CN103189355B - Electron transport material and use its organic electroluminescent element - Google Patents

Electron transport material and use its organic electroluminescent element Download PDF

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CN103189355B
CN103189355B CN201180052069.3A CN201180052069A CN103189355B CN 103189355 B CN103189355 B CN 103189355B CN 201180052069 A CN201180052069 A CN 201180052069A CN 103189355 B CN103189355 B CN 103189355B
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phenyl
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CN103189355A (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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JNC Corp
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    • C07—ORGANIC CHEMISTRY
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO

Abstract

Compound represented by formula of the present invention (1) is the electron transport material being used as organic EL, contributes to the life etc. of organic EL by using this electron transport material.In formula (1), the base of Py independently represented by formula (2), (3) or (4); M and n is 0 or 1, m+n=1; Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1) be substituted by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6.

Description

Electron transport material and use its organic electroluminescent element
Technical field
The present invention relates to a kind of new electronic transport material, the organic electroluminescent element (following, sometimes referred to as organic EL, or only referred to as element) etc. that uses this electron transport material with pyridyl.
Background technology
In recent years, organic EL as the secondary generation full color flat panel indicating meter (full color flat paneldisplay) and get most of the attention, current industry is studied it just actively.In order to promote the practical of organic EL, the reduction of element drive voltage, life are indispensable key elements, and in order to realize these key elements, industry is developing new electron transport material always.The driving voltage that especially must realize blue element reduces, life.Following situation is recorded: by will as 2 of coffee quinoline (phenanthroline) derivative or its analogue in patent documentation 1 (Japanese Patent Laid-Open 2003-123983 publication), 2'-Bipyridine compound is used for electron transport material, can with low voltage drive organic EL.But it is the relative value of benchmark that the element characteristic (driving voltage, luminous efficiency etc.) that the example of the document is reported is only with comparative example, does not record the measured value that can be judged as practical value.In addition, 2,2'-Bipyridine compound is used for the example of electron transport material at non-patent literature 1 (Proceedings of the 10 thinternational Workshop on Inorganic and Organic Electroluminescence, the tenth inorganic and organic electric-excitation luminescent international symposium collected works), have announcement in patent documentation 2 (Japanese Patent Laid-Open 2002-158093 publication) and patent documentation 3 (International Publication 2007/86552 handbook).The Tg of the compound recorded in non-patent literature 1 is low, and impracticable.Although the compound recorded in patent documentation 2 and patent documentation 3 can drive organic EL with relative low voltage, still expect during practical application to make life further.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2003-123983 publication
Patent documentation 2: Japanese Patent Laid-Open 2002-158093 publication
Patent documentation 3: International Publication 2007/86552 handbook
Non-patent literature
Non-patent literature 1:Proceedings of the 10 thinternational Workshop on Inorganicand Organic Electroluminescence (2000) (the tenth inorganic and organic electric-excitation luminescent international symposium collected works (2000))
Summary of the invention
The problem of invention for solving
The present invention is that the subject study of Given this planting existing for prior art forms.Problem of the present invention is to provide a kind of electron transport material contributing to the life of organic EL etc.In addition, problem of the present invention is to provide a kind of organic EL using this electron transport material.
Deal with problems adopt means
The people such as the present inventor study through great efforts, found that: by following compound being used for the electron transfer layer of organic EL, the organic EL that can drive with the long lifetime can be obtained, this compound is that any one in the naphthyl or phenyl of 9-(2-naphthyl)-10-phenylanthracene has pyridyl, bipyridyl or pyridinylphenyl, and at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring be substituted by carbon number be 1 ~ 6 alkyl or carbon number be the compound of the cycloalkyl of 3 ~ 6, complete the present invention based on this discovery.
Above-mentioned problem is by shown below every and solve.
[1] compound, it represents with following formula (1),
[changing 1]
In formula (1),
The base of Py independently represented by formula (2), (3) or (4);
[changing 2]
M and n is 0 or 1, m+n=1; Further,
At least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1) be substituted by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6.
[2] compound as described in above-mentioned [1] item, it represents with following formula (1-1) or (1-2),
[changing 3]
In formula (1-1) and (1-2),
Py is formula (2), base represented by (3) or (4);
[changing 4]
Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1-1) and (1-2) be substituted by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6.
[3] compound as described in above-mentioned [1] item, it represents with following formula (1-3), (1-4), (1-5) or (1-6),
[changing 5]
In formula (1-3) ~ (1-6),
Py is formula (2), base represented by (3) or (4);
[changing 6]
Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1-3) ~ (1-6) be substituted by carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6.
[4] compound as described in above-mentioned [1], it represents with following formula (1-7) or (1-8),
[changing 7]
In formula (1-7) and (1-8),
Py is formula (2), base represented by (3) or (4);
[changing 8]
R to be carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6; Further,
P is the integer of 1 ~ 5.
[5] compound as described in above-mentioned [1] item, it represents with following formula (1-9) or (1-10),
[changing 9]
In formula (1-9) and (1-10),
Py is formula (2), base represented by (3) or (4);
[changing 10]
R to be carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6; Further,
Q is the integer of 1 ~ 5.
[6] compound as described in above-mentioned [1] item, it represents with following formula (1-11) or (1-12),
[changing 11]
In formula (1-11) and (1-12),
Py1 is (2'), the (3') or (4') represented base of formula;
[changing 12]
Formula (2'), (3') and (4') in, R to be carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6; Further, s is the integer of 1 ~ 4.
[7] compound as described in above-mentioned [1] item, it represents with following formula (1-13) or (1-14),
[changing 13]
In formula (1-13) and (1-14),
Py1 is (2'), the (3') or (4') represented base of formula;
[changing 14]
Formula (2'), (3') or (4') in, R to be carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6; Further, s is the integer of 1 ~ 4.
[8] compound as described in above-mentioned [1] item, it represents with following formula (1-15) or (1-16),
[changing 15]
In formula (1-15) and (1-16),
Py is formula (2), base represented by (3) or (4);
[changing 16]
R to be carbon number be 1 ~ 6 alkyl or carbon number be the cycloalkyl of 3 ~ 6; Further, t is the integer of 1 ~ 4.
[9] compound as described in above-mentioned [1] item, it represents with following formula (1-7-26)
[changing 17]
[10] compound as described in above-mentioned [1] item, it represents with following formula (1-7-74)
[changing 18]
[11] compound as described in above-mentioned [1] item, it represents with following formula (1-7-98)
[changing 19]
[12] compound as described in above-mentioned [1] item, it represents with following formula (1-7-96)
[changing 20]
[13] compound as described in above-mentioned [1] item, it represents with following formula (1-14-14)
[changing 21]
[14] compound as described in above-mentioned [1] item, it represents with any one in 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)
[changing 22]
[changing 23]
[15] electron transport material, it is containing, for example the compound according to any one of above-mentioned [1] to [14].
[16] organic electroluminescent element, it comprises: comprise the pair of electrodes of 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 containing, for example the electron transfer layer of the electron transport material described in above-mentioned [15] item and/or electron injecting layer.
[17] organic electroluminescent element as described in above-mentioned [16] item, at least one deck wherein in above-mentioned electron transfer layer and electron injecting layer also comprises at least one in the group being selected from and being made up of hydroxyquinoline system metal misfit thing, dipyridyl derivatives, coffee quinoline derivant and borane derivative.
[18] organic electroluminescent element as described in above-mentioned [16] or [17] item, at least one deck wherein in electron transfer layer and electron injecting layer also comprises at least one in the group selecting free alkali metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, the oxide compound of alkaline-earth metal, the halogenide of alkaline-earth metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic misfit thing, organic misfit thing of alkaline-earth metal and organic misfit thing of rare earth metal to form.
The effect of invention
Also stablize even if compound of the present invention applies voltage under filminess, in addition, there is the feature that the transmittability of electric charge is high.Compound of the present invention is suitable as the charge transfer material in organic EL.By compound of the present invention being used for electron transfer layer and/or the electron injecting layer of organic EL, can obtaining and there is long-life organic EL.The organic EL of the application of the invention, can make the Performance Monitor device of full-color display etc.
Embodiment
Below, the present invention is illustrated in greater detail.In addition, in this manual, such as sometimes " compound represented by formula (1-7-26) " is called " compound (1-7-26) ".Sometimes " compound represented by 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
1st invention of this case is the compound with pyridyl, bipyridyl or pyridinylphenyl represented by a kind of following formula (1).
[changing 24]
In formula (1), the base of Py independently represented by formula (2), (3) or (4), m and n is 0 or 1, m+n=1.Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1) be substituted by carbon number be 1 ~ 6 alkyl or carbon number be 3 ~ 6 cycloalkyl be the feature of this compound.
Pyridyl represented by formula (2) is specially 2-pyridyl, 3-pyridyl or 4-pyridyl.
Bipyridyl represented by formula (3) is specially 2, 2'-dipyridyl-5-base, 2, 2'-dipyridyl-6-base, 2, 2'-dipyridyl-4-base, 2, 3'-dipyridyl-5-base, 2, 3'-dipyridyl-6-base, 2, 3'-dipyridyl-4-base, 2, 4'-dipyridyl-5-base, 2, 4'-dipyridyl-6-base, 2, 4'-dipyridyl-4-base, 3, 2'-dipyridyl-6-base, 3, 2'-dipyridyl-5-base, 3, 3'-dipyridyl-6-base, 3, 3'-dipyridyl-5-base, 3, 4'-dipyridyl-6-base, 3, 4'-dipyridyl-5-base, 4, 2'-dipyridyl-3-base, 4, 3'-dipyridyl-3-base, or 4, 4'-dipyridyl-3-base.
