CN104292152A - Electron transporting material and organic electroluminescent device using same - Google Patents

Electron transporting material and organic electroluminescent device using same Download PDF

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CN104292152A
CN104292152A CN201410447272.6A CN201410447272A CN104292152A CN 104292152 A CN104292152 A CN 104292152A CN 201410447272 A CN201410447272 A CN 201410447272A CN 104292152 A CN104292152 A CN 104292152A
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base
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dipyridyl
formula
naphthalene
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小野洋平
马场大辅
内田学
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JNC Corp
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JNC Corp
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Abstract

A compound represented by formula (1) is useful as an electron transporting material for an organic EL device. Use of the electron transporting material contributes to the prolongation of the life of the organic EL device and so on. In the formula (1), Py's independently represent each a group represented by formula (2), (3), (4) or (5); m and n represent 0 or 1, provided that m+n is 1; and hydrogen atoms in the benzene, naphthalene and pyridine rings in the formulae may be independently substituted by C1-6 alkyl or C3-6 cycloalkyl.

Description

Electron transport material and use its organic electroluminescent device
The application is the applying date is on 05 28th, 2010, and application number is 201080018916.X, and denomination of invention is the divisional application of the patent of electron transport material and the organic electroluminescent device using it.
Technical field
The present invention relates to a kind of there is pyridyl Novel electronic transmission material, use this electron transport material organic electroluminescent device (following, sometimes be slightly designated as organic EL (Electroluminescence, electroluminescent) element or be only slightly designated as element) etc.
Background technology
In recent years, organic EL is attracted attention as follow-on full color flat panel indicating meter, and is just obtaining positive research.In order to promote the practical of organic EL, the reduction of the driving voltage of element, long lifetime are indispensable key elements, develop new electron transport material to reach these key elements.Especially, the driving voltage of blue element must be made to decline and make its long lifetime.In patent documentation 1 (Japanese Patent Laid-Open 2003-123983 publication), record using phenanthroline derivative or as 2 of its analogue, 2 '-bipyridyl compound is used for electron transport material, thus can with low voltage drive organic EL.But the characteristic (driving voltage, luminous efficiency etc.) of the element reported in the example of the document is only take comparative example as the relative value of benchmark, does not record the measured value that can be judged as practical value.In addition, at non-patent literature 1 (record (the Proceedings of the 10 of the tenth " inorganic and organic electroluminescent " international symposium thinternational Workshop on Inorganic and Organic Electroluminescence)), disclose the example having and 2,2 '-bipyridyl compound is used for electron transport material in patent documentation 2 (Japanese Patent Laid-Open 2002-158093 publication) and patent documentation 3 (International Publication 2007/86552 handbook).The Tg of compound described in non-patent literature 1 is low and and impracticable.Although compound described in patent documentation 2 and patent documentation 3 can with lower voltage driven organic EL, towards practical and expect long lifetime more.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2003-123983 publication
Patent documentation 2: Japanese Patent Laid-Open 2002-158093 publication
Patent documentation 3: International Publication 2007/86552 handbook
Non-patent literature
Record (the Proceedings of the 10 of non-patent literature 1: the ten " inorganic and organic electroluminescent " international symposium thinternational Workshop on Inorganic and Organic Electroluminescence) (2000)
Summary of the invention
The technical task that invention will solve
Given this present invention plants the problem that prior art has and the invention completed.Problem of the present invention is to provide a kind of electron transport material contributing to the long lifetime of organic EL etc.And then problem of the present invention is to provide a kind of organic EL using this electron transport material.
Solve the technique means of problem
The people such as the present inventor make great efforts the result studied, find by by the naphthyl of 9-(2-naphthyl)-10-phenylanthracene or phenyl any one on there is the electron transfer layer of compound for organic EL of pyridyl, bipyridyl, phenylpyridyl or pyridinylphenyl, the organic EL that can drive with the long lifetime can be obtained, and complete the present invention based on this discovery.
Described problem everyly to be solved by shown below.
[1] compound, it is represented by following formula (1):
In formula (1),
Py is independently the base represented by formula (2), formula (3), formula (4) or formula (5);
M and n is 0 or 1, but m+n=1;
-the H of the phenyl ring in formula, naphthalene nucleus and pyridine ring can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.
[2] compound according to described [1], it is represented by following formula (1-1) or following formula (1-2):
In formula (1-1) or formula (1-2),
Py is the base represented by formula (2), formula (3), formula (4) or formula (5);
-the H of the phenyl ring in formula, naphthalene nucleus and pyridine ring can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.
[3] compound according to described [1], it is represented by following formula (1-3), following formula (1-4), following formula (1-5) or following formula (1-6):
Formula (1-3) ~ formula (1-6) various in,
Py is the base represented by formula (2), formula (3), formula (4) or formula (5);
-the H of the phenyl ring in formula, naphthalene nucleus and pyridine ring can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.
[4] compound according to described [1], it is represented by following formula (1-3) or following formula (1-4):
In formula (1-3) and formula (1-4),
Py is the base represented by formula (2), formula (3), formula (4) or formula (5);
-the H of the phenyl ring in formula, naphthalene nucleus and pyridine ring can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.
[5] compound according to described [1], it is represented by following formula (1-5) or following formula (1-6):
In formula (1-5) and formula (1-6),
Py is the base represented by formula (2), formula (3), formula (4) or formula (5);
-the H of the phenyl ring in formula, naphthalene nucleus and pyridine ring can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.
[6] compound according to described [1], it is represented by following formula (1-3-1):
[7] compound according to described [1], it is represented by following formula (1-3-2):
[8] compound according to described [1], it is represented by following formula (1-3-3):
[9] compound according to described [1], it is represented by following formula (1-3-5):
[10] compound according to described [1], it is represented by following formula (1-3-12):
[11] compound according to described [1], it is represented by following formula (1-3-21):
[12] compound according to described [1], it is represented by following formula (1-3-22):
[13] compound according to described [1], it is represented by following formula (1-3-24):
[14] compound according to described [1], it is represented by following formula (1-3-25):
[15] compound according to described [1], it is represented by following formula (1-3-27):
[16] compound according to described [1], it is represented by following formula (1-4-2):
[17] compound according to described [1], it is represented by following formula (1-5-11):
[18] compound according to described [1], it is represented by following formula (1-5-24):
[19] compound according to described [1], it is represented by following formula (1-6-1):
[20] compound according to described [1], it is represented by following formula (1-6-2):
[21] compound according to described [1], it is represented by following formula (1-6-4):
[22] compound according to described [1], it is represented by following formula (1-6-5):
[23] electron transport material, it is containing with good grounds described compound according to any one of [1] to [22].
[24] a kind of organic electroluminescent device, it comprises: the pair of electrodes comprising anode and negative electrode, be configured in the luminescent layer between this pair of electrodes, and be configured between described negative electrode and this luminescent layer and containing the electron transfer layer of with good grounds described electron transport material described in [23] and/or electron injecting layer.
[25] organic electroluminescent device according to described [24], wherein at least one deck of electron transfer layer and electron injecting layer also comprises at least one in the cohort being selected from and being made up of hydroxyquinoline system metal complex, dipyridyl derivatives, phenanthroline derivative and borane derivative.
[26] organic electroluminescent device according to described [24] or [25], wherein at least one deck of electron transfer layer and electron injecting layer also comprises at least one in the cohort selecting free alkali metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, the oxide compound of alkaline-earth metal, the halogenide of alkaline-earth metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic complex, the organic complex of alkaline-earth metal and the organic complex of rare earth metal to form.
The effect of invention
Even if compound of the present invention has to apply the also stable and feature that the transmittability of electric charge is high of voltage under filminess.Compound of the present invention is suitable as the charge transfer material in organic EL.By compound of the present invention being used for the electron transfer layer of organic EL, can obtaining and there is long-life organic EL.The organic EL of the application of the invention, can make the high performance display equipment of full-color display etc.
Embodiment
Below, the present invention is illustrated in greater detail.Moreover, in this manual, sometimes such as " compound by represented by formula (1-3-1) " is called " compound (1-3-1) ".Sometimes " compound by represented by formula (1-3-2) " is called " compound (1-3-2) ".For other formula mark, formula numbering, process similarly.
The explanation > of < compound
1st invention of this case is the compound with pyridyl, bipyridyl, phenylpyridyl or pyridinylphenyl represented by following formula (1).
In formula (1), Py is independently the base represented by formula (2), formula (3), formula (4) or formula (5), m and n is 0 or 1, but m+n=1.
Pyridyl represented by formula (2) is specially 2-pyridyl, 3-pyridyl or 4-pyridyl.
