CN104507927A - Cyclic azine compound, method for producing same, and organic electroluminescent element containing same - Google Patents

Cyclic azine compound, method for producing same, and organic electroluminescent element containing same Download PDF

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CN104507927A
CN104507927A CN201380030110.6A CN201380030110A CN104507927A CN 104507927 A CN104507927 A CN 104507927A CN 201380030110 A CN201380030110 A CN 201380030110A CN 104507927 A CN104507927 A CN 104507927A
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carbonatoms
aromatic group
alkyl
fluorine atom
separately
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内田直树
田中刚
本间阳子
饭田尚志
野村桂甫
太田惠理子
藤田华奈
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Tosoh Corp
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
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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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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

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  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
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Abstract

Provided are a 1,3,5-cyclic triazine compound represented by formula (1), an organic electroluminescent element which uses this compound as an electron transport material and which can be operated for a long period of time, and use of this compound as a constituent component of an organic electroluminescent element. (In the formula, Cz is an (n+1) valent carbazole group or an (n+1) valent carboline group (these groups may each independently have a substituent group such as a fluorine atom), Ar1 and Ar2 are each independently an aromatic hydrocarbon group having 6-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), Ar3 is an arylene group having 6-30 carbon atoms (and may have a substituent group such as a fluorine atom), the Ar4 groups are each independently a nitrogen-containing heteroaryl group having 3-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom) or a substituent group represented by general formula (A), and Y and Z are each independently a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom. n is an integer between 1 and [maximum number of bonds able to be formed on Cz-1]) (In the formula, Ar5 is an (m+1) valent aryl group having 6-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), the Ar6 groups are each independently a nitrogen-containing heteroaryl group having 3-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), and m is an integer between 1 and [maximum number of bonds able to be formed on Ar5-1]).

Description

Cyclic azine compound, its manufacture method and the organic electroluminescent device containing it
Technical field
The present invention relates to a kind of be used as the constituent of organic electroluminescent device the cyclic azine compound with the carbazyl replaced by nitrogen-containing hetero aryl and its manufacture method and containing its organic electroluminescent device.
Background technology
The basic structure of organic electroluminescent device is the luminescent layer containing luminescent material with hole transmission layer and electron transfer layer clamping, and anode and negative electrode are installed outside it, be the element utilizing light to discharge (fluorescence or phosphorescence) along with the exciton inactivation produced because of institute's injected holes in luminescent layer and combining again of electronics, be applied in indicating meter etc.It should be noted that, hole transmission layer is sometimes divided into hole transmission layer and hole injection layer and forms, and luminescent layer is sometimes divided into electronic barrier layer, luminescent layer and hole blocking layer and forms, and electron transfer layer is sometimes divided into electron transfer layer and electron injecting layer and forms.
In recent years, report organic electroluminescent device triazine and pyrimidine compound being used for luminescent layer and electron transfer layer etc. in a large number, but in light-emitting efficiency characteristics, driving voltage characteristic, long-life characteristics, full up sufficient market demands cannot be finished, and then seek excellent material.
As electron transport material etc., disclose the cyclic azine compound (such as with reference to patent documentation 1 ~ 4) that a kind of carbazyl replaces via arylidene, propose and use these to improve the life-span of element.But, in element high driving voltage and seek that the life-span extends further in expect to improve.
In addition, disclose a kind of example (such as with reference to patent documentation 5) the 1,3,5-triazines compound with carbazyl being used for organic electroluminescent device, but this compound at 2 of triazine ring directly and the nitrogen atom bonding of carbazyl.Therefore, when being used as electron transport material, having and reducing the indispensable electronics acceptability of electron transport material, the tendency of element high driving voltage, seek to improve.
Prior art document
Patent documentation
Patent documentation 1: International Publication No. 2003/078541 brochure
Patent documentation 2: International Publication No. 2003/080760 brochure
Patent documentation 3: Japanese Unexamined Patent Publication 2009-21336 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-193952 publication
Patent documentation 5: International Publication No. 2008/123189 brochure
Summary of the invention
Invent problem to be solved
Organic electroluminescent device starts to be used in various display equipment, but requires the more high performance of the elements such as life, high-luminous-efficiency, low driving voltage.More specifically, require that exploitation realizes the carrier transmission material of long lifetime, high-luminous-efficiency, low driving voltage.
