CN103189355A - Electron transport material and organic electroluminescence element using same - Google Patents

Electron transport material and organic electroluminescence element using same Download PDF

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CN103189355A
CN103189355A CN2011800520693A CN201180052069A CN103189355A CN 103189355 A CN103189355 A CN 103189355A CN 2011800520693 A CN2011800520693 A CN 2011800520693A CN 201180052069 A CN201180052069 A CN 201180052069A CN 103189355 A CN103189355 A CN 103189355A
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CN103189355B (en
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小野洋平
马场大辅
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SK Materials JNC Co Ltd
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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
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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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    • 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
    • C07D213/22—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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Abstract

The compound of the invention represented by formula (1) is useful as an electron transport material for organic EL elements and use of said electron transport material contributes to the increased life, etc. of organic EL elements. In formula (1), the (Py)s are independent and are groups represented by formulas (2), (3) or (4); m and n are 0 or 1 and m + n = 1; and at least one of the hydrogens of the benzene ring, naphthalene ring or pyridine ring in formula (1) is substituted with a C1-6 alkyl group or C3-6 cycloalkyl group.

Description

Electron transport material and use its organic electroluminescent element
Technical field
The present invention relates to a kind of novel electron transport material with pyridyl, use organic electroluminescent element (below, abbreviate organic EL sometimes as, or only abbreviate element as) of this electron transport material etc.
Background technology
In recent years, organic EL gets most of the attention as time full-color flat-panel monitor (full color flat panel display) of generation, and industry is studied it just actively at present.In order to promote the practicability of organic EL, it is indispensable key element that the reduction of element drives voltage, life-span prolong, and in order to realize these key elements, industry is being developed new electron transport material always.Especially the driving voltage that must realize blue element reduces, the life-span prolongation.Patent documentation 1(Japanese Patent spy opens the 2003-123983 communique) in record following situation: by will be as 2 of coffee quinoline (phenanthroline) derivative or its analogue, the 2'-Bipyridine compound is used for electron transport material, can be with the low voltage drive organic EL.Yet the element characteristic that the example of the document is reported (driving voltage, luminous efficiency etc.) is only for being the relative value of benchmark with the comparative example, and record can not be judged as the measured value of practical value.In addition, 2,2'-Bipyridine compound is used for the example of electron transport material at non-patent literature 1(Proceedings of the10 ThInternational Workshop on Inorganic and Organic Electroluminescence, the tenth inorganic and organic electric-excitation luminescent international symposium collected works), patent documentation 2(Japanese Patent spy opens the 2002-158093 communique) and international 2007/86552 handbook that discloses of patent documentation 3() in announcement is arranged.The Tg of the compound of record is low in the non-patent literature 1, and impracticable.Though the compound of record can drive organic EL with relative low voltage in patent documentation 2 and the patent documentation 3, still expect further to make the life-span to prolong during practical application.
The prior art document
Patent documentation
Patent documentation 1: the Japanese Patent spy opens the 2003-123983 communique
Patent documentation 2: the Japanese Patent spy opens the 2002-158093 communique
Patent documentation 3: international 2007/86552 handbook that discloses
Non-patent literature
Non-patent literature 1:Proceedings of the10 ThInternational Workshop on Inorganic and Organic Electroluminescence (2000) (the tenth inorganic and organic electric-excitation luminescent international symposium collected works (2000))
Summary of the invention
The problem that the invention desire solves
Given this present invention plants the existing in prior technology subject study to form.Problem of the present invention is to provide the electron transport material that a kind of life-span that helps organic EL prolongs etc.In addition, problem of the present invention is to provide a kind of organic EL that uses this electron transport material.
The means of dealing with problems and adopting
People such as the inventor study through great efforts, found that: by following compound being used for the electron transfer layer of organic EL, can obtain can be with the organic EL of long lifetime driving, this compound is to have pyridyl, bipyridyl or pyridyl phenyl at 9-(2-the naphthyl)-naphthyl of 10-phenylanthracene or any in the phenyl, and it is that 1～6 alkyl or carbon number are the compound of 3～6 cycloalkyl that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring is substituted by carbon number, finishes the present invention based on this discovery.
Above-mentioned problem is by every solution the shown below.
[1] a kind of compound, it is with following formula (1) expression,
[changing 1]
Figure BDA00003113040000021
In the formula (1),
Py independently is formula (2), (3) or (4) represented base;
[changing 2]
Figure BDA00003113040000022
M and n are 0 or 1, m+n=1; And,
It is that 1～6 alkyl or carbon number are 3～6 cycloalkyl that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring in the formula (1) is substituted by carbon number.
[2] as above-mentioned [1] described compound, it is with following formula (1-1) or (1-2) expression,
[changing 3]
Figure BDA00003113040000031
During formula (1-1) reaches (1-2),
Py is formula (2), (3) or (4) represented base;
[changing 4]
Figure BDA00003113040000032
And, formula (1-1) and (1-2) in phenyl ring, naphthalene nucleus and pyridine ring at least one hydrogen to be substituted by carbon number be that 1～6 alkyl or carbon number are 3～6 cycloalkyl.
[3] as above-mentioned [1] described compound, it is with following formula (1-3), (1-4), (1-5) or (1-6) expression,
[changing 5]
Figure BDA00003113040000033
In the formula (1-3)～(1-6),
Py is formula (2), (3) or (4) represented base;
[changing 6]
Figure BDA00003113040000041
And it is that 1～6 alkyl or carbon number are 3～6 cycloalkyl that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring in the formula (1-3)～(1-6) is substituted by carbon number.
[4] as above-mentioned [1] described compound, its with following formula (1-7) or (1-8) expression,
[changing 7]
Figure BDA00003113040000042
During formula (1-7) reaches (1-8),
Py is formula (2), (3) or (4) represented base;
[changing 8]
Figure BDA00003113040000043
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And,
P is 1～5 integer.
[5] as above-mentioned [1] described compound, it is with following formula (1-9) or (1-10) expression,
[changing 9]
Figure BDA00003113040000044
During formula (1-9) reaches (1-10),
Py is formula (2), (3) or (4) represented base;
[changing 10]
Figure BDA00003113040000045
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And,
Q is 1～5 integer.
[6] as above-mentioned [1] described compound, it is with following formula (1-11) or (1-12) expression,
[changing 11]
Figure BDA00003113040000051
During formula (1-11) reaches (1-12),
Py1 is formula (2'), (3') or (4') represented base;
[changing 12]
Figure BDA00003113040000052
Formula (2'), (3') and (4') in, R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And s is 1～4 integer.
[7] as above-mentioned [1] described compound, it is with following formula (1-13) or (1-14) expression,
[changing 13]
Figure BDA00003113040000053
During formula (1-13) reaches (1-14),
Py1 is formula (2'), (3') or (4') represented base;
[changing 14]
Formula (2'), (3') or (4') in, R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And s is 1～4 integer.
[8] as above-mentioned [1] described compound, it is with following formula (1-15) or (1-16) expression,
[changing 15]
Figure BDA00003113040000061
During formula (1-15) reaches (1-16),
Py is formula (2), (3) or (4) represented base;
[changing 16]
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And t is 1～4 integer.
[9] as above-mentioned [a 1] described compound, it is represented with following formula (1-7-26)
[changing 17]
[10] as above-mentioned [a 1] described compound, it is represented with following formula (1-7-74)
[changing 18]
Figure BDA00003113040000064
[11] as above-mentioned [a 1] described compound, it is represented with following formula (1-7-98)
[changing 19]
Figure BDA00003113040000071
[12] as above-mentioned [a 1] described compound, it is represented with following formula (1-7-96)
[changing 20]
[13] as above-mentioned [a 1] described compound, it is represented with following formula (1-14-14)
[changing 21]
Figure BDA00003113040000073
[14] as above-mentioned [1] described compound, its with following formula (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-5), (1-11-6), (1-11-8), (1-11-18), (1-11-39), (1-14-2), (1-14-3), (1-14-11), (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and (1-14-20) in any expression
[changing 22]
Figure BDA00003113040000081
[changing 23]
Figure BDA00003113040000091
[15] a kind of electron transport material, it contains as each described compound in above-mentioned [1] to [14].
[16] a kind of organic electroluminescent element, it comprises: comprise anode and negative electrode pair of electrodes, be configured in the luminescent layer between this pair of electrodes and be configured in above-mentioned negative electrode and this luminescent layer between and contain electron transfer layer and/or electron injecting layer as above-mentioned [15] described electron transport material.
[17] as above-mentioned [16] described organic electroluminescent element, wherein the one deck at least in above-mentioned electron transfer layer and the electron injecting layer comprises that also being selected from by hydroxyquinoline is at least a among the group that forms of metal misfit thing, dipyridyl derivatives, coffee quinoline derivant and borane derivative.
[18] as above-mentioned [16] or [17] described organic electroluminescent element, wherein the one deck at least in electron transfer layer and the electron injecting layer also comprises and is selected from least a among the group who is made up of organic misfit thing of organic misfit thing of the oxide compound of basic metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, 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 misfit thing, alkaline-earth metal and rare earth metal.
The effect of invention
Even compound of the present invention applies voltage under filminess also stable, in addition, has the high feature of transmittability of electric charge.Compound of the present invention is suitable as the charge transfer material in the organic EL.By compound of the present invention being used for electron transfer layer and/or the electron injecting layer of organic EL, can obtain to have long-life organic EL.The organic EL of the application of the invention can be made the Performance Monitor device of full-color demonstration etc.
Embodiment
Below, illustrate in greater detail the present invention.In addition, in this manual, for example sometimes " the represented compound of formula (1-7-26) " is called " compound (1-7-26) ".Sometimes " the represented compound of formula (1-7-74) " is called " compound (1-7-74) ".The symbol of other formulas, the numbering of formula are also identical.
The explanation of＜compound＞
The 1st invention of this case is the represented compound with pyridyl, bipyridyl or pyridyl phenyl of a kind of following formula (1).
[changing 24]
Figure BDA00003113040000101
In the formula (1), Py independently is formula (2), (3) or (4) represented base, and m and n are 0 or 1, m+n=1.And it is that 1～6 alkyl or carbon number are that 3～6 cycloalkyl is the feature of this compound that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring in the formula (1) is substituted by carbon number.
The represented pyridyl of formula (2) is specially 2-pyridyl, 3-pyridyl or 4-pyridyl.
The represented bipyridyl of 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.
The represented pyridyl phenyl of formula (4) 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.
In the formula (1), the position that Py links all can be the optional position on phenyl, 2-naphthyl, is preferably 4 and 3 at phenyl, is preferably 6 and 7 at the 2-naphthyl.Just do not enlarge the conjugated system aspect, and do not reduce LUMO(lowest unoccupied molecular orbital, minimum vacant molecule orbital) can the aspect, rank, You Jia is 3 of phenyl.In addition, with regard to raw material acquisition aspect easily, You Jia is 6 of 2-naphthyl.
Phenyl ring in the formula (1), naphthalene nucleus, and pyridine ring on the carbon number that replaces be that the example of 1～6 alkyl is: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, tributyl, n-pentyl, isopentyl, 2,2-dimethyl propyl, n-hexyl, and isohexyl.Wherein preferable alkyl is methyl, ethyl, sec.-propyl, reaches tributyl, is more preferred from methyl and tributyl.Carbon number is that the example of 3～6 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.Wherein, if consider the acquisition of raw material, synthetic easy degree, then preferable cycloalkyl is cyclohexyl.
The represented compound of formula (1) is specially following formula (1-1) or (1-2) represented compound.
[changing 25]
Figure BDA00003113040000111
The definition of Py during formula (1-1) reaches (1-2) is same as described above.
The represented compound of formula (1) more specifically is any the represented compound in the following formula (1-3)～(1-6).