Bipyridyl represented by formula (3) is specially 2, 2 '-dipyridyl-5-base, 2, 2 '-dipyridyl-6-base, 2, 2 '-dipyridyl-4-base, 2, 3 '-dipyridyl-5-base, 2, 3 '-dipyridyl-6-base, 2, 3 '-dipyridyl-4-base, 2, 4 '-dipyridyl-5-base, 2, 4 '-dipyridyl-6-base, 2, 4 '-dipyridyl-4-base, 3, 2 '-dipyridyl-6-base, 3, 2 '-dipyridyl-5-base, 3, 3 '-dipyridyl-6-base, 3, 3 '-dipyridyl-5-base, 3, 4 '-dipyridyl-6-base, 3, 4 '-dipyridyl-5-base, 4, 2 '-dipyridyl-3-base, 4, 3 '-dipyridyl-3-base, or 4, 4 '-dipyridyl-3-base.Wherein, preferred 2,2 '-dipyridyl-5-bases, 2,2 '-dipyridyl-6-base, 2,3 '-dipyridyl-5-bases, 2,3 '-dipyridyl-6-bases, 2,4 '-dipyridyl-5-base, 2,4 '-dipyridyl-6-bases, 3,2 '-dipyridyl-6-bases, 3,2 '-dipyridyl-5-base, 3,3 '-dipyridyl-6-bases, 3,3 '-dipyridyl-5-bases, 3,4 '-dipyridyl-6-base, 3,4 '-dipyridyl-5-bases, 4,2 '-dipyridyl-3-bases, 4,3 '-dipyridyl-3-base and 4,4 '-dipyridyl-3-base.And, more preferably 2,2 '-dipyridyl-5-bases, 2,2 '-dipyridyl-6-bases, 2,3 '-dipyridyl-5-base, 2,3 '-dipyridyl-6-base, 2,4 '-dipyridyl-5-bases, 2,4 '-dipyridyl-6-bases, 3,2 '-dipyridyl-5-base, 3,2 '-dipyridyl-6-base, 3,4 '-dipyridyl-6-base and 3,4 '-dipyridyl-5-base.
Phenylpyridyl represented by formula (4) is specially 3-phenylpyridine-2-base, 4-phenylpyridine-2-base, 5-phenylpyridine-2-base, 6-phenylpyridine-2-base, 2-phenylpyridine-3-base, 4-phenylpyridine-3-base, 5-phenylpyridine-3-base, 6-phenylpyridine-3-base, 2-phenylpyridine-4-base or 3-phenylpyridine-4-base.Wherein, preferred 5-phenylpyridine-2-base, 6-phenylpyridine-2-base, 5-phenylpyridine-3-base and 6-phenylpyridine-3-base.
Pyridinylphenyl represented by formula (5) is specially 4-(2-pyridyl) phenyl, 4-(3-pyridyl) phenyl, 4-(4-pyridyl) phenyl, 3-(2-pyridyl) phenyl, 3-(3-pyridyl) phenyl, 3-(4-pyridyl) phenyl, 2-(2-pyridyl) phenyl, 2-(3-pyridyl) phenyl or 2-(4-pyridyl) phenyl.Wherein, preferred 4-(2-pyridyl) phenyl, 4-(3-pyridyl) phenyl, 4-(4-pyridyl) phenyl, 3-(2-pyridyl) phenyl, 3-(3-pyridyl) phenyl and 3-(4-pyridyl).
In formula (1), Py can be attached at the arbitrary position on phenyl, also can be attached at the arbitrary position on 2-naphthyl, but on phenyl, is preferably attached at 4 and 3, on 2-naphthyl, is preferably attached at 6 and 7.Especially, with regard to the energy level this point not expanding conjugated system this point and do not reduce LUMO, 3 of preferred phenyl.In addition, just easily obtain with regard to raw material this point, 6 of particularly preferably 2-naphthyl.
-the H of phenyl ring, naphthalene nucleus and pyridine ring in formula (1) can independently by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl substituted of 3 ~ 6.Carbon number is the example of the alkyl of 1 ~ 6 is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, 2,2-dimethyl propyls, n-hexyl, isohexyl.Carbon number is the example of the cycloalkyl of 3 ~ 6 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
The concrete example > of < compound
The concrete example of compound of the present invention is represented by following drawn up formula, but the present invention can't help the announcement of these concrete structures and limited.
The concrete example > of the compound of < represented by formula (1-3)
The concrete example of the compound represented by formula (1-3) is represented by following formula (1-3-1) ~ formula (1-3-30).In these formulas, preferred compound is formula (1-3-1) ~ formula (1-3-6), formula (1-3-10) ~ formula (1-3-12) and formula (1-3-16) ~ formula (1-3-27).Preferred compound is formula (1-3-1) ~ formula (1-3-3), formula (1-3-5), formula (1-3-10) ~ formula (1-3-12), formula (1-3-21), formula (1-3-22), formula (1-3-24), formula (1-3-25) and formula (1-3-27).
The concrete example > of the compound of < represented by formula (1-4)
The concrete example of the compound represented by formula (1-4) is represented by following formula (1-4-1) ~ formula (1-4-27).In these formulas, preferred compound is formula (1-4-1) ~ formula (1-4-6), formula (1-4-10) ~ formula (1-4-12) and formula (1-4-16) ~ formula (1-4-21).
The concrete example > of the compound of < represented by formula (1-5)
The concrete example of the compound represented by formula (1-5) is represented by following formula (1-5-1) ~ formula (1-5-30).In these formulas, preferred compound is formula (1-5-1) ~ formula (1-5-6), formula (1-5-10) ~ formula (1-5-12) and formula (1-5-16) ~ formula (1-5-24).Preferred compound is formula (1-5-1) ~ formula (1-5-3), formula (1-5-10) ~ formula (1-5-12) and formula (1-5-24).
The concrete example > of the compound of < represented by formula (1-6)
The concrete example of the compound represented by formula (1-6) is represented by following formula (1-6-1) ~ formula (1-6-30).In these formulas, preferred compound is formula (1-6-1) ~ formula (1-6-6), formula (1-6-10) ~ formula (1-6-12) and formula (1-6-16) ~ formula (1-6-21).Better compound is formula (1-6-1) ~ formula (1-6-6) and formula (1-6-10) ~ formula (1-6-12).
The synthesis method > of < compound
Compound of the present invention can utilize known synthetic method to synthesize.Be described for the synthesis method of compound to compound of the present invention of formula (1-3-1).
First, 9-phenylanthracene is synthesized by reacting 1.Make bromobenzene and MAGNESIUM METAL at tetrahydrofuran (THF) (Tetrahydrofuran, THF) carry out reaction in make Grignard reagent (Grignard reagent), then make itself and 9-bromine anthracene carry out reaction to make 9-phenylanthracene in the presence of a catalyst.Phenyl ring and anthracene nucleus coupling are not limited to described method, also can pass through root bank linked reaction (Negishi Coupling Reaction), Suzuki linked reaction (Suzuki Coupling Reaction) etc. to carry out, can be suitable for according to situation using these ordinary methods.In addition, 9-phenylanthracene also can use commercially available product.
In reaction 2, use N-bromosuccinimide by 10 of 9-phenylanthracene brominations.Herein, the conventional bromizating agent beyond N-bromosuccinimide can also be used.
In reaction 3, by anthracene nucleus and naphthalene nucleus coupling.First, according to conventional methods bromo-for 2-6-methoxynaphthalene is made Grignard reagent, then make itself and the bromo-10-phenylanthracene of 9-carry out reaction to synthesize 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene in the presence of a catalyst.
In reaction 4, make the methoxyl group demethylation of 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene and become naphthols.Herein, also can be suitable for using in demethylation reaction the reagent commonly used.
In reaction 5 ,-the OH of naphthols is made to become trifluoromethyl sulfonic acid (fluoroform sulphonate).-OTf in reaction formula is-OSO 2cF 3summary note.
In reaction 6, make pyridine ring bond on naphthalene nucleus by root bank linked reaction.First, 4-bromopyridine is made Grignard reagent.Herein, due to stable 4-bromopyridine hydrochloride is used for raw material, therefore use the isopropylmagnesium chloride of 2 times moles, but for the raw material without the need to using hydrochloride, also can be grade mole.In Grignard reagent, add the zinc chloride complex compound that zinc chloride Tetramethyl Ethylene Diamine complex compound carrys out pyridine synthesis, under the existence of palladium catalyst, then make the fluoroform sulphonate obtained in itself and reaction 5 carry out reaction to synthesize target compound.
As the concrete example of the palladium catalyst used in root bank linked reaction, can enumerate: Pd (PPh 3) 4, PdCl 2(PPh 3) 2, Pd (OAc) 2, three (dibenzalacetone) two palladium (0), three (dibenzalacetone) two palladium (0) chloroform complex compound, two (dibenzalacetone) palladium (0), two (tri-tert phosphino-) palladium (0) or (1,1 '-bis-(diphenylphosphino) ferrocene) dichloro palladium (II).
In this stage, beyond bank linked reaction of digging up the roots, also can be suitable for the linked reaction using Suzuki linked reaction etc. to commonly use.Described in root bank linked reaction, Suzuki linked reaction such as have in " " metal catalysed cross linked reaction " second edition (completely newly revising expansion of page volume) (Metal-Catalyzed Cross-Coupling Reactions-Second, Completely Revised and Enlarged Edition) " etc.
About the compound beyond formula (1-3-1), also can be suitable for using raw material by coordinating target compound, and synthesize according to described synthesis method.Such as, be described for the compound of formula (1-3-4).
By reacting the bromide that the zinc chloride complex compound of the pyridine synthesized by reaction 7 and dibromo pyridine coupling to be obtained dipyridyl by 8.According to reaction 6, this bromide is made zinc chloride complex compound again, then make it react with the fluoroform sulphonate that obtains in reaction 5, thus can the compound of synthesis type (1-3-4).
