CN103408484A - Tetra-alkyl periflanthene derivatives and applications thereof - Google Patents
Tetra-alkyl periflanthene derivatives and applications thereof Download PDFInfo
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- CN103408484A CN103408484A CN2013103081379A CN201310308137A CN103408484A CN 103408484 A CN103408484 A CN 103408484A CN 2013103081379 A CN2013103081379 A CN 2013103081379A CN 201310308137 A CN201310308137 A CN 201310308137A CN 103408484 A CN103408484 A CN 103408484A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 102
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 23
- 238000005401 electroluminescence Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims description 59
- 230000005540 biological transmission Effects 0.000 claims description 38
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
- 238000007738 vacuum evaporation Methods 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- SIFHTIHFPPIGBL-UHFFFAOYSA-N ctk2i0750 Chemical class C12=C3C4=CC=CC3=CC=C2C=CC=C1C1=C4CC2=CC=CC=C21 SIFHTIHFPPIGBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 45
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 56
- 238000004128 high performance liquid chromatography Methods 0.000 description 44
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- 239000000843 powder Substances 0.000 description 37
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- 239000000047 product Substances 0.000 description 30
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- 230000009286 beneficial effect Effects 0.000 description 6
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- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 2
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- Electroluminescent Light Sources (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides tetra-alkyl periflanthene derivatives and applications thereof in the technical filed of organic electroluminescence. The novel compounds provided by the invention have stable properties, simple preparation technology and a high current carrier migration rate, and can be used as electron transfer layers of OLED devices. The devices using the compounds have reduced driving voltage and enhanced current efficiency. The general structure formula of the compounds is shown as below.
Description
Technical field
The present invention relates to a kind of new [1,1,1', 1'] tetraalkyl two indenos [3,2-b; 3', 2'-i] derivative of pyrene, and the application of this material in electron transport material, organic electroluminescence device.
Background technology
The origin of organic electroluminescence device (OLED) can be traced back to nineteen sixties, the people such as Pope make it luminous with the anthracene single crystal impressed DC voltage, but because of driving voltage high (100V) and luminosity and efficiency all lower, do not cause too many attention.Along with technology is updated. the people such as C.W.Tang of Kodak company in 1987 with oxine aluminium (AIq
3) be luminescent material, adopt the method for vacuum evaporation to make double layer sandwich structure OLED device, opening bright voltage only has several volts, and brightness reaches as high as 1000cd/m
2, sign OLED has stepped an important step towards practical, becomes an important milestone in organic electroluminescent field.
Electron transfer layer is requisite integral part in organic electroluminescence device, as a rule, electron transport material all has the plane aromatics of large conjugated structure, they have electron acceptability preferably mostly, under certain forward bias, can effectively transmit again simultaneously electronics (electroluminescent organic material and device introduction, Huang Chunhui, Li Fuyou, yellow dimension, 143).Available electron transport material mainly contains oxine aluminium compounds, furodiazole compound, glyoxaline compound at present, the oxazole compounds, triazole class compounds, nitrogenous hexa-member heterocycle class, perfluorination electron-like transport material, silicone based electron transport material etc.
Design an electron transport material that organic electroluminescence device efficiency is significantly promoted, need possess following character: have reversible electrochemical reduction and higher reduction potential; Need to there be suitable HOMO and LUMO to make electronics that minimum injection energy gap be arranged, to reduce the initial sum operating voltage; Higher electron mobility need to be arranged; The glass transition temp had and thermostability; Has noncrystalline film.(organic electroluminescent and element, Chen Jinxin, Huang Xiaowen work, 52 pages).
Compound of fluorene class is the important OLED device material of a class, and the fused ring compound pyrene is because the reason of large planar conjugate has the good photoelectric characteristics such as high-luminous-efficiency and high carrier mobility.In research process, we have prepared the class fluorene compound of a series of two indeno pyrenes, and this material has had the advantage of fused ring compound pyrene and compound of fluorene class concurrently, has the characteristics of high electron mobility and high thermal stability, be convenient to the transmission of electronics, thereby be applicable to the electron transfer layer in the OLED device.At present, this series compound, there is no the pertinent literature report both at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of new [1,1,1', 1'] tetraalkyl two indenos [3,2-b; 3', 2'-i] derivative of pyrene, and in the application of electron transport material and organic electroluminescence device.
Two indenos [3,2-b; 3', 2'-i] thus the derivative of pyrene has large conjugate planes structure can provide high electronics mobility, and pyridine groups has lower reduction potential, is beneficial to the reception electronics, by pyridine groups be incorporated into two indenos [3,2-b; 3', 2'-i] both sides of pyrene, can improve the charge transporting ability of this compounds, make it have good electronic transmission performance.And adding of both sides aromatic yl group can reduce the coplanarity of this compounds, thereby improve its film-forming properties.In addition, the symmetry of molecular structure can increase the regularity of molecular stacks, can improve the compound carrier mobility.Therefore this compound has higher electronic transmission performance, and good film-forming property, at room temperature have stability preferably, and applied device also has higher stability.
The invention provides a kind of new [1,1,1', 1'] tetraalkyl two indenos [3,2-b; 3', 2'-i] derivative of pyrene, have following general formula:
Wherein R is that carbon number is the alkyl of 1-8; R
1For the pyrimidyl of pyrimidyl, dipyridyl, phenyl substituted, the pyrimidyl of xenyl replacement or the pyrimidyl of naphthyl substituted.
Preferably, R is butyl, isobutyl-, n-pentyl, n-hexyl, heptyl or octyl group.