Pyridinylphenyl represented by 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 formula (1), the position that Py links all can be optional position on phenyl, 2-naphthyl, and phenyl is preferably 4 and 3, and 2-naphthyl is preferably 6 and 7.What just do not expand conjugated system aspect and do not reduce LUMO (lowest unoccupied molecular orbital, minimum vacant molecular orbital) can aspect, rank, and You Jia is 3 of phenyl.In addition, with regard to raw material easily acquisition aspect, You Jia is 6 of 2-naphthyl.
The carbon number that phenyl ring, naphthalene nucleus and pyridine ring in formula (1) replace is the example of the alkyl of 1 ~ 6: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, 2,2-dimethyl propyls, n-hexyl and isohexyl.Wherein preferably alkyl is methyl, ethyl, sec.-propyl and the tertiary butyl, is more preferred from methyl and the tertiary butyl.Carbon number is the example of the cycloalkyl of 3 ~ 6 is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.Wherein, if consider the acquisition of raw material, the easy degree of synthesis, then preferably cycloalkyl is cyclohexyl.
Compound represented by formula (1) is specially following formula (1-1) or the compound represented by (1-2).
[changing 25]
The definition of the Py in formula (1-1) and (1-2) is same as described above.
The compound of compound represented by formula (1) more specifically represented by any one in following formula (1-3) ~ (1-6).
[changing 26]
The definition of the Py in formula (1-3) ~ (1-6) is same as described above.
The compound of compound represented by formula (1) more specifically represented by any one in following formula (1-7) ~ (1-10).
[changing 27]
The definition of Py and R in formula (1-7) ~ (1-10) is same as described above.P in formula (1-7) and (1-8) is the integer of 1 ~ 5, is preferably the integer of 1 ~ 2, is more preferred from 1.The position of the phenyl that R replaces is also unrestricted, is preferably 3 or 4.Q in formula (1-9) and (1-10) is the integer of 1 ~ 5, is preferably the integer of 1 ~ 2, is more preferred from 1.The position of the naphthyl that R replaces is also unrestricted, is preferably 6 or 7.
In addition, the compound of the compound represented by formula (1) more specifically represented by any one in following formula (1-11) ~ (1-14).
[changing 29]
[changing 30]
[changing 31]
The definition of the Py1 in 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 the integer of 1 ~ 4, 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 compound of the compound represented by formula (1) more specifically represented by following formula (1-15) or (1-16).
[changing 32]
The definition of Py and R in formula (1-15) and (1-16) is same as described above.T is the integer of 1 ~ 4, is preferably 1 or 2, is more preferred from 1.The position of the phenylene that R replaces is also unrestricted, if consider the easy degree of synthesis, then when for when Isosorbide-5-Nitrae-phenylene with the carbon linked with anthracene for benchmark is preferably 3.For when 1,3-phenylene with the carbon linked with anthracene for benchmark is preferably 4.
Specifically, the compound represented by above-mentioned formula (1) is roughly divided into the compound represented by formula (1-7) ~ (1-16).In these, preferably 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 represented by < formula (1-7)
The concrete example of the compound represented by formula (1-7) is as shown in following formula (1-7-1) ~ (1-7-144).In these, preferably 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]
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
[changing 39]
[changing 40]
[changing 41]
[changing 42]
[changing 43]
[changing 45]
[changing 46]
[changing 47]
[changing 48]
[changing 49]
[changing 50]
The concrete example > of the compound represented by < formula (1-8)
The concrete example of the compound represented by formula (1-8) is as shown in following formula (1-8-1) ~ (1-8-105).
[changing 51]
[changing 52]
[changing 53]
[changing 54]
[changing 55]
[changing 56]
[changing 57]
[changing 58]
[changing 59]
[changing 60]
The concrete example > of the compound represented by < formula (1-9)
The concrete example of the compound represented by formula (1-9) is as shown in following formula (1-9-1) ~ (1-9-48).In these, preferably 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]
[changing 62]
[changing 63]
[changing 64]
The concrete example > of the compound represented by < formula (1-10)
The concrete example of the compound represented by formula (1-10) is as shown in following formula (1-10-1) ~ (1-10-48).In these, preferably compound is formula (1-10-1) ~ (1-10-6), (1-10-10) ~ (1-10-12) and (1-10-16) ~ (1-10-21).
[changing 65]
[changing 66]
[changing 67]
[changing 68]
The concrete example > of the compound represented by < formula (1-11)
The concrete example of the compound represented by formula (1-11) is as shown in following formula (1-11-1) ~ (1-11-60).In these, preferably compound is formula (1-11-3) ~ (1-11-10), (1-11-25) ~ (1-11-28) and (1-11-51) ~ (1-11-60).
[changing 69]
[changing 70]
[changing 71]
[changing 72]
[changing 73]
The concrete example > of the compound represented by < formula (1-12)
The concrete example of the compound represented by formula (1-12) is as shown in following formula (1-12-1) ~ (1-12-60).
[changing 74]
[changing 75]
[changing 76]
[changing 77]
[changing 78]
The concrete example > of the compound represented by < formula (1-13)
The concrete example of the compound represented by formula (1-13) is as shown in following formula (1-13-1) ~ (1-13-60).In these, preferably compound is formula (1-13-21) ~ (1-13-28) and formula (1-13-31) ~ (1-31-40).
[changing 79]
[changing 80]
[changing 81]
[changing 82]
[changing 83]
The concrete example > of the compound represented by < formula (1-14)
The concrete example of the compound represented by formula (1-14) is as shown in following formula (1-14-1) ~ (1-14-60).In these, preferably compound is formula (1-14-1) ~ (1-14-18).
[changing 84]
[changing 85]
[changing 86]
[changing 87]
[changing 88]
The concrete example > of the compound represented by < formula (1-15)
The concrete example of the compound represented by formula (1-15) is as shown in following formula (1-15-1) ~ (1-15-48).In these, preferably 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]
[changing 90]
[changing 91]
[changing 92]
The concrete example > of the compound represented by < formula (1-16)
The concrete example of the compound represented by formula (1-16) is as shown in following formula (1-16-1) ~ (1-16-24).In these, preferably compound is formula (1-16-1) ~ (1-16-5).
[changing 93]
[changing 94]
The synthetic method > of < compound
Below, the synthetic method of compound of the present invention is described.Compound of the present invention utilizes general known synthetic method by proper combination and synthesizes.
The synthetic method > of the compound represented by < formula (1-7-1) ~ formula (1-7-144)
[changing 95]
R: the alkyl of carbon number 1 ~ 6 or the cycloalkyl of carbon number 3-6
The integer of m:1 to 5
First, by reacting the 9-phenylanthracene that 1 synthesis of phenyl replaces through alkyl (cycloalkyl).The bromobenzene replaced through alkyl is reacted with MAGNESIUM METAL in THF, makes jesse greener reagent (Grignard reagent), under the existence of catalyst, make itself and 9-bromine anthracene react, make the 9-phenylanthracene that phenyl replaces through alkyl (cycloalkyl).Phenyl ring and anthracene nucleus coupling are not limited to aforesaid method, such as, can adopt the root bank coupled reaction using zinc misfit thing, the Suzuki coupled reaction etc. using boric acid or boric acid ester, can be suitable for according to situation using these ordinary methods.
[changing 96]
Reaction 2 is 10 brominations of the 9-phenylanthracene using N-bromine succinimide and replaced through alkyl (cycloalkyl) by phenyl.Herein, the conventional bromizating agent beyond N-bromine succinimide can also be used.
[changing 97]
Reaction 3 is by anthracene nucleus and naphthalene nucleus coupling.First according to ordinary method, bromo-for 2-6-methoxynaphthalene is made jesse greener reagent, under the existence of catalyst, make it react with the 9-bromine anthracene derivant of reaction synthesized by 2, synthesis 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene derivative.In the same manner as reaction 1, phenyl ring and anthracene nucleus coupling are not limited to aforesaid method, such as, can adopt the root bank coupled reaction using zinc misfit thing, the Suzuki coupled reaction etc. using boric acid or boric acid ester, can be suitable for according to situation using these ordinary methods.
[changing 98]
Reaction 4 is that the methoxyl group demethylation of 9-(6-methoxynaphthalene-2-base)-10-phenylanthracene derivative is formed naphthols.Herein, the reagent using demethylation reaction conventional can be also suitable for.
[changing 99]
Naphthols-OH is converted into triflate (triflate) by reaction 5.-OTf in reaction formula is-OSO 2cF 3abbreviation.
[changing 100]
Reaction 6 by root bank coupling (Negishi coupling) reaction, pyridine ring is combined.First, 4-bromopyridine is made jesse greener reagent.Herein, owing to being use the stable 4-bromopyridine hydrochloride of raw material, so use the isopropylmagnesium chloride of 2 times moles, but for the raw material of hydrochloride need not be used, then mole also harmless for waiting.In jesse greener reagent, add zinc chloride Tetramethyl Ethylene Diamine misfit thing, the zinc chloride misfit thing of pyridine synthesis, under the existence of palladium catalyst, make it react with the triflate that reaction 5 obtains, and synthesize target compound.
Reaction 6 is dug up the roots beyond bank coupled reaction, also can be suitable for using the conventional coupled reactions such as Suzuki coupling (Suzuki coupling) reaction.When using Suzuki coupled reaction, preparing optimal boric acid or boric acid ester according to target compound, such as, the boric acid ester shown in following reaction 7 can be used to obtain target compound.