In addition, if the compound of formula (1-3-16), in reaction 8, then use paradibromobenzene to replace dibromo pyridine, synthesize 4-(2-pyridyl) bromobenzene thus, and zinc chloride complex compound is made in the same manner as described, then it is made to react with the fluoroform sulphonate that obtains in reaction 5, thus can the compound of synthesis type (1-3-16).
When the compound of formula (1-4-1) ~ formula (1-4-27), as long as use 2-bromo-7-methoxynaphthalene to replace the bromo-6-methoxynaphthalene of 2-in described reaction 3.
When the compound of formula (1-5-1) ~ formula (1-5-30) or formula (1-6-1) ~ formula (1-6-30), as long as the benzene skeleton of the raw material used in described reaction 1 ~ reaction 3 and naphthalene skeleton are exchanged, also can similarly synthesize.Namely, by the Grignard reagent of 2-bromine anthracene and the coupling of 9-bromine anthracene, and according to reaction 2 by 10 of anthracene brominations, then make this bromide with reacting the Grignard reagent of methoxybromobenzene or meta-methoxy bromobenzene and obtain 9-(4-or 3-p-methoxy-phenyl)-10-(2-naphthyl) anthracene.About this compound, as long as the later program of the demethylation reaction of methoxyl group is carried out according to described.And then about the compound beyond concrete illustrated compound, also can be suitable for using raw material by coordinating target compound, and synthesize according to described synthesis method, this point is self-evident.
When electron injecting layer compound of the present invention is used in organic EL or electron transfer layer, this stability of compounds when a field is applied.Its represent compound of the present invention as the electron injection material of electroluminescence type element or electron transport material excellent.Electron injecting layer described herein refers to the layer receiving electronics from negative electrode towards organic layer, and electron transfer layer refers to for the layer towards luminescent layer transmission institute injected electrons.In addition, electron transfer layer also can double as electron injecting layer.The material being used for each layer is called electron injection material and electron transport material.
The explanation > of < organic EL
2nd invention of this case is the organic EL containing the compound represented by formula (1) of the present invention in electron injecting layer or electron transfer layer.The driving voltage of organic EL of the present invention is low and weather resistance when driving is high.
Organic EL of the present invention be configured with various form, but be the multi-ply construction being at least clamped with hole transmission layer, luminescent layer, electron transfer layer between the anode and the cathode substantially.The concrete configuration example of element is (1) anode/hole transmission layer/luminescent layer/electron transfer layer/negative electrode, (2) anode/electric hole input horizon/hole transmission layer/luminescent layer/electron transfer layer/negative electrode, (3) anode/electric hole input horizon/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/negative electrode etc.
Compound of the present invention has higher electron injection and electron-transporting, therefore can with monomer or other materials and with and for electron injecting layer or electron transfer layer.Organic EL of the present invention, by being combined with using the electric hole input horizon, hole transmission layer, luminescent layer etc. of other materials by electron transport material of the present invention, also can obtain blueness, green, redness or white luminescence.
The luminescent material of organic EL used in the present invention or luminous doping agent are as polymer association compiles, polymer-function material series " optical function material ", co-publicate (1991), the luminescent material such as daylight fluorescent material, white dyes, laser pigment, organic scintillator, various fluorometric analysis reagent described in P236, as Chuner Mitsumasa supervision, " organic EL Material and indicating meter " CMC Cinema Magnetique Communication publishes the luminescent material etc. of triplet state material described in dopant material described in (2001) P155 ~ P156, P170 ~ P172.
The compound that can be used as luminescent material or luminous doping agent is polycyclc aromatic compound, heterocyclic aromatic compound, organometallic complex, pigment, macromolecular luminescent material, styryl derivative, aromatic amine derivative, coumarin derivatives, borane derivative, oxazines derivative, the whorled compound of tool, oxadiazoles derivative, fluorene derivatives etc.The example of polycyclc aromatic compound is anthracene derivant, phenanthrene derivative, tetracene derivative, pyrene derivatives, 1,2-triphenylene, perylene derivative, cool derivative, rubrene derivative etc.The example of heterocyclic aromatic compound be there is the oxadiazoles derivative of dialkyl amido or ammonia diaryl base, pyrazolo quinoline, pyridine derivate, pyran derivate, phenanthroline derivative, thiophene cough up derivative, have the thiophene derivant of triphenylamino, quinacridone derivative etc.The example of organometallic complex is zinc, aluminium, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold etc. and the complex compound of quinolinol derivative, benzoxazoles derivative, benzothiazole derivant, oxadiazoles derivative, thiadiazoles derivative, benzimidizole derivatives, pyrrole derivative, pyridine derivate, phenanthroline derivative etc.The example of pigment can be enumerated dibenzo piperazine and to mutter the pigments such as derivative, polymethine derivative, derivatives of porphyrin, coumarin derivatives, dicyanomethylene pyran derivative, dicyanomethylenethiopyrans derivative, oxo benzanthrene derivative, quinolone derivative, perylene derivative, benzoxazoles derivative, benzothiazole derivant, benzimidizole derivatives.The example of macromolecular luminescent material is for gathering phenylethylene derivative, polythiofuran derivative, Polyvinyl carbazole derivative, polysilane derivative, polyfluorene derivative, polyparaphenylene's derivative etc.The example of styryl derivative is styryl derivative, styryl arylene derivatives etc. containing amine.
Other electron transport materials used in organic EL of the present invention can from can be used as light conductive material electron transport compound compound, to can be used in the electron transfer layer of organic EL and the compound of electron injecting layer at random selecting to use.
The concrete example of this kind of electron transport material is hydroxyquinoline system metal complex, 2, 2 '-bipyridinyl derivative, phenanthroline derivative, diphenoquinone, perylene derivative, oxadiazoles derivative, thiophene derivant, triazole derivative, thiadiazoles derivative, the metal complex of oxine derivative, quinoxaline derivatives, the polymkeric substance of quinoxaline derivatives, benzazoles compound, gallium complex, pyrazole derivatives, perfluorination crystalline 1,2-phenylene derivatives, pyrrolotriazine derivatives, pyrazines derivatives, benzoquinoline derivative, imidazopyridine derivatives, borane derivative etc.
About the electric hole injecting material used in organic EL of the present invention and electric hole transport material, can from since before light conductive material as the compound that the charge transfer material in electric hole is usual, or for the arbitrary material of choice for use in the electric hole input horizon of organic EL and the known material of hole transmission layer.The concrete example of these materials is carbazole derivative, triarylamine derivative, phthalocyanine derivates etc.
The each layer forming organic EL of the present invention is made film to be formed by the material utilizing the methods such as vapour deposition method, spin-coating method or teeming practice and should form each layer.The thickness of each layer formed in this way is not particularly limited, and may correspond to the character in material and is suitable for setting, being generally the scope of 2nm ~ 5000nm.Moreover, the method for luminescent material thin-film is just easily obtained the film of homogeneous and with regard to the viewpoint not easily generating pin hole etc., preferably adopts vapour deposition method.When utilizing vapour deposition method to carry out filming, its evaporation condition is different according to the kind of luminescent material of the present invention.Evaporation condition is generally preferred in boat Heating temperature 50 DEG C ~ 400 DEG C, vacuum tightness 10 -6pa ~ 10 -3pa, evaporation rate 0.01nm/ second ~ 50nm/ second, substrate temperature-150 DEG C ~+300 DEG C, thickness 5nm ~ 5 μm scope in suitable setting.
No matter organic EL of the present invention is preferably any one described structure, by base plate supports.As long as substrate has physical strength, thermostability and the transparency, glass, overlay etc. can be used.Anode material can use metal, alloy, conductive compound and their mixture with the work function being greater than 4eV.Its concrete example is the metals such as Au, CuI, tin indium oxide (following, to be slightly designated as ITO), SnO 2, ZnO etc.
Cathode substance can use work function to be less than the metal of 4eV, alloy, conductive compound and their mixture.Its concrete example is aluminium, calcium, magnesium, lithium, magnesium alloy, aluminium alloy etc.The concrete example of alloy is aluminium/lithium fluoride, aluminium/lithium, magnesium/silver, magnesium/indium etc.In order to obtain the luminescence of organic EL efficiently, comparatively ideal is that the transmittance of at least one of electrode is set to more than 10%.Preferably the electrical sheet resistance as electrode is set to hundreds of Ω/below.Moreover, although thickness also depends on the character of electrode materials, be usually set as 10nm ~ 1 μm, be preferably set to the scope of 10nm ~ 400nm.This kind of electrode, by using described electrode substance, forms film with the method such as evaporation or sputtering and makes.
Secondly, routine as of the method using luminescent materials organic EL of the present invention, the manufacture method of the organic EL comprising described anode/electric hole input horizon/hole transmission layer/luminescent layer/electron transport material/negative electrode of the present invention is described.On suitable substrate, utilize vapour deposition method to form the film of anode material to after making anode, this anode is formed the film of electric hole input horizon and hole transmission layer.Form the film of luminescent layer thereon.Vacuum evaporation electron transport material of the present invention and form film and be used as electron transfer layer over the light-emitting layer.And then utilize vapour deposition method to form the film comprising negative electrode material to be used as negative electrode, to obtain the organic EL as target thus.Moreover, in the making of described organic EL, production order also can be made contrary, and with the sequentially built of negative electrode, electron transfer layer, luminescent layer, hole transmission layer, electric hole input horizon, anode.