About electron injection material and electron transport material, special expectation utilizes excellent electron injection and electron transport property to make element with low voltage drive, and meanwhile, luminous efficiency is high, makes the novel material that element drives for a long time.
The object of the invention is to, providing a kind of for realizing long lifetime, high-luminous-efficiency, the electron injection material of low driving voltage and electron transport material.
For solving the technical scheme of problem
The present inventor etc. concentrate on studies in order to the problem solved above, found that, in the cyclic azine compound that existing known carbazyl replaces via arylidene, by making the substituting group that this carbazyl has containing nitrogen-containing hetero aryl, electron injection and the electron transport property of this cyclic azine compound can be significantly improved.
In addition, when by such compound (the cyclic azine compound shown in general formula of the present invention (1)) as electron transfer layer in organic electroluminescent device, compared with using the situation of known or general electron transport material, find that there is electro-luminescence element driving voltage significantly to reduce, luminous efficiency improves, and organic electroluminescent device life, so that complete the present invention.
That is, the present invention relates to the cyclic azine compound (hereinafter referred to as " cyclic azine compound (1) ") shown in a kind of following general formula (1), its manufacture method and the organic electroluminescent device containing it.
(carbolinyl of the carbazyl of in formula, Cz represents (n+1) valency or (n+1) valency (and these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4).
Ar 1and Ar 2separately represent carbonatoms 6 ~ 30 aromatic hydrocarbyl (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4).
Ar 3represent carbonatoms 6 ~ 30 arylidene (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4).
Ar 4separately represent carbonatoms 3 ~ 30 nitrogen-containing hetero aryl (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4) or the substituting group shown in general formula (A).
Y and Z separately represents nitrogen-atoms or CH.Wherein, at least one in Y and Z is nitrogen-atoms.
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz].)
-Ar 5-(Ar 6) m(A)
(in formula, Ar 5separately represent the carbonatoms 6 ~ 30 of (m+1) valency aryl (can separately have fluorine atom, carbonatoms 1 ~ 4 alkyl, can fluorine atom be had and the alkyl of the aromatic group of carbonatoms 3 ~ 18 or carbonatoms 1 ~ 4 aromatic group alternatively base of carbonatoms 3 ~ 18 that can replace).
Ar 6separately represent carbonatoms 3 ~ 30 nitrogen-containing hetero aryl (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4).
M separately represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.)
The effect of invention
The cyclic azine compound of the application of the invention, compared with employing the organic electroluminescent device of existing known electron transport material, can provide a kind of with more low voltage drive, organic electroluminescent device that luminous efficiency is higher and more excellent in the long lifetime.
Accompanying drawing explanation
Fig. 1 is the constructed profile of the single-layer element made in embodiment-45 grade;
Fig. 2 is the constructed profile of the single-layer element made in embodiment-50 grade.
Description of symbols
1. be with the glass substrate of ito transparent electrode
2. hole injection layer
3. hole transmission layer
4. luminescent layer
5. electron transfer layer
6. cathode layer
The glass substrate of 11. band ito transparent electrodes
12. hole injection layers
13. first hole transmission layers
14. second hole transmission layers
15. luminescent layers
16. electron transfer layers
17. cathode layers
Embodiment
Below, the present invention is described in detail.
The present invention relates to above-mentioned cyclic azine compound (1), its manufacture method and the organic electroluminescent device containing it.
Good from the viewpoint of the performance as material for organic electroluminescence device, cyclic azine compound (1) of the present invention is preferably following general formula (B), (C) or the cyclic azine compound shown in (D).
(in general formula (B), (C) and (D), Ar 1, Ar 2, Ar 3, Ar 4, Y, Z and n separately represent the substituting group with general formula (1) identical definition.In general formula (D), the carbolinyl of Cb represents (n+1) valency.)
Substituting group in cyclic azine compound (1) of the present invention is respectively as given a definition.
As the alkyl of carbonatoms 1 ~ 4, be not particularly limited, such as, can enumerate: methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl.
As the aromatic hydrocarbyl of carbonatoms 6 ~ 18, be not particularly limited, such as, can enumerate: phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, phenanthryl, perylene base or benzo phenanthryl etc.