[changing 101]
As the concrete example of the palladium catalyst that coupled reaction uses, can enumerate: Pd (PPh 3) 4, PdCl 2(PPh 3) 2, Pd (OAc) 2, three (dibenzalacetone) two palladium (0), three (dibenzalacetone) two palladium (0) chloroform misfit thing, two (dibenzalacetone) palladium (0), two (tri-tert phosphino-) palladium (0) or (two (diphenylphosphino) ferrocene of 1,1'-) dichloro palladium (II).
In addition, in order to promote reaction, also optionally phosphine compound can be added in these palladium compounds.As the concrete example of this phosphine compound, can enumerate: three (tertiary butyl) phosphine, tricyclohexyl phosphine, 1-(N, N-dimethylaminomethyl)-2-(di-t-butyl phosphino-) ferrocene, 1-(N, N-dibutylamine ylmethyl)-2-(di-t-butyl phosphino-) ferrocene, 1-(methoxymethyl)-2-(di-t-butyl phosphino-) ferrocene, 1, two (di-t-butyl phosphino-) ferrocene of 1'-, 2, two (the di-t-butyl phosphino-)-1 of 2'-, 1'-dinaphthalene, 2-methoxyl group-2'-(di-t-butyl phosphino-)-1, 1'-dinaphthalene, or 2-dicyclohexyl phosphino--2', 6'-dimethoxy-biphenyl.
As the concrete example reacting the alkali used, can enumerate: sodium carbonate, 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 reacting the solvent used, can enumerate: benzene,toluene,xylene, 1,2,4-Three methyl Benzene, DMF, tetrahydrofuran (THF), Anaesthetie Ether, t-butyl methyl ether, Isosorbide-5-Nitrae-dioxan, methyl alcohol, ethanol, cyclopentyl-methyl ether or Virahol.These solvents can be suitable for selecting, and can be used alone, and also can be made into mixed solvent and use.
The synthetic method > of the compound represented by < formula (1-8-1) ~ formula (1-8-105)
In above-mentioned reaction 3, if use 2-bromo-7-methoxynaphthalene to replace the bromo-6-methoxynaphthalene of 2-, then can similarly synthesize.
The synthetic method > of < formula (1-9-1) ~ formula (1-9-48) and the compound represented by formula (1-10-1) ~ formula (1-10-48)
Replace above-mentioned reaction 1 ~ react the raw material used in 3 by the raw material using these benzene skeletons and naphthalene skeleton to be substituted, can synthesize as described above.Namely, by the jesse greener reagent of 2-bromine anthracene and the coupling of 9-bromine anthracene, according to reaction 2 by 10 of anthracene brominations, then make this bromide and the jesse greener reagent react to methoxybromobenzene or meta-methoxy bromobenzene, and obtain 9-(4-or 3-p-methoxy-phenyl)-10-(2-naphthyl) anthracene.For this compound, the order that the demethylation reaction of methoxyl group is later is carried out according to above-mentioned.In addition, except the compound of particular instantiation, certainly also by being suitable for using raw material according to target compound, synthesize according to above-mentioned synthetic method.
The synthetic method > of < 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 the compound represented by formula (1-14-1) ~ formula (1-14-60)
The pyridine derivate of the raw material replacing above-mentioned reaction 6 or reaction 7 to use by using the pyridine derivate replaced through alkyl or cycloalkyl, as raw material, can synthesize as described above.
The pyridine derivate replaced through alkyl or cycloalkyl can synthesize as shown in following reaction 8 ~ reaction 9.Herein, although exemplified with the synthetic method at the pyridine position in the compound represented by formula (1-11-11), formula (1-12-11), formula (1-13-11) and formula (1-14-11), but by being suitable for changing raw material, the various pyridine derivate replaced through alkyl or cycloalkyl can be synthesized.
[changing 102]
[changing 103]
The synthetic method > of < formula (1-15-1) ~ formula (1-15-48) and the compound represented by formula (1-16-1) ~ formula (1-16-24)
In the steps for importing of the phenyl in above-mentioned " synthetic method of the compound represented by formula (1-9-1) ~ formula (1-9-48) and formula (1-10-1) ~ formula (1-10-48) ", use the phenyl replaced through alkyl or cycloalkyl.Such as can use the synthetic method shown in following reaction 10.
[changing 104]
The definition of the R in formula is same as described above.O is the integer of 1 ~ 4.Only can link the R of desired number in the optional position of phenyl ring according to target compound.
When electron injecting layer compound of the present invention is used in organic EL or electron transfer layer, more stable when applying electric field.This situation represents that compound of the present invention is excellent as the electron injection material or electron transport material being electrically excited light type element.So-called electron injecting layer herein, refers to and receives electronics from negative electrode and inject the layer of organic layer; So-called electron transfer layer, refers to the layer for injected electrons being transferred to luminescent layer.In addition, electron transfer layer also can be held concurrently as electron injecting layer.The material that each layer uses is called electron injection material and electron transport material.
The explanation > of < organic EL
2nd invention of this case is the organic EL of the compound comprised in electron injecting layer or electron transfer layer represented by formula of the present invention (1).The driving voltage of organic EL of the present invention is low, and weather resistance during driving is high.
The structure of organic EL of the present invention has various kenel, the basic multilayered structure for being at least clamped with electric hole transport layer, luminescent layer, electron transfer layer between the anode and the cathode.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 owing to having high electron injection and electron-transporting, so can separately or with other materials and with and for electron injecting layer or electron transfer layer.Organic EL of the present invention, by being combined in electron transport material of the present invention the electric hole input horizon using other materials, electric hole transport layer, luminescent layer etc., also can obtain blueness, green, redness or white luminescence.
The luminescent material of organic EL used in the present invention or luminous doping agent for: polymer association volume, polymer function material series " ray machine energy material ", co-publicate the luminescent material such as color of sunshine fluorescent material, fluorescent bleaches, laser pigment, organic scintillator (scintillator), various florescence analysis reagent described in (1991), P236; Chuner Mitsumasa chief editor, " organic EL Material and indicating meter " CMC society publish the luminescent material etc. of the dopant material described in (2001) P155 ~ 156, the triplet state material described in P170 ~ 172.
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 whorled compound of tool, 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 the oxadiazoles derivative of dialkyl amino or diaryl amido, pyrazolo quinoline, pyridine derivate, pyran derivate, coffee quinoline derivant, Silole derivative, the thiophene derivant with triphenyl amido, quinacridone derivative 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: the pigment such as xanthene (xanthene) derivative, polymethine derivative, derivatives of porphyrin, coumarin derivatives, dicyanomethylene pyran derivative, dicyanomethylenethiopyrans derivative, side oxygen base benzanthrene derivative, qualone derivative, perylene derivative, benzoxazoles derivative, benzothiazole derivant, benzimidizole derivatives.The example of macromolecular luminescent material is: gather styrene derivatives, polythiofuran derivative, Polyvinyl carbazole derivative, polysilane derivative, poly-Fluorene derivative, gather benzene derivative etc.The example of styryl derivative is: containing the styryl derivative, styryl arylene derivatives etc. of amine.
Other electron transport materials that organic EL of the present invention uses can from can be used as in light conductive material electron transport compound compound, can be used for any choice for use in the electron transfer layer of organic EL and the compound of electron injecting layer.
The concrete example of this kind of electron transport material is: the polymkeric substance, Benzazole compounds, gallium misfit thing, pyrazole derivatives, perfluor crystalline 1,2-phenylene derivatives, pyrrolotriazine derivatives, pyrazines derivatives, benzoquinoline derivative, imidazopyridine derivatives, borane derivative etc. of the metal misfit thing of hydroxyquinoline system metal misfit thing, 2,2'-dipyridyl derivatives, coffee quinoline derivant, diphenoquinone, perylene derivative, oxadiazoles derivative, thiophene derivant, triazole derivative, thiadiazoles derivative, oxine derivative, quinoxaline derivative, quinoxaline derivative.
The electric hole injecting material used about organic EL of the present invention and electric hole transport material, can from before light conductive material as the charge transfer material in electric hole any choice for use in the well-known material that the electric hole input horizon of usual compound or organic EL and electric hole transport layer use.These concrete example is: carbazole derivative, triarylamine derivatives, phthalocyanine derivates etc.
The each layer forming organic EL of the present invention is made film by the material that should form each layer with methods such as vapour deposition method, method of spin coating or teeming practices and is formed.So and the thickness of each layer formed is not particularly limited, can be suitable for according to the character of material setting, be generally the scope of 2nm ~ 5000nm.In addition, the method for luminescent material thin-film is preferably employing vapour deposition method, its reason is the film easily obtaining homogeneous, and not easily generates aperture (pinholes) etc.When using vapour deposition method to carry out filming, its evaporation condition is different according to the kind of luminescent material of the present invention.Evaporation condition is preferably suitable setting in following scope usually: heating boat temperature is 50 DEG C ~ 400 DEG C, vacuum tightness is 10 -6pa ~ 10 -3pa, evaporation rate be 0.01nm/ second ~ 50nm/ second, substrate temperature be-150 DEG C ~+300 DEG C, thickness is 5nm ~ 5 μm.
No matter organic EL of the present invention is above-mentioned any structure, is all preferably by base plate supports.As long as substrate has physical strength, thermostability and the transparency, glass, clear plastics film etc. can be used.Anode material can use work function to be greater than the metal of 4eV, alloy, conductive compound and these mixture.Its concrete example is: the metals such as Au, CuI, tin indium oxide (hreinafter referred to as ITO), SnO 2, ZnO etc.