When R was above-mentioned substituting group, compound was easier to prepare, and cost is lower, and compound molecule has carrier mobility preferably, demonstrated electronic transmission performance preferably.
Preferably, R is ethyl, propyl group or sec.-propyl.
When R was ethyl, propyl group or sec.-propyl, compound easily prepared, and cost is lower, and compound molecule has carrier mobility preferably, demonstrates electronic transmission performance preferably.
Preferably, R is methyl.
When R was methyl, compound more easily prepared, and cost is lower, and compound molecule has carrier mobility preferably, demonstrated electronic transmission performance preferably.
Preferably, R
1Structural formula be a kind of in following formula:
When substituting group was the said structure formula, compound provided by the invention had carrier mobility preferably, demonstrated electronic transmission performance preferably.
Preferably, R
1Structural formula be a kind of in following formula:
Work as R
1During for the said structure formula, the carrier mobility of compound provided by the invention obviously promotes, and electronic transmission performance is significantly improved.
Preferred R is methyl, R
1Structural formula is following formula
Now, compound provided by the invention easily obtains and has a relatively outstanding electronic transmission performance.
The invention provides the midbody compound of the described compound of preparation, its structural formula is as follows:
The present invention also provides a kind of organic electroluminescence device, comprise the anode layer and the cathode layer that form pair of electrodes, and the luminescent layer arranged in electrode, and according to optional principle, hole injection layer also is set in electrode, hole transmission layer, electron transfer layer and/or electron injecting layer, wherein each layer is according to anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the order of cathode layer is arranged, mode with plating between adjacent layers connects, form rhythmo structure, it is characterized in that, the material of main part of described luminescent layer is selected from compound provided by the present invention.
As previously mentioned, compound provided by the invention has higher electronic transmission performance, good film-forming property, at room temperature has stability preferably, therefore can reduce driving voltage, easily the feature of film forming makes manufacturing cost lower, and at room temperature stability makes the device more stable work preferably, and practical life is longer.
Preferably, described organic electroluminescence device, the mode of plating is vacuum evaporation.
Adopt vacuum evaporation, during by material film, easily obtain uniform rete, and be difficult for generating pin hole.
Preferably, described organic electroluminescence device also comprises the base version, and anode layer is attached on the base version.
The application of base version makes more easy-formation of device.
The present invention also provides a kind of organic electroluminescence device, comprise the anode layer and the cathode layer that form pair of electrodes, and the luminescent layer arranged in electrode and electron transfer layer, and according to optional principle, hole injection layer also is set in electrode, hole transmission layer and/or electron injecting layer, wherein each layer is according to anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the order of cathode layer is arranged, mode with plating between adjacent layers connects, form rhythmo structure, it is characterized in that, the material of described electron transfer layer is selected from compound provided by the present invention.
As previously mentioned, compound provided by the invention has higher electronic transmission performance, good film-forming property, at room temperature has stability preferably, and easily the feature of film forming makes manufacturing cost lower, and at room temperature stability makes the device more stable work preferably, and practical life is longer.In addition, due to its higher electronic transmission performance, make as electron transport material, can obviously reduce driving voltage, have high carrier mobility, improved current efficiency.
Preferably, described organic electroluminescence device, the mode of plating is vacuum evaporation.
Adopt vacuum evaporation, during by material film, easily obtain uniform rete, and be difficult for generating pin hole.
Preferably, described organic electroluminescence device also comprises the base version, and anode layer is attached on the base version.
The application of base version makes more easy-formation of device.
The accompanying drawing explanation
Fig. 1 is the structural representation of a kind of simpler organic electroluminescence device provided by the invention.
Fig. 2 is the structural representation of a kind of organic electroluminescence device provided by the invention.
Embodiment
For clearer explanation content of the present invention, below in conjunction with the involved particular compound of technical solution of the present invention, by embodiment, set forth of the present invention.It should be noted that embodiment is for explaining but not limiting the present invention.
Enforceable particular compound is numerous, the mutual-through type compound, and the R of take is methyl, R
1Following compound during for the substituting group described in technical scheme of the present invention is example:
For ease of quoting, under the structural formula of above-mentioned each compound, use numeric suffix, and corresponding with compound difference in Preparation Example, for example, compound 1-1 in the corresponding Preparation Example one of structural formula 1-1, the compound 1-2 in the corresponding Preparation Example two of structural formula 1-2, remaining is by that analogy.
Used 1 in the present invention, 6-dibromo pyrene, adjacent bromo-iodobenzene, n-Butyl Lithium, the compounds such as boric acid ester Chemical market at home can have been bought.Phenylo boric acid, the 1-naphthalene boronic acids, the 2-naphthalene boronic acids, biphenyl boric acid, 2-pyridine boric acid, the pyridine boric acid of 3-pyridine boric acid or replacement adopt common methodology of organic synthesis synthetic.
Embodiment
The preparation of target compound, by 1,6-dibromo pyrene process linked reaction, grignard reaction, cyclization, bromo, linked reaction prepares target molecule.
Preparation Example
Preparation Example one
Compound 1-1's is synthetic, for succinct brief, has wherein comprised the midbody compound with the 1-1-F representative
In above each structural formula, Br is bromine, and B is boron, and O is oxygen, and H is hydrogen, and Mg is magnesium, and N is nitrogen, all adopts the unified representation in the periodic table of elements.
For ease of quoting, in said synthesis route figure, adopted the numeral of 1-1-A, 1-1-B to 1-1-F to add alphabetical subscript under partial structural formula, and corresponded respectively to compound 1-1-A, compound 1-1-B in following embodiment to compound 1-1-F.For example, the compound 1-1-A in the preparation of the corresponding compound 1-1-A of structural formula 1-1-A, the compound 1-1-B in the preparation of the corresponding compound 1-1-B of structural formula 1-1-B, all the other are by that analogy.