[changing 26]
Figure BDA00003113040000121
The definition of Py in the formula (1-3)～(1-6) is same as described above.
The represented compound of formula (1) more specifically is any the represented compound in the following formula (1-7)～(1-10).
[changing 27]
Figure BDA00003113040000122
Py in the formula (1-7)～(1-10) and the definition of R are same as described above.P during formula (1-7) reaches (1-8) is 1～5 integer, is preferably 1～2 integer, is more preferred from 1.The position of the phenyl that R replaces is also unrestricted, is preferably 3 or 4.Q during formula (1-9) reaches (1-10) is 1～5 integer, is preferably 1～2 integer, is more preferred from 1.The position of the naphthyl that R replaces is also unrestricted, is preferably 6 or 7.
In addition, the represented compound of formula (1) more specifically is any the represented compound in the following formula (1-11)～(1-14).
[changing 29]
Figure BDA00003113040000131
The definition of Py1 in the formula (1-11)～(1-14) is same as described above.Above-mentioned formula (2'), (3') or (4') in the definition of R same as described above.S is 1～4 integer, is preferably 1 or 2, is more preferred from 1.There is no particular restriction in the position of the pyridyl that R replaces.
In addition, the represented compound of formula (1) more specifically is following formula (1-15) or (1-16) represented compound.
[changing 32]
Figure BDA00003113040000132
Py during formula (1-15) reaches (1-16) and the definition of R are same as described above.T is 1～4 integer, is preferably 1 or 2, is more preferred from 1.The position of the phenylene that R replaces is also unrestricted, if consider synthetic easy degree, is that benchmark is preferably 3 with the carbon that links with anthracene under the situation that is 1,4-phenylene then.Under the situation that is 1,3-phenylene, be that benchmark is preferably 4 with the carbon that links with anthracene.
Particularly, roughly be divided into the represented compound of formula (1-7)～(1-16) as the represented compound of above-mentioned formula (1).In these, preferable structure is formula (1-7), formula (1-9)～(1-11) and formula (1-13)～(1-16), and better structure is formula (1-7).
The concrete example of＜compound＞
The concrete example of compound of the present invention can be disclosed as following cited formula, but the present invention is not limited to the announcement of these concrete structures.
The concrete example of the compound that＜formula (1-7) is represented＞
The concrete example of the compound that formula (1-7) is represented is shown in following formula (1-7-1)～(1-7-144).In these, preferable compound is formula (1-7-1)～(1-7-6), formula (1-7-10)～(1-7-12), formula (1-7-16)～(1-7-30), formula (1-7-34)～(1-7-36), formula (1-7-40)～(1-7-48), formula (1-7-73)～(1-7-78), formula (1-7-82)～(1-7-84), formula (1-7-88)～(1-7-102), formula (1-7-106)～(1-7-108) and formula (1-7-112)～(1-7-120).
[changing 33]
Figure BDA00003113040000141
[changing 34]
Figure BDA00003113040000151
[changing 35]
Figure BDA00003113040000161
[changing 36]
Figure BDA00003113040000162
[changing 37]
Figure BDA00003113040000171
[changing 38]
Figure BDA00003113040000181
[changing 39]
Figure BDA00003113040000182
[changing 40]
Figure BDA00003113040000191
[changing 41]
Figure BDA00003113040000192
[changing 42]
Figure BDA00003113040000201
[changing 43]
Figure BDA00003113040000211
Figure BDA00003113040000212
[changing 45]
Figure BDA00003113040000221
[changing 46]
Figure BDA00003113040000231
[changing 47]
Figure BDA00003113040000232
[changing 48]
Figure BDA00003113040000241
[changing 49]
[changing 50]
The concrete example of the compound that＜formula (1-8) is represented＞
The concrete example of the compound that formula (1-8) is represented is shown in following formula (1-8-1)～(1-8-105).
[changing 51]
Figure BDA00003113040000261
[changing 52]
Figure BDA00003113040000271
[changing 53]
Figure BDA00003113040000281
[changing 54]
Figure BDA00003113040000291
[changing 55]
Figure BDA00003113040000301
[changing 56]
Figure BDA00003113040000311
[changing 57]
Figure BDA00003113040000321
[changing 58]
[changing 59]
Figure BDA00003113040000341
[changing 60]
The concrete example of the compound that＜formula (1-9) is represented＞
The concrete example of the compound that formula (1-9) is represented is shown in following formula (1-9-1)～(1-9-48).In these, preferable compound is formula (1-9-10)～(1-9-12), (1-9-16)～(1-9-18), formula (1-9-34)～(1-9-36) and formula (1-9-40)～(1-9-42).
[changing 61]
Figure BDA00003113040000361
[changing 62]
Figure BDA00003113040000371
[changing 63]
Figure BDA00003113040000381
[changing 64]
Figure BDA00003113040000391
The concrete example of the compound that＜formula (1-10) is represented＞
The concrete example of the compound that formula (1-10) is represented is shown in following formula (1-10-1)～(1-10-48).In these, preferable compound is that formula (1-10-1)～(1-10-6), (1-10-10)～(1-10-12) reach (1-10-16)～(1-10-21).
[changing 65]
Figure BDA00003113040000401
[changing 66]
Figure BDA00003113040000411
[changing 67]
Figure BDA00003113040000421
[changing 68]
Figure BDA00003113040000431
The concrete example of the compound that＜formula (1-11) is represented＞
The concrete example of the compound that formula (1-11) is represented is shown in following formula (1-11-1)～(1-11-60).In these, preferable compound is that formula (1-11-3)～(1-11-10), (1-11-25)～(1-11-28) reach (1-11-51)～(1-11-60).
[changing 69]
Figure BDA00003113040000441
[changing 70]
Figure BDA00003113040000451
[changing 71]
Figure BDA00003113040000461
[changing 72]
[changing 73]
Figure BDA00003113040000481
The concrete example of the compound that＜formula (1-12) is represented＞
The concrete example of the compound that formula (1-12) is represented is shown in following formula (1-12-1)～(1-12-60).
[changing 74]
Figure BDA00003113040000491
[changing 75]
Figure BDA00003113040000501
[changing 76]
Figure BDA00003113040000511
[changing 77]
[changing 78]
Figure BDA00003113040000531
The concrete example of the compound that＜formula (1-13) is represented＞
The concrete example of the compound that formula (1-13) is represented is shown in following formula (1-13-1)～(1-13-60).In these, preferable compound is formula (1-13-21)～(1-13-28) and formula (1-13-31)～(1-31-40).
[changing 79]
Figure BDA00003113040000541
[changing 80]
Figure BDA00003113040000551
[changing 81]
Figure BDA00003113040000561
[changing 82]
Figure BDA00003113040000571
[changing 83]
Figure BDA00003113040000581
The concrete example of the compound that＜formula (1-14) is represented＞
The concrete example of the compound that formula (1-14) is represented is shown in following formula (1-14-1)～(1-14-60).In these, preferable compound is formula (1-14-1)～(1-14-18).
[changing 84]
Figure BDA00003113040000591
[changing 85]
Figure BDA00003113040000601
[changing 86]
Figure BDA00003113040000611
[changing 87]
Figure BDA00003113040000621
[changing 88]
Figure BDA00003113040000631
The concrete example of the compound that＜formula (1-15) is represented＞
The concrete example of the compound that formula (1-15) is represented is shown in following formula (1-15-1)～(1-15-48).In these, preferable compound is formula (1-15-10)～(1-15-12), (1-15-16)～(1-15-18), formula (1-15-34)～(1-15-36) and (1-15-40)～(1-15-42).
[changing 89]
Figure BDA00003113040000641
[changing 90]
Figure BDA00003113040000651
[changing 91]
Figure BDA00003113040000661
[changing 92]
Figure BDA00003113040000671
The concrete example of the compound that＜formula (1-16) is represented＞
The concrete example of the compound that formula (1-16) is represented is shown in following formula (1-16-1)～(1-16-24).In these, preferable compound is formula (1-16-1)～(1-16-5).
[changing 93]
Figure BDA00003113040000681
[changing 94]
Figure BDA00003113040000691
The synthetic method of＜compound＞
Below, the synthetic method of compound of the present invention is described.Compound of the present invention can utilize general known synthetic method to synthesize by suitable combination.
The synthetic method of the compound that＜formula (1-7-1)～formula (1-7-144) is represented＞
[changing 95]
Figure BDA00003113040000701
R: the cycloalkyl of the alkyl of carbon number 1～6 or carbon number 3-6
The integer of m:l to 5
At first, by reacting the 9-phenylanthracene that 1 synthesis of phenyl replaces through alkyl (cycloalkyl).The bromobenzene that replaces through alkyl is reacted with MAGNESIUM METAL in THF, make jesse greener reagent (Grignard reagent), itself and 9-bromine anthracene are reacted, make the 9-phenylanthracene that phenyl replaces through alkyl (cycloalkyl).Phenyl ring and anthracene nucleus coupling are not limited to aforesaid method, for example can adopt the root bank coupled reaction of using zinc misfit thing, the Suzuki coupled reaction of using boric acid or boric acid ester etc., can suit to use these ordinary methods according to situation.
[changing 96]
Reaction 2
Figure BDA00003113040000702
Reaction 2 is to use N-bromine succinimide and 10 brominations of 9-phenylanthracene that phenyl is replaced through alkyl (cycloalkyl).Also can use N-bromine succinimide bromizating agent commonly used in addition herein.
[changing 97]
Figure BDA00003113040000711
Reaction 3 is with anthracene nucleus and naphthalene nucleus coupling.At first according to ordinary method 2-bromo-6-methoxynaphthalene is made jesse greener reagent, the 9-bromine anthracene derivant reaction that itself and reaction 2 are synthesized, synthetic 9-(6-methoxynaphthalene-2-yl)-10-phenylanthracene derivative.With reaction 1 similarly, phenyl ring and anthracene nucleus coupling are not limited to aforesaid method, for example can adopt the root bank coupled reaction of using zinc misfit thing, the Suzuki coupled reaction of using boric acid or boric acid ester etc., can be according to situation these ordinary methods of use that suit.
[changing 98]
Figure BDA00003113040000712
Reaction 4 is that the methoxyl group demethylation of 9-(6-methoxynaphthalene-2-yl)-10-phenylanthracene derivative is formed naphthols.Also can suit to use demethylation reaction reagent commonly used herein.
[changing 99]
Reaction 5
Reaction 5 is converted into triflate (triflate) with naphthols-OH.In the reaction formula-OTf is-OSO 2CF 3Abbreviation.
[changing 100]
Reaction 6
Figure BDA00003113040000721
Reaction 6 is by root bank coupling (Negishi coupling) reaction pyridine ring to be combined with naphthalene nucleus.At first, the 4-bromopyridine is made jesse greener reagent.Herein, owing to be to use the stable 4-bromopyridine hydrochloride of raw material, so use the isopropylmagnesium chloride of 2 times of moles, but for the raw material that needn't use hydrochloride, then for waiting mole also harmless.In jesse greener reagent, add zinc chloride Tetramethyl Ethylene Diamine misfit thing, the zinc chloride misfit thing of pyridine synthesis, the triflate reaction that itself and reaction 5 are obtained, and synthetic target compound.
Reaction 6 is dug up the roots beyond the bank coupled reaction, also can suit to use coupled reactions commonly used such as Suzuki coupling (Suzuki coupling) reaction.Under the situation of using the Suzuki coupled reaction, prepare optimal boric acid or boric acid ester gets final product according to target compound, for example can use the boric acid ester shown in the following reaction 7 to obtain target compound.
[changing 101]
Reaction 7
Figure BDA00003113040000731
As the concrete example of the employed palladium catalyst of coupled reaction, can enumerate: Pd (PPh 3) 4, PdCl 2(PPh 3) 2, Pd (OAc) 2, three (dibenzalacetones), two palladiums (0), three (dibenzalacetones), two palladiums (0) chloroform misfit thing, two (dibenzalacetone) palladium (0), two (three tributyl phosphino-s) palladium (0) or (two (diphenylphosphino) ferrocene of 1,1'-) dichloro palladium (II).