Cathode substance can use work function to be 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.In order to efficiency takes out the luminescence of organic EL well, the more satisfactory transmittance at least one electrode is more than 10%.Sheet resistance as electrode is preferably hundreds of Ω/below.In addition, although thickness also depends on the character of electrode materials, usually 10nm ~ 1 μm, be preferably 10nm ~ 400nm scope in set.This kind of electrode, by using above-mentioned electrode substance, forms film by the method such as evaporation or sputter and makes.
Secondly, as the example using luminescent material of the present invention to make the method for organic EL, the making method of the organic EL comprising above-mentioned anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transport material/negative electrode of the present invention is described.Suitable substrate forms the film of anode material by vapour deposition method and after making anode, this anode forms the film of electric hole input horizon and electric hole transport layer.Form the film of luminescent layer thereon.Vacuum evaporation electron transport material of the present invention over the light-emitting layer, forms film, and makes electron transfer layer.Then, formed the film comprising negative electrode material by vapour deposition method, and make negative electrode, obtain 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.
When to so and the organic EL obtained applies volts DS, using anode as+polarity and using negative electrode as-polarity apply voltage, if apply the voltage of about 2V ~ 40V, then can observe luminescence from transparent or semitransparent electrode side (male or female and both sides).In addition, this organic EL is also luminous in the case of an ac applied voltage.In addition, the waveform of the alternating-current applied can be arbitrarily.
[example]
Below, Case-based Reasoning illustrates in greater detail the present invention.First, the synthesis example of the compound that example uses is described as follows.
The synthesis of [synthesis example 1] compound (1-7-74)
The synthesis > of < 9-(4-tert-butyl-phenyl) anthracene
In a nitrogen environment, 9-bromine anthracene 31g, 4-tert-butylphenylboronic acid 25g, Pd (PPh will be added with 3) 4the flask of 1.3g, potassiumphosphate 51g and 1，2，4-trimethylbenzene 150ml stirs 21 hours at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation (liquid separation).By the solid that suction strainer collection is separated out except desolventizing by underpressure distillation, utilize methanol cleaning, recycling ethyl acetate is cleaned, and obtains 9-(4-tert-butyl-phenyl) anthracene 28g.
The synthesis > of the bromo-10-of < 9-(4-tert-butyl-phenyl) anthracene
To in the flask being added with 9-(4-tert-butyl-phenyl) anthracene 27g, iodine 0.1g and THF 300ml, in a nitrogen environment, N-bromine succinimide 19g is added.At room temperature stir 18 hours, add sodium thiosulfate solution and stopped reaction.This solution is transferred in liquid separation funnel, utilizes chloroform to extract.By the solid that suction strainer collection is separated out except desolventizing by underpressure distillation, from chlorobenzene, then carry out recrystallize, obtain 9-bromo-10-(4-tert-butyl-phenyl) anthracene 29g.
The synthesis > of < 3-(6-bromonaphthalene-2-base) pyridine
The flask being added with 3-bromopyridine 10g and THF 60ml is cooled in ice bath, in a nitrogen environment, stirs the THF solution 35ml of the isopropylmagnesium chloride dripping 2M.Dropwise rear be temporarily warmed up to room temperature after, cool in frozen water, stir and add zinc chloride Tetramethyl Ethylene Diamine misfit thing 17g.Thereafter, at room temperature stir after 1 hour, add trifluoromethanesulfonic acid 6-bromonaphthalene-2-ester 18g and PdCl 2(dppp) 1.6g, stirs 3 hours at a reflux temperature.Reaction solution is cooled to room temperature Hou, in order to remove the metal ion of catalyst, and add and the tetrasodium salt of EDTA dihydrate being about equivalent to 3 times moles relative to target compound is dissolved into solution (hreinafter referred to as the EDTA4Na aqueous solution) in appropriate water and toluene carries out liquid separation.After underpressure distillation is except desolventizing, carry out purifying by column chromatography on silica gel (toluene/ethyl acetate=7/3 (volumetric ratio)), obtain 3-(6-bromonaphthalene-2-base) pyridine 12g.
The synthesis > of < compound (1-7-74)
To be added with 3-(6-bromonaphthalene-2-base) 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 flask in a nitrogen environment, stir 4 hours at a reflux temperature.In this solution, add the bromo-10-of 9-(4-tert-butyl-phenyl) anthracene 8.6g, potassiumphosphate 9.3g and 1，2，4-trimethylbenzene 50ml, use Dien-Rodney Stark pipe glycol dimethyl ether to be added at normal temperatures thermal distillation removing.Add the 3rd butanols 5ml, water 5ml, two (dibenzalacetone) palladium (0) 0.4g and tricyclohexyl phosphine 0.5g, stir 5 hours further at a reflux temperature.By reaction solution cool to room temperature, carry out washing and make salt dissolve after, gather solid by suction strainer.Utilize the solid that methanol cleaning obtains, after recycling ethyl acetate is cleaned, carry out purifying by column chromatography on silica gel (toluene/ethyl acetate=9/1 (volumetric ratio)), obtain compound (1-7-74): 3-(6-(10-(the 4-tertiary butyl) phenyl) anthracene-9-base) naphthalene-2-base) pyridine 1.0g.Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 2] compound (1-7-26)
The synthesis > of < 9-(3-tolyl) anthracene
In a nitrogen environment, 9-bromine anthracene 36g, 3-methylphenylboronic acid 21g, Pd (PPh will be added with 3) 4the flask of 1.4g, potassiumphosphate 59g and 1，2，4-trimethylbenzene 150ml stirs 2.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation.After the toluene solution utilizing short silicone tube column purification to obtain, underpressure distillation is except desolventizing.In obtained oil, add heptane, the solid of being separated out by suction strainer collection, obtain 9-(3-tolyl) anthracene 31g.
The synthesis > of the bromo-10-of < 9-(3-tolyl) anthracene
To in the flask being added with 9-(3-tolyl) anthracene 30g and THF 200ml, cool in ice bath in a nitrogen environment, add N-bromine succinimide 20g and iodine 0.1g.At room temperature stir 15 hours, add sodium thiosulfate solution and stopped reaction.This solution is transferred in liquid separation funnel, after utilizing toluene to extract, carries out purifying with short silica gel tubing string.Underpressure distillation, except desolventizing, adds heptane, the solid of being separated out by suction strainer collection in obtained solution, obtains 9-bromo-10-(3-tolyl) anthracene 30g.
The synthesis > of < 4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-base)-1,3,2-dioxa boron penta rings
To be added with the bromo-10-of 9-(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 flask in a nitrogen environment, stir 16 hours at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation, utilize the toluene solution that short silicone tube column purification obtains.Underpressure distillation, except desolventizing, adds heptane, the solid of being separated out by suction strainer collection in obtained oil, obtains 4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-base)-1,3,2-dioxa boron penta ring 24g.
The synthesis > of < compound (1-7-26)
4,4,5,5-tetramethyl--2-(10-(3-tolyl) anthracene-9-base)-1,3,2-dioxa boron penta ring 12g, 3-(6-bromonaphthalene-2-base) pyridine 10g, Pd (PPh will be added with 3) 4the flask of 1.0g, potassiumphosphate 13g, 1，2，4-trimethylbenzene 50ml, the 3rd butanols 10ml and water 10ml stirs 1 hour at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation, and underpressure distillation is except desolventizing.After the crude product obtained by column chromatography on silica gel (toluene/ethyl acetate=20/1 (volumetric ratio)) purifying, from toluene/heptane mixing solutions, carry out recrystallize, obtain compound (1-7-26): 3-(6-(10-(3-tolyl) anthracene-9-base) naphthalene-2-base) pyridine 7.1g.Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 3] compound (1-7-98)
The synthesis > of < 9-(3-tert-butyl-phenyl) anthracene
In a nitrogen environment, 9-bromine anthracene 23g, 2-(3-tert-butyl-phenyl)-4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring 25g, Pd (PPh will be added with 3) 4the flask of 3.1g, potassiumphosphate 37g, 1，2，4-trimethylbenzene 250ml, the 3rd butanols 50ml and water 30ml stirs 21 hours at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation.Utilize the toluene solution that short silicone tube column purification obtains, underpressure distillation is except desolventizing, and the solid of being separated out by adding methyl alcohol by suction strainer collection, obtains 9-(3-tert-butyl-phenyl) anthracene 24g.
The synthesis > of the bromo-10-of < 9-(3-tert-butyl-phenyl) anthracene
To in the flask being added with 9-(3-tert-butyl-phenyl) anthracene 23g, iodine 0.1g and THF 100ml, add N-bromine succinimide 13g in a nitrogen environment.At room temperature stir 1 hour, add sodium thiosulfate solution and stopped reaction.This solution is transferred in liquid separation funnel, utilizes toluene to extract.Utilize the toluene solution that short silicone tube column purification obtains, after underpressure distillation is except desolventizing, carry out toluene and methanol redeposition, obtain 9-bromo-10-(3-tert-butyl-phenyl) anthracene 23g.