As there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18, be not particularly limited, such as can enumerate: 2-difluorophenyl, 3-difluorophenyl, 4-difluorophenyl, 2, 3-phenyl-difluoride base, 2, 4-phenyl-difluoride base, 2, 5-phenyl-difluoride base, 2, 6-phenyl-difluoride base, 3, 4-phenyl-difluoride base, 3, 5-phenyl-difluoride base, 2, 3, 4-trifluoro-benzene base, 2, 3, 5-trifluoro-benzene base, 2, 3, 6-trifluoro-benzene base, 2, 4, 5-trifluoro-benzene base, 2, 4, 6-trifluoro-benzene base, 3, 4, 5-trifluoro-benzene base, 2, 3, 4, 5-tetra-difluorophenyl, 2, 3, 4, 6-tetra-difluorophenyl, 2, 3, 5, 6-tetra-difluorophenyl, phenyl-pentafluoride base, 4-naphthalene fluoride-1-base, 5-naphthalene fluoride-1-base, 6-naphthalene fluoride-1-base, 7-naphthalene fluoride-1-base, 4-naphthalene fluoride-2-base, 5-naphthalene fluoride-2-base, 6-naphthalene fluoride-2-base, 7-naphthalene fluoride-2-base, anthryl, pyrenyl, phenanthryl, perylene base, benzo phenanthryl etc.
As the aromatic hydrocarbyl of the carbonatoms 6 ~ 18 replaced by the alkyl of carbonatoms 1 ~ 4, the alkyl of the above-mentioned carbonatoms of same expression 1 ~ 4 replaces to the group on the aromatic hydrocarbyl of above-mentioned carbonatoms 6 ~ 18, be not particularly limited, such as, can enumerate: p-methylphenyl, between tolyl, o-tolyl, 4-trifluoromethyl, 3-trifluoromethyl, 2-trifluoromethyl, 2,4-3,5-dimethylphenyl, 3,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, Lai Ji, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,4-diethyl phenyl, 3,5-diethyl phenyl, 2-propyl group phenyl, 3-propyl group phenyl, 4-propyl group phenyl, 2,4-dipropyl phenyl, 3,5-dipropyl phenyl, 2-isopropyl phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,4-diisopropyl phenyl, 3,5-diisopropyl phenyl, 2-butyl phenyl, 3-butyl phenyl, 4-butyl phenyl, 2,4-dibutylphenyl, 3,5-dibutylphenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,4-di-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 4-methylnaphthalene-1-base, 4-trifluoromethyl naphthalene-1-base, 4-ethyl naphthalene-1-base, 4-propyl group naphthalene-1-base, 4-dibutyl naphthalene-1-base, 4-t-butyl naphthalin-1-base, 5-methylnaphthalene-1-base, 5-trifluoromethyl naphthalene-1-base, 5-ethyl naphthalene-1-base, 5-propyl group naphthalene-1-base, 5-dibutyl naphthalene-1-base, 5-t-butyl naphthalin-1-base, 6-methylnaphthalene-2-base, 6-trifluoromethyl naphthalene-2-base, 6-ethyl naphthalene-2-base, 6-propyl group naphthalene-2-base, 6-dibutyl naphthalene-2-base, 6-t-butyl naphthalin-2-base, 7-methylnaphthalene-2-base, 7-trifluoromethyl naphthalene-2-base, 7-ethyl naphthalene-2-base, 7-propyl group naphthalene-2-base, 7-dibutyl naphthalene-2-base, 7-t-butyl naphthalin-2-base, anthryl, pyrenyl, phenanthryl, perylene base, benzo phenanthryl etc.
As the aromatic hydrocarbyl of carbonatoms 6 ~ 30, be not particularly limited, such as, can enumerate: phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, phenanthryl, perylene base, benzo phenanthryl etc.
As the aromatic group of carbonatoms 3 ~ 18, be not particularly limited, such as, can enumerate: furyl, benzofuryl, dibenzofuran group, thienyl, benzo thienyl, dibenzo thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 2-pyrazinyl, 4-pyrazinyl, 5-pyrazinyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 9-acridyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-[4-morpholinodithio base, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, quinazolyl, quinoxalinyl, 1,6-naphthyridines-2-base, 1,8-naphthyridines-2-base, 4-thiazolyl, 5-thiazolyl, imidazo [1,2-a] pyridine-2-base, 2-thiazolyl, indolizine base, azepine indolizine base etc.