In addition, in order to promote reaction, also can in these palladium compounds, add phosphine compound according to circumstances.Concrete example as this phosphine compound, can enumerate: three (tributyl) phosphine, tricyclohexyl phosphine, 1-(N, N-dimethyl amine ylmethyl)-2-(two tributyl phosphino-s) ferrocene, 1-(N, N-dibutylamine ylmethyl)-2-(two tributyl phosphino-s) ferrocene, 1-(methoxymethyl)-2-(two tributyl phosphino-s) ferrocene, 1, two (the two tributyl phosphino-s) ferrocene of 1'-, 2, two (the two tributyl phosphino-s)-1 of 2'-, the 1'-dinaphthalene, 2-methoxyl group-2'-(two tributyl phosphino-s)-1, the 1'-dinaphthalene, or 2-dicyclohexyl phosphino--2', the 6'-dimethoxy-biphenyl.
As the concrete example of the employed alkali of reaction, can enumerate: yellow soda ash, salt of wormwood, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, hydrated barta, sodium ethylate, the 3rd sodium butylate, sodium acetate, Tripotassium phosphate or Potassium monofluoride.
In addition, as the concrete example of the employed solvent of reaction, can enumerate: benzene,toluene,xylene, 1,2,4-Three methyl Benzene, N, dinethylformamide, tetrahydrofuran (THF), Anaesthetie Ether, tributyl-methyl phosphonium ether, 1,4-dioxan, methyl alcohol, ethanol, cyclopentyl-methyl ether or Virahol.These solvents can suit to select, and can use separately, also can be made into mixed solvent and use.
The synthetic method of the compound that＜formula (1-8-1)～formula (1-8-105) is represented＞
In above-mentioned reaction 3, if use 2-bromo-7-methoxynaphthalene to replace 2-bromo-6-methoxynaphthalene, then can similarly synthesize.
The synthetic method of the compound that＜formula (1-9-1)～formula (1-9-48) and formula (1-10-1)～formula (1-10-48) is represented＞
Replace employed raw material in above-mentioned reaction 1～reaction 3 by the raw material that uses these benzene skeletons and naphthalene skeleton to be substituted, can similarly synthesize with above-mentioned.Namely, jesse greener reagent and the coupling of 9-bromine anthracene with 2-bromine anthracene, according to reaction 2 10 brominations with anthracene, then make this bromide with to the jesse greener reagent react of methoxyl group bromobenzene or meta-methoxy bromobenzene, and obtain 9-(4-or 3-p-methoxy-phenyl)-10-(2-naphthyl) anthracene.At this compound, above-mentioned the getting final product of order foundation that the demethylation reaction of methoxyl group is later.In addition, except the compound of particular instantiation, also can synthesize according to above-mentioned synthetic method by according to the suitable raw material that uses of target compound certainly.
The synthetic method of the compound that＜formula (1-11-1)～formula (1-11-60), formula (1-12-1)～formula (1-12-60), formula (1-13-1)～formula (1-13-60) and formula (1-14-1)～formula (1-10-60) are represented＞
The pyridine derivate that the pyridine derivate that replaces through alkyl or cycloalkyl by use replaces above-mentioned reaction 6 or reacts 7 employed raw materials can similarly synthesize with above-mentioned as raw material.
The pyridine derivate that replaces through alkyl or cycloalkyl can synthesize shown in following reaction 8～reaction 9.Herein, though illustration the synthetic method at the pyridine position in the represented compound of formula (1-11-11), formula (1-12-11), formula (1-13-11) and formula (1-14-11), but by suitable change raw material, can synthesize the various pyridine derivates that replace through alkyl or cycloalkyl.
[changing 102]
Reaction 8
Figure BDA00003113040000741
[changing 103]
Figure BDA00003113040000742
The synthetic method of the compound that＜formula (1-15-1)～formula (1-15-48) and formula (1-16-1)～formula (1-16-24) is represented＞
In the importing step of the phenyl in above-mentioned " synthetic method of the compound that formula (1-9-1)～formula (1-9-48) and formula (1-10-1)～formula (1-10-48) is represented ", use the phenyl that replaces through alkyl or cycloalkyl to get final product.For example can use the synthetic method shown in the following reaction 10.
[changing 104]
Reaction 10
Figure BDA00003113040000751
The definition of R in the formula is same as described above.0 is 1～4 integer.The R that can only link desired number according to target compound in the optional position of phenyl ring.
Under the situation of the electron injecting layer that compound of the present invention is used for organic EL or electron transfer layer, more stable when applying electric field.This situation represents that compound of the present invention is as electronics injecting material or the electron transport material excellence of electroluminescence type element.So-called electron injecting layer herein refers to receive electronics and inject the layer of organic layer from negative electrode; So-called electron transfer layer refers to for the layer that injected electrons is transferred to luminescent layer.In addition, electron transfer layer also can be held concurrently and is electron injecting layer.The employed material of each layer is called electronics injecting material and electron transport material.
The explanation of＜organic EL＞
The 2nd invention of this case is the organic EL that comprises the represented compound of formula of the present invention (1) in electron injecting layer or electron transfer layer.The driving voltage of organic EL of the present invention is low, the weather resistance height during driving.
The structure of organic EL of the present invention has various kenels, basic between anode and negative electrode at least clamping the multilayered structure of electric hole transport layer, luminescent layer, electron transfer layer is arranged.The example of the concrete formation of element is: (1) anode/electric hole transport layer/luminescent layer/electron transfer layer/negative electrode, (2) anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transfer layer/negative electrode, (3) anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transfer layer/electron injecting layer/negative electrode etc.
Compound of the present invention is owing to have high electronics injection and an electron-transporting, so can be separately or with other materials and with and for electron injecting layer or electron transfer layer.Organic EL of the present invention is by being combined in the electron transport material of the present invention the electric hole input horizon that uses other materials, electric hole transport layer, luminescent layer etc., also can obtain blueness, green, redness or white luminous.
The luminescent material or the luminous doping agent that can be used for organic EL of the present invention are: polymer association compiles, polymer function material series " ray machine can material ", co-publicate luminescent materials such as color of sunshine fluorescent material that (1991), P236 put down in writing, fluorescent bleaches, laser pigment, organic scintillator (scintillator), various florescence analysis reagent; The luminescent material of the triplet state material that Chuner Mitsumasa chief editor, " organic EL Material and indicating meter " CMC society publication (2001) P155～156 dopant materials of putting down in writing, P170～172 are put down in writing etc.
The compound that can be used as luminescent material or luminous doping agent is: polycyclc aromatic compound, heterocyclic aromatic compound, organo-metallic misfit thing, pigment, macromolecular luminescent material, styryl derivative, aromatic amine derivative, coumarin derivatives, borane derivative, oxazines derivative, the compound with volution, oxadiazoles derivative, Fluorene derivative etc.The example of polycyclc aromatic compound is: anthracene derivant, phenanthrene derivative, thick four benzene derivatives, pyrene derivatives, thick two naphthalene derivativeses, perylene derivative, cool derivative, lycid ene derivative etc.The example of heterocyclic aromatic compound is: have oxadiazoles derivative, pyrazolo quinoline, pyridine derivate, pyran derivate, coffee quinoline derivant, sila cyclopentadiene derivant, the thiophene derivant with triphenyl amido, quinacridone derivative of dialkyl amino or diaryl amido etc.The example of organo-metallic misfit thing is: the misfit thing of zinc, aluminium, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold etc. and quinolinol derivative, benzoxazoles derivative, benzothiazole derivant, oxadiazoles derivative, thiadiazoles derivative, benzimidizole derivatives, pyrrole derivative, pyridine derivate, coffee quinoline derivant etc.The example of pigment can be enumerated as: pigments such as xanthene (xanthene) derivative, polymethine derivative, derivatives of porphyrin, coumarin derivatives, dicyano methylene radical pyran derivate, dicyano methylene radical thiapyran derivative, side oxygen base benzanthrene derivative, qualone derivative, perylene derivative, benzoxazoles derivative, benzothiazole derivant, benzimidizole derivatives.The example of macromolecular luminescent material is: poly-to styrene derivatives, polythiofuran derivative, Polyvinyl carbazole derivative, polysilane derivative, poly-Fluorene derivative, poly-to benzene derivative etc.The example of styryl derivative is: contain styryl derivative, styryl arylene derivatives of amine etc.
Employed other electron transport materials of organic EL of the present invention can be selected arbitrarily to use in the compound that can be used as the compound of electron transport compound, the electron transfer layer that can be used for organic EL and electron injecting layer in light conductive material.
The concrete example of this kind electron transport material is: hydroxyquinoline is metal misfit thing, 2, the polymkeric substance of the metal misfit thing of 2'-dipyridyl derivatives, coffee quinoline derivant, diphenoquinone derivative, perylene derivative, oxadiazoles derivative, thiophene derivant, triazole derivative, thiadiazoles derivative, oxine derivative, quinoxaline derivative, quinoxaline derivative, Benzazole compounds, gallium misfit thing, pyrazole derivatives, perfluor crystalline 1,2-phenylene derivatives, pyrrolotriazine derivatives, pyrazines derivatives, benzoquinoline derivative, imidazopyridine derivatives, borane derivative etc.
About organic EL of the present invention employed electric hole injecting material and electric hole transport material, can be from light conductive material, selecting arbitrarily in the electric hole input horizon of habitual compound or organic EL and the employed well-known material of electric hole transport layer to use as the charge transfer material in electric hole before.These concrete example is: carbazole derivative, triarylamine derivative, phthalocyanine derivates etc.
Each layer that constitutes organic EL of the present invention can be made film with methods such as vapour deposition method, method of spin coating or teeming practices by the material that should constitute each layer and form.So and the thickness of each layer that forms is not particularly limited, the setting that can suit according to the character of material is generally the scope of 2nm～5000nm.In addition, the method for luminescent material thin-filmization is preferably the employing vapour deposition method, its reason is easily to obtain the film of homogeneous, and is difficult for generating aperture (pinholes) etc.Using vapour deposition method to carry out under the situation of filming, its evaporation condition is according to the kind of luminescent material of the present invention and different.The evaporation condition is preferably in following scope suitable the setting usually: heating boat temperature is that 50 ℃～400 ℃, vacuum tightness are 10 -6Pa～10 -3Pa, evaporation rate are that second 0.01nm/ second～50nm/, substrate temperature are that-150 ℃～+ 300 ℃, thickness are 5nm～5 μ m.
No matter organic EL of the present invention is above-mentioned any structure, all is preferably and is subjected to base plate supports.As long as substrate has physical strength, thermostability and the transparency, can use glass, clear plastics film etc.Anode material can use work function greater than metal, alloy, conductive compound and these the mixture of 4eV.Its concrete example is: metals such as Au, CuI, tin indium oxide (below, abbreviate ITO as), SnO 2, ZnO etc.
Cathode substance can use work function less than the metal of 4eV, alloy, conductive compound, and these 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.For efficient is taken out the luminous of organic EL well, more satisfactory for the transmittance of at least one electrode be more than 10%.Sheet resistance as electrode is preferably below hundreds of Ω/.In addition, though thickness also depends on the character of electrode materials, usually at 10nm～1 μ m, be preferably in the scope of 10nm～400nm and set.This kind electrode can form film by methods such as evaporation or sputters and make by using above-mentioned electrode substance.