The preparation of compound 1-1-A
By 36.0g(0.1mol) 1, 6-dibromo pyrene is dissolved in the 720g tetrahydrofuran (THF), be put in the low temperature bath and lower the temperature, interior temperature drop is to-85 ℃ the time, start to drip 100mL n-Butyl Lithium (hexane solution of 2.2mol/L), in during dropping, controlling, temperature is less than-78 ℃, after dripping fully, after insulation reaction 1h, rise to-45 ℃ and continue reaction 1h, cooling is below-78 ℃ again, start to drip the 51.6g trimethyl borate, controlling rate of addition makes interior temperature be no more than-70 ℃, after insulation reaction 2h, move into room temperature reaction, to the HCl that adds 2M in system, room temperature reaction 2h, revolve to steam and remove THF, suction filtration, after filter cake is washed till neutrality, according to the ratio of 3g toluene/1g crude product at 60 ℃ of making beating 0.5h, suction filtration while being cooled to 10 ℃, obtain 11.6g1-1-A, product appearance is white powder, yield is 40%, GC>99%.
The preparation of compound 1-1-B
Take successively 28.9g(0.1mol) compound 1-1-A, 59.4g adjacent bromo-iodobenzene (0.21mol), the THF of 360g (5mol), then add 150mL wet chemical (concentration is 2mol/L), after logical nitrogen 20min, add 1.16g(0.001mol in system) Pd (PPh
3)
4, under 60 ℃, reacting 2h, TLC detection compound 1-1-A reacts completely, the fully rear desolvation of question response, suction filtration, filter cake with the THF of 20 times complete molten after, column chromatography, after removing chromatographic solution, obtain 38.4g compound 1-1-B, product appearance is yellow powder, and yield is 75%, HPLC:98.5%.
The preparation of compound 1-1-D
In there-necked flask, add successively 2.4g(0.1mol) magnesium chips and 2 iodine, simultaneously by 25.6g(0.05mol) 1-1-B is dissolved in 140g THF, to dripping the THF solution (not having magnesium chips to be advisable) of a small amount of 1-1-B in there-necked flask, if bathing temperature is 65 ℃, after question response causes, slowly drip the THF solution of 1-1-B, about 1h drips fully, system now becomes brown muddiness, insulation reaction 2h, when the bath temperature is 15 ℃, slowly to the THF mixing solutions (5.8g acetone is dissolved in 30g THF) that drips acetone in Grignard reagent, about 1h drips fully, system is by the brown yellow that becomes, insulation reaction 5h, the TLC detection reaction is complete, to the hydrochloric acid that adds 200mL10% in system, after stirring at room 3h, static layering, 300mL ethyl acetate extraction three times of lower floor's water, merge organic phase, add the 30g anhydrous sodium sulfate drying, column chromatography, obtain 1-1-D crude product 24.6g, not purifiedly be directly used in next step.
The preparation of compound 1-1-E
The 1-1-D crude product 24.6g prepared is moved in the 500mL there-necked flask, add 200g acetic acid, after system refluxes, in system, add the 2.1g concentrated hydrochloric acid, continue back flow reaction 3h, the TLC detection reaction is complete, stopped heating, cooling naturally, when interior temperature is 80 ℃, system has yellow solid to separate out, when interior temperature is 15 ℃, and suction filtration, filter cake is pale yellow powder, crude product weight is 18.7g, and yield is that 86.2%, HPLC is 96%.Crude product by the 1-1-E that obtains, add 180g methyl alcohol, and establishing and bathing temperature is 50 ℃, and after making beating 30min, suction filtration, filter cake are pale yellow powder, and weight is 15.6g, and refining yield is that 83%, HPLC is 99.6%.
1H NMR (CDCl
3, TMS, 500MHz): δ=8.06 (dd, J
1=7.6, J
2=1.2,2H), 7.11-7.86 (m, 20H), 1.66 (s, 12H); Molecular formula C34H26; High resolution mass spectrum, theoretical value 434.2035, test value [M+1] 435.2107.
The preparation of midbody compound 1-1-F
In the 500mL there-necked flask, add 8.6g(0.02mol successively) 1-1-E, 0.1g aluminum trichloride (anhydrous), the 200mL tetracol phenixin, under room temperature, slowly drip the carbon tetrachloride solution (6.56g (0.041mol) bromine is dissolved in the 30mL tetracol phenixin) of bromine in there-necked flask, about 2h drips fully, reaction soln becomes orange, the system that is warming up to refluxes, after back flow reaction 3h, the TLC detection reaction is complete, reaction solution is washed three times with 3 * 200mL, the anhydrous sodium sulfate drying organic phase, revolve the steaming desolventizing, obtain 10.8g incarnadine powder, HPLC:95.6%, the crude product yield is 91.5%, high resolution mass spectrum is theoretical value 592.0224, test value [M+1] 593.0303.
The preparation of compound 1-1
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 2.71g(0.022mol) 3-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 2h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 4.12g, HPLC:97.9%, yield are 70%.
The distillation of compound 1-1
Take 4g compound 1-1 crude product, in the vacuum-sublimation instrument, the distillation parameter is 2 * 10 for distillation vacuum tightness
-5Pa, distillation three district's temperature are 260 ℃, and distillation two district's temperature are 160 ℃, and distillation one district's temperature is 100 ℃, established temperature is gradient increased temperature, and every 15min raises 50 ℃, after being increased to target temperature, and insulation distillation 5h, distillation obtains elaboration 3.6g altogether, HPLC:99.5%, and the distillation yield is 90%.