When applying volts DS to organic EL obtained in this way, as long as using anode as+polarity, using negative electrode as-polarity apply, if apply the voltage of about 2V ~ 40V, then can be luminous from the observation of transparent or semitransparent electrode side (male or female and both sides).In addition, this organic EL is also luminous when being applied with voltage of alternating current.Moreover the waveform of the interchange of applying can be any.
[example]
Below, the present invention is illustrated in greater detail according to example.First, below the synthesis example of the compound used in example is described.
The synthesis of [synthesis example 1] compound (1-3-1)
The synthesis > of the bromo-10-phenylanthracene of <9-
In a nitrogen environment, one side stirs under room temperature, and one drips the chloroformic solution 10ml containing iodine 0.2g in the chloroformic solution 580ml containing 9-phenylanthracene 104g and N-bromosuccinimide 80g.After dropping terminates, stir 3 hours at a reflux temperature.After till reaction solution is cooled to room temperature, remove throw out by suction filtration, then add toluene 500ml and carry out separatory.Organic layer is washed, and desolventizing is heated up in a steamer in decompression, then utilizes methyl alcohol 250ml to clean obtained solid, thus obtain 9-bromo-10-phenylanthracene 135g.
The synthesis > of <9-(6-methoxynaphthalene-2-base)-10-phenylanthracene
In a nitrogen environment, in the flask being added with magnesium 10.7g and a small amount of iodine, THF solution containing 2-bromo-6-methoxynaphthalene 70g is dripped to prepare Grignard reagent.In a nitrogen environment, one side stirs under room temperature, and one drips this Grignard reagent in the flask being added with 9-bromo-10-phenylanthracene 67g, nickelous chloride 0.5g and THF 140ml.After dropping terminates, and then stir 30 minutes, then add toluene and carry out separatory.Organic layer is washed, and desolventizing is heated up in a steamer in decompression, then carries out vacuum-drying to obtained solid, thus obtain 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene 80g.
The synthesis > of <6-(10-phenylanthracene-9-base) naphthalene-2-alcohol
One side stirs under salt ice temperature, and one drips the dichloromethane solution 120ml containing boron tribromide 39g in the dichloromethane solution 400ml containing 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene 50g.After dropping terminates, and then at room temperature stir after 14 hours, one side utilizes frozen water to carry out cooling one side interpolation water 300ml.Use ethyl acetate 11 to extract from this reaction mixture, and organic layer is washed.The solid that desolventizing obtains is heated up in a steamer to decompression and carries out vacuum-drying, thus obtain 6-(10-phenylanthracene-9-base) naphthalene-2-alcohol 51g.
The synthesis > of < trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester
In a nitrogen environment, one side stirs at ice bath temperature, and one drips and makes trifluoromethanesulfanhydride anhydride 40g be dissolved in the solution of toluene 100ml in the flask being added with 6-(10-phenylanthracene-9-base) naphthalene-2-alcohol 51g, pyridine 12.3g and toluene 600ml.After dropping terminates, and then at room temperature stir 19 hours.Use toluene 700ml to extract from this reaction mixture, and organic layer is washed.Temporary transient decompression is dissolved in toluene after heating up in a steamer desolventizing again, then through alumina (toluene).Utilize heptane (250ml) that the solid that desolventizing obtains is heated up in a steamer in decompression and clean 3 times, thus obtain trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 50g.
The synthesis > of < compound (1-3-1)
Utilize dry ice/methanol bath to cool the flask being added with 4-bromopyridine hydrochloride 9.3g and THF 45ml, then in a nitrogen environment, one side is carried out stirring one side and is dripped 2M isopropylmagnesium chloride THF solution 25ml.After dropping terminates, after till being temporarily warming up to 0 DEG C, utilize frozen water to cool, then one side carries out stirring one side dropping 2M isopropylmagnesium chloride THF solution 25ml.After dropping terminates, and then at room temperature stir 1 and a half hours, after confirming that 4-bromopyridine is consumed, utilize frozen water to cool flask, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound (12.6g).Thereafter at room temperature stir 14 hours, add trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 19g, Pd (PPh 3) 41.7g and THF 50ml, then heated and stirred 9 hours at a reflux temperature.Till reaction solution is cooled to room temperature, carries out washing and make a return journey after desalination, by alumina column chromatography method (toluene/ethyl acetate=10/1 (volume ratio)), the organic layer through separatory is refined.From methyl-phenoxide, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-1): 4-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 3.2g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：8.75(d，2H)，8.3(m，1H)，8.15(dd，1H)，8.05(m，2H)，7.85(d，1H)，7.65-7.75(m，7H)，7.6(t，2H)，7.55-7.6(m，1H)，7.5(m，2H)，7.35(m，4H)。
The synthesis of [synthesis example 2] compound (1-3-2)
3-pyridine boronic acid 2.8g, trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 10.0g, Pd (PPh is added in flask 3) 40.7g, potassiumphosphate 8.0g, 1，2，4-trimethylbenzene 40ml, 2-propyl alcohol 4ml and water 4ml, and stir 6 hours at a reflux temperature.After till reaction solution is cooled to room temperature, carries out washing and to make a return journey desalination, then by silica gel column chromatography (toluene/ethyl acetate=95/5 (volume ratio)), the organic layer through separatory is refined.Utilize methyl alcohol to heat up in a steamer to decompression the solid that desolventizing obtains to clean, thus obtain compound (1-3-2): 3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 2.1g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.1(dd，1H)，8.7(dd，1H)，8.2(d，1H)，8.2～8.1(d，1H)，8.1～8.0(m，1H)，8.0(m，2H)，7.8(dd，1H)，7.7(m，4H)，7.7～7.6(dd，1H)，7.6(m，2H)，7.6～7.5(m，1H)，7.5(m，2H)，7.5～7.4(m，1H)，7.4～7.3(m，4H)。
The synthesis of [synthesis example 3] compound (1-3-3)
In a nitrogen environment, one side stirs under room temperature, and one drips 2M isopropylmagnesium chloride THF solution 14.3ml in the flask being added with 2-bromopyridine 4.1g and THF 20ml.Utilize frozen water to cool after dropping terminates, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 7.2g.Thereafter at room temperature stir 0.5 hour, then add trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 12.4g, Pd (PPh 3) 40.3g, and stir 0.5 hour at a reflux temperature.After till reaction solution is cooled to room temperature, in order to remove the metal ion of catalyzer, the tetrasodium salt of EDTA dihydrate that makes that interpolation is probably equivalent to 2 times moles relative to target compound is dissolved in the solution of appropriate water (below, slightly be designated as the EDTA4Na aqueous solution), and stirred.The solid in solution is extracted by suction filtration, utilize methyl alcohol, then utilize ethyl acetate to clean after make it be dissolved in toluene, then refined by silica gel column chromatography (toluene/ethyl acetate=95/5 (volume ratio)).From chlorobenzene, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-3): 2-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 5.6g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：8.8(m，1H)，8.7(m，1H)，8.25(dd，1H)，8.2(d，1H)，8.0(m，2H)，7.95(d，1H)，7.8(td，1H)，7.75(m，4H)，7.65～7.5(m，6H)，7.35～7.25(m，5H)。
The synthesis of [synthesis example 4] compound (1-3-5)
The synthesis > of <4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes
Under ar gas environment, in flask, add trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 180.9g, two tetramethyl ethylene ketone closes two boron 129.5g, two (dibenzalacetone) palladium (0) 19.6g, tricyclohexyl phosphine 19.1g, potassium acetate 66.7g, salt of wormwood 47.0g and methyl-phenoxide 300ml, and stir 3 hours at a reflux temperature.Add toluene after till reaction solution is cooled to room temperature and stir, after organism is dissolved, utilizing and be paved with diatomaceous paulownia mountain funnel and carried out the inorganic solid substance of filtering by suction filtration.In obtained filtrate, add heptane, and utilize heptane to clean separated out solid, thus obtain 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 109.0g.