Secondly, as using luminescent material of the present invention to make an example of the method for organic EL, the making method of the organic EL that comprises above-mentioned anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transport material/negative electrode of the present invention is described.After the film that forms anode material on the suitable substrate by vapour deposition method is made anode, form the film of electric hole input horizon and electric hole transport layer at this anode.Form the film of luminescent layer thereon.Vacuum evaporation electron transport material of the present invention on this luminescent layer forms film, and makes electron transfer layer.Then, comprise the film that negative electrode is used material by vapour deposition method formation, and make negative electrode, obtain the target organic EL by this.In addition, in the making of above-mentioned organic EL, also can put upside down production order, and make with the order of negative electrode, electron transfer layer, luminescent layer, electric hole transport layer, electric hole input horizon, anode.
To so and the organic EL that obtains applies under the situation of volts DS, with anode as+polarity and with negative electrode as-polarity apply voltage and get final product, if apply voltage about 2V～40V, then can observe luminous from transparent or semitransparent electrode side (male or female, and both sides).In addition, this organic EL apply under the situation of voltage of alternating current also luminous.The waveform of the alternating-current that applies in addition, can be arbitrarily.
[example]
Below, illustrate in greater detail the present invention based on example.At first, the synthesis example to the employed compound of example is described as follows.
Synthesizing of [synthesis example 1] compound (1-7-74)
＜9-(4-tributyl phenyl) anthracene synthetic＞
Under nitrogen environment, will be added with 9-bromine anthracene 31g, 4-tributyl phenyl-boron dihydroxide 25g, Pd (PPh 3) 41.3g, the flask of potassiumphosphate 51g and 1 150ml stirred 21 hours under reflux temperature.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation (liquid separation).Solid by the suction strainer collection is separated out by the underpressure distillation desolventizing utilizes methanol cleaning, and the recycling ethyl acetate is cleaned, and obtains 9-(4-tributyl phenyl) anthracene 28g.
＜9-bromo-10-(4-tributyl phenyl) anthracene synthetic＞
In the flask that is added with 9-(4-tributyl phenyl) anthracene 27g, iodine 0.1g and THF300ml, under nitrogen environment, add N-bromine succinimide 19g.At room temperature stirred 18 hours, and added sodium thiosulfate solution and stopped reaction.This solution is transferred in the liquid separation funnel, utilizes chloroform to extract.Solid by the suction strainer collection is separated out by the underpressure distillation desolventizing then carries out recrystallize from chlorobenzene, obtain 9-bromo-10-(4-tributyl phenyl) anthracene 29g.
＜3-(6-bromonaphthalene-2-yl) pyridine synthetic＞
The flask that is added with 3-bromopyridine 10g and THF60ml is cooled off in ice bath, under nitrogen environment, while stir the THF solution 35ml of the isopropylmagnesium chloride that drips 2M.After temporarily being warmed up to room temperature after dropwising, in frozen water, cool off, add zinc chloride Tetramethyl Ethylene Diamine misfit thing 17g while stir.Thereafter, at room temperature stir 1 hour after, add trifluoromethanesulfonic acid 6-bromonaphthalene-2-ester 18g and PdCl2(dppp) 1.6g, under reflux temperature, stirred 3 hours.Reaction solution is cooled to room temperature Hou, in order to remove the metal ion of catalyst, to be dissolved into the solution that forms in an amount of water (below, abbreviate the EDTA4Na aqueous solution as) with respect to the tetrasodium salt of EDTA dihydrate that target compound is equivalent to 3 times of moles approximately and toluene carries out liquid separation and add.After the underpressure distillation desolventizing, by silicone tube column chromatography (toluene/ethyl acetate=7/3(volumetric ratio)) carry out purifying, obtain 3-(6-bromonaphthalene-2-yl) pyridine 12g.
＜compound (1-7-74) synthetic＞
To be added with the flask of 3-(6-bromonaphthalene-2-yl) pyridine 6.2g, connection boric acid pinacol ester 5.9g, two (dibenzalacetone) palladium (0) 0.4g, tricyclohexyl phosphine 0.5g, potassium acetate 3.9g and glycol dimethyl ether 50ml under nitrogen environment, under reflux temperature, stir 4 hours.In this solution, add 9-bromo-10-(4-tributyl) phenyl) anthracene 8.6g, potassiumphosphate 9.3g and 1 50ml, use Dien-Rodney Stark pipe that glycol dimethyl ether is added thermal distillation at normal temperatures and remove.Add the 3rd butanols 5ml, water 5ml, two (dibenzalacetone) palladium (0) 0.4g and tricyclohexyl phosphine 0.5g, under reflux temperature, further stirred 5 hours.With the reaction solution cool to room temperature, wash and after making salt dissolving, gather solid by suction strainer.The solid that utilizes methanol cleaning to obtain, after the recycling ethyl acetate is cleaned, by silicone tube column chromatography (toluene/ethyl acetate=9/1(volumetric ratio)) carry out purifying, obtain compound (1-7-74): 3-(6-(10-(4-tributyl) phenyl) anthracene-9-yl) naphthalene-2-yl) pyridine 1.0g.Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.07（m,1H）,8.68（dd,1H）,8.23（m,1H）,8.15（d,1H）,8.08（m,1H）,8.03（m,2H）,7.83（dd,1H）,7.78（d,2H）,7.72（d,2H）,7.68（dd,1H）,7.63（d,2H）,7.42-7.48（m,3H）,7.30-7.38（m,4H）,1.49（s,9H）。
Synthesizing of [synthesis example 2] compound (1-7-26)
＜9-(3-tolyl) anthracene synthetic＞
Under nitrogen environment, will be added with 9-bromine anthracene 36g, 3-aminomethyl phenyl boric acid 21g, Pd (PPh 3) 41.4g, the flask of potassiumphosphate 59g and 1 150ml stirred 2.5 hours under reflux temperature.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation.Behind the toluene solution that the short silicone tube column purification of utilization obtains, the underpressure distillation desolventizing.Add heptane in the oil that obtains, the solid by the suction strainer collection is separated out obtains 9-(3-tolyl) anthracene 31g.
＜9-bromo-10-(3-tolyl) anthracene synthetic＞
In the flask that is added with 9-(3-tolyl) anthracene 30g and THF200ml, under nitrogen environment, in ice bath, cool off, add N-bromine succinimide 20g and iodine 0.1g.At room temperature stirred 15 hours, and added sodium thiosulfate solution and stopped reaction.This solution is transferred in the liquid separation funnel, utilize toluene to extract after, carry out with short silica gel tubing string.The underpressure distillation desolventizing is added heptane in the solution that obtains, the solid by the suction strainer collection is separated out obtains 9-bromo-10-(3-tolyl) anthracene 30g.
＜4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-yl)-1,3,2-two oxa-boron penta ring synthetic＞
To be added with the flask of 9-bromo-10-(3-tolyl) anthracene 30g, connection boric acid pinacol ester 26g, two (dibenzalacetone) palladium (0) 1.5g, tricyclohexyl phosphine 1.4g, potassium acetate 15g, salt of wormwood 12g and cyclopentyl-methyl ether 100ml under nitrogen environment, under reflux temperature, stir 16 hours.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation, the toluene solution that utilizes short silicone tube column purification to obtain.The underpressure distillation desolventizing is added heptane in the oil that obtains, the solid by the suction strainer collection is separated out obtains 4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-yl)-1,3,2-two oxa-boron penta ring 24g.
＜compound (1-7-26) synthetic＞
To be added with 4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-yl)-1,3, the flask of 2-two oxa-boron penta ring 12g, 3-(6-bromonaphthalene-2-yl) pyridine 10g, Pd (PPh3) 41.0g, potassiumphosphate 13g, 1 50ml, the 3rd butanols 10ml and water 10ml stirred 1 hour under reflux temperature.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation, the underpressure distillation desolventizing.By silicone tube column chromatography (toluene/ethyl acetate=20/1(volumetric ratio)) behind the crude product that obtains of purifying, from the toluene/heptane mixing solutions, carry out recrystallize, obtain compound (1-7-26): 3-(6-(10-(3-tolyl) anthracene-9-yl) naphthalene-2-yl) pyridine 7.1g.Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.06（m,1H）,8.67（dd,1H）,8.22（m,1H）,8.14（d,1H）,8.06（m,1H）,8.02（m,2H）,7.81（m,1H）,7.75（d,2H）,7.72（d,2H）,7.66（dd,1H）,7.50（t,1H）,7.45（m,1H）,7.27-7.39（m,7H）,2.50（s,3H）。
Synthesizing of [synthesis example 3] compound (1-7-98)
＜9-(3-tributyl phenyl) anthracene synthetic＞
Under nitrogen environment, to be added with 9-bromine anthracene 23g, 2-(3-tributyl phenyl)-4,4,5,5-tetramethyl--1,3,2-two oxa-boron penta ring 25g, Pd (PPh3) 43.1g, potassiumphosphate 37g, 1, the flask of 2,4-Three methyl Benzene 250ml, the 3rd butanols 50ml and water 30ml stirred 21 hours under reflux temperature.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation.The toluene solution that utilizes short silicone tube column purification to obtain, the underpressure distillation desolventizing by adding the solid that methyl alcohol is separated out, obtains 9-(3-tributyl phenyl) anthracene 24g by the suction strainer collection.
＜9-bromo-10-(3-tributyl phenyl) anthracene synthetic＞
In the flask that is added with 9-(3-tributyl phenyl) anthracene 23g, iodine 0.1g and THF100ml, under nitrogen environment, add N-bromine succinimide 13g.At room temperature stirred 1 hour, and added sodium thiosulfate solution and stopped reaction.This solution is transferred in the liquid separation funnel, utilizes toluene to extract.The toluene solution that utilizes short silicone tube column purification to obtain after the underpressure distillation desolventizing, carries out the toluene and methanol redeposition, obtains 9-bromo-10-(3-tributyl phenyl) anthracene 23g.
＜compound (1-7-98) synthetic＞
To be added with the flask of 3-(6-bromonaphthalene-2-yl) pyridine 6.2g, connection boric acid pinacol ester 5.9g, two (dibenzalacetone) palladium (0) 0.4g, tricyclohexyl phosphine 0.5g, potassium acetate 3.9g and glycol dimethyl ether 50ml under nitrogen environment, under reflux temperature, stir 4 hours.In this solution, add 9-bromo-10-(3-tributyl phenyl) anthracene 8.6g, potassiumphosphate 9.3g and 1 50ml, use Dien-Rodney Stark pipe, glycol dimethyl ether is added thermal distillation at normal temperatures remove.Add the 3rd butanols 5ml, water 5ml, two (dibenzalacetone) palladium (0) 0.4g and tricyclohexyl phosphine 0.5g, under reflux temperature, further stirred 2 hours.With the reaction solution cool to room temperature, wash and after making salt dissolving, gather solid by suction strainer.By silicone tube column chromatography (toluene/ethyl acetate=9/1(volumetric ratio)) behind the solid that obtains of purifying, from toluene, carry out recrystallize, obtain compound (1-7-98): 3-(6-(10-(3-tributyl phenyl) anthracene-9-yl) naphthalene-2-yl) pyridine 1.5g.Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.07（m,1H）,8.68（dd,1H）,8.23（s,1H）,8.16（d,1H）,8.08（m,1H）,8.03（m,2H）,7.83（m,1H）,7.75（d,2H）,7.72（d,2H）,7.68（m,1H）,7.52-7.61（m,3H）,7.46（m,1H）,7.30-7.38（m,5H）,1.41（s,9H）。
Synthesizing of [synthesis example 4] compound (1-7-96)
＜2-(10-(4-tributyl phenyl) anthracene-9-yl)-4,4,5,5-tetramethyl--1,3,2-two oxa-boron penta ring synthetic＞
To be added with 9-bromo-10-(4-tributyl phenyl) anthracene 7.8g, connection boric acid pinacol ester 6.1g, two (dibenzalacetone) palladium (0) 0.3g, tricyclohexyl phosphine 0.3g, potassium acetate 3.9g, salt of wormwood 2.8g, and the flask of cyclopentyl-methyl ether 40ml under nitrogen environment, under reflux temperature, stirred 6.5 hours.After reaction solution is cooled to room temperature, adds water and toluene and carry out liquid separation, the underpressure distillation desolventizing.Add heptane in the oil that obtains, the solid by the suction strainer collection is separated out obtains 2-(10-(4-tributyl phenyl) anthracene-9-yl)-4,4,5,5-tetramethyl--1,3,2-two oxa-boron penta ring 6.9g.