1H NMR (DMSO, TMS, 500MHz): δ=8.78(s, 2H), 8.53 (d, J=7.6,2H), 7.12-8.16 (m, 16H), 1.68 (s, 12H); High resolution mass spectrum, theoretical value 588.2565, test value [M+1] 589.2636.
Preparation Example two
Compound 1-2's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 2.71g(0.022mol) 2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 5h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 4.41g, HPLC:97.6%, yield are 75%.
By above solid 4.0g in 290 ℃/2 * 10
-5The Pa 5h that distils, obtain 3.3g glassy yellow powder, HPLC:99.4%,
1H NMR (DMSO, TMS, 500MHz): δ=8.50(d, J=7.6,2H), 8.33 (s, 2H), 7.12-8.16 (m, 16H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 588.2565, test value [M+1] 588.2642.
Preparation Example three
Compound 1-3's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 4.4g(0.022mol) the 2-(2-pyridyl)-6-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 4h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 5.05g, HPLC:97.3%, yield are 68%.
By above solid 5.0g in 310 ℃/2 * 10
-5The Pa 5h that distils, obtain the 3.8g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=7.20-8.52 (m, 26H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 742.9063, test value [M+1] 743.3166.
Preparation Example four
Compound 1-4's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 4.38g(0.022mol) 6-phenyl-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 4h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 5.33g, HPLC:97.3%, yield are 72%.
By above solid 5.0g in 290 ℃/2 * 10
-5The Pa 5h that distils, obtain the 3.8g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=8.48 (s, 2H), 7.31-8.22 (m, 26H), 1.69 (s, 12H); High resolution mass spectrum, theoretical value 740.3191, test value [M+1] 741.3266.
Preparation Example five
Compound 1-5's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 4.38g(0.022mol) 4-phenyl-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 5h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 5.11g, HPLC:98.1%, yield are 69%.
By above solid 5.0g in 310 ℃/2 * 10
-5The Pa 5h that distils, obtain the 3.8g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=8.71 (d, J=7.3,2H), 8.42 (s, 2H), 7.16-8.25 (m, 24H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 740.3191, test value [M+1] 741.3259.
Preparation Example six
Compound 1-6's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 6.06g(0.022mol) the 6-(4-xenyl)-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 3h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 5.80g, HPLC:97.6%, yield are 65%.
By above solid 5.0g in 320 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.2g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=8.42 (s, 2H), 7.16-8.31 (m, 34H), 1.66 (s, 12H); High resolution mass spectrum, theoretical value 892.3817, test value [M+1] 893.3886.
Preparation Example seven
Compound 1-7's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 6.06g(0.022mol) the 4-(4-xenyl)-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 6h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.86g, HPLC:98.2%, yield are 77%.
By above solid 5.0g in 340 ℃/2 * 10
-5The Pa 5h that distils, obtain the 3.8g pale yellow powder, HPLC:99.5%,
1H NMR (DMSO, TMS, 500MHz): δ=8.73 (d, J=7.8,2H), 8.40 (s, 2H), 7.16-8.31 (m, 32H), 1.68 (s, 12H); High resolution mass spectrum, theoretical value 892.3817, test value [M+1] 893.3892.
Preparation Example eight
Compound 1-8's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 6.06g(0.022mol) the 6-(3-xenyl)-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 3h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.56g, HPLC:97.6%, yield are 74%.
By above solid 5.0g in 320 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.2g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=8.38 (s, 2H), 7.16-8.26 (m, 34H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 892.3817, test value [M+1] 893.3889.
Preparation Example nine
Compound 1-9's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 6.06g(0.022mol) the 4-(3-xenyl)-2-pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 3h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.28g, HPLC:97.6%, yield are 70%.
By above solid 5.0g in 320 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.2g pale yellow powder, HPLC:99.2%,
1H NMR (DMSO, TMS, 500MHz): δ=8.68 (d, J=7.2,2H), 8.36 (s, 2H), 7.18-8.21 (m, 32H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 892.3817, test value 893.3896.
Preparation Example ten
Compound 1-10's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 5.48g(0.022mol) the 6-(1-naphthyl)-2 pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 6h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.26g, HPLC:97.6%, yield are 75%.
By above solid 5.0g in 330 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.2g pale yellow powder, HPLC:99.5%,
1H NMR (DMSO, TMS, 500MHz): δ=8.46 (s, 2H), 7.12-8.26 (m, 30H), 1.70 (s, 12H); High resolution mass spectrum, theoretical value 840.3504, test value [M+1] 841.3576.
Preparation Example 11
Compound 1-11's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 5.48g(0.022mol) the 4-(1-naphthyl)-2 pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 3h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.56g, HPLC:97.8%, yield are 78%.
By above solid 5.0g in 330 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.1g pale yellow powder, HPLC:99.6%,
1H NMR (DMSO, TMS, 500MHz): δ=8.71 (d, J=7.2,2H), 8.39 (s, 2H), 7.22-8.26 (m, 28H), 1.66 (s, 12H); High resolution mass spectrum, theoretical value 840.3504, test value [M+1] 841.3569.
Preparation Example 12
Compound 1-12's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 5.48g(0.022mol) the 6-(2-naphthyl)-2 pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 5h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 5.96g, HPLC:98.2%, yield are 71%.