The synthesis > of < compound (1-3-5)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 15.0g, 5-bromo-2,3 '-dipyridyl 8.3g, Pd (PPh is added in flask 3) 41.0g, potassiumphosphate 12.6g, 1，2，4-trimethylbenzene 60ml, 2-propyl alcohol 12ml and water 2.4ml, and stir 5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, utilize EDTA4Na water, then utilize ethanol to clean.This solid is fed in chlorobenzene, after making it dissolve at a reflux temperature, carrys out filtering insolubles by suction filtration.Solution is concentrated, carries out recrystallize from chlorobenzene, thus obtain compound (1-3-5): 5-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-2,3 '-dipyridyl 5.7g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.3(s，1H)，9.2(s，1H)，8.7(m，1H)，8.45(d，1H)，8.3(s，1H)，8.2(m，2H)，8.05(m，2H)，7.95(d，1H)，7.9(dd，1H)，7.4-7.8(m，11H)，7.35(m，4H)。
The synthesis of [synthesis example 5] compound (1-3-12)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 5.0g, 6-bromo-2,4 '-dipyridyl 2.3g, Pd (PPh is added in flask 3) 40.3g, potassiumphosphate 4.2g, 1，2，4-trimethylbenzene 20ml, 2-propyl alcohol 4ml and water 1ml, and stir 3 hours at a reflux temperature.Add water and methyl alcohol after till reaction solution is cooled to room temperature, extract separated out solid by suction filtration.Utilize water, then utilize methyl alcohol to clean this solid, make it be dissolved in toluene, then refined by silica gel chromatography (toluene/ethyl acetate=60/40 (volume ratio)).After desolventizing is heated up in a steamer in decompression, carry out recrystallize from chlorobenzene, thus obtain compound (1-3-12): 6-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-2,4 '-dipyridyl 1.3g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：8.8(dd，2H)，8.75(m，1H)，8.45(dd，1H)，8.2(d，1H)，8.1(dd，2H)，8.05(m，3H)，8.0(t，1H)，7.85(d，1H)，7.75(m，4H)，7.7(dd，1H))，7.6(m，2H)，7.55(m，1H)，7.5(m，2H)，7.35(m，4H)。
The synthesis of [synthesis example 6] compound (1-3-21)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 15.0g, 4-(3-bromophenyl) pyridine 6.9g, Pd (PPh is added in flask 3) 41.0g, potassiumphosphate 12.6g, 1，2，4-trimethylbenzene 60ml, 2-propyl alcohol 12ml and water 3ml, and stir 4 hours at a reflux temperature.After till reaction solution is cooled to room temperature, adds water and chlorobenzene and carry out separatory.After desolventizing is heated up in a steamer in decompression, be again dissolved in toluene, then refined by silica gel chromatography (toluene/ethyl acetate=80/20 (volume ratio)).From chlorobenzene, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-21): 4-(3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) phenyl) pyridine 9.7g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：8.7(dd，2H)，8.3(m，1H)，8.15(d，1H)，8.0(m，3H)，7.9(m，2H)，7.50-7.75(m，14H)，7.3(m，4H)。
The synthesis of [synthesis example 7] compound (1-3-22)
<5-bromo-3, the synthesis > of 2 '-dipyridyl
In a nitrogen environment, one side stirs under room temperature, and one drips 2M isopropylmagnesium chloride THF solution 121ml in the flask being added with 3,5-dibromo pyridine 52.1g and THF 300ml.After dropping terminates, utilize frozen water to cool, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 81.0g.Thereafter, and then at room temperature stir 1 hour, add 2-iodine pyridine 45.1g, Pd (PPh 3) 42.5g, then one side utilizes water-bath to carry out cooling one side stirring 3 hours.In reaction soln, add EDTA4Na water and toluene and carry out separatory.The solvent of organic layer is heated up in a steamer in temporary transient decompression, is refined after making dissolution of solid in toluene by silica gel column chromatography (toluene/ethyl acetate=90/10 (volume ratio)).From heptane, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain 5-bromo-3,2 '-dipyridyl 39.0g.
The synthesis > of < compound (1-3-22)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 11.1g, 5-bromo-3,2 '-dipyridyl 5.6g, Pd (PPh is added in flask 3) 40.8g, potassiumphosphate 9.3g, 1，2，4-trimethylbenzene 50ml, tertiary butyl alcohol 5ml and water 5ml, and stir 3 hours at a reflux temperature.After till reaction solution is cooled to room temperature, adds water and toluene and carry out separatory.The solvent of organic layer is heated up in a steamer in temporary transient decompression, is refined after making dissolution of solid in toluene by silica gel chromatography (toluene/ethyl acetate=80/20 (volume ratio)).From toluene, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-22): 5-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-3,2 '-dipyridyl 7.6g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：9.25(m，1H)，9.1(m，1H)，8.8(m，1H)，8.75(t，1H)，8.35(m，1H)，8.15(d，1H)，8.05(m，2H)，7.85～7.95(m，3H)，7.75(dd，4H)，7.7(dd，1H)，7.6(m，2H)，7.55(m，1H)，7.5(m，2H)，73～7.4(m，5H)。
The synthesis of [synthesis example 8] compound (1-3-24)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 15.0g, 5-bromo-3 are added, 4 '-dipyridyl (8.3g), Pd (PPh in flask 3) 41.0g, potassiumphosphate 12.6g, 1，2，4-trimethylbenzene 60ml, 2-propyl alcohol 12ml and water 2.4ml, and stir 3 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration.Utilize EDTA4Na water, then utilize ethanol to clean this solid, make it be dissolved in after in toluene and refined by activated carbon short column (toluene).From chlorobenzene, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-24): 5-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-3,4 '-dipyridyl 6.2g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：9.15(m，1H)，8.95(m，1H)，8.8(dd，2H)，8.3(m，2H)，8.2(d，1H)，8.05(m，2H)，7.9(dd，1H)，7.5～7.75(m，12H)，7.4～7.3(m，4H)。
The synthesis of [synthesis example 9] compound (1-3-25)
The synthesis > of the bromo-5-phenylpyridine of <3-
In a nitrogen environment, one side stirs under room temperature, and one drips 2M isopropylmagnesium chloride THF solution 77ml in the flask being added with 3,5-dibromo pyridine 33.2g and THF 150ml.After dropping terminates, and then at room temperature stir after 1 hour, utilize frozen water to cool, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 34.3g lentamente.At room temperature stir after 1 hour, add iodobenzene 57.1g and Pd (PPh 3) 4(1.6g), then at room temperature stir 43 hours.In reaction soln, add EDTA4Na water and toluene, and carry out separatory.The solvent of organic layer is heated up in a steamer in temporary transient decompression, is refined after making dissolution of solid in toluene by silica gel column chromatography (toluene/ethyl acetate=90/10 (volume ratio)).Decompression is heated up in a steamer desolventizing and obtains the 3-bromo-5-phenylpyridine 25.0g of solid.
The synthesis > of < compound (1-3-25)
4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxaborolanes 10.1g, 3-bromo-5-phenylpyridine 5.2g, Pd (PPh is added in flask 3) 40.7g, potassiumphosphate 8.5g, 1，2，4-trimethylbenzene 50ml, tertiary butyl alcohol 5ml and water 5ml, and stir 3 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration.Utilize water, then utilize methyl alcohol to clean this solid, make it be dissolved in after in toluene and refined by silica gel chromatography (toluene/ethyl acetate=90/10 (volume ratio)).Desolventizing is heated up in a steamer in decompression, thus obtains compound (1-3-25): 3-phenyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 6.4g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：9.05(m，1H)，8.9(m，1H)，8.3(s，1H)，8.25(m，1H)，8.15(d，1H)，8.05(m，2H)，7.9(dd，1H)，7.45～7.75(m，15H)，7.4～7.3(m，4H)。
The synthesis of [synthesis example 10] compound (1-3-27)
The synthesis > of the bromo-2-phenylpyridine of <5-
Phenyl-boron dihydroxide 23.4g, 2,5-dibromo pyridine 50g, Pd (PPh are added in flask 3) 44.4g, make sodium carbonate 40.3g be dissolved in solution in water 150ml and toluene 500ml, then under ar gas environment, stir 3 and a half hours with reflux temperature.Till reaction solution is cooled to room temperature, the solvent of the organic layer through separatory is temporarily reduced pressure and heats up in a steamer, refined by short column of silica gel (toluene) after making dissolution of solid in toluene.From heptane, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain 5-bromo-2-phenylpyridine 28.8g.
The synthesis > of < compound (1-3-27)
In a nitrogen environment, one side stirs under room temperature, and one drips 2M isopropylmagnesium chloride THF solution 12.1ml in the flask being added with 5-bromo-2-phenylpyridine 5.2g and THF 20ml.After dropping terminates, and then at room temperature stir 7 hours.Utilize frozen water to cool flask, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 6.1g.Thereafter at room temperature stir 0.5 hour, add trifluoromethanesulfonic acid 6-(10-phenylanthracene-9-base) naphthalene-2-base ester 10.5g, Pd (PPh 3) 40.3g, then stirs 2 hours at a reflux temperature.Till reaction solution is cooled to room temperature, adds EDTA4Na water, then extracted the solid in solution by suction filtration.Utilize methyl alcohol, then utilize ethyl acetate to clean this solid, make it be dissolved in after in toluene and refined by silica gel column chromatography (toluene).From chlorobenzene, the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain compound (1-3-27): 2-phenyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 2.2g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：9.15(m，1H)，8.3(s，1H)，8.2(m，2H)，8.1(m，2H)，8.05(m，2H)，7.9(m，2H)，7.75(dd，4H)，7.7(dd，1H)，7.65(m，2H)，7.5～7.6(m，5H)，7.45(m，1H)，7.3～7.4(m，4H)。
The synthesis of [synthesis example 11] compound (1-4-2)
The synthesis > of < naphthalene-2,7-bis-base two (fluoroform sulphonate)
Profit is cooled with an ice bath and is added with the flask of 2,7 dihydroxy naphthalene 22.7g and pyridine 200ml, and then in a nitrogen environment, one side is carried out stirring one side and dripped trifluoromethanesulfanhydride anhydride 100g.After dropping terminates, and then at room temperature stir after 3 hours, add water and utilize ethyl acetate to extract.The solvent of organic layer is heated up in a steamer in temporary transient decompression, is refined after making dissolution of solid in toluene by silica gel chromatography (heptane/toluene=80/20 (volume ratio)).Desolventizing is heated up in a steamer in decompression, thus obtains two (fluoroform sulphonate) 42.8g of naphthalene-2,7-bis-base.