The synthesis > of < compound (1-7-98)
To be added with 3-(6-bromonaphthalene-2-base) 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 flask in a nitrogen environment, stir 4 hours at a reflux temperature.In this solution, add the bromo-10-of 9-(3-tert-butyl-phenyl) anthracene 8.6g, potassiumphosphate 9.3g and 1，2，4-trimethylbenzene 50ml, use Dien-Rodney Stark pipe, glycol dimethyl ether is added at normal temperatures thermal distillation removing.Add the 3rd butanols 5ml, water 5ml, two (dibenzalacetone) palladium (0) 0.4g and tricyclohexyl phosphine 0.5g, stir 2 hours further at a reflux temperature.By reaction solution cool to room temperature, carry out washing and make salt dissolve after, gather solid by suction strainer.After the solid obtained by column chromatography on silica gel (toluene/ethyl acetate=9/1 (volumetric ratio)) purifying, from toluene, carry out recrystallize, obtain compound (1-7-98): 3-(6-(10-(3-tert-butyl-phenyl) anthracene-9-base) naphthalene-2-base) pyridine 1.5g.Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 4] compound (1-7-96)
The synthesis > of < 2-(10-(4-tert-butyl-phenyl) anthracene-9-base)-4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring
To be added with the bromo-10-of 9-(4-tert-butyl-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 cyclopentyl-methyl ether 40ml flask in a nitrogen environment, stir 6.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, interpolation water and toluene carry out liquid separation, and underpressure distillation is except desolventizing.In obtained oil, add heptane, the solid of being separated out by suction strainer collection, obtain 2-(10-(4-tert-butyl-phenyl) anthracene-9-base)-4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring 6.9g.
The synthesis > of < 4-(3-(6-bromonaphthalene-2-base) phenyl) pyridine
In a nitrogen environment, the flask being added with 4-(3-bromophenyl) pyridine 9.8g and THF 20ml is cooled to less than-70 DEG C in dry ice/methanol bath, slowly drips the n-Butyl Lithium 17ml of 2.6M.After dropwising, synthermal lower stirring 0.5 hour, add zinc chloride Tetramethyl Ethylene Diamine misfit thing 12g.Thereafter, at room temperature stir after 0.5 hour, add trifluoromethanesulfonic acid 6-bromonaphthalene-2-ester 15g, two (dibenzalacetone) palladium (0) and two (diphenylphosphino) propane 0.5g of 1,2-, stir 1 hour at a reflux temperature.After completion of the reaction, the interpolation EDTA4Na aqueous solution, ethyl acetate carry out liquid separation, after underpressure distillation is except desolventizing, carry out purifying by activated alumina column chromatography (toluene/ethyl acetate=9/1 (volumetric ratio)).Then, utilize methanol cleaning, from ethyl acetate/methanol mixed solvent, carry out recrystallize, obtain 4-(3-(6-bromonaphthalene-2-base) phenyl) pyridine 5.3g.
The synthesis > of < compound (1-7-96)
2-(10-(4-tert-butyl-phenyl) anthracene-9-base)-4,4,5,5-tetramethyl--1,3,2-dioxa boron penta ring 6.1g, 4-(3-(6-bromonaphthalene-2-base) phenyl) pyridine 5.0g, Pd (PPh will be added with 3) 4the flask of 0.5g, potassiumphosphate 3.0g, 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 5ml stirs 6 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation, and underpressure distillation is except desolventizing.By the crude product that activated alumina column chromatography (toluene/ethyl acetate=9/1 (volumetric ratio)) purifying obtains.After the solid utilizing ethyl acetate underpressure distillation to be obtained except desolventizing is cleaned, from toluene, carry out recrystallize, obtain compound (1-7-96): 4 (3-(6-(10-(4-tert-butyl-phenyl) anthracene-9-base) naphthalene-2-base) phenyl) pyridine 3.3g.Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 5] compound (1-14-14)
The synthesis > of < 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene
1-bromo-3-phenetole 72.4g, (10-(naphthalene-2-base) anthracene-9-base) boric acid 104.5g, Pd (PPh is added in flask 3) 410.4g, potassiumphosphate 127.4g, 1，2，4-trimethylbenzene 600ml, 2-propyl alcohol 120ml and water 120ml, in a nitrogen environment, stir 6 hours at a reflux temperature.After reaction solution is cooled to room temperature, gathers the solid in liquid by suction strainer, utilize methanol cleaning, obtain 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 82g.
The synthesis > of < 3-(10-(naphthalene-2-base) anthracene-9-base) phenol
In flask, add 9-(3-ethoxyl phenenyl)-10-(naphthalene-2-base) anthracene 82g and pyridine hydrochloride 446.0g, in a nitrogen environment, stir 8 hours at a reflux temperature.After reaction solution is cooled to room temperature, add water, the solid of being separated out by suction strainer collection, utilizes methanol cleaning, and recycling toluene is cleaned, and obtains 3-(10-(naphthalene-2-base) anthracene-9-base) phenol 76.0g.
The synthesis > of < trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester
The flask being added with 3-(10-(naphthalene-2-base) anthracene-9-base) phenol (76.0g) and pyridine (1L) is cooled in ice bath, in a nitrogen environment, drips trifluoromethanesulfanhydride anhydride 65.0g wherein.After dropwising, at room temperature stir 15 hours further, add water, the solid of being separated out by suction strainer collection.Utilize methyl alcohol to be cleaned by this solid, obtain trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) phenyl ester 90.3g.
The synthesis > of < 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta rings
In flask, add trifluoromethayl sulfonic acid 3-(10-(naphthalene-2-base) anthracene-9-base) 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, stir 5 hours at a reflux temperature.After reaction solution is cooled to room temperature, utilization is coated with diatomaceous paulownia mountain funnel and carries out suction strainer and remove insolubles, utilizes the EDTA4Na aqueous solution filtrate to be cleaned.Utilize that underpressure distillation is removed the solvent of filtrate by heptane and the solid that obtains is cleaned, obtain 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta rings (52.0g).
The synthesis > of < compound (1-14-14)
4 are added in flask, 4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring 8.6g, 5'-bromo-3-methyl-2,2'-dipyridyl 5.1g, Pd (PPh synthesized by the method recorded in Japanese Patent Laid-Open 2009-124114 3) 40.6g, potassiumphosphate 7.2g, 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 1ml, stir 2.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, after adding water, gather the solid in liquid by suction strainer, utilize methanol cleaning.By column chromatography on silica gel (toluene/ethyl acetate=9/1 (volumetric ratio)) this solid of purifying, be then further purified by Activated charcoal tube column chromatography.Concentrated solution, carries out recrystallize from chlorobenzene, obtains compound (1-14-14): 3-methyl-5'-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,2'-dipyridyl 2.3g.Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 6] compound (1-11-1)
The synthesis > of < 2-methyl-4-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), 4-bromine-2-methylpyridine (0.8g), Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, stirs 7.5 hours at a reflux temperature in a nitrogen environment.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution (developing solvent): toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Gather underpressure distillation and remove the crystallization of separating out in the process of the filtrate obtained, obtain compound 2-methyl-4-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (0.7g) represented by (1-11-1).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 7] compound (1-11-2)
The synthesis > of < 3-methyl-4-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), the bromo-3-methyl pyridinium chloride (1.0g) of 4-, Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1,2,4-Three methyl Benzene (20ml), the 3rd butanols (5ml) and water (1ml) add in flask, in a nitrogen environment, stir 24.5 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Gather underpressure distillation and remove the crystallization of separating out in the process of the filtrate obtained, in toluene, carry out recrystallize further, obtain compound 3-methyl-4-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (0.5g) represented by (1-11-2).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 8] compound (1-11-3)
The synthesis > of < 2-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), 5-bromine-2-methylpyridine (0.8g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 5 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.The solid that underpressure distillation obtains except desolventizing is carried out recrystallize from toluene, obtains compound 2-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (1.2g) represented by (1-11-3).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 9] compound (1-11-4)
The synthesis > of < 3-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), the bromo-5-picoline (0.8g) of 3-, Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 7.5 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation, except desolventizing, is added heptane and is carried out redeposition, obtain compound 3-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (1.3g) represented by (1-11-4).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 10] compound (1-11-5)
The synthesis > of < 4-methyl-3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), the bromo-4-methyl pyridinium chloride (1.0g) of 3-, Pd (PPh 3) 4(0.3g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 7 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, obtained solid is carried out recrystallize from toluene, obtains compound 4-methyl-3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (0.6g) represented by (1-11-5).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 11] compound (1-11-6)
The synthesis > of < 2-methyl-3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), 3-bromine-2-methylpyridine (0.8g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 4 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation, except desolventizing, is added heptane and is carried out redeposition, obtain compound 2-methyl-3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (1.1g) represented by (1-11-6).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 12] compound (1-11-8)
The synthesis > of < 5-methyl-2-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.5g), 3-bromine-2-methylpyridine (1.0g), Pd (PPh 3) 4(0.15g), potassiumphosphate (2.1g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 18 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, the solid of being separated out by suction strainer collection.By the solid that column chromatography on silica gel (developping solution: toluene) purifying obtains.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation, except desolventizing, is added ethyl acetate and is carried out redeposition, obtain compound 5-methyl-2-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine (1.5g) represented by (1-11-8).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 13] compound (1-11-39)
The synthesis > of < 5-bromo-2'-methyl-3,4'-dipyridyl
The flask being added with 4-bromine-2-methylpyridine (13.8g) and toluene (150ml) is cooled in acetone/the dry ice bath.The hexane solution (55ml) of the n-Butyl Lithium of 1.6M is dripped in this solution.After dropwising, cooling in acetone/the dry ice bath, while stir 1 hour, is added zinc chloride Tetramethyl Ethylene Diamine (29.3g) and THF (45ml), is removed acetone/the dry ice bath and heat up.After being warmed up to room temperature, add toluene (20ml), 3,5-dibromo pyridines (19.0g) and Pd (PPh 3) 4(2.8g), stir 2 hours at a reflux temperature.Reaction solution is cooled to room temperature Hou, in order to remove the metal ion of catalyst, and add and the tetrasodium salt of EDTA dihydrate being about equivalent to 3 times moles relative to target compound is dissolved into solution (hreinafter referred to as the EDTA4Na aqueous solution) in appropriate water and toluene carries out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate) purifying.Now, publish limited-liability company, method described in the 94th page with reference to " Experiment of Organic Chemistry introduction (1)-mass treatment method with separation and purification method-" chemistry with people, the ratio of the ethyl acetate lentamente in increase developping solution, makes target compound stripping.Then, obtained solid, except desolventizing, is carried out recrystallize from heptane by underpressure distillation, obtains 5-bromo-2'-methyl-3,4'-dipyridyl (5.3g).