By above solid 5.0g in 310 ℃/2 * 10
-5The Pa 5h that distils, obtain the 4.5g pale yellow powder, HPLC:99.4%,
1H NMR (DMSO, TMS, 500MHz): δ=7.18-8.42 (m, 32H), 1.68 (s, 12H); High resolution mass spectrum, theoretical value 840.3504, test value [M+1] 841.3576.
Preparation Example 13
Compound 1-13's is synthetic
In the 500mL there-necked flask, add 5.9g (0.01mol) 1-1-F successively, 5.48g(0.022mol) the 4-(2-naphthyl)-2 pyridine boric acid, 100g toluene, 0.06mol2M/L wet chemical, nitrogen flow rate is 50mL/min, after stirring at room 20min, add 578mg(0.0005mol in system) Pd (PPh
3)
4, establishing and bathing temperature is 85 ℃, starts reacting by heating, after reaction 6h, the TLC detection reaction is complete, separatory, with 100mL ethyl acetate washing water, merge organic phase, and column chromatography is removed catalyzer, revolve the steaming chromatographic solution, obtain pale yellow powder 6.16g, HPLC:97.9%, yield are 74%.
By above solid 4.0g in 330 ℃/2 * 10
-5The Pa 5h that distils, obtain the 3.8g pale yellow powder, HPLC:99.6%,
1H NMR (DMSO, TMS, 500MHz): δ=8.65 (d, J=7.5,2H), 8.36 (s, 2H), 7.16-8.22 (m, 28H), 1.68 (s, 12H); High resolution mass spectrum, theoretical value 840.3504, test value [M+1] 841.3575.
The device embodiment
Below in conjunction with accompanying drawing 2 narrations.Electroluminescent device has a kind of structure, and this structure contains at least one luminescent layer 5, according to optional principle, hole injection layer 3, hole transmission layer 4, electron transfer layer 6 and/or electron injecting layer 7 is set in this layer.Described optional principle is: from hole injection layer 3, hole transmission layer 4, electron transfer layer 6, electron injecting layer 7, choose arbitrarily one or both or three kinds or four kinds this, or the principle of not choosing.Particularly, the concrete formation of electroluminescent device can be if following:
(1) anode layer 1/ luminescent layer 5/ cathode layer 8
(2) anode layer 1/ hole injection layer 3/ luminescent layer 5/ cathode layer 8
(3) anode layer 1/ luminescent layer 5/ electron injecting layer 7/ cathode layer 8
(4) anode layer 1/ hole injection layer 3/ luminescent layer 5/ electron injecting layer 7/ cathode layer 8
(5) anode layer 1/ hole transmission layer 4/ luminescent layer 5/ electron injecting layer 7/ cathode layer 8
(6) anode layer 1/ hole injection layer 3/ hole transmission layer 4/ luminescent layer 5/ electron injecting layer 7/ cathode layer 8
(7) anode layer 1/ hole injection layer 3/ hole transmission layer 4/ luminescent layer 5/ electron transfer layer 6/ cathode layer 8
(8) anode layer 1/ hole injection layer 3/ hole transmission layer 4/ luminescent layer 5/ electron transfer layer 6/ electron injecting layer 7/ cathode layer 8
In device, above each layer need to sequentially be arranged according to the overall structure of anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer.More than for from layer, to be minimized to maximum enumerating, not exhaustive.
Wherein hole injection layer and/or hole transmission layer by electronic injection, be transferred to luminescent layer.Electron transfer layer and/or electron injecting layer transmit, are injected into negative electrode by electronics from luminescent layer., for from the simplest structure to containing enumerating of each layer, be not more than exhaustive.When only having anode, luminescent layer and negative electrode, function still can realize.Other consist of each layer under structural framing device, still within protection domain of the present invention.
Make such electro-luminescence display device and can use all known or following materials that are expected to develop as the material that forms each layer, each layer can be made film by material by methods such as vapour deposition method, spin-coating method or teeming practices and form.The thickness of each layer formed in this way is not particularly limited, but the character of respective material and suitable setting are generally the scope of 2nm～5000nm.Moreover, the method for luminescent material thin-film is easily obtained to uniform rete and the difficult experience that generates pin hole, preferably vapour deposition method.The evaporation condition is general preferred at boat, 50 ℃～400 ℃ of Heating temperatures, vacuum tightness 10
-6Pa～10
-3Pa, evaporation rate 0.01nm/s～50nm/s, suitable setting in the scope of substrate temperature-150 ℃～300 ℃, thickness 5nm～5um.
Anode has the function that hole is injected into to hole transmission layer 4, and anode consists of later material usually: as metals such as aluminium, gold and silver, nickel, palladium or platinum; As metal oxides such as Indium sesquioxide, stannic oxide, zinc oxide, indium tin composite oxides, indium zinc composite oxides; As metal halides such as cupric iodides; Carbon black; Or the partially conductive polymer etc.
Hole transmission layer is from the high-level efficiency of anode injected hole and can effectively transmits the material of injected holes.Therefore, need the ionizing potential of this material low, high to the perviousness of visible light, hole mobility is high, stable in properties, also need to be in preparation or the light that is difficult for producing while using become the impurity of trap (trap).In addition owing to luminescent layer 5, contacting, need hole transmission layer 4 not make the light delustring from luminescent layer 5, and form exciplex not and between luminescent layer 5 and the common hole mobile material that lowers efficiency can enumerate with, N ,-phenylbenzene-N, N,-(1-naphthyl)-1, ,-biphenyl-4,4 ,-diamines (NPB) is the aromatic diamine that contains plural tertiary amine of representative, aromatic amine compounds that the triphen amine has the star radial configuration, carbazoles derivative etc.These compounds namely can be used alone, but also also mix together two or more.