The synthesis > of < trifluoromethanesulfonic acid 7-(pyridin-3-yl) naphthalene-2-base ester
Profit is cooled with an ice bath and is added with the flask of 3-bromopyridine 14.0g and THF 50ml, and then in a nitrogen environment, one side is carried out stirring one side and dripped 2M isopropylmagnesium chloride THF solution 48.7ml.After dropping terminates, and then at room temperature stir, after confirming that 3-bromopyridine is consumed, again utilize ice bath to cool, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 24.6g.Thereafter at room temperature stir 0.5 hour, add two (fluoroform sulphonate) 41.4g, Pd (PPh of naphthalene-2,7-bis-base 3) 40.5g, and stir 0.5 hour at a reflux temperature.Till reaction solution is cooled to room temperature, adds EDTA4Na water, then utilize ethyl acetate to extract.The solvent of organic layer is heated up in a steamer in temporary transient decompression, is refined after making dissolution of solid in toluene by silica gel column chromatography (toluene/ethyl acetate=80/20 (volume ratio)).Desolventizing is heated up in a steamer in decompression, thus obtains trifluoromethanesulfonic acid 7-(pyridin-3-yl) naphthalene-2-base ester 11.4g.
The synthesis > of < compound (1-4-2)
(10-phenylanthracene-9-base) boric acid 8.0g, trifluoromethanesulfonic acid 7-(pyridin-3-yl) naphthalene-2-base ester 11.4g, Pd (PPh is added in flask 3) 40.9g, potassiumphosphate 11.4g, 1，2，4-trimethylbenzene 54ml, 2-propyl alcohol 11ml and water 2.2ml, and stir 4 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration.Utilize water, then utilize EDTA4Na water to clean this solid, make it be dissolved in after in toluene and refined by activated alumina chromatography (toluene/ethyl acetate=60/40 (volume ratio)).Desolventizing is heated up in a steamer in decompression, thus obtains compound (1-4-2): 3-(7-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine 6.3g.The structure confirming compound is measured by NMR.
1H-NMR(CDCL3)：9.05(m，1H)，8.65(m，1H)，8.1-8.15(m，3H)，8.05(m，2H)，7.85(d，1H)，7.7～7.75(m，4H)，7.6～7.7(m，3H)，7.55(m，1H)，7.5(m，2H)，7.45(m，1H)，7.3～7.4(m，4H)。
The synthesis example of [synthesis example 12] compound (1-5-11)
The synthesis > of <9-(4-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene
The bromo-10-of 4-ethoxyphenyl boronic acid 38.0g, 9-(naphthalene-2-base) anthracene 57.7g, Pd (PPh is added in flask 3) 41.7g, potassiumphosphate 63.9g and 1，2，4-trimethylbenzene 350ml, then under ar gas environment, stir 4 hours with 100 DEG C.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, utilize methyl alcohol, then utilize water to clean.By this solid heating for dissolving in chlorobenzene, remove insolubles by suction filtration.Solution is concentrated, carries out recrystallize from chlorobenzene, thus obtain 9-(4-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 58.2g.
The synthesis > of <4-(10-(naphthalene-2-base) anthracene-9-base) phenol
In flask, add 9-(4-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 45.1g and pyridine hydrochloride 500.0g, then in a nitrogen environment, stir 10 hours with reflux temperature.After till reaction solution is cooled to room temperature, the solid of separating out after extracting interpolation water by suction filtration, then utilizes methyl alcohol to clean, thus obtains 4-(10-(naphthalene-2-base) anthracene-9-base) phenol 42.0g.
The synthesis > of < trifluoromethanesulfonic acid 4-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester
In a nitrogen environment, one side utilizes ice bath to carry out cooling one and drip trifluoromethanesulfanhydride anhydride 45.2g in the flask being added with 4-(10-(naphthalene-2-base) anthracene-9-base) phenol 42.0g and pyridine 500ml.After dropping terminates, and then at room temperature stir 15 hours.The solid of separating out after extracting interpolation water by suction filtration.Utilize methyl alcohol to clean this solid, carry out recrystallize from chlorobenzene, thus obtain trifluoromethanesulfonic acid 4-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester 38.3g.
The synthesis > of <4,4,5,5-tetramethyl--2-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes
In flask, add trifluoromethanesulfonic acid 4-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester 35.0g, two tetramethyl ethylene ketone closes diboron hexahydride 25.2g, two (dibenzalacetone) palladium (0) 2.2g, tricyclohexyl phosphine 2.8g, potassium acetate 13.0g and cyclopentyl methyl ether 250ml, and stir 5.5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, remove insolubles by suction filtration, then the solvent of filtrate is heated up in a steamer in decompression.Refined by silica gel column chromatography (toluene) after making dissolution of solid in toluene.Desolventizing is heated up in a steamer in decompression, thus obtains 4,4,5,5-tetramethyl--2-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes 16.0g.
The synthesis > of < compound (1-5-11)
4,4,5,5-tetramethyl--2-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes 5.0g, 6-bromo-2,3 '-dipyridyl 2.8g, Pd (PPh is added in flask 3) 40.7g, potassiumphosphate 4.2g, 1，2，4-trimethylbenzene 20ml, tertiary butyl alcohol 4ml and water 4.0ml, and stir 9.5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, then utilize methyl alcohol to clean.By this solid heating for dissolving in toluene, remove insolubles by suction filtration.Solution is concentrated, carries out recrystallize from toluene, thus obtain compound (1-5-11): 6-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3 '-dipyridyl 3.3g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.4(m，1H)，8.7(d，1H)，8.55(dd，1H)，8.4(d，2H)，8.1(d，1H)，8.05(m，1H)，7.9-8.0(m，4H)，7.8(m，3H)，7.75(d，2H)，7.65(d，2H)，7.6(m，3H)，7.45(m，1H)，7.35(m，4H)。
The synthesis of [synthesis example 13] compound (1-5-24)
4,4,5,5-tetramethyl--2-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes 5.0g, 5-bromo-3,4 '-dipyridyl 2.8g, Pd (PPh is added in flask 3) 40.4g, potassiumphosphate 4.2g, 1，2，4-trimethylbenzene 20ml, tertiary butyl alcohol 4ml and water 0.8ml, and stir 4 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, then utilize methyl alcohol to clean.By this solid heating for dissolving in toluene, remove insolubles by suction filtration.Solution is concentrated, carries out recrystallize from toluene, thus obtain compound (1-5-24): 5-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-3,4 '-dipyridyl 3.9g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.1(m，1H)，8.95(m，1H)，8.8(dd，2H)，8.3(m，1H)，8.1(d，1H)，8.05(m，1H)，8.0(s，1H)，7.9-7.95(m，3H)，7.75-7.8(m，4H)，7.6-7.7(m，7H)，7.3-7.4(m，4H)。
The synthesis of [synthesis example 14] compound (1-6-1)
The synthesis > of the bromo-10-of <9-(naphthalene-2-base) anthracene
In a nitrogen environment, one side stirs under room temperature, and one makes iodine 0.1g be dissolved in the solution of chloroform 3ml towards making 9-(naphthalene-2-base) anthracene 39.7g and N-bromosuccinimide 25.5g be dissolved in the solution of chloroform 200ml to drip.After dropping terminates, stir 3 hours at a reflux temperature, till then reaction solution being cooled to room temperature, remove throw out by suction filtration.In this filtrate, add toluene 2000ml and wash.The solid that the solvent utilizing methyl alcohol 100ml to heat up in a steamer organic layer to reducing pressure obtains cleans, thus obtains 9-bromo-10-(naphthalene-2-base) anthracene 45g.
The synthesis > of <4,4,5,5-tetramethyl--2-(10-(naphthalene-2-base) anthracene-9-base) 1,3,2-dioxaborolanes
Under ar gas environment, in flask, add the bromo-10-of 9-(naphthalene-2-base) anthracene 20.0g, two tetramethyl ethylene ketone close two boron 15.8g, two (dibenzalacetone) palladium (0) 0.9g, tricyclohexyl phosphine 1.1g, potassium acetate (10.2g and cyclopentyl methyl ether 100ml, and at a reflux temperature stir 14 hours.Till reaction solution is cooled to room temperature, after interpolation toluene 100ml makes organism dissolve, carries out suction filtration and remove insolubles.By silica gel column chromatography (heptane/toluene=2/1 (volume ratio)), toluene solution is refined, from THF/ heptane mixed solvent (1/10 (volume ratio)), the solid that desolventizing obtains is heated up in a steamer to decompression and carry out recrystallize, thus obtain 4,4,5,5-tetramethyl--2-(10-(naphthalene-2-base) anthracene-9-base) 1,3,2-dioxaborolanes 17.9g.