As there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, being not particularly limited, such as, can enumerating: fluoro furyl, fluoro benzofuryl, fluoro dibenzofuran group, fluoro thienyl, fluoro benzo thienyl, fluoro dibenzo thienyl, the fluoro-2-pyridyl of 3-, the fluoro-2-pyridyl of 4-, the fluoro-2-pyridyl of 5-, the fluoro-2-pyridyl of 6-, 2-fluoro-3-pyridine base, 4-fluoro-3-pyridine base, 5-fluoro-3-pyridine base, 6-fluoro-3-pyridine base, 2-fluoro-4-pyridinyl, 3-fluoro-4-pyridinyl, the fluoro-2-pyridyl of 3,4-bis-, the fluoro-2-pyridyl of 3,5-bis-, the fluoro-2-pyridyl of 3,6-bis-, the fluoro-3-pyridyl of 2,4-bis-, the fluoro-3-pyridyl of 2,5-bis-, the fluoro-3-pyridyl of 2,6-bis-, the fluoro-3-pyridyl of 4,5-bis-, the fluoro-3-pyridyl of 4,6-bis-, the fluoro-3-pyridyl of 5,6-bis-, 2,3-bis-fluoro-4-pyridinyl, 2,5-bis-fluoro-4-pyridinyl, 2,6-bis-fluoro-4-pyridinyl, 3,5-bis-fluoro-4-pyridinyl, 3,6-bis-fluoro-4-pyridinyl, the fluoro-2-pyridyl of 3,4,5-tri-, the fluoro-2-pyridyl of 3,4,6-tri-, the fluoro-2-pyridyl of 3,5,6-tri-, the fluoro-2-pyridyl of 4,5,6-tri-, four fluoro-2-pyridyl, the fluoro-3-pyridyl of 2,4,5-tri-, the fluoro-3-pyridyl of 2,4,6-tri-, the fluoro-3-pyridyl of 2,5,6-tri-, the fluoro-3-pyridyl of 4,5,6-tri-, four fluoro-3-pyridyl, 2,3,5-tri-fluoro-4-pyridinyl, 2,3,6-tri-fluoro-4-pyridinyl, four fluoro-4-pyridinyls, the fluoro-2-pyrimidyl of 4-, the fluoro-2-pyrimidyl of 5-, the fluoro-4-pyrimidyl of 2-, the fluoro-4-pyrimidyl of 5-, the fluoro-4-pyrimidyl of 6-, the fluoro-5-pyrimidyl of 2-, the fluoro-5-pyrimidyl of 4-, 2-fluoro pyrazinyl, 4-fluoro pyrazinyl, 5-fluoro pyrazinyl, the fluoro-2-quinolyl of 3-, the fluoro-2-quinolyl of 4-, the fluoro-2-quinolyl of 5-, the fluoro-2-quinolyl of 6-, the fluoro-2-quinolyl of 7-, the fluoro-2-quinolyl of 8-, the fluoro-3-quinolyl of 2-, the fluoro-3-quinolyl of 4-, the fluoro-3-quinolyl of 5-, the fluoro-3-quinolyl of 6-, the fluoro-3-quinolyl of 7-, the fluoro-3-quinolyl of 8-, the fluoro-4-quinolyl of 2-, the fluoro-4-quinolyl of 3-, the fluoro-4-quinolyl of 5-, the fluoro-4-quinolyl of 6-, the fluoro-4-quinolyl of 7-, the fluoro-4-quinolyl of 8-, the fluoro-1-isoquinolyl of 3-, the fluoro-1-isoquinolyl of 4-, the fluoro-1-isoquinolyl of 5-, the fluoro-1-isoquinolyl of 6-, the fluoro-1-isoquinolyl of 7-, the fluoro-1-isoquinolyl of 8-, the fluoro-3-isoquinolyl of 1-, the fluoro-3-isoquinolyl of 4-, the fluoro-3-isoquinolyl of 5-, the fluoro-3-isoquinolyl of 6-, the fluoro-3-isoquinolyl of 7-, the fluoro-3-isoquinolyl of 8-, the fluoro-4-isoquinolyl of 1-, the fluoro-4-isoquinolyl of 3-, the fluoro-4-isoquinolyl of 5-, the fluoro-4-isoquinolyl of 6-, the fluoro-4-isoquinolyl of 7-, the fluoro-4-isoquinolyl of 8-, fluoro acridyl, fluoro thiazolyl, fluorobenzene benzothiazolyl, fluoro quinazolyl, fluoroquinoxaline base, fluoro naphthyridinyl, fluoro thianthrenyl, fluoro indolizine base, fluorine azepine indolizine base etc.