＜4-(3-(6-bromonaphthalene-2-yl) phenyl) pyridine synthetic＞
Under nitrogen environment, the flask that will be added with 4-(3-bromophenyl) pyridine 9.8g and THF20ml is cooled to slowly drip the n-Butyl Lithium 17ml of 2.6M below-70 ℃ in dry ice/methanol bath.After dropwising, stirred 0.5 hour down synthermal, add zinc chloride Tetramethyl Ethylene Diamine misfit thing 12g.Thereafter, at room temperature stir 0.5 hour after, add two (diphenylphosphino) propane 0.5g of trifluoromethanesulfonic acid 6-bromonaphthalene-2-ester 15g, two (dibenzalacetone) palladium (0) and 1,2-, under reflux temperature, stirred 1 hour.After reaction finishes, add the EDTA4Na aqueous solution, ethyl acetate is carried out liquid separation, after the underpressure distillation desolventizing, by activated alumina tubing string chromatography (toluene/ethyl acetate=9/1(volumetric ratio)) carry out purifying.Then, utilize methanol cleaning, from the ethyl acetate/methanol mixed solvent, carry out recrystallize, obtain 4-(3-(6-bromonaphthalene-2-yl) phenyl) pyridine 5.3g.
＜compound (1-7-96) synthetic＞
To be added with 2-(10-(4-tributyl phenyl) anthracene-9-yl)-4,4,5,5-tetramethyl--1,3,2-two oxa-boron penta ring 6.1g, 4-(3-(6-bromonaphthalene-2-yl) phenyl) pyridine 5.0g, Pd (PPh 3) 40.5g, the flask of potassiumphosphate 3.0g, 1 25ml, the 3rd butanols 5ml and water 5ml stirred 6 hours under reflux temperature.After reaction solution is cooled to room temperature, adds EDTANa water and toluene and carry out liquid separation, the underpressure distillation desolventizing.By activated alumina tubing string chromatography (toluene/ethyl acetate=9/1(volumetric ratio)) crude product that obtains of purifying.After the solid that utilizes ethyl acetate that the underpressure distillation desolventizing is obtained is cleaned, from toluene, carry out recrystallize, obtain compound (1-7-96): 4(3-(6-(10-(4-tributyl phenyl) anthracene-9-yl) naphthalene-2-yl) phenyl) pyridine 3.3g.Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：8.73（dd,2H）,8.27（m,1H）,8.15（d,1H）,8.03（m,3H）,7.99（m,2H）,7.78（d,2H）,7.73（d,2H）,7.61～7.70（m,7H）,7.44（m,2H）,7.30～7.38（m,4H）、1.49（s,9H）。
Synthesizing of [synthesis example 5] compound (1-14-14)
＜9-(3-ethoxyl phenenyl)-10-(naphthalene-2-yl) anthracene synthetic＞
In flask, add 1-bromo-3-phenetole 72.4g, (10-(naphthalene-2-yl) anthracene-9-yl) boric acid 104.5g, Pd (PPh 3) 410.4g, potassiumphosphate 127.4g, 1 600ml, 2-propyl alcohol 120ml, and water 120ml, under nitrogen environment, under reflux temperature, stirred 6 hours.After reaction solution is cooled to room temperature, gather solid in the liquid by suction strainer, utilize methanol cleaning, obtain 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-yl) anthracene 82g.
＜3-(10-(naphthalene-2-yl) anthracene-9-yl) phenol synthetic＞
In flask, add 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-yl) anthracene 82g and pyridine hydrochloride 446.0g, under nitrogen environment, under reflux temperature, stirred 8 hours.After reaction solution is cooled to room temperature, add water, the solid by the suction strainer collection is separated out utilizes methanol cleaning, and recycling toluene is cleaned, and obtains 3-(10-(naphthalene-2-yl) anthracene-9-yl) phenol 76.0g.
＜trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl ester synthetic＞
The flask that will be added with 3-(10-(naphthalene-2-yl) anthracene-9-yl) phenol (76.0g) and pyridine (1L) cools off in ice bath, under nitrogen environment, to wherein dripping trifluoromethanesulfanhydride anhydride 65.0g.After dropwising, further at room temperature stirred 15 hours, add water, the solid of separating out by the suction strainer collection.Utilize methyl alcohol that this solid is cleaned, obtain trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl ester 90.3g.
＜4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring synthetic＞
Add trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl ester 90.3g, connection boric acid pinacol ester 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 in the flask, under reflux temperature, stirred 5 hours.After reaction solution is cooled to room temperature, utilize to be coated with diatomaceous paulownia mountain funnel and to carry out suction strainer and remove insolubles, utilize EDTA4Na water that filtrate is cleaned.The solid that utilizes heptane that the solvent of filtrate is removed in underpressure distillation and obtain is cleaned, and obtains 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (52.0g).
＜compound (1-14-14) synthetic＞
In flask, add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-, two oxa-boron penta ring 8.6g, open the method put down in writing among the 2009-124114 and synthetic 5'-bromo-3-methyl-2 by the Japanese Patent spy, 2'-dipyridyl 5.1g, Pd (PPh 3) 40.6g, potassiumphosphate 7.2g, 1 25ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 2.5 hours.After reaction solution is cooled to room temperature, add water after, gather solid in the liquid by suction strainer, utilize methanol cleaning.By silicone tube column chromatography (toluene/ethyl acetate=9/1(volumetric ratio)) this solid of purifying, then be further purified by activated carbon tubing string chromatography.Concentrated solution carries out recrystallize from chlorobenzene, obtain compound (1-14-14): 3-methyl-5'-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,2'-dipyridyl 2.3g.Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.05（m,1H）,8.55（d,1H）,8.11（dd,1H）,8.09（d,1H）,8.02（m,1H）,8.00（s,1H）,7.73-7.95（m,9H）,7.60（m,5H）,7.30-7.40（m,4H）,7.23（m,1H）,2.56（s,3H）。
Synthesizing of [synthesis example 6] compound (1-11-1)
＜2-methyl-4-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 4-bromo-2-picoline (0.8g), Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 7.5 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution (developing solvent): the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.Gather underpressure distillation and remove the crystallization of separating out in the process of the filtrate that obtains, obtain (1-11-1) represented compound 2-methyl-4-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (0.7g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.66（d,1H）,8.30（s,1H）,8.17（d,1H）,8.03（m,2H）,7.87（d,1H）,7.72-7.78（m,4H）,7.70（d,1H）,7.65（m,2H）,7.58（m,2H）,7.56（m,3H）,7.31-7.39（m,4H）,2.73（s,3H）。
Synthesizing of [synthesis example 7] compound (1-11-2)
＜3-methyl-4-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 4-bromo-3-picoline hydrochloride (1.0g), Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 24.5 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.Gather underpressure distillation and remove the crystallization of separating out in the process of the filtrate that obtains, further in toluene, carry out recrystallize, obtain (1-11-2) represented compound 3-methyl-4-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (0.5g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.62（s,1H）,8.58（d,1H）,8.13（d,1H）,8.06（s,1H）,8.02（d,1H）,7.99（s,1H）,7.75（d,4H）,7.70（dd,1H）,7.65（t,2H）,7.59（t,2H）,7.53（m,2H）,7.33-7.39（m,5H）,2.44（s,3H）。
Synthesizing of [synthesis example 8] compound (1-11-3)
＜2-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-2-picoline (0.8g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 5 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.The solid that the underpressure distillation desolventizing is obtained carries out recrystallize from toluene, obtain (1-11-3) represented compound 2-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (1.2g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.95（m,1H）,8.20（s,1H）,8.14（d,1H）,8.01（m,2H）,7.96（dd,1H）,7.81（dd,1H）,7.74（m,4H）,7.67（dd,1H）,7.63（t,2H）,7.57（t,1H）,7.52（m,2H）,7.30-7.37（m,5H）,2.67（s,3H）。
Synthesizing of [synthesis example 9] compound (1-11-4)
＜3-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 3-bromo-5-picoline (0.8g), Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 7.5 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is added heptane and is carried out redeposition, obtains (1-11-4) represented compound 3-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (1.3g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.87（m,1H）,8.51（m,1H）,8.22（s,1H）,8.15（d,1H）,8.03（m,2H）,7.89（m,1H）,7.83（dd,1H）,7.73（m,4H）,7.67（dd,1H）,7.63（m,2H）,7.57（t,1H）,7.52（m,2H）,7.30-7.37（m,4H）,2.49（s,3H）。
Synthesizing of [synthesis example 10] compound (1-11-5)
＜4-methyl-3-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 3-bromo-4-picoline hydrochloride (1.0g), Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 7 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is carried out recrystallize with the solid that obtains from toluene, obtain (1-11-5) represented compound 4-methyl-3-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (0.6g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.64（s,1H）,8.55（d,1H）,8.14（d,1H）,8.06（s,1H）,8.02（d,1H）,7.99（s,1H）,7.76（m,4H）,7.70（dd,1H）,7.63（m,2H）,7.59（t,2H）,7.53（m,2H）,7.32-7.39（m,4H）,7.30（d,1H）,2.45（s,3H）。
Synthesizing of [synthesis example 11] compound (1-11-6)
＜2-methyl-3-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 3-bromo-2-picoline (0.8g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 4 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is added heptane and is carried out redeposition, obtains (1-11-6) represented compound 2-methyl-3-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (1.1g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.60（m,1H）,8.11（d,1H）,8.05（s,1H）,8.00（d,1H）,7.96（s,1H）,7.74（m,4H）,7.69（m,2H）,7.63（m,2H）,7.57（m,2H）,7.52（m,2H）,7.30-7.37（m,4H）,7.28（m,1H）,2.66（s,3H）。
Synthesizing of [synthesis example 12] compound (1-11-8)
＜5-methyl-2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.5g), 3-bromo-2-picoline (1.0g), Pd (PPh 3) 4(0.15g), potassiumphosphate (2.1g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 18 hours.After heating finishes, with the reaction solution cool to room temperature, the solid of separating out by the suction strainer collection.By silicone tube column chromatography (developping solution: the solid that obtains of purifying toluene).Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is added ethyl acetate and is carried out redeposition, obtains (1-11-8) represented compound 5-methyl-2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine (1.5g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.63（m,2H）,8.23（dd,1H）,8.16（d,1H）,8.00（m,2H）,7.86（d,1H）,7.73（m,4H）,7.60-7.67（m,4H）,7.56（t,1H）,7.51（m,2H）,7.30-7.36（m,4H）,2.44（s,3H）。
Synthesizing of [synthesis example 13] compound (1-11-39)
＜5-bromo-2'-methyl-3, the 4'-dipyridyl synthetic＞
The flask that will be added with 4-bromo-2-picoline (13.8g) and toluene (150ml) cools off in acetone/the dry ice bath.Drip the hexane solution (55ml) of the n-Butyl Lithium of 1.6M in this solution.After dropwising, on one side in acetone/the dry ice bath cooling stirred 1 hour on one side, add zinc chloride Tetramethyl Ethylene Diamine (29.3g) and THF(45ml), remove acetone/the dry ice bath and heat up.After being warmed up to room temperature, add toluene (20ml), 3,5-dibromo pyridine (19.0g) and Pd (PPh 3) 4(2.8g), under reflux temperature, stirred 2 hours.Reaction solution is cooled to room temperature Hou, in order to remove the metal ion of catalyst, to be dissolved into the solution that forms in an amount of water (below, abbreviate the EDTA4Na aqueous solution as) with respect to the tetrasodium salt of EDTA dihydrate that target compound is equivalent to 3 times of moles approximately and toluene carries out liquid separation and add.After the underpressure distillation desolventizing, by silicone tube column chromatography (developping solution: the toluene/ethyl acetate) solid that obtains of purifying.At this moment, publish limited-liability company, the 94th page of method of putting down in writing with reference to " the ABC of (1)-mass treatment method of Experiment of Organic Chemistry and separation and purification method-" chemistry with the people, increase the ratio of the ethyl acetate in the developping solution lentamente, make the target compound stripping.Then, the underpressure distillation desolventizing is carried out recrystallize with the solid that obtains from heptane, obtains 5-bromo-2'-methyl-3,4'-dipyridyl (5.3g).