As at the hole-injecting material functional materials, can be from material known to the hole transmission layer 4 of electroluminescent device, selecting material arbitrarily to use.
The material of main part of luminescent layer not only needs to possess ambipolar charge-transporting matter, need simultaneously appropriate energy rank, excitation energy is delivered to the object luminescent material effectively, and the material of this class can be enumerated diphenylethyllene aryl derivatives, stibene derivative, carbazole derivative, triarylamine derivatives, anthracene derivant, pyrene derivatives, coronene derivative etc.Adopt compound provided by the invention as material of main part, can realize this device, can obtain the beneficial effect of setting forth in summary of the invention.
With respect to material of main part, more than the incorporation of guest materials is preferably 0.01 % by weight, below 20 % by weight.The material of this class can be enumerated the metal complexes of iridium, nail, platinum, rhenium, palladium etc.
The material that forms the electron transfer layer 6 of above-mentioned electroluminescent device, can in the electroluminescent material that possesses electronic transport property, select to use arbitrarily, such material can be enumerated as 1,3,5-tri-(benzimidazoles derivative such as benzene (TPBI) of 1-naphthyl-1H-benzimidazolyl-2 radicals-yl), three (oxine) aluminium (Alq
3) etc. metal complexes, 2-(4 ,-trimethylphenylmethane base)-5-(4 ,-xenyl)-1,3,4-oxadiazole (oxadiazole derivative such as PBD) Deng, 4,7-phenylbenzene-1, the phenanthroline derivatives such as 10-phenanthroline (BPhen), triazole derivative, quinoline, quinoxaline derivatives etc.Adopt compound provided by the invention, can obtain the beneficial effect of setting forth in summary of the invention.
Optional metal, alloy, conductive compound and their mixture that is less than 4eV by work function of the spendable cathode material of above-mentioned electroluminescent device.Its concrete example is aluminium, calcium, magnesium, lithium, magnesium alloy, aluminium alloy etc.In order to obtain efficiently the electroluminescent effect, comparatively ideal is that at least one transmitance of electrode is made as more than 10%.Negative electrode can form by dry method such as vacuum evaporation, vapour deposition or sputter.
Device embodiment:
Designs:
Here first with compound provided by the invention, be applied as example in the electron transfer layer of electroluminescent device, embody its beneficial effect.
For the convenient relatively transmission performance of these electron transport materials, the present invention has designed simple electroluminescent device.Wherein, using compound 1-1 provided by the invention, 1-2,1-3,1-4,1-5,1-6,1-7,1-8,1-9,1-10,1-11,1-12,1-13 as the electron transport material illustration, efficent electronic transport material Bphen is material as a comparison, EM1 is as the luminescent material illustration, to give prominence to compound provided by the invention at electroluminescent device, the beneficial effect aspect electron transport material especially.
The structure of Bphen and EM1 is as follows:
In the present invention, selecting glass is substrate, and ITO is anode material, and the hole transmission layer select materials is NPB, and the electronic injection layer material is LiF, and cathode material is Al.
(1) device manufacture
By reference to the accompanying drawings, sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer will be coated with, in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent, under clean environment, be baked to and remove moisture fully, by UV-light and ozone clean, and with low energy positron bundle bombarded surface;
The above-mentioned version of glass-based with anode 12 is placed in vacuum chamber, is evacuated to 9 X 10
-5Pa, vacuum evaporation NPB is as hole transmission layer 3 on above-mentioned anode tunic, and evaporation speed is 0.05nm/s, and the evaporation thickness is 50nm;
Vacuum evaporation EM1 is as device luminescent layer 4 on hole transmission layer, and evaporation speed is 0.05nm/s, and the evaporation total film thickness is 40nm;
Vacuum evaporation one deck compound 1-1,1-2,1-3,1-4,1-5,1-6,1-7,1-8,1-9,1-10,1-11,1-12,1-13 or Bphen are as the electron transfer layer 5 of device on luminescent layer; its evaporation speed is 0.05nm/s, and the evaporation total film thickness is 30nm;
Upper vacuum evaporation Al is the negative electrode 6 of device at electron transfer layer (ETL), and film thickness is 150nm.
Device performance see the following form (device architecture: ITO/NPB (50nm)/EM1 (40nm)/ETL (30nm)/LiF (0.5nm)/Al (150nm)).
Above graph results shows: the compound provided of the present invention, in organic electroluminescent, have more outstanding performance, and can be preferably as the electric transmission layer material.
In addition, with above-mentioned preparation method, using general formula compound provided by the present invention as the material of main part of luminescent layer, also can prepare organic electroluminescence device provided by the invention.Its beneficial effect is, can reduce driving voltage, and easily the feature of film forming makes manufacturing cost lower, and at room temperature stability makes device work more stable preferably, and practical life is longer.
Other Preparation Examples
For fully setting forth the technical scheme of this law, it is the embodiment of different substituents that the R base below is provided.
Preparation Example 14
When R was ethyl, a compound provided by the present invention, as following structural formula B
Synthesizing of compd B
Adopt the preparation technology of compound 1-1-E, with propione, react after compound 1-1-C is prepared to Grignard reagent, hydrochloric acid catalysis prepares to close and encircles product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 2-(2-pyridyl)-6-pyridine boric acid carries out Suzuki linked reaction (Suzuki linked reaction) and can obtain compd B, and crude product HPLC is 97.8%, and total yield of products is 6.3%.
