、R6Is not phenyl at the same time;
in the general formulas (3) and (4), X is1Represented by-O-, -S-, -C (R)7)(R8) -or-Si (R)9)(R10)-；X2、X3Each independently represents a single bond, -O-, -S-, -C (R)7)(R8) -or-Si (R)9)(R10)-；
Z1 is represented, identically or differently on each occurrence, as a nitrogen atom or C-R11；
At L1Or L2In the case of bonding to Z1, Z1Can only be represented as C;
the R is7～R10Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r7And R8、R9And R10Can be connected with each other to form a ring;
the R is11Represented by hydrogen atom, cyano group, halogen, C1-20Alkyl of (C)2-20Alkenyl of (a), substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R12Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from halogen, cyano, C1-20Alkyl of (C)6-30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. A compound of claim 1, wherein R is1、R2、R3、R4Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a furyl group, or a structure represented by general formula (2);
the L, L1、L2Each independently represents one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group and a substituted or unsubstituted benzothiophenyl group;
the R is7～R10Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl or pyridyl; r7And R8、R9And R10Can also be connected with each other to form a ring;
the R is11Represented by a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group or a pyridyl group; two or more adjacent R11Can be bonded to each other to form a ring;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, phenyl group, naphthyl group, biphenyl group, pyridyl group or furyl group.
3. The compound of claim 1, wherein the compound has a structure represented by any one of general formula (5) to general formula (9):
4. a compound according to any one of claims 1 to 3, of the specific structure:
5. A process for the preparation of a compound according to any one of claims 1 to 4, characterized in that it comprises the following two cases:
(1) when L in the general formula (2) represents a single bond, the compound represented by the general formula (1) is prepared by the following method:
in the above formula, Ra、Rb、Rc、RdEach independently represents H, Cl, Br or I, and Ra、Rb、Rc、RdAt least one of them is represented by Cl, Br or I; intermediate B is selected from R1-H、R2-H、R3-H or R4-H；
The preparation method comprises the following steps: weighing a reactant A and an intermediate B, and dissolving the reactant A and the intermediate B by using toluene; then adding Pd2(dba)3、P(t-Bu)3Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate B is 1:1.2-3.0, and Pd2(dba)3The molar ratio of the reactant A to the reactant A is 0.006-0.02:1, P (t-Bu)3The molar ratio of the sodium tert-butoxide to the reactant A is 0.006-0.02:1, and the molar ratio of the sodium tert-butoxide to the reactant A is 1.0-3.0: 1;
(2) when L in the general formula (2) is not a single bond, the compound represented by the general formula (1) is prepared by:
in the above formula, Ra、Rb、Rc、RdEach independently is H, Cl, Br or I, and Ra、Rb、Rc、RdAt least one of them is represented by Cl, Br or I; intermediate C is selected from
The preparation method comprises the following steps: weighing a reactant A and an intermediate C, and dissolving the reactant A and the intermediate C in a mixed solvent of toluene, ethanol and water in a volume ratio of 2:1: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a product D; the molar ratio of the reactant A to the intermediate C is 1: 1.0-2.0; na in aqueous solution2CO3The molar ratio of the reactant A to the reactant A is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the reactant A to the reactant A is 0.006-0.02: 1.
6. An organic electroluminescent device comprising at least one functional layer, wherein at least one functional layer of the organic electroluminescent device comprises the spirofluorene structure-based compound according to any one of claims 1 to 4.
7. An organic electroluminescent device comprising an electron blocking layer or a hole transporting layer, wherein the electron blocking layer or the hole transporting layer of the organic electroluminescent device contains the spirofluorene structure-based compound according to any one of claims 1 to 4.
8. A lighting or display element comprising the organic electroluminescent device according to any one of claims 6 to 7.
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|---|---|---|---|---|
| CN112552275A (en) * | 2020-04-30 | 2021-03-26 | 上海钥熠电子科技有限公司 | Spiro compound and application thereof |
| WO2021059086A1 (en) * | 2019-09-27 | 2021-04-01 | 株式会社半導体エネルギー研究所 | Organic compound, optical device, light emitting device, light emitting apparatus, electronic device, and lighting device |
| CN113816862A (en) * | 2020-06-19 | 2021-12-21 | 广州华睿光电材料有限公司 | Aromatic amine compound, mixture, composition and organic electronic device |
| CN116057039A (en) * | 2020-10-14 | 2023-05-02 | 株式会社Lg化学 | Compound and organic light emitting device comprising the same |
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| WO2012128509A2 (en) * | 2011-03-21 | 2012-09-27 | 덕산하이메탈(주) | Compound and organic electric element using same, and electronic device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012128509A2 (en) * | 2011-03-21 | 2012-09-27 | 덕산하이메탈(주) | Compound and organic electric element using same, and electronic device thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021059086A1 (en) * | 2019-09-27 | 2021-04-01 | 株式会社半導体エネルギー研究所 | Organic compound, optical device, light emitting device, light emitting apparatus, electronic device, and lighting device |
| CN112552275A (en) * | 2020-04-30 | 2021-03-26 | 上海钥熠电子科技有限公司 | Spiro compound and application thereof |
| CN112552275B (en) * | 2020-04-30 | 2022-11-01 | 上海钥熠电子科技有限公司 | Spiro compound and application thereof |
| CN113816862A (en) * | 2020-06-19 | 2021-12-21 | 广州华睿光电材料有限公司 | Aromatic amine compound, mixture, composition and organic electronic device |
| CN116057039A (en) * | 2020-10-14 | 2023-05-02 | 株式会社Lg化学 | Compound and organic light emitting device comprising the same |
| CN116057039B (en) * | 2020-10-14 | 2024-04-23 | 株式会社Lg化学 | Compound and organic light emitting device comprising the same |
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