＜2'-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-3, the 4'-dipyridyl synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.5g), 5-bromo-2'-methyl-3,4'-dipyridyl (1.1g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 3 hours.After heating finishes, with the reaction solution cool to room temperature, add water and toluene and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=1/1) solid that obtains of purifying.The underpressure distillation desolventizing is carried out recrystallize with the solid that obtains from toluene, obtain (1-11-39) represented compound 2'-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-3,4'-dipyridyl (0.3g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.11（m,1H）,8.92（m,1H）,8.65（d,1H）,8.28（m,2H）,8.17（d,1H）,8.05（m,2H）,7.87（d,1H）,7.68-7.75（m,5H）,7.61（m,2H）,7.56（t,1H）,7.51（m,3H）,7.45（m,1H）,7.30-7.37（m,4H）,2.70（s,3H）。
Synthesizing of [synthesis example 14] compound (1-14-2)
＜3-methyl-4-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl) pyridine synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.5g), 4-bromo-3-picoline hydrochloride (1.3g), Pd (PPh 3) 4(0.35g), potassiumphosphate (3.2g), 1 20ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 11.5 hours.After reaction solution is cooled to room temperature, adds toluene and water and carry out liquid separation.The underpressure distillation desolventizing is by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is added heptane and is carried out redeposition, obtains (1-14-2) represented compound 3-methyl-4-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl) pyridine (1.4g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.53（s,1H）,8.50（d,1H）,8.08（dd,1H）,8.02（m,1H）,7.97（d,1H）,7.92（m,1H）,7.70-7.78（m,5H）,7.48-7.63（m,6H）,7.35-7.39（m,2H）,7.29-7.34（m,3H）,2.41（s,3H）。
Synthesizing of [synthesis example 15] compound (1-14-3)
＜2-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl) pyridine synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.5g), 5-bromo-2-picoline (1.0g), Pd (PPh 3) 4(0.35g), potassiumphosphate (3.2g), 1 20ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 8.5 hours.After reaction solution is cooled to room temperature, the solid of separating out by the suction strainer collection.By silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying.Then, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing utilizes ethyl acetate to clean the solid that obtains, and obtains (1-14-3) represented compound 2-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl) pyridine (1.5g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝8.45（m,1H）,8.08（d,1H）,8.03（m,1H）,7.99（s,1H）,7.93（m,1H）,7.87（dd,1H）,7.70-7.81（m,7H）,7.57-7.63（m,3H）,7.54（m,1H）,7.30-7.40（m,4H）,7.23（d,1H）,2.61（s,3H）。
Synthesizing of [synthesis example 16] compound (1-14-11)
＜5-bromo-6'-methyl-2, the 2'-dipyridyl synthetic＞
The flask that will be added with 2-bromo-6-picoline (5.2g) and cyclopentyl-methyl ether (30ml) cools off in methyl alcohol/the dry ice bath.Drip the hexane solution (22ml) of the n-Butyl Lithium of 1.6M in this solution.After dropwising, on one side in methyl alcohol/the dry ice bath cooling stirred 2 hours on one side, add zinc chloride Tetramethyl Ethylene Diamine (8.3g), remove methyl alcohol/the dry ice bath and heat up.After being warmed up to room temperature, add 2,5-dibromo pyridine (7.1g) and Pd (PPh 3) 4(1.0g), under reflux temperature, stirred 3.5 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, by silicone tube column chromatography (developping solution: the toluene/ethyl acetate) solid that obtains of purifying.At this moment, increase the ratio of the ethyl acetate in the developping solution lentamente, make the target compound stripping.Then, the underpressure distillation desolventizing is carried out recrystallize with the solid that obtains from heptane, obtains 5-bromo-6'-methyl-2,2'-dipyridyl (1.4g).
＜6'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 2'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-6'-methyl-2,2'-dipyridyl (1.0g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 20ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 7.5 hours.After reaction solution is cooled to room temperature, the solid of separating out by the suction strainer collection.By the silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying, directly use the paulownia mountain funnel that is coated with activated carbon to carry out suction strainer the dissolution fluid that obtains, remove coloring components.The underpressure distillation desolventizing is added ethyl acetate and is carried out redeposition, obtains (1-14-11) represented compound 6'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,2'-dipyridyl (1.2g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.03（m,1H）,8.49（dd,1H）,8.22（d,1H）,8.09（m,2H）,8.03（m,1H）,8.00（s,1H）,7.93（m,1H）,7.87（d,1H）,7.68-7.83（m,7H）,7.55-7.64（m,4H）,7.30-7.40（m,4H）,7.17（d,1H）,2.65（s,3H）。
Synthesizing of [synthesis example 17] compound (1-14-12)
＜5-bromo-5'-methyl-2, the 2'-dipyridyl synthetic＞
To be added with 2-bromo-5-picoline (1.7g) and flask THF(5ml) and in ice bath, cool off, drip the THF solution (5.5ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 3.5 hours, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (2.8g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (2.4g) and Pd (PPh 3) 4(0.35g), under reflux temperature, stirred 1.5 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=9/1) solid that obtains of purifying.The underpressure distillation desolventizing is added heptane and is carried out redeposition, obtains 5-bromo-5'-methyl-2,2'-dipyridyl (1.5g).
＜5-methyl-5'-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 2'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-5'-methyl-2,2'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 20ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 6 hours.After reaction solution is cooled to room temperature, adds toluene and water and carry out liquid separation.The underpressure distillation desolventizing, by the silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing, add ethyl acetate and carry out redeposition, the solid that obtains is further carried out recrystallize from toluene, obtain (1-14-12) represented compound 5-methyl-5'-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,2'-dipyridyl (1.2g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.03（m,1H）,8.52（s,1H）,8.44（dd,1H）,8.33（d,1H）,8.09（m,1H）,8.03（m,1H）,8.00（s,2H）,7.93（m,1H）,7.87（m,1H）,7.73-7.83（m,6H）,7.56-7.66（m,5H）,7.31-7.39（m,4H）,2.41（s,3H）。
Synthesizing of [synthesis example 18] compound (1-14-13)
＜5'-bromo-4-methyl-2, the 2'-dipyridyl synthetic＞
To be added with 2-bromo-4-picoline (6.9g) and flask THF(20ml) and in ice bath, cool off, drip the THF solution (24ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 1 hour, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (12.1g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (9.5g) and Pd (PPh 3) 4(1.4g), under reflux temperature, stirred 2.5 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=9/1) solid that obtains of purifying.The underpressure distillation desolventizing is carried out recrystallize with the solid that obtains from heptane, obtain 5'-bromo-4-methyl-2,2'-dipyridyl (5.5g).
＜4-methyl-5'-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 2'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), '-bromo-4-methyl-2,2'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 20ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 16 hours.After reaction solution is cooled to room temperature, adds toluene and water and carry out liquid separation.The underpressure distillation desolventizing, by the silicone tube column chromatography (developping solution: the toluene/ethyl acetate=95/5) solid that obtains of purifying, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing utilizes heptane to clean, and obtains (1-14-13) represented compound 4-methyl-5'-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,2'-dipyridyl (1.4g) by this.
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.04（m,1H）,8.55（d,1H）,8.47（dd,1H）,8.28（s,1H）,8.11（dd,1H）,8.09（d,1H）,8.03（m,1H）,8.00（s,1H）,7.93（m,1H）,7.88（d,1H）,7.73-7.83（m,6H）,7.57-7.63（m,4H）,7.30-7.40（m,4H）,7.14（d,1H）,2.45（s,3H）。
Synthesizing of [synthesis example 19] compound (1-14-15)
＜5-bromo-6'-methyl-2, the 3'-dipyridyl synthetic＞
To be added with 5-bromo-2-picoline (3.4g) and flask THF(10ml) and in ice bath, cool off, drip the THF solution (11ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 3 hours, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (5.5g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (4.7g) and Pd (PPh 3) 4(0.7g), under reflux temperature, stirred 5 hours.Reaction solution is cooled to room temperature Hou, adds EDTA4Na water と and slightly remember the The Ru.) and toluene carry out liquid separation.After the underpressure distillation desolventizing, (developping solution: the toluene/ethyl acetate=7/3) solid that obtains of purifying obtains 5-bromo-6'-methyl-2,3'-dipyridyl (1.5g) by the silicone tube column chromatography.
＜6'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 3'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 25ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 5 hours.After reaction solution was cooled to room temperature, the solid by the suction strainer collection is separated out utilized methanol cleaning, and the recycling ethyl acetate is cleaned.Then, by silicone tube column chromatography (developping solution: toluene/ethyl acetate=4/1) carry out purifying, the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is further carried out recrystallize with the solid that obtains from chlorobenzene, obtain (1-14-15) represented compound 6'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,3'-dipyridyl (1.3g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.13（m,1H）,9.07（m,1H）,8.28（dd,1H）,8.01-8.11（m,3H）,8.00（s,1H）,7.93（m,1H）,7.86（m,1H）,7.73-7.83（m,7H）,7.57-7.64（m,4H）,7.31-7.39（m,4H）,7.28（d,1H）,2.63（s,3H）。
Synthesizing of [synthesis example 20] compound (1-14-16)
＜5-bromo-5'-methyl-2, the 3'-dipyridyl synthetic＞
To be added with 3-bromo-5-picoline (3.4g) and flask THF(10ml) and in ice bath, cool off, drip the THF solution (11ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 1.5 hours, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (5.5g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (4.7g) and Pd (PPh 3) 4(0.7g), under reflux temperature, stirred 5 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, (developping solution: the toluene/ethyl acetate=7/3) solid that obtains of purifying obtains 5-bromo-5'-methyl-2,3'-dipyridyl (1.4g) by the silicone tube column chromatography.
＜5'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 3'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 25ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 5 hours.After reaction solution was cooled to room temperature, the solid by the suction strainer collection is separated out utilized methanol cleaning, and the recycling ethyl acetate is cleaned.Then, by silicone tube column chromatography (developping solution: toluene/ethyl acetate=4/1) carry out purifying, again the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is further carried out recrystallize with the solid that obtains from chlorobenzene, obtain (1-14-16) represented compound 5'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,3'-dipyridyl (1.3g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.08（m,1H）,9.04（s,1H）,8.50（s,1H）,8.21（s,1H）,8.09（m,2H）,8.04（m,1H）,8.00（s,1H）,7.93（m,1H）,7.73-7.88（m,8H）,7.62（m,4H）,7.31-7.40（m,4H）,2.45（s,3H）。
Synthesizing of [synthesis example 21] compound (1-14-17)
＜5-bromo-4'-methyl-2, the 3'-dipyridyl synthetic＞
To be added with 3-bromo-4-picoline (5.2g) and flask THF(10ml) and in ice bath, cool off, drip the THF solution (17ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 9 hours, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (8.3g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (7.1g), Pd-137(Britain village letter Wan Feng company) (0.4g) and NMP(25ml), under reflux temperature, stirred 6 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, by silicone tube column chromatography (developping solution: the toluene/ethyl acetate=7/3) solid that obtains of purifying.The underpressure distillation desolventizing utilizes heptane to clean the solid that obtains, and obtains 5-bromo-4'-methyl-2,3'-dipyridyl (2.4g).