Represented that the alkyl of above-mentioned carbonatoms 1 ~ 4 replaces to the group on the aromatic group of above-mentioned carbonatoms 3 ~ 18 equally by the aromatic group of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement, be not particularly limited, such as, can enumerate: methyl furan base, methyl-benzofuranyl, methyldiphenyl furyl, methyl thienyl, methyl benzo thienyl, methyldiphenyl thienyl, 3-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 6-methyl-2-pyridyl, 2-methyl-3-pyridyl, 4-methyl-3-pyridyl, 5-methyl-3-pyridyl, 6-methyl-3-pyridyl, 2-methyl-4-pyridyl, 3-methyl-4-pyridyl, 3,4-dimethyl-2-pyridyl, 3,5-dimethyl-2-pyridyl, 3,6-dimethyl-2-pyridyl, 2,4-dimethyl-3-pyridyl, 2,5-dimethyl-3-pyridyl, 2,6-dimethyl-3-pyridyl, 4,5-dimethyl-3-pyridyl, 4,6-dimethyl-3-pyridyl, 5,6-dimethyl-3-pyridyl, 2,3-dimethyl-4-pyridyl, 2,5-dimethyl-4-pyridyl, 2,6-dimethyl-4-pyridyl, 3,5-dimethyl-4-pyridyl, 3,6-dimethyl-4-pyridyl, 4-methyl-2-pyrimidyl, 5-methyl-2-pyrimidyl, 2-methyl-4-pyrimidyl, 5-methyl-4-pyrimidyl, 6-methyl-4-pyrimidyl, 2-methyl-5-pyrimidyl, 4-methyl-5-pyrimidyl, 2-methylpyrazine base, TMP base, 5-methylpyrazine base, 3-methyl-2-quinolyl, 4-methyl-2-quinolyl, 5-methyl-2-quinolyl, 6-methyl-2-quinolyl, 7-methyl-2-quinolyl, 8-methyl-2-quinolyl, 2-methyl-3-quinolin base, 4-methyl-3-quinolin base, 5-methyl-3-quinolin base, 6-methyl-3-quinolin base, 7-methyl-3-quinolin base, 8-methyl-3-quinolin base, 2-methyl-4-quinolyl, 3-methyl-4-quinolyl, 5-methyl-4-quinolyl, 6-methyl-4-quinolyl, 7-methyl-4-quinolyl, 8-methyl-4-quinolyl, 2-methyl-5-quinolyl, 3-methyl-5-quinolyl, 4-methyl-5-quinolyl, 6-methyl-5-quinolyl, 7-methyl-5-quinolyl, 8-methyl-5-quinolyl, 2-methyl-6-quinolyl, 3-methyl-6-quinolyl, 4-methyl-6-quinolyl, 5-methyl-6-quinolyl, 7-methyl-6-quinolyl, 8-methyl-6-quinolyl, 2-methyl-7-quinolyl, 3-methyl-7-quinolyl, 4-methyl-7-quinolyl, 5-methyl-7-quinolyl, 6-methyl-7-quinolyl, 8-methyl-7-quinolyl, 2-methyl-8-quinolyl, 3-methyl-8-quinolyl, 4-methyl-8-quinolyl, 5-methyl-8-quinolyl, 6-methyl-8-quinolyl, 7-methyl-8-quinolyl, 3-methyl isophthalic acid-isoquinolyl, 4-methyl isophthalic acid-isoquinolyl, 5-methyl isophthalic acid-isoquinolyl, 6-methyl isophthalic acid-isoquinolyl, 7-methyl isophthalic acid-isoquinolyl, 8-methyl isophthalic acid-isoquinolyl, 1-methyl-3-isoquinolyl, 4-methyl-3-isoquinolyl, 5-methyl-3-isoquinolyl, 6-methyl-3-isoquinolyl, 7-methyl-3-isoquinolyl, 8-methyl-3-isoquinolyl, 1-methyl-4-isoquinolyl, 3-methyl-4-isoquinolyl, 5-methyl-4-isoquinolyl, 6-methyl-4-isoquinolyl, 7-methyl-4-isoquinolyl, 8-methyl-4-isoquinolyl, methylacridine base, methylthiazol base, methylbenzothiazole base, methylquinazolin base, methyl-quinoxaline base, methyl naphthyridinyl, methyl thiazolium anthryl, methyl indolizine base, methyl azepine indolizine base etc.