The synthesis > of <4-(3-bromophenyl) pyridine
The flask being added with 4-bromopyridine hydrochloride (200g) and THF (800ml) is cooled to-40 DEG C, and in a nitrogen environment, one side is carried out stirring one side and is dripped 2M isopropylmagnesium chloride THF solution 540ml wherein.After dropping terminates, after till being temporarily warming up to 0 DEG C, utilize frozen water to cool, then one side carries out stirring one side dropping 2M isopropylmagnesium chloride THF solution 540ml.After dropping terminates, at room temperature stir 1 hour, after confirming that 4-bromopyridine is consumed, utilize frozen water to cool, then one side is carried out stirring one side and is added zinc chloride Tetramethyl Ethylene Diamine complex compound 273g.Thereafter, at room temperature stir 0.5 hour, add 1,3-dibromobenzene 485g and Pd (PPh 3) 41.2g, and stir 3 hours at a reflux temperature.Till reaction solution is cooled to room temperature, adds EDTANa water, carry out separatory and organic layer is washed.Desolventizing is heated up in a steamer in decompression, thus obtains 4-(3-bromophenyl) pyridine 165.7g.
The synthesis > of the compound of < represented by formula (1-6-1)
4,4,5,5-tetramethyl--2-(10-(naphthalene-2-base) anthracene-9-base) 1,3,2-dioxaborolanes 4.0g, 4-(3-bromophenyl) pyridine 2.6g, Pd (PPh3) is added in flask 40.3g, potassiumphosphate 4.0g, 1，2，4-trimethylbenzene 20ml, 2-propyl alcohol 4ml and water 1ml, and stir 6.5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, utilize methyl alcohol, then utilize water to clean.And then after utilizing methyl alcohol, ethyl acetate to clean this solid, recrystallize is carried out from toluene, then carry out recrystallize from chlorobenzene, thus obtain compound (1-6-1): 4-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine 2.1g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：8.7(m，2H)，8.1(d，1H)，8.05(m，1H)，8.0(m，1H)，7.95(m，1H)，7.85(m，1H)，7.8(m，1H)，7.7-7.75(m，5H)，7.6(m，6H)，7.3-7.4(m，4H)。
The synthesis of [synthesis example 15] compound (1-6-2)
4,4,5,5-tetramethyl--2-(10-(naphthalene-2-base) anthracene-9-base) 1,3,2-dioxaborolanes 6.0g, 3-(3-bromophenyl) pyridine 3.9g, Pd (PPh is added in flask 3) 40.5g, potassiumphosphate 5.9g, 1，2，4-trimethylbenzene 28ml, 2-propyl alcohol 5.5ml and water 1ml, and stir 9.5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, utilize methyl alcohol, then utilize water to clean.And then after utilizing methyl alcohol, ethyl acetate to clean this solid, carry out recrystallize from chlorobenzene, thus obtain compound (1-6-2): 3-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine 3.5g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.0(m，1H)，8.6(m，1H)，8.1(d，1H)，8.05(m，1H)，8.0(m，2H)，7.9(m，1H)，7.7-7.8(m，7H)，7.55-7.65(m，4H)，7.3-7.4(m，5H)。
The synthesis of [synthesis example 16] compound (1-6-4)
The synthesis > of the bromo-3-phenetole of <1-
In flask, add 3-bromophenol 100.0g, monobromethane 69.4g, salt of wormwood 95.8g and DMF500ml, then stir 6 hours with 55 DEG C in a nitrogen environment.After till reaction solution is cooled to room temperature, interpolation water and heptane extract.The solvent of organic layer is heated up in a steamer in decompression, thus obtains 1-bromo-3-phenetole 109.0g.
The synthesis > of <9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene
1-bromo-3-phenetole 72.4g, (10-(naphthalene-2-base) anthracene-9-base) boric acid 104.5g, Pd (PPh is added in flask 3) 410.4g, potassiumphosphate 127.4g, 1，2，4-trimethylbenzene 600ml, 2-propyl alcohol 120ml and water 120ml, then stir 6 hours with reflux temperature in a nitrogen environment.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, then utilize methyl alcohol to clean, thus obtain 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 82g.
The synthesis > of <3-(10-(naphthalene-2-base) anthracene-9-base) phenol
In flask, add 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 82g and pyridine hydrochloride 446.0g, then stir 8 hours with reflux temperature in a nitrogen environment.After till reaction solution is cooled to room temperature, the solid of separating out after extracting interpolation water by suction filtration, utilizes methyl alcohol, then utilizes toluene to clean, thus obtain 3-(10-(naphthalene-2-base) anthracene-9-base) phenol 76.0g.
The synthesis > of < trifluoromethanesulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester
Profit is cooled with an ice bath and is added with the flask of 3-(10-(naphthalene-2-base) anthracene-9-base) phenol (76.0g) and pyridine (1L), then drips trifluoromethanesulfanhydride anhydride 65.0g wherein in a nitrogen environment.After dropping terminates, and then at room temperature stir 15 hours, the solid of separating out after extracting interpolation water by suction filtration.Utilize methyl alcohol to clean this solid, thus obtain trifluoromethanesulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester 90.3g.
The synthesis > of <4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes
In flask, add trifluoromethanesulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester 90.3g, two tetramethyl ethylene ketone closes diboron hexahydride 52.1g, two (dibenzalacetone) palladium (0) 7.4g, tricyclohexyl phosphine 7.2g, potassium acetate 33.6g, salt of wormwood 23.6g and methyl-phenoxide 500ml, and stir 5 hours at a reflux temperature.After till reaction solution is cooled to room temperature, utilizes and be paved with diatomaceous paulownia mountain funnel and carry out suction filtration and remove insolubles, then utilize EDTA4Na water to clean filtrate.The solid that the solvent utilizing heptane to heat up in a steamer filtrate to reducing pressure obtains cleans, thus obtains 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes (52.0g).
The synthesis > of < compound (1-6-4)
4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes 15.2g, 5-bromo-2,2 '-dipyridyl 8.5g, Pd (PPh is added in flask 3) 41.0g, potassiumphosphate 12.7g, 1，2，4-trimethylbenzene 120ml, tertiary butyl alcohol 12.0ml and water 2.4ml, and stir 3 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, then utilize methyl alcohol to clean.By this solid heating for dissolving in toluene, remove insolubles by suction filtration.Solution is concentrated, carries out recrystallize from toluene, thus obtain compound (1-6-4): 5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,2 '-dipyridyl 8.3g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.05(m，1H)，8.7(m，1H)，8.45-8.5(m，2H)，8.1-8.15(m，2H)，8.05(m，1H)，8.0(s，1H)，7.5-7.75(m，9H)，7.55-7.65(m，4H)，7.3-7.4(m，5H)。
The synthesis of [synthesis example 17] compound (1-6-5)
4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxaborolanes 9.6g, 5-bromo-2,3 '-dipyridyl 5.3g, Pd (PPh is added in flask 3) 40.7g, potassiumphosphate 8.1g, 1，2，4-trimethylbenzene 40ml, 2-propyl alcohol 8.0ml and water 1.6ml, and stir 4 hours at a reflux temperature.After till reaction solution is cooled to room temperature, extracted the solid in solution by suction filtration, then utilize methyl alcohol to clean.By this solid heating for dissolving in chlorobenzene, remove insolubles by suction filtration.Solution is concentrated, carries out recrystallize from chlorobenzene, thus obtain compound (1-6-5): 5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3 '-dipyridyl 7.1g.The structure confirming compound is measured by NMR.
1H-NMR(CDCl 3)：9.25(m，1H)，9.1(m，1H)，8.65(dd，1H)，8.4(m，1H)，8.1(d，2H)，8.05(m，1H)，8.0(s，1H)，7.95(m，1H)，7.85(t，2H)，7.7-7.8(m，6H)，7.6(m，4H)，7.4(m，1H)，7.3-7.4(m，4H)。
By being suitable for the compound changing raw material, and with the method according to described synthesis example, other derivative compounds of the present invention can be synthesized.
Below, in order to illustrate in greater detail the present invention, disclose the example employing the organic EL of compound of the present invention, but the present invention is not limited to these examples.
The element of example of making 1 and comparative example 1, and carry out driving starting voltage (V) in constant current driven test respectively, keep the mensuration of the time (hr) of the brightness of more than 90% of initial value.Below, example and comparative example are described in detail.
The material of each layer in the element of made example 1 and comparative example 1 is formed and is shown in following table 1.
Table 1
In table 1, " CuPc " is copper phthalocyanine, " NPD " is N4, N4 '-two (naphthalene-1-base)-N4, N4 '-phenylbenzene-[1,1 '-biphenyl]-4,4 '-diamines, compound (A) is 9-((6-[1,1 ': 3,1 " terphenyl]-5 '-Ji) naphthalene-2-base)-10-phenylanthracene, compound (B) is N 5, N 5, N 9, N 9-7,7-hexaphenyl-7H-benzo [C] fluorenes-5,9-diamines, compound (C) is 5,5 '-(2-phenylanthracene-9,10-bis-base) two-2,2 '-dipyridyls, and has following chemical structure respectively.
[example 1]
< is by element (1) > of compound (1-3-1) for electron transfer layer
Using the glass substrate (Optoelectronics Technology (Optoscience) (share) manufacture) of the 26mm × 28mm × 0.7mm to gained till masking becomes the ITO of the thickness of 180nm to be ground to 150nm by sputtering as transparent support substrate.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (vacuum machine work (share) manufacture), then install and be added with the molybdenum evaporation boat of CuPc, the molybdenum evaporation boat being added with NPD, the molybdenum evaporation boat being added with compound (A), be added with compound (B) molybdenum evaporation boat, be added with compound (1-3-1) molybdenum evaporation boat, be added with the molybdenum evaporation boat of lithium fluoride and be added with the tungsten evaporation boat of aluminium.