＜4'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 3'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 25ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 5 hours.After reaction solution is cooled to room temperature, adds toluene and water and carry out liquid separation.The underpressure distillation desolventizing, by the silicone tube column chromatography (developping solution: the toluene/ethyl acetate=7/3) solid that obtains of purifying, again the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing is further carried out recrystallize with the solid that obtains from toluene, obtain (1-14-17) represented compound 4'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,3'-dipyridyl (0.7g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.09（s,1H）,8.67（s,1H）,8.51（d,1H）,8.09（m,2H）,8.03（m,1H）,8.00（m,1H）,7.93（m,1H）,7.88（d,1H）,7.73-7.84（m,6H）,7.61（m,4H）,7.52（d,1H）,7.31-7.40（m,4H）,7.23（d,1H）,2.46（s,3H）。
Synthesizing of [synthesis example 22] compound (1-14-18)
＜5-bromo-2'-methyl-2, the 3'-dipyridyl synthetic＞
To be added with 3-bromo-2-picoline (5.2g) and flask THF(10ml) and in ice bath, cool off, drip the THF solution (17ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove after ice bath at room temperature stirs 2 hours, in ice bath, cool off again, add zinc chloride Tetramethyl Ethylene Diamine (8.3g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (7.1g), Pd (PPh 3) 4(1.0g) and dimethylbenzene (10ml), under reflux temperature, stirred 7 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and toluene and carry out liquid separation.After the underpressure distillation desolventizing, (developping solution: the toluene/ethyl acetate=4/1) solid that obtains of purifying obtains 5-bromo-2'-methyl-2,3'-dipyridyl (1.3g) by the silicone tube column chromatography.
＜2'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 3'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 25ml, the 3rd butanols 5ml, and water 1ml, under reflux temperature, stirred 12 hours.After reaction solution is cooled to room temperature, adds toluene and water and carry out liquid separation.The underpressure distillation desolventizing, by the silicone tube column chromatography (developping solution: the toluene/ethyl acetate=4/1) solid that obtains of purifying, again the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing, the solid by the suction strainer collection is separated out obtains (1-14-18) represented compound 2'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,3'-dipyridyl (0.8g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.08（m,1H）,8.57（m,1H）,7.99-8.10（m,4H）,7.92（m,1H）,7.88（d,1H）,7.73-7.83（m,7H）,7.61（m,4H）,7.51（dd,1H）,7.30-7.40（m,4H）,7.25（m,1H）,2.66（s,3H）。
Synthesizing of [synthesis example 23] compound (1-14-20)
＜5-bromo-3'-methyl-2, the 4'-dipyridyl synthetic＞
To be added with 4-bromo-3-picoline (5.0g) and flask THF(30ml) and in dry ice/methanol bath, cool off, drip the THF solution (16ml) of the isopropylmagnesium chloride of 2M in this solution.After dropwising, remove cooling with bathing, at room temperature stir 2.5 hours after, in ice bath, cool off, add zinc chloride Tetramethyl Ethylene Diamine (8.0g).After removing ice bath and being warmed up to room temperature, add 2,5-dibromo pyridine (7.6g) and Pd (PPh 3) 4(1.0g), under reflux temperature, stirred 2 hours.After reaction solution is cooled to room temperature, adds the EDTA4Na aqueous solution and ethyl acetate and carry out liquid separation.After the underpressure distillation desolventizing, (developping solution: the toluene/ethyl acetate=5/1) solid that obtains of purifying obtains 5-bromo-3'-methyl-2,4'-dipyridyl (5.6g) by the silicone tube column chromatography.
＜3'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2, the 4'-dipyridyl synthetic＞
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-3'-methyl-2,4'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 1ml, the 3rd butanols 1ml, and water 1ml, under reflux temperature, stirred 4 hours.After reaction solution is cooled to room temperature, add water, gather precipitate by suction strainer.After the solid that obtains utilized water and methanol cleaning, by NH base modified silica-gel (DM1020: chemistry of silicones company of Fuji makes) tubing string chromatography (developping solution: toluene) carry out purifying, obtain (1-14-20) represented compound 3'-methyl-5-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,4'-dipyridyl (1.7g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.09（m,1H）,8.56（s,1H）,8.55（d,1H）,8.10（m,2H）,8.03（m,1H）,8.00（d,1H）,7.93（d,1H）,7.88（d,1H）,7.73-7.83（m,6H）,7.61（m,4H）,7.53（d,1H）,7.31-7.41（m,5H）,2.44（s,3H）。
Synthesizing of [synthesis example 24] compound (1-11-18)
＜2'-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) 2, the 3'-dipyridyl synthetic＞
With 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl)-1,3,2-two oxa-boron penta ring (2.0g), 5-bromo-2'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1 (20ml), the 3rd butanols (5ml) and water (1ml) adds in the flask, under nitrogen environment, under reflux temperature, stirred 8 hours.After heating finishes, reaction solution is cooled to room temperature after, the solid by the suction strainer collection is separated out utilizes methanol cleaning, the recycling ethyl acetate is cleaned.Then, by silicone tube column chromatography (developping solution: toluene/ethyl acetate=7/3) carry out purifying, again the dissolution fluid that obtains is fed short activated carbon tubing string, remove coloring components.The underpressure distillation desolventizing, the solid by the suction strainer collection is separated out obtains (1-11-18) represented compound 2'-methyl-5-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) 2,3'-dipyridyl (1.1g).
Measure the structure of confirming compound by NMR.
1H-NMR（CDCl 3）：δ＝9.17（m,1H）,8.60（dd,1H）,8.230（s,1H）,8.19（m,2H）,8.06（m,2H）,7.87（dd,1H）,7.85（dd,1H）,7.73（m,4H）,7.69（dd,1H）,7.55-7.65（m,4H）,7.51（m,2H）,7.26-7.37（m,5H）,2.73（s,3H）。
Can pass through the compound of suitable change raw material, and by the method according to above-mentioned synthesis example, and synthesize other derivative compounds of the present invention.
Below, in order to further describe the present invention, and disclose the example of the organic EL that uses compound of the present invention, but the present invention is not limited to these.
The element of example of making 1 to example 4 and comparative example 1 to comparative example 2, measure respectively driving in the constant current driven test begin voltage (V), keep the brightness more than 90% of initial value time (hour).Below, explain example and comparative example.
The material of the example 1 of made each layer in to example 4 and comparative example 1 to the element of comparative example 2 constituted be shown in following table 1.
Table 1
Figure BDA00003113040000961
Figure BDA00003113040000971
In table 1, " HI " is N 4, N 4'-phenylbenzene-N 4, N 4'-two (9-phenyl-9H-carbazole-3-yl)-[1,1'-biphenyl]-4,4'-diamines, " NPD " are N 4, N 4'-two (naphthalene-1-yl)-N 4, N 4'-phenylbenzene-[1,1'-biphenyl]-4,4'-diamines, compound (A) are 9-phenyl-10-(4-phenylnaphthalene-1-yl) anthracene, and compound (B) is N 5, N 5, N 9, N 9-7,7-hexaphenyl-7H-benzo [c] Fluorene-5,9-diamines, compound (C) are 9,10-two ([2,2'-dipyridyl]-5-yl) anthracene, and compound (D) is two (4-(pyridin-3-yl) naphthalene-1-yl) anthracenes of 9,10-.With these compounds and be formed on electron transfer layer and negative electrode between the layer employed " Liq " chemical structure disclose as follows in the lump.
[changing 105]
Figure BDA00003113040000972
[example 1]
＜with compound (1-7-74) be used for the element of electron transfer layer＞
Be that the glass substrate (Opto Science(share) that the ITO of the film of 180nm is ground to 26mm * 28mm * 0.7mm of 150nm is made making thickness by sputter) as the transparent support substrate.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (clear and vacuum (share) make), install the evaporation that is added with HI with molybdenum boat, be added with NPD evaporation with molybdenum boat, be added with compound (A) evaporation with molybdenum boat, be added with compound (B) evaporation with molybdenum boat, be added with compound (1-7-74) evaporation with molybdenum boat, be added with Liq evaporation with molybdenum boat, be added with the molybdenum boat of magnesium and be added with silver-colored evaporation tungsten boat.
On the ITO of transparent support substrate film, form following each layer in regular turn.Vacuum tank is reduced pressure 5 * 10 -4Pa, at first, heating is added with the evaporation boat of HI, and the mode that becomes 40nm with thickness is carried out evaporation and is formed electric hole input horizon, and then, heating is added with the evaporation boat of NPD, and the mode that becomes 30nm with thickness is carried out evaporation and is formed electric hole transport layer.Secondly, the evaporation that heating simultaneously is added with compound (A) is with boat and be added with the evaporation boat of compound (B), and the mode that becomes 35nm with thickness is carried out evaporation and formed luminescent layer.The mode that becomes about 95:5 with the weight ratio of compound (A) and compound (B) is regulated evaporation rate.Secondly, heating is added with the evaporation boat of compound (1-7-74), and the mode that becomes 15nm with thickness is carried out evaporation and formed electron transfer layer.The evaporation rate of each layer is second 0.01nm/ second～1nm/.
Thereafter, heating is added with the evaporation boat of Liq, and the mode that becomes 1nm with thickness is carried out evaporation with the evaporation rate of second 0.01nm/ second～0.1nm/.Then, heating simultaneously is added with the boat and the boat that is added with silver of magnesium, and the mode that becomes 100nm with thickness is carried out evaporation and formed negative electrode.At this moment, regulate evaporation rate with magnesium and the atomicity of silver than the mode that becomes 10:1, the mode that becomes second 0.1nm/ second～10nm/ with evaporation rate forms negative electrode, obtains organic electroluminescent element.
If apply volts DS as anode and with magnesium/silver electrode as negative electrode with the ITO electrode, then obtain the blue-light-emitting that wavelength is about 460nm.In addition, by being used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test, it is 7.33V that the result drives on-test voltage, keeps the 90%(1800cd/m of initial value 2) time of above brightness is 45 hours.
[example 2]
＜with compound (1-7-26) be used for the element of electron transfer layer＞
Except compound (1-7-74) being changed to compound (1-7-26), by the method acquisition organic EL of foundation example 2.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 6.36V, and keeping the time of the brightness more than 90% of initial value is 151 hours.
[example 3]
＜with compound (1-7-98) be used for the element of electron transfer layer＞
Except compound (1-7-74) being changed to compound (1-7-98), by the method acquisition organic EL of foundation example 2.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 7.34V, and keeping the time of the brightness more than 90% of initial value is 265 hours.
[example 4]
＜with compound (1-7-96) be used for the element of electron transfer layer＞
Except compound (1-7-74) being changed to compound (1-7-96), by the method acquisition organic EL of foundation example 2.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 5.33V, and keeping the time of the brightness more than 90% of initial value is 103 hours.
[comparative example 1]
Except compound (1-7-96) being changed to compound (C), by the method acquisition organic EL of foundation example 1.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.It is 5.06V that the result drives on-test voltage, and keeping the time of the brightness more than 90% of initial value is 6 hours.
[comparative example 2]
Except compound (1-7-96) being changed to compound (D), by the method acquisition organic EL of foundation example 1.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.It is 5.05V that the result drives on-test voltage, and keeping the time of the brightness more than 90% of initial value is 10 hours.
The results are summarized in table 2 more than inciting somebody to action.
Table 2
Figure BDA00003113040000991
The element of example of making 5 to example 20 and comparative example 3 to comparative example 5, measure respectively driving in the constant current driven test begin voltage (V), keep the brightness more than 90% of initial value time (hour).Below, explain example and comparative example.