As the arylidene of carbonatoms 6 ~ 30, be not particularly limited, such as, can enumerate: phenylene, biphenylene, naphthylidene, anthrylene, sub-pyrenyl, three biphenylenes (タ ー Off ェ ニ リ レ Application), phenanthrylene, sub-perylene base, triphenylenyl two base (ト リ Off ェ ニ レ Application ジ イ Le) etc.
As the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, be not particularly limited, such as can enumerate: 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 2-pyrazinyl, 4-pyrazinyl, 5-pyrazinyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 9-acridyl, 2-[4-morpholinodithio base, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, quinazolyl, quinoxalinyl, naphthyridinyl, thianthrenyl, indolizine base, azepine indolizine base etc.
As the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, (wherein, m represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.), be not particularly limited, such as, can enumerate: virtue four base etc. of the arylidene of carbonatoms 6 ~ 30, virtue three base of carbonatoms 6 ~ 30, carbonatoms 6 ~ 30.
In cyclic azine compound (1), Ar 5-(Ar 6) mrepresent m Ar 6substituting group and Ar 5bonding.That is, be not particularly limited, such as, at Ar 5when for phenylene, m represents the integer of 1 ~ 5.
It should be noted that, good from the viewpoint of the performance as material for organic electroluminescence device, m is preferably 1 or 2, is more preferably 1.
As the arylidene of above-mentioned carbonatoms 6 ~ 30, such as, can illustrate the substituting group identical with the concrete example shown in the arylidene of above-mentioned carbonatoms 6 ~ 30.
As virtue three base of above-mentioned carbonatoms 6 ~ 30, be not particularly limited, such as, can enumerate: benzene three base, xenyl three base, naphthalene three base, anthracene three base, pyrene three base, terphenyl three base, luxuriant and rich with fragrance three bases, perylene three base, three biphenylene three bases etc.
In addition, as virtue four base of above-mentioned carbonatoms 6 ~ 30, be not particularly limited, such as, can enumerate: benzene four base, xenyl four base, naphthalenetetrayl, anthracene four base, pyrene four base, terphenyl four base, luxuriant and rich with fragrance four bases, perylene four base, three biphenylene four bases etc.
As (n+1) valency in Cz carbazyl (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4), be not particularly limited, can enumerate: carbazole two base, carbazole three base, carbazole four base etc.
As (n+1) valency in Cz carbolinyl (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4), be not particularly limited, can enumerate: carboline two base, carboline three base, carboline four base etc.
It should be noted that, n represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz], in cyclic azine compound (1), and Cz-(Ar 4) nrepresent n Ar 4substituting group and Cz bonding.Good from the viewpoint of the performance as material for organic electroluminescence device, n is preferably 1,2 or 3, is more preferably 1 or 2, and more preferably 1.
As Cz, be not particularly limited, such as, can enumerate: carbazole-1,9-bis-base, carbazole-2,9-bis-base, carbazole-1,3-bis-base, carbazole-2,7-bis-base, N-phenyl carbazole-2,7-bis-base, N-phenyl carbazole-3,6-bis-base, α-carboline-2,9-bis-base, α-carboline-3,9-bis-base, α-carboline-4,9-bis-base, α-carboline-5,9-bis-base, α-carboline-6,9-bis-base, α-carboline-7,9-bis-base, α-carboline-8,9-bis-base, β-carboline-1,9-bis-base, β-carboline-3,9-bis-base, β-carboline-4,9-bis-base, β-carboline-5,9-bis-base, β-carboline-6,9-bis-base, β-carboline-7,9-bis-base, β-carboline-8,9-bis-base, gamma-carbolines-1,9-bis-base, gamma-carbolines-2,9-bis-base, gamma-carbolines-4,9-bis-base, gamma-carbolines-5,9-bis-base, gamma-carbolines-6,9-bis-base, gamma-carbolines-7,9-bis-base, gamma-carbolines-8,9-bis-base, δ-carboline-1,9-bis-base, δ-carboline-2,9-bis-base, δ-carboline-3,9-bis-base, δ-carboline-5,9-bis-base, δ-carboline-6,9-bis-base, δ-carboline-7,9-bis-base, δ-carboline-8,9-bis-base etc.