The ito film of transparent support substrate forms following each layer successively.Vacuum tank is decompressed to 5 × 10 -4till Pa, first, the evaporation boat being added with CuPc is heated and carries out evaporation to form electric hole input horizon in the mode making thickness become 70nm, then, the evaporation boat being added with NPD heated and carry out evaporation to form hole transmission layer in the mode making thickness become 30nm.Secondly, the evaporation boat being added with compound (A) is heated simultaneously with the evaporation boat being added with compound (B) and carries out evaporation to form luminescent layer in the mode making thickness become 35nm.With make the weight ratio of compound (A) and compound (B) roughly become 95 to 5 mode regulate evaporation rate.Secondly, the evaporation boat being added with compound (1-3-1) is heated and carries out evaporation to form electron transfer layer in the mode making thickness become 15nm.The evaporation rate of each layer be 0.01nm/ second ~ 1nm/ second.
Thereafter, the evaporation boat being added with lithium fluoride is heated and with the mode making thickness become 0.5nm with 0.003nm/ second ~ evaporation rate of 0.1nm/ second carries out evaporation, then the evaporation boat being added with aluminium is heated and with the mode making thickness become 100nm with 0.01nm/ second ~ evaporation rate of 10nm/ second carries out evaporation to form negative electrode, thus obtains organic EL.
If using ITO electrode as anode, using lithium fluoride/aluminium electrode is as negative electrode and apply volts DS, then the blue-light-emitting that wavelength is about 455nm can be obtained.Utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test, result drives test starting voltage to be 5.65V, keeps 90% (1800cd/m of initial value 2) more than time of brightness be 110 hours.
< comparative example 1>
Replace to except compound (C) except by compound (1-3-1), obtain organic EL with the method according to example 1.Using ITO electrode as anode, using lithium fluoride/aluminium electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 4.59V, the time keeping the brightness of more than 90% of initial value is 39 hours.
Above be the results are summarized in table 2.
Table 2
The material being used for electric hole input horizon is replaced to from the CuPc of example 1 compound and the HI that compound does not originally have luminescence peak in red area, and use the compound shown in table 3 to carry out the element of example of making 2 ~ example 9 as the material of electron transfer layer, and carry out driving starting voltage (V) in constant current driven test respectively, keep the mensuration of the time (hr) of the brightness of more than 90% of initial value.Below, example and comparative example are described in detail.Moreover HI is N4, N4 '-phenylbenzene-N4, N4 '-bis-(9-phenyl-9H-carbazole-3-base)-[1,1 '-biphenyl]-4,4 '-diamines, and it has following chemical structure.
The material of each layer in the element of made example 2 ~ example 9 is formed and is shown in following table 3.
Table 3
[example 2]
< is by element (2) > of compound (1-3-1) for electron transfer layer
Using to the glass substrate (Optoscience (share) manufacture) of 26mm × 28mm × 0.7mm of gained till masking becomes the ITO of the thickness of 180nm to be ground to 150nm by sputtering as transparent support substrate.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (vacuum machine work (share) manufacture), then install and be added with the molybdenum evaporation boat of HI, the molybdenum evaporation boat being added with NPD, the molybdenum evaporation boat being added with compound (A), be added with compound (B) molybdenum evaporation boat, be added with compound (1-3-1) molybdenum evaporation boat, be added with quinoline lithium molybdenum evaporation boat, be added with magnesium molybdenum boat and be added with silver-colored tungsten evaporation boat.
The ito film of transparent support substrate forms following each layer successively.Vacuum tank is decompressed to 5 × 10 -4till Pa, first, the evaporation boat being added with HI is heated and carries out evaporation to form electric hole input horizon in the mode making thickness become 40nm, then, the evaporation boat being added with NPD heated and carry out evaporation to form hole transmission layer in the mode making thickness become 30nm.Secondly, the evaporation boat being added with compound (A) is heated simultaneously with the evaporation boat being added with compound (B) and carries out evaporation to form luminescent layer in the mode making thickness become 35nm.With make the weight ratio of compound (A) and compound (B) roughly become 95 to 5 mode regulate evaporation rate.Secondly, the evaporation boat being added with compound (1-3-1) is heated and carries out evaporation to form electron transfer layer in the mode making thickness become 15nm.The evaporation rate of each layer be 0.01nm/ second ~ 1nm/ second.
Thereafter, the evaporation boat being added with quinoline lithium is heated and with the mode making thickness become 1nm with 0.01nm/ second ~ evaporation rate of 0.1nm/ second carries out evaporation.Then, the boat being added with magnesium is heated simultaneously with the boat being added with silver and carries out evaporation to form negative electrode in the mode making mould become 100nm.Now, with make the atomicity of magnesium and silver than become 10 to 1 mode regulate evaporation rate, and form negative electrode to obtain organic electroluminescent device in the mode making evaporation rate become 10nm from 0.1nm.
If using ITO electrode as anode, magnesium/silver electrode is applied volts DS as negative electrode, then can obtain the blue-light-emitting that wavelength is about 460nm.In addition, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test, result drives test starting voltage to be 6.77V, keeps 90% (1800cd/m of initial value 2) more than time of brightness be 108 hours.
[example 3]
< is by the element > of compound (1-3-2) for electron transfer layer
Replace to except compound (1-3-2) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 5.71V, the time keeping the brightness of more than 90% of initial value is 74 hours.
[example 4]
< is by the element > of compound (1-3-5) for electron transfer layer
Replace to except compound (1-3-5) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 5.71V, the time keeping the brightness of more than 90% of initial value is 88 hours.
[example 5]
< is by the element > of compound (1-3-22) for electron transfer layer
Replace to except compound (1-3-22) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 6.97V, the time keeping the brightness of more than 90% of initial value is 98 hours.
[example 6]
< is by the element > of compound (1-3-24) for electron transfer layer
Replace to except compound (1-3-24) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 7.16V, the time keeping the brightness of more than 90% of initial value is 143 hours.
[example 7]
< is by the element > of compound (1-3-25) for electron transfer layer
Replace to except compound (1-3-25) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 7.35V, the time keeping the brightness of more than 90% of initial value is 165 hours.
[example 8]
< is by the element > of compound (1-5-24) for electron transfer layer
Replace to except compound (1-5-24) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 6.36V, the time keeping the brightness of more than 90% of initial value is 103 hours.
[example 9]
< is by the element > of compound (1-6-4) for electron transfer layer
Replace to except compound (1-6-4) except by compound (1-3-1), obtain organic EL with the method according to example 2.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, utilize for obtaining 2000cd/m 2the current density of original intensity implement constant current driven test.Drive test starting voltage to be 6.34V, the time keeping the brightness of more than 90% of initial value is 120 hours.
Above be the results are summarized in table 4.
Table 4
Utilizability in industry
According to preferred form of the present invention, especially the life-span upgrading and the organic electroluminescent device also excellent with the balance of driving voltage that make luminous element can be provided, possess the display unit of this organic electroluminescent device and possess the means of illumination etc. of this organic electroluminescent device.

Claims (7)

1. a compound, it is represented by following formula (1-5):
In formula (1-5),
Py is the base represented by formula (3);
Formula (3) is selected from 2,2 '-dipyridyl-5-base, 2,2 '-dipyridyl-6-base, 2,3 '-dipyridyl-5-base, 2,3 '-dipyridyl-6-base, 2,4 '-dipyridyl-5-base, 2,4 '-dipyridyl-6-bases, 3,2 '-dipyridyl-6-bases, 3,2 '-dipyridyl-5-base, 3,3 '-dipyridyl-6-base, 3,3 '-dipyridyl-5-bases, 3,4 '-dipyridyl-6-bases, 3,4 '-dipyridyl-5-base, 4,2 '-dipyridyl-3-base, 4,3 '-dipyridyl-3-base and 4,4 '-dipyridyl-3-base one of them of cohort organized.
2. compound according to claim 1, it is represented by following formula (1-5-11):
3. compound according to claim 1, it is represented by following formula (1-5-24):
4. an electron transport material, it contains compound according to any one of claim 1 to 3.
5. an organic electroluminescent device, it comprises: the pair of electrodes comprising anode and negative electrode, be configured in the luminescent layer between this pair of electrodes, and be configured between described negative electrode and this luminescent layer and electron transfer layer containing electron transport material according to claim 4 and/or electron injecting layer.
6. organic electroluminescent device according to claim 5, at least one deck of wherein said electron transfer layer and electron injecting layer also comprises at least one in the cohort being selected from and being made up of hydroxyquinoline system metal complex, dipyridyl derivatives, phenanthroline derivative and borane derivative.
7. the organic electroluminescent device according to claim 5 or 6, wherein at least one deck of electron transfer layer and electron injecting layer also comprises at least one in the cohort selecting free alkali metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, the oxide compound of alkaline-earth metal, the halogenide of alkaline-earth metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic complex, the organic complex of alkaline-earth metal and the organic complex of rare earth metal to form.
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