The material of the example 5 of made each layer in to example 20 and comparative example 3 to the element of comparative example 5 constituted be shown in following table 3.
Table 3
Figure BDA00003113040001001
In table 3, HT is N-([1,1'-biphenyl]-the 4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl) phenyl)-9H-Fluorene-2-amine, compound (E) is 9-(4-(naphthalene-1-yl) phenyl)-10-phenylanthracene, compound (F) is 4,4'-((7,7-phenylbenzene-7H-benzo [c] Fluorene-5,9-two bases) two ((phenyl) amidos)) two benzonitriles, compound (G) is 4'-(4-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2,2':6', 2''-terpyridyl, compound (H) are 3-(6-(10-phenylanthracene-9-yl) naphthalene-2-yl) pyridine, compound (I) is 6-(4-(10-(naphthalene-1-yl) anthracene-9-yl) phenyl)-2, the 4'-dipyridyl.
[changing 106]
Figure BDA00003113040001011
[example 5]
＜with compound (1-11-1) be used for the element of electron transfer layer＞
Be that the glass substrate (Opto Science(share) that the ITO of the film of 180nm is ground to 26mm * 28mm * 0.7mm of 150nm is made making thickness by sputter) as the transparent support substrate.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (clear and vacuum (share) make), install the evaporation that is added with HI with molybdenum boat, be added with HT evaporation with molybdenum boat, be added with compound (E) evaporation with molybdenum boat, be added with compound (F) evaporation with molybdenum boat, be added with compound (1-11-1) evaporation with molybdenum boat, be added with Liq evaporation with molybdenum boat, be added with the molybdenum boat of magnesium and be added with silver-colored evaporation tungsten boat.
On the ITO of transparent support substrate film, form following each layer in regular turn.Vacuum tank is reduced pressure 5 * 10 -4Pa, at first, heating is added with the evaporation boat of HI, and the mode that becomes 40nm with thickness is carried out evaporation and is formed electric hole input horizon, and then heating is added with the evaporation boat of HT, and the mode that becomes 30nm with thickness is carried out evaporation and is formed electric hole transport layer.Secondly, the evaporation that heating simultaneously is added with compound (E) is with boat and be added with the evaporation boat of compound (F), and the mode that becomes 35nm with thickness is carried out evaporation and formed luminescent layer.The mode that becomes about 95:5 with the weight ratio of compound (E) and compound (F) is regulated evaporation rate.Secondly, the evaporation that heating simultaneously is added with compound (1-11-1) is with boat and be added with the evaporation boat of Liq, and the mode that becomes 25nm with thickness is carried out evaporation and formed electron transfer layer.The mode that becomes about 1:1 with the weight ratio of compound (1-11-1) and Liq is regulated evaporation rate.The evaporation rate of each layer is second 0.01nm/ second～1nm/.
Thereafter, heating is added with the evaporation boat of Liq, and the mode that becomes 1nm with thickness is carried out evaporation with the evaporation rate of second 0.01nm/ second～0.1nm/.Then, heating simultaneously is added with the boat and the boat that is added with silver of magnesium, and the mode that becomes 100nm with thickness is carried out evaporation and formed negative electrode.At this moment, regulate evaporation rate with magnesium and the atomicity of silver than the mode that becomes 10:1, the mode that becomes second 0.1nm/ second～10nm/ with evaporation rate forms negative electrode, obtains organic electroluminescent element.
If as anode, apply volts DS with magnesium/silver electrode as negative electrode with the ITO electrode, then obtain the blue-light-emitting that wavelength is about 450nm.In addition, by being used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test, it is 4.00V that the result drives on-test voltage, keeps the 90%(1800cd/m of initial value 2) time of above brightness is 87 hours.
[example 6]
＜with compound (1-11-2) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-2), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.12V, and keeping the time of the brightness more than 90% of initial value is 85 hours.
[example 7]
＜with compound (1-11-3) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-3), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.78V, and keeping the time of the brightness more than 90% of initial value is 97 hours.
[example 8]
＜with compound (1-11-4) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-4), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.95V, and keeping the time of the brightness more than 90% of initial value is 83 hours.
[example 9]
＜with compound (1-11-5) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-5), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.88V, and keeping the time of the brightness more than 90% of initial value is 93 hours.
[example 10]
＜with compound (1-11-39) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-39), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.16V, and keeping the time of the brightness more than 90% of initial value is 74 hours.
[example 11]
＜with compound (1-14-2) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-2), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.61V, and keeping the time of the brightness more than 90% of initial value is 76 hours.
[example 12]
＜with compound (1-14-3) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-3), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.85V, and keeping the time of the brightness more than 90% of initial value is 141 hours.
[example 13]
＜with compound (1-14-11) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-11), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.16V, and keeping the time of the brightness more than 90% of initial value is 162 hours.
[example 14]
＜with compound (1-14-12) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-12), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.87V, and keeping the time of the brightness more than 90% of initial value is 75 hours.
[example 15]
＜with compound (1-14-14) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-14), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.82V, and keeping the time of the brightness more than 90% of initial value is 227 hours.
[example 16]
＜with compound (1-14-15) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-15), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.98V, and keeping the time of the brightness more than 90% of initial value is 101 hours.
[example 17]
＜with compound (1-14-16) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-16), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.25V, and keeping the time of the brightness more than 90% of initial value is 70 hours.
[example 18]
＜with compound (1-14-18) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-18), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 3.75V, and keeping the time of the brightness more than 90% of initial value is 125 hours.
[example 19]
＜with compound (1-14-20) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-14-20), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.19V, and keeping the time of the brightness more than 90% of initial value is 63 hours.
[example 20]
＜with compound (1-11-18) be used for the element of electron transfer layer＞
Except compound (1-11-1) being changed to compound (1-11-18), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.Driving on-test voltage is 4.29V, and keeping the time of the brightness more than 90% of initial value is 60 hours.
[comparative example 3]
Except compound (1-11-1) being changed to compound (G), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.It is 5.36V that the result drives on-test voltage, and keeping the time of the brightness more than 90% of initial value is 2 hours.
[comparative example 4]
Except compound (1-11-1) being changed to compound (H), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.It is 4.12V that the result drives on-test voltage, and keeping the time of the brightness more than 90% of initial value is 26 hours.
[comparative example 5]
Except compound (1-11-1) being changed to compound (I), by the method acquisition organic EL of foundation example 5.With the ITO electrode as anode, with magnesium/silver electrode as negative electrode, by be used for obtaining original intensity 2000cd/m 2Current density and implement constant current driven test.It is 4.15V that the result drives on-test voltage, and keeping the time of the brightness more than 90% of initial value is 30 hours.
The results are summarized in table 4 more than inciting somebody to action.
Table 4
[utilizability on the industry]
According to preferable kenel of the present invention, a kind of life-span that especially promotes luminous element can be provided, with the balance of driving voltage also excellent organic electroluminescent element, possess its display unit and possess its means of illumination etc.

Claims (18)

1. compound, it is with following formula (1) expression,
[changing 1]
Figure FDA00003113039900011
In the formula (1),
Py independently is formula (2), (3) or (4) represented base;
[changing 2]
M and n are 0 or 1, m+n=1; And,
It is that 1～6 alkyl or carbon number are 3～6 cycloalkyl that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring in the formula (1) is substituted by carbon number.
2. compound according to claim 1, it is with following formula (1-1) or (1-2) expression,
[changing 3]
Figure FDA00003113039900013
During formula (1-1) reaches (1-2),
Py is formula (2), (3) or (4) represented base;
[changing 4]
Figure FDA00003113039900014
And, formula (1-1) and (1-2) in phenyl ring, naphthalene nucleus and pyridine ring at least one hydrogen to be substituted by carbon number be that 1～6 alkyl or carbon number are 3～6 cycloalkyl.
3. compound according to claim 1, it is with following formula (1-3), (1-4), (1-5) or (1-6) expression,
[changing 5]
Figure FDA00003113039900021
In the formula (1-3)～(1-6),
Py is formula (2), (3) or (4) represented base;
[changing 6]
Figure FDA00003113039900022
And it is that 1～6 alkyl or carbon number are 3～6 cycloalkyl that at least one hydrogen on phenyl ring, naphthalene nucleus and the pyridine ring in the formula (1-3)～(1-6) is substituted by carbon number.
4. compound according to claim 1, it is with following formula (1-7) or (1-8) expression,
[changing 7]
Figure FDA00003113039900023
During formula (1-7) reaches (1-8),
Py is formula (2), (3) or (4) represented base;
[changing 8]
Figure FDA00003113039900031
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And,
P is 1～5 integer.
5. compound according to claim 1, it is with following formula (1-9) or (1-10) expression,
[changing 9]
Figure FDA00003113039900032
During formula (1-9) reaches (1-10),
Py is formula (2), (3) or (4) represented base;
[changing 10]
Figure FDA00003113039900033
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And,
Q is 1～5 integer.
6. compound according to claim 1, it is with following formula (1-11) or (1-12) expression,
[changing 11]
Figure FDA00003113039900034
During formula (1-11) reaches (1-12),
Py 1Be formula (2'), (3') or (4') represented base;
[changing 12]
Figure FDA00003113039900041
Formula (2'), (3') and (4') in, R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And s is 1～4 integer.
7. compound according to claim 1, it is with following formula (1-13) or (1-14) expression,
[changing 13]
During formula (1-13) reaches (1-14),
Py 1Be formula (2'), (3') or (4') represented base;
[changing 14]
Figure FDA00003113039900043
Formula (2'), (3') or (4') in, R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And s is 1～4 integer.
8. compound according to claim 1, it is with following formula (1-15) or (1-16) expression,
[changing 15]
Figure FDA00003113039900044
During formula (1-15) reaches (1-16),
Py is formula (2), (3) or (4) represented base;
[changing 16]
Figure FDA00003113039900051
R is that carbon number is that 1～6 alkyl or carbon number are 3～6 cycloalkyl; And t is 1～4 integer.
9. compound according to claim 1, it is represented with following formula (1-7-26)
[changing 17]
Figure FDA00003113039900052
10. compound according to claim 1, it is represented with following formula (1-7-74)
[changing 18]
Figure FDA00003113039900053
11. compound according to claim 1, it is represented with following formula (1-7-98)
[changing 19]
Figure FDA00003113039900054
12. compound according to claim 1, it is represented with following formula (1-7-96)
[changing 20]
Figure FDA00003113039900055
13. compound according to claim 1, it is represented with following formula (1-14-14)
[changing 21]
Figure FDA00003113039900061
14. compound according to claim 1, its with following formula (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-5), (1-11-6), (1-11-8), (1-11-18), (1-11-39), (1-14-2), (1-14-3), (1-14-11), (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and (1-14-20) in any expression:
[changing 22]
Figure FDA00003113039900071
[changing 23]
Figure FDA00003113039900081
15. an electron transport material, it contains just like each described compound among the claim 1-14.
16. an organic electroluminescent element comprises: the pair of electrodes that comprises anode and negative electrode; Be configured in the luminescent layer between this pair of electrodes; And be configured between above-mentioned negative electrode and this luminescent layer and contain electron transfer layer and/or the electron injecting layer of electron transport material as claimed in claim 15.
17. organic electroluminescent element according to claim 16, the one deck at least in wherein said electron transfer layer and the described electron injecting layer also comprise be selected from by hydroxyquinoline be metal misfit thing, dipyridyl derivatives, coffee quinoline derivant and borane derivative form group at least a.
18. according to claim 16 or 17 described organic electroluminescent elements, the one deck at least in wherein said electron transfer layer and the described electron injecting layer also comprises and is selected from least a among the group who is made up of organic misfit thing of organic misfit thing of the oxide compound of basic metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, 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 misfit thing, alkaline-earth metal and rare earth metal.
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