The synthesis > of < 2'-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-3,4'-dipyridyls
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.5g), 5-bromo-2'-methyl-3,4'-dipyridyl (1.1g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 3 hours at a reflux temperature.After heating, by reaction solution cool to room temperature, interpolation water and toluene carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=1/1) purifying.Underpressure distillation is except desolventizing, obtained solid is carried out recrystallize from toluene, obtain compound 2'-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-3, the 4'-dipyridyls (0.3g) represented by (1-11-39).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 14] compound (1-14-2)
The synthesis > of < 3-methyl-4-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1, the bromo-3-methyl pyridinium chloride (1.3g) of 3,2-dioxa boron penta ring (2.5g), 4-, Pd (PPh 3) 4(0.35g), potassiumphosphate (3.2g), 1，2，4-trimethylbenzene 20ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 11.5 hours.After reaction solution is cooled to room temperature, interpolation toluene and water carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation, except desolventizing, is added heptane and is carried out redeposition, obtain compound 3-methyl-4-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine (1.4g) represented by (1-14-2).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 15] compound (1-14-3)
The synthesis > of < 2-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta rings (2.5g), 5-bromine-2-methylpyridine (1.0g), Pd (PPh 3) 4(0.35g), potassiumphosphate (3.2g), 1，2，4-trimethylbenzene 20ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 8.5 hours.After reaction solution is cooled to room temperature, the solid of being separated out by suction strainer collection.By the solid that column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying obtains.Then, obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, utilize ethyl acetate to clean obtained solid, obtain compound 2-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl) pyridine (1.5g) represented by (1-14-3).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 16] compound (1-14-11)
The synthesis > of < 5-bromo-6'-methyl-2,2'-dipyridyl
The flask being added with the bromo-6-picoline (5.2g) of 2-and cyclopentyl-methyl ether (30ml) is cooled in methyl alcohol/the dry ice bath.The hexane solution (22ml) of the n-Butyl Lithium of 1.6M is dripped in this solution.After dropwising, cooling in methyl alcohol/the dry ice bath, while stir 2 hours, is added zinc chloride Tetramethyl Ethylene Diamine (8.3g), is removed 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), stir 3.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate) purifying.Now, increase the ratio of the ethyl acetate in developping solution lentamente, make target compound stripping.Then, obtained solid, except desolventizing, is carried out recrystallize by underpressure distillation from heptane, obtains 5-bromo-6'-methyl-2,2'-dipyridyl (1.4g).
The synthesis > of < 6'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,2'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-6'-methyl-2,2'-dipyridyl (1.0g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 20ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 7.5 hours.After reaction solution is cooled to room temperature, the solid of being separated out by suction strainer collection.By the solid that column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying obtains, the paulownia mountain funnel being coated with activated carbon is directly used by obtained dissolution fluid to carry out suction strainer, removing coloring components.Underpressure distillation is except desolventizing, add ethyl acetate and carry out redeposition, obtain compound 6'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 2'-dipyridyls (1.2g) represented by (1-14-11).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 17] compound (1-14-12)
The synthesis > of < 5-bromo-5'-methyl-2,2'-dipyridyl
The flask being added with the bromo-5-picoline (1.7g) of 2-and THF (5ml) is cooled in ice bath, in this solution, drips the THF solution (5.5ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 3.5 hours, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (2.8g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (2.4g) and Pd (PPh 3) 4(0.35g), stir 1.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=9/1) purifying.Underpressure distillation, except desolventizing, is added heptane and is carried out redeposition, obtain 5-bromo-5'-methyl-2,2'-dipyridyl (1.5g).
The synthesis > of < 5-methyl-5'-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,2'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-5'-methyl-2,2'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 20ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 6 hours.After reaction solution is cooled to room temperature, interpolation toluene and water carry out liquid separation.Underpressure distillation is except desolventizing, and the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying, passes into short activated carbon tubing string by obtained dissolution fluid, removing coloring components.Underpressure distillation is except desolventizing, add ethyl acetate and carry out redeposition, obtained solid is carried out recrystallize further from toluene, obtain compound 5-methyl-5'-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 2'-dipyridyls (1.2g) represented by (1-14-12).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 18] compound (1-14-13)
The synthesis > of < 5'-bromo-4-methyl-2,2'-dipyridyl
The flask being added with the bromo-4-picoline (6.9g) of 2-and THF (20ml) is cooled in ice bath, in this solution, drips the THF solution (24ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 1 hour, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (12.1g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (9.5g) and Pd (PPh 3) 4(1.4g), stir 2.5 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=9/1) purifying.Obtained solid, except desolventizing, is carried out recrystallize by underpressure distillation from heptane, obtains 5'-bromo-4-methyl-2,2'-dipyridyl (5.5g).
The synthesis > of < 4-methyl-5'-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,2'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5'-bromo-4-methyl-2,2'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 20ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 16 hours.After reaction solution is cooled to room temperature, interpolation toluene and water carry out liquid separation.Underpressure distillation is except desolventizing, and the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=95/5) purifying, passes into short activated carbon tubing string by obtained dissolution fluid, removing coloring components.Underpressure distillation is except desolventizing, heptane is utilized to clean, obtain compound 4-methyl-5'-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 2'-dipyridyls (1.4g) represented by (1-14-13) by this.
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 19] compound (1-14-15)
The synthesis > of < 5-bromo-6'-methyl-2,3'-dipyridyl
The flask being added with 5-bromine-2-methylpyridine (3.4g) and THF (10ml) is cooled in ice bath, in this solution, drips the THF solution (11ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 3 hours, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (5.5g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (4.7g) and Pd (PPh 3) 4(0.7g), stir 5 hours at a reflux temperature.Reaction solution is cooled to room temperature Hou, and the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=7/3) purifying, obtains 5-bromo-6'-methyl-2,3'-dipyridyl (1.5g).
The synthesis > of < 6'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 5 hours.After reaction solution is cooled to room temperature, the solid of being separated out by suction strainer collection, utilizes methanol cleaning, and recycling ethyl acetate is cleaned.Then, carry out purifying by column chromatography on silica gel (developping solution: toluene/ethyl acetate=4/1), obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, obtained solid is carried out recrystallize further from chlorobenzene, obtain compound 6'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 3'-dipyridyls (1.3g) represented by (1-14-15).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 20] compound (1-14-16)
The synthesis > of < 5-bromo-5'-methyl-2,3'-dipyridyl
The flask being added with the bromo-5-picoline (3.4g) of 3-and THF (10ml) is cooled in ice bath, in this solution, drips the THF solution (11ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 1.5 hours, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (5.5g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (4.7g) and Pd (PPh 3) 4(0.7g), stir 5 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=7/3) purifying, obtains 5-bromo-5'-methyl-2,3'-dipyridyl (1.4g).
The synthesis > of < 5'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 5 hours.After reaction solution is cooled to room temperature, the solid of being separated out by suction strainer collection, utilizes methanol cleaning, and recycling ethyl acetate is cleaned.Then, carry out purifying by column chromatography on silica gel (developping solution: toluene/ethyl acetate=4/1), then obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, obtained solid is carried out recrystallize further from chlorobenzene, obtain compound 5'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 3'-dipyridyls (1.3g) represented by (1-14-16).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 21] compound (1-14-17)
The synthesis > of < 5-bromo-4'-methyl-2,3'-dipyridyl
The flask being added with the bromo-4-picoline (5.2g) of 3-and THF (10ml) is cooled in ice bath, in this solution, drips the THF solution (17ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 9 hours, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (8.3g).Remove ice bath and after being warmed up to room temperature, adding 2,5-dibromo pyridine (7.1g), Pd-137 (village letter Wan Feng company of Britain) (0.4g) and NMP (25ml), stir 6 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=7/3) purifying.Obtained solid, except desolventizing, utilizes heptane to clean by underpressure distillation, obtains 5-bromo-4'-methyl-2,3'-dipyridyl (2.4g).
The synthesis > of < 4'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 5 hours.After reaction solution is cooled to room temperature, interpolation toluene and water carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=7/3) purifying, then obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, obtained solid is carried out recrystallize further from toluene, obtain compound 4'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 3'-dipyridyls (0.7g) represented by (1-14-17).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 22] compound (1-14-18)
The synthesis > of < 5-bromo-2'-methyl-2,3'-dipyridyl
The flask being added with 3-bromine-2-methylpyridine (5.2g) and THF (10ml) is cooled in ice bath, in this solution, drips the THF solution (17ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove after ice bath at room temperature stirs 2 hours, again cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (8.3g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (7.1g), Pd (PPh 3) 4(1.0g) and dimethylbenzene (10ml), stir 7 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and toluene carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=4/1) purifying, obtains 5-bromo-2'-methyl-2,3'-dipyridyl (1.3g).