By above solid 5.0g in 330 ℃/2 * 10
-5The Pa 6h that distils, obtain the 4.2g pale yellow powder, HPLC:99.2%,,
1HNMR (DMSO, TMS, 500MHz): δ=7.20-8.52 (m, 26H), 1.95 (q, J=7.3,8H) 1.05 (t, J=7.3,12H); The product structure formula is C58H46N4, high resolution mass spectrum, theoretical value 798.3722, test value [M+1] 799.3882.
Preparation Example 15
When the R propyl group, a compound provided by the present invention, as following structural formula C
Synthesizing of Compound C
Adopt the preparation technology of compound 1-1-E, with dipropyl ketone, react after compound 1-1-C is prepared to Grignard reagent, hydrochloric acid catalysis prepares to close and encircles product in acetic acid then.After pass ring product employing NBS bromo, carry out Suzuki linked reaction (Suzuki linked reaction) with 4-phenyl-2-pyridine boric acid and can obtain compd B, crude product HPLC is 97.5%, and total yield of products is 5.8%.
By crude product 5.0g in 300 ℃/2 * 10
-5The Pa 6h that distils, obtain the 4.0g pale yellow powder, HPLC:99.6%,
1HNMR (DMSO, TMS, 500MHz): δ=8.70 (d, J=7.3,2H), 8.42 (s; 2H), 7.16-8.25 (m, 24H), 1.78-1.85 (m, J=7.3,8H); (1.30-1.38 m, 8H), 1.01 (t, J=6.9,12H); The product structure formula is C64H56N2, high resolution mass spectrum, theoretical value 852.4443, test value [M+1] 853.4520.
Preparation Example 16
When the R sec.-propyl, a compound provided by the present invention, as following structural formula D
Synthesizing of Compound D
Adopt the preparation technology of compound 1-1-E, be prepared after Grignard reagent and 2,4-dimethyl-penten reactive ketone by compound 1-1-C, hydrochloric acid catalysis prepares and closes the ring product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 4-(1-naphthyl)-2 pyridine boric acid carry out Suzuki linked reaction (Suzuki linked reaction) and can obtain compd B, and crude product HPLC is 97.9%, and total yield of products is 4.2%.
By crude product 5.0g in 300 ℃/2 * 10
-5The Pa 6h that distils, obtain the 4.4g pale yellow powder, HPLC:99.5%,
1HNMR (DMSO, TMS, 500MHz): δ=8.71 (d, J=7.2,2H), 8.39 (s, 2H), 7.22-8.26 (m, 28H), 2.46(q, J=6.8,4H), 1.03 (d, J=6.8,24H) product structure formula is C72H60N2, high resolution mass spectrum, theoretical value 952.4756, test value [M+1] 953.4736.
Preparation Example 17
When the R butyl, a compound provided by the present invention, as following structural formula E
Synthesizing of embodiment compd E
Adopt the preparation technology of compound 1-1-E, with butyl ketone, react after compound 1-1-C is prepared to Grignard reagent, hydrochloric acid catalysis prepares to close and encircles product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 6-(3-xenyl)-2-pyridine boric acid carries out Suzuki linked reaction (Suzuki linked reaction) and can obtain compd E, and crude product HPLC is 97.2%, and total yield of products is 3.3%.
By above solid 5.0g in 300 ℃/2 * 10
-5The Pa 6h that distils, obtain the 4.2g pale yellow powder, HPLC:99.2%,
1HNMR (DMSO, TMS, 500MHz): δ=8.38 (s, 2H), 7.16-8.26 (m, 34H), 1.86-1.92 (m, J=6.8,8H), 1.33-1.38 (m, 16H), 1.03 (q, J=7.0,12H); Products molecule formula C80H72N2, high resolution mass spectrum, theoretical value 1060.5696, test value [M+1] 1061.5766.
Preparation Example 18
When the R isobutyl-, a compound provided by the present invention, as following structural formula F
Synthesizing of embodiment compound F 17-hydroxy-corticosterone
Adopt the preparation technology of compound 1-1-E, be prepared after Grignard reagent and 2,3-dimethyl-g reactive ketone by compound 1-1-C, hydrochloric acid catalysis prepares and closes the ring product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 4-(3-xenyl)-2-pyridine boric acid carries out Suzuki linked reaction (Suzuki linked reaction) and can obtain compound F 17-hydroxy-corticosterone, and crude product HPLC is 97.5%, and total yield of products is 3.6%.
By above solid 5.0g in 290 ℃/2 * 10
-5The Pa 6h that distils, obtain the 4.6g pale yellow powder, HPLC:99.1%,
1HNMR (DMSO, TMS, 500MHz): δ=8.68 (d, J=7.2,2H), 8.36 (s, 2H), 7.18-8.21 (m, 32H), 1.85-1.91 (m, 12H), 1.03 (d, J=7.2,24H); Products molecule formula C80H72N2, high resolution mass spectrum, theoretical value 1060.5696, test value [M+1] 1061.5763.
Preparation Example 19
When R was n-pentyl, a compound provided by the present invention, as following structural formula G
Embodiment compound G's is synthetic
Adopt the preparation technology of compound 1-1-E, with the 6-hendecanone, react after compound 1-1-C is prepared to Grignard reagent, hydrochloric acid catalysis prepares to close and encircles product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 6-(3-xenyl)-2-pyridine boric acid carries out Suzuki linked reaction (Suzuki linked reaction) and can obtain compound G, and crude product HPLC is 96.8%, and total yield of products is 2.5%.