The synthesis > of < 2'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,3'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-6'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 25ml, the 3rd butanols 5ml and water 1ml, at a reflux temperature stirring 12 hours.After reaction solution is cooled to room temperature, interpolation toluene and water carry out liquid separation.Underpressure distillation removes desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=4/1) purifying, then obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, by the solid that suction strainer collection is separated out, obtain compound 2'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 3'-dipyridyls (0.8g) represented by (1-14-18).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 23] compound (1-14-20)
The synthesis > of < 5-bromo-3'-methyl-2,4'-dipyridyl
The flask being added with the bromo-3-picoline (5.0g) of 4-and THF (30ml) is cooled in dry ice/methanol bath, in this solution, drips the THF solution (16ml) of the isopropylmagnesium chloride of 2M.After dropwising, remove cooling bath, at room temperature stir after 2.5 hours, cool in ice bath, add zinc chloride Tetramethyl Ethylene Diamine (8.0g).Remove ice bath and after being warmed up to room temperature, add 2,5-dibromo pyridine (7.6g) and Pd (PPh 3) 4(1.0g), stir 2 hours at a reflux temperature.After reaction solution is cooled to room temperature, the interpolation EDTA4Na aqueous solution and ethyl acetate carry out liquid separation.After underpressure distillation is except desolventizing, the solid obtained by column chromatography on silica gel (developping solution: toluene/ethyl acetate=5/1) purifying, obtains 5-bromo-3'-methyl-2,4'-dipyridyl (5.6g).
The synthesis > of < 3'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2,4'-dipyridyls
Add 4,4,5,5-tetramethyl--2-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-1,3,2-dioxa boron penta ring (2.0g), 5-bromo-3'-methyl-2,4'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene 1ml, the 3rd butanols 1ml and water 1ml, at a reflux temperature stirring 4 hours.After reaction solution is cooled to room temperature, adds water, gather precipitate by suction strainer.After obtained solid is utilized water and methanol cleaning, purifying is carried out by NH base modified silica-gel (DM1020: chemistry of silicones company of Fuji manufactures) column chromatography (developping solution: toluene), obtain compound 3'-methyl-5-(3-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, the 4'-dipyridyls (1.7g) represented by (1-14-20).
Measured by NMR and confirm the structure of compound.
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)。
The synthesis of [synthesis example 24] compound (1-11-18)
The synthesis > of < 2'-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) 2,3'-dipyridyls
By 4,4,5,5-tetramethyl--2-(6-(10-phenylanthracene-9-base) naphthalene-2-base)-1,3,2-dioxa boron penta rings (2.0g), 5-bromo-2'-methyl-2,3'-dipyridyl (1.2g), Pd (PPh 3) 4(0.15g), potassiumphosphate (1.7g), 1，2，4-trimethylbenzene (20ml), the 3rd butanols (5ml) and water (1ml) adds in flask, in a nitrogen environment, stirs 8 hours at a reflux temperature.After heating, after reaction solution is cooled to room temperature, the solid of being separated out by suction strainer collection, utilizes methanol cleaning, and recycling ethyl acetate is cleaned.Then, carry out purifying by column chromatography on silica gel (developping solution: toluene/ethyl acetate=7/3), then obtained dissolution fluid is passed into short activated carbon tubing string, removing coloring components.Underpressure distillation is except desolventizing, and the solid of being separated out by suction strainer collection, obtains compound 2'-methyl-5-(6-(10-phenylanthracene-9-base) naphthalene-2-base) 2, the 3'-dipyridyls (1.1g) represented by (1-11-18).
Measured by NMR and confirm the structure of compound.
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)。
By being suitable for the compound changing 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 using 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, the driving measured respectively in constant current driven test starts voltage (V), keeps the time (hour) of the brightness of more than 90% of initial value.Below, example and comparative example is explained.
The material of each layer in the element of made example 1 to example 4 and comparative example 1 to comparative example 2 is formed and is shown in following table 1.
Table 1
In Table 1, " HI " is N 4, N 4'-phenylbenzene-N 4, N 4'-bis-(9-phenyl-9H-carbazole-3-base)-[1,1'-biphenyl]-4,4'-diamines, " NPD " is N 4, N 4'-two (naphthalene-1-base)-N 4, N 4'-phenylbenzene-[1,1'-biphenyl]-4,4'-diamines, compound (A) is 9-phenyl-10-(4-phenylnaphthalene-1-base) 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) is 9,10-bis-([2,2'-dipyridyl]-5-base) anthracene, compound (D) is two (4-(pyridin-3-yl) naphthalene-1-base) anthracene of 9,10-.The chemical structure of " Liq " that these compounds and the layer be formed between electron transfer layer and negative electrode used discloses as follows in the lump.
[changing 105]
[example 1]
< is by the element > of compound (1-7-74) for electron transfer layer
The ITO being made the film that thickness is 180nm by sputter is ground to the glass substrate (Opto Science (share) manufacture) of the 26mm × 28mm × 0.7mm of 150nm as transparent support substrate.This transparent support substrate is fixed in the substrate holder of commercially available evaporation coating device (Showa vacuum (share) manufacture), install be added with HI evaporation molybdenum boat, be added with NPD evaporation molybdenum boat, be added with compound (A) evaporation molybdenum boat, be added with compound (B) evaporation molybdenum boat, be added with compound (1-7-74) evaporation molybdenum boat, be added with Liq evaporation molybdenum boat, be added with magnesium molybdenum boat and be added with silver evaporation tungsten boat.
In the ito film of transparent support substrate, sequentially form following each layer.Vacuum tank is reduced pressure to 5 × 10 -4pa, first, heating is added with the evaporation boat of HI, and the mode becoming 40nm with thickness is carried out evaporation and forms electric hole input horizon, and then, heating is added with the evaporation boat of NPD, and the mode becoming 30nm with thickness is carried out evaporation and forms electric hole transport layer.Secondly, heating is simultaneously added with the evaporation boat of compound (A) and is added with the evaporation boat of compound (B), and the mode becoming 35nm with thickness is carried out evaporation and forms luminescent layer.Evaporation rate is regulated in the mode that compound (A) and the weight ratio of compound (B) become about 95:5.Secondly, heating is added with the evaporation boat of compound (1-7-74), and the mode becoming 15nm with thickness is carried out evaporation and forms electron transfer layer.The evaporation rate of each layer be 0.01nm/ second ~ 1nm/ second.
Thereafter, heating is added with the evaporation boat of Liq, the mode becoming 1nm with thickness with 0.01nm/ second ~ evaporation rate of 0.1nm/ second carries out evaporation.Then, the boat that heating is simultaneously added with magnesium and the boat being added with silver, the mode becoming 100nm with thickness is carried out evaporation and forms negative electrode.Now, regulate evaporation rate with magnesium and the atomicity of silver than the mode becoming 10:1, with evaporation rate become 0.1nm/ second ~ mode of 10nm/ second forms negative electrode, obtains organic electroluminescent element.
If apply volts DS using magnesium/silver electrode as negative electrode using ITO electrode as anode, then obtain the blue-light-emitting that wavelength is about 460nm.In addition, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test, result drives on-test voltage to be 7.33V, keeps 90% (1800cd/m of initial value 2) more than time of brightness be 45 hours.
[example 2]
< is by the element > of compound (1-7-26) for electron transfer layer
Except being changed to except compound (1-7-26) by compound (1-7-74), obtain organic EL by the method according to example 1.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 6.36V, and the time keeping the brightness of more than 90% of initial value is 151 hours.
[example 3]
< is by the element > of compound (1-7-98) for electron transfer layer
Except being changed to except compound (1-7-98) by compound (1-7-74), obtain organic EL by the method according to example 1.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 7.34V, and the time keeping the brightness of more than 90% of initial value is 265 hours.
[example 4]
< is by the element > of compound (1-7-96) for electron transfer layer
Except being changed to except compound (1-7-96) by compound (1-7-74), obtain organic EL by the method according to example 1.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 5.33V, and the time keeping the brightness of more than 90% of initial value is 103 hours.
[comparative example 1]
Except being changed to except compound (C) by compound (1-7-74), obtain organic EL by the method according to example 1.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Result driving on-test voltage is 5.06V, and the time keeping the brightness of more than 90% of initial value is 6 hours.
[comparative example 2]
Except being changed to except compound (D) by compound (1-7-74), obtain organic EL by the method according to example 1.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Result driving on-test voltage is 5.05V, and the time keeping the brightness of more than 90% of initial value is 10 hours.
Table 2 will be the results are summarized in above.
Table 2
The element of example of making 5 to example 20 and comparative example 3 to comparative example 5, the driving measured respectively in constant current driven test starts voltage (V), keeps the time (hour) of the brightness of more than 90% of initial value.Below, example and comparative example is explained.
The material of each layer in the element of made example 5 to example 20 and comparative example 3 to comparative example 5 is formed and is shown in following table 3.
Table 3
In table 3, HT is N-([1, 1'-biphenyl]-4-base)-9, 9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-base) phenyl)-9H-Fluorene-2-amine, compound (E) is 9-(4-(naphthalene-1-base) phenyl)-10-phenylanthracene, compound (F) is 4, 4'-((7, 7-phenylbenzene-7H-benzo [c] Fluorene-5, 9-bis-base) two ((phenyl) amido)) two benzonitriles, compound (G) is 4'-(4-(10-(naphthalene-2-base) anthracene-9-base) phenyl)-2, 2':6', 2 "-terpyridyls, compound (H) is 3-(6-(10-phenylanthracene-9-base) naphthalene-2-base) pyridine, compound (I) is 6-(4-(10-(naphthalene-1-base) anthracene-9-base) phenyl)-2, 4'-dipyridyl.
[changing 106]
[example 5]
< is by the element > of compound (1-11-1) for electron transfer layer
The ITO being made the film that thickness is 180nm by sputter is ground to the glass substrate (Opto Science (share) manufacture) of the 26mm × 28mm × 0.7mm of 150nm as transparent support substrate.This transparent support substrate is fixed in the substrate holder of commercially available evaporation coating device (Showa vacuum (share) manufacture), install be added with HI evaporation molybdenum boat, be added with HT evaporation molybdenum boat, be added with compound (E) evaporation molybdenum boat, be added with compound (F) evaporation molybdenum boat, be added with compound (1-11-1) evaporation molybdenum boat, be added with Liq evaporation molybdenum boat, be added with magnesium molybdenum boat and be added with silver evaporation tungsten boat.
The ito film of transparent support substrate sequentially forms following each layer.Vacuum tank is reduced pressure to 5 × 10 -4pa, first, heating is added with the evaporation boat of HI, and the mode becoming 40nm with thickness is carried out evaporation and forms electric hole input horizon, and then heating is added with the evaporation boat of HT, and the mode becoming 30nm with thickness is carried out evaporation and forms electric hole transport layer.Secondly, heating is simultaneously added with the evaporation boat of compound (E) and is added with the evaporation boat of compound (F), and the mode becoming 35nm with thickness is carried out evaporation and forms luminescent layer.Evaporation rate is regulated in the mode that compound (E) and the weight ratio of compound (F) become about 95:5.Secondly, heating is simultaneously added with the evaporation boat of compound (1-11-1) and is added with the evaporation boat of Liq, and the mode becoming 25nm with thickness is carried out evaporation and forms electron transfer layer.Evaporation rate is regulated in the mode that compound (1-11-1) and the weight ratio of Liq become about 1:1.The evaporation rate of each layer be 0.01nm/ second ~ 1nm/ second.
Thereafter, heating is added with the evaporation boat of Liq, the mode becoming 1nm with thickness with 0.01nm/ second ~ evaporation rate of 0.1nm/ second carries out evaporation.Then, the boat that heating is simultaneously added with magnesium and the boat being added with silver, the mode becoming 100nm with thickness is carried out evaporation and forms negative electrode.Now, regulate evaporation rate with magnesium and the atomicity of silver than the mode becoming 10:1, with evaporation rate become 0.1nm/ second ~ mode of 10nm/ second forms negative electrode, obtains organic electroluminescent element.
If using ITO electrode as anode, apply volts DS using magnesium/silver electrode as negative electrode, then obtain the blue-light-emitting that wavelength is about 450nm.In addition, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test, result drives on-test voltage to be 4.00V, keeps 90% (1800cd/m of initial value 2) more than time of brightness be 87 hours.
[example 6]
< is by the element > of compound (1-11-2) for electron transfer layer
Except being changed to except compound (1-11-2) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.12V, and the time keeping the brightness of more than 90% of initial value is 85 hours.
[example 7]
< is by the element > of compound (1-11-3) for electron transfer layer
Except being changed to except compound (1-11-3) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.78V, and the time keeping the brightness of more than 90% of initial value is 97 hours.
[example 8]
< is by the element > of compound (1-11-4) for electron transfer layer
Except being changed to except compound (1-11-4) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.95V, and the time keeping the brightness of more than 90% of initial value is 83 hours.
[example 9]
< is by the element > of compound (1-11-5) for electron transfer layer
Except being changed to except compound (1-11-5) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.88V, and the time keeping the brightness of more than 90% of initial value is 93 hours.
[example 10]
< is by the element > of compound (1-11-39) for electron transfer layer
Except being changed to except compound (1-11-39) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.16V, and the time keeping the brightness of more than 90% of initial value is 74 hours.
[example 11]
< is by the element > of compound (1-14-2) for electron transfer layer
Except being changed to except compound (1-14-2) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.61V, and the time keeping the brightness of more than 90% of initial value is 76 hours.
[example 12]
< is by the element > of compound (1-14-3) for electron transfer layer
Except being changed to except compound (1-14-3) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.85V, and the time keeping the brightness of more than 90% of initial value is 141 hours.
[example 13]
< is by the element > of compound (1-14-11) for electron transfer layer
Except being changed to except compound (1-14-11) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.16V, and the time keeping the brightness of more than 90% of initial value is 162 hours.
[example 14]
< is by the element > of compound (1-14-12) for electron transfer layer
Except being changed to except compound (1-14-12) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.87V, and the time keeping the brightness of more than 90% of initial value is 75 hours.
[example 15]
< is by the element > of compound (1-14-14) for electron transfer layer
Except being changed to except compound (1-14-14) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.82V, and the time keeping the brightness of more than 90% of initial value is 227 hours.
[example 16]
< is by the element > of compound (1-14-15) for electron transfer layer
Except being changed to except compound (1-14-15) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.98V, and the time keeping the brightness of more than 90% of initial value is 101 hours.
[example 17]
< is by the element > of compound (1-14-16) for electron transfer layer
Except being changed to except compound (1-14-16) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.25V, and the time keeping the brightness of more than 90% of initial value is 70 hours.
[example 18]
< is by the element > of compound (1-14-18) for electron transfer layer
Except being changed to except compound (1-14-18) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 3.75V, and the time keeping the brightness of more than 90% of initial value is 125 hours.
[example 19]
< is by the element > of compound (1-14-20) for electron transfer layer
Except being changed to except compound (1-14-20) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.19V, and the time keeping the brightness of more than 90% of initial value is 63 hours.
[example 20]
< is by the element > of compound (1-11-18) for electron transfer layer
Except being changed to except compound (1-11-18) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Driving on-test voltage is 4.29V, and the time keeping the brightness of more than 90% of initial value is 60 hours.
[comparative example 3]
Except being changed to except compound (G) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Result driving on-test voltage is 5.36V, and the time keeping the brightness of more than 90% of initial value is 2 hours.
[comparative example 4]
Except being changed to except compound (H) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Result driving on-test voltage is 4.12V, and the time keeping the brightness of more than 90% of initial value is 26 hours.
[comparative example 5]
Except being changed to except compound (I) by compound (1-11-1), obtain organic EL by the method according to example 5.Using ITO electrode as anode, using magnesium/silver electrode as negative electrode, by for obtaining original intensity 2000cd/m 2current density and implement constant current driven test.Result driving on-test voltage is 4.15V, and the time keeping the brightness of more than 90% of initial value is 30 hours.
Table 4 will be the results are summarized in above.
Table 4
[utilizability in industry]
According to better kenel of the present invention, a kind of life-span especially promoting luminous element can be provided, the organic electroluminescent element also excellent with the balance of driving voltage, possess its display unit and possess its means of illumination etc.

Claims (13)

1. a compound, it represents with following formula (1-1),
[changing 3]
In formula (1-1),
Py is formula (2), base represented by (3) or (4);
[changing 4]
Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1-1) is substituted by the alkyl that carbon number is 1 ~ 6.
2. compound according to claim 1, it represents with following formula (1-3) or (1-4),
[changing 5]
In formula (1-3) ~ (1-4),
Py is formula (2), base represented by (3) or (4);
[changing 6]
Further, at least one hydrogen on phenyl ring, naphthalene nucleus and pyridine ring in formula (1-3) ~ (1-4) is substituted by the alkyl that carbon number is 1 ~ 6.
3. compound according to claim 1, it represents with following formula (1-7) or (1-8),
[changing 7]
In formula (1-7) and (1-8),
Py is formula (2), base represented by (3) or (4);
[changing 8]
R to be carbon number be 1 ~ 6 alkyl; Further,
P is the integer of 1 ~ 5.
4. compound according to claim 1, it represents with following formula (1-11) or (1-12),
[changing 11]
In formula (1-11) and (1-12),
Py 1for the base represented by formula (2 '), (3 ') or (4 ');
[changing 12]
Formula (2 '), in (3 ') and (4 '), R to be carbon number be 1 ~ 6 alkyl; Further, s is the integer of 1 ~ 4.
5. compound according to claim 1, it represents with following formula (1-7-26)
[changing 17]
6. compound according to claim 1, it represents with following formula (1-7-74)
[changing 18]
7. compound according to claim 1, it represents with following formula (1-7-98)
[changing 19]
8. compound according to claim 1, it represents with following formula (1-7-96)
[changing 20]
9. compound according to claim 1, it represents with any one in 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) and (1-11-39):
[changing 22]
10. an electron transport material, it contains compound as claimed in any one of claims 1-9 wherein.
11. 1 kinds of organic electroluminescent elements, comprising: the pair of electrodes comprising anode and negative electrode; Be configured in the luminescent layer between this pair of electrodes; And to be configured between above-mentioned negative electrode and this luminescent layer and containing, for example the electron transfer layer of electron transport material according to claim 10 and/or electron injecting layer.
12. organic electroluminescent elements according to claim 11, at least one deck in wherein said electron transfer layer and described electron injecting layer also comprises at least one in the group being selected from and being made up of hydroxyquinoline system metal misfit thing, dipyridyl derivatives, coffee quinoline derivant and borane derivative.
13. organic electroluminescent elements according to claim 11 or 12, at least one deck in wherein said electron transfer layer and described electron injecting layer also comprises at least one in the group selecting free alkali metal, alkaline-earth metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, the oxide compound of alkaline-earth metal, the halogenide of alkaline-earth metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic misfit thing, organic misfit thing of alkaline-earth metal and organic misfit thing of rare earth metal to form.
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