By above solid 3.0g in 290 ℃/2 * 10
-5The Pa 6h that distils, obtain the 2.6g pale yellow powder, HPLC:99.2%,
1HNMR (DMSO, TMS, 500MHz): δ=8.38 (s, 2H), 7.16-8.26 (m, 34H), 1.84-1.90 (m, J=6.8,8H), 1.33-1.38 (m, 24H), 1.03 (t, J=7.0,12H); Products molecule formula C84H80N2, high resolution mass spectrum, theoretical value 1116.6322, test value [M+1] 1116.6356.
Preparation Example 20
When R was n-hexyl, a compound provided by the present invention, as following structural formula H
Synthesizing of embodiment compound H
Adopt the preparation technology of compound 1-1-E, be prepared after Grignard reagent and 7-tridecane reactive ketone by compound 1-1-C, hydrochloric acid catalysis prepares and closes the ring product in acetic acid then.Closing the ring product adopts after the NBS bromo and the 6-(3-xenyl)-2-pyridine boric acid carries out Suzuki linked reaction (Suzuki linked reaction) and can obtain compound H, and crude product HPLC is 96.9%, and total yield of products is 1.8%.
By above solid 3.0g in 280 ℃/2 * 10
-5The Pa 6h that distils, obtain the 2.8g pale yellow powder, HPLC:99.5%,
1HNMR (DMSO, TMS, 500MHz): δ=8.36 (s, 2H), 7.14-8.23 (m, 34H), 1.82-1.88 (m, J=6.8,8H), 1.33-1.45 (m, 32H), 1.01 (t, J=7.0,12H); Products molecule formula C88H88N2, high resolution mass spectrum, theoretical value 1172.6948, test value [M+1] 1173.7016.
The effect data
Above compound is that the experimental data of electric transmission layer material is as follows, can find out, still has preferably performance.
Device data
Generally, although by embodiment and preferred implementation, disclose the present invention, should be understood that and the invention is not restricted to disclosed embodiment.On the contrary, it will be understood by those skilled in the art that it is intended to contain various modification and similarly arranges.Therefore, the scope of claims should be consistent with the widest explanation to contain all such modification and similarly to arrange.
Claims (14)
1. the derivative of tetraalkyl two indeno pyrenes, its general structure is as follows:
Wherein, R
1For the pyrimidyl of pyrimidyl, dipyridyl, phenyl substituted, the pyrimidyl of xenyl replacement or the pyrimidyl of naphthyl substituted;
R is that carbon number is the alkyl of 1-8.
2. compound according to claim 1, wherein R is butyl, isobutyl-, n-pentyl, n-hexyl, heptyl or octyl group.
3. compound according to claim 1, wherein R is ethyl, propyl group or sec.-propyl.
4. compound according to claim 1, wherein R is methyl.
5. according to the described compound of claim 1 to 4, R wherein
1Structural formula be a kind of in following formula
6. according to the described compound of claim 1 to 4, wherein R
1Structural formula be a kind of in following formula:
7. compound according to claim 1, wherein, R is methyl, R
1Structural formula is following formula
8. midbody compound for preparing the described compound of claim 4, its structural formula is as follows
9. organic electroluminescence device, comprise the anode layer and the cathode layer that form pair of electrodes, and the luminescent layer arranged in electrode, and according to optional principle, hole injection layer also is set in electrode, hole transmission layer, electron transfer layer and/or electron injecting layer, wherein each layer is according to anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the order of cathode layer is arranged, mode with plating between adjacent layers connects, form rhythmo structure, it is characterized in that: the material of main part of described luminescent layer is selected from the arbitrary described compound of claim 1 to 7.
10. organic electroluminescence device according to claim 9, the mode of plating is vacuum evaporation.
11. organic electroluminescence device according to claim 9, also comprise the base version, anode layer is attached on the base version.
12. organic electroluminescence device, comprise the anode layer and the cathode layer that form pair of electrodes, and the luminescent layer arranged in electrode and electron transfer layer, and according to optional principle, hole injection layer also is set in electrode, hole transmission layer and/or electron injecting layer, wherein each layer is according to anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the order of cathode layer is arranged, mode with plating between adjacent layers connects, form rhythmo structure, it is characterized in that: the material of described electron transfer layer is selected from the arbitrary described compound of claim 1 to 7.
13. organic electroluminescence device according to claim 12, the mode of plating are vacuum evaporation.
14. organic electroluminescence device according to claim 12, also comprise the base version, anode layer is attached on the base version.
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| KR20110041726A (en) * | 2009-10-16 | 2011-04-22 | 에스에프씨 주식회사 | Aromatic compound and organic electroluminescent device using the same |
| WO2012141273A1 (en) * | 2011-04-12 | 2012-10-18 | 富士フイルム株式会社 | Organic electroluminescent element, material for organic electroluminescent elements, film, light-emitting layer, and method for manufacturing organic electroluminescent element |
| JP2012222255A (en) * | 2011-04-12 | 2012-11-12 | Fujifilm Corp | Organic electroluminescent element, material and film for organic electroluminescent element, and manufacturing method for organic electroluminescent element |
| CN102916131A (en) * | 2011-08-05 | 2013-02-06 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| WO2013024730A1 (en) * | 2011-08-18 | 2013-02-21 | ユーディーシー アイルランド リミテッド | Organic electroluminescent element, compound for organic electroluminescent element, and light-emitting device, display device, and illumination device using said element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106008138A (en) * | 2016-05-23 | 2016-10-12 | 中节能万润股份有限公司 | Organic electroluminescent material, application and luminescent device |
| CN106008138B (en) * | 2016-05-23 | 2019-04-09 | 中节能万润股份有限公司 | A kind of electroluminescent organic material, application and luminescent device |
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