Good from the viewpoint of the performance as material for organic electroluminescence device, Cz is preferably carbazole-2,9-bis-base, carbazole-3,9-bis-base, carbazole-4,9-bis-base, carbazole-3,6-bis-base, carbazole-3,6,9-tri-base, α-carboline-7,9-bis-base, β-carboline-6,9-bis-base, β-carboline-7,9-bis-base, δ-carboline-3,6-bis-base, (these groups separately can have fluorine atom for δ-carboline-3,9-bis-base or δ-carboline-6,9-bis-base, the alkyl of carbonatoms 1 ~ 4, the aromatic hydrocarbyl of carbonatoms 6 ~ 18, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18, or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4), more preferably carbazole-2,9-bis-base, carbazole-3,9-bis-base, carbazole-4,9-bis-base, carbazole-3,6-bis-base, β-carboline-6,9-bis-base, δ-carboline-3,9-bis-base, or δ-carboline-6,9-bis-base (these groups separately can have the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18).
In cyclic azine compound (1), as Ar 1or Ar 2be not particularly limited, such as, can separately enumerate: phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, phenanthryl, perylene base, benzo phenanthryl, aminomethyl phenyl, methyl biphenyl, methyl naphthyl, methylanthryl, methyl terphenyl, methyl phenanthryl, first base perylene base, methylbenzphenanthrene base, difluorophenyl, fluorodiphenyl base, fluoro naphthyl, fluorine anthryl, fluorine terphenyl, fluorine phenanthryl, fluorine perylene base, fluoro benzo phenanthryl etc.
Good from the viewpoint of the performance as material for organic electroluminescence device, Ar 1or Ar 2separately be preferably phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, or phenanthryl (these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement), separately be more preferably phenyl, (these groups can have fluorine atom for naphthyl or xenyl, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement), separately more preferably phenyl, aminomethyl phenyl, naphthyl, or xenyl.
As above-mentioned phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, or phenanthryl (these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of carbonatoms 3 ~ 18 that the alkyl of carbonatoms 1 ~ 4 replaces) shown in substituting group, be not particularly limited, such as can enumerate: phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl, phenanthryl, perylene base, aminomethyl phenyl, methyl biphenyl, methyl naphthyl, methylanthryl, methyl terphenyl, methyl phenanthryl, Jia Ji perylene base, difluorophenyl, fluorodiphenyl base, fluoro naphthyl, fluorine anthryl, fluorine terphenyl, fluorine phenanthryl, Fu perylene base etc.
In addition, as above-mentioned phenyl or xenyl (these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4) shown in substituting group, be not particularly limited, such as, can enumerate: phenyl, xenyl, aminomethyl phenyl, methyl biphenyl, difluorophenyl, fluorodiphenyl base etc.
In cyclic azine compound (1), as Ar 3be not particularly limited, such as, can enumerate: phenylene, biphenylene, naphthylidene, anthrylene, sub-pyrenyl, three biphenylenes, fluoro substituted phenylen, difluorophenyl biphenylene, fluoronaphthylenes, phenylphenylene, phenyl biphenylene, phenyl naphthylidene, naphthylphenylene, naphthylbiphenylene, naphthyl naphthylidene etc.
Good from the viewpoint of the performance as material for organic electroluminescence device, Ar 3be preferably phenylene or biphenylene (these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4), be separately more preferably phenylene, biphenylene or fluoro substituted phenylen.
As above-mentioned phenylene or biphenylene (wherein, these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of carbonatoms 3 ~ 18 that the alkyl of carbonatoms 1 ~ 4 replaces) shown in substituting group, be not particularly limited, such as can enumerate: phenylene, biphenylene, naphthylidene, three biphenylenes, fluoro substituted phenylen, fluoronaphthylenes, phenylphenylene, phenyl naphthylidene, naphthylphenylene, naphthyl naphthylidene etc.
In cyclic azine compound (1), as Ar 5, be not particularly limited, such as can enumerate: the phenyl of (m+1) valency, (m+1) xenyl of valency, (m+1) naphthyl of valency, (m+1) anthryl of valency, (m+1) pyrenyl of valency, (m+1) terphenyl of valency, (m+1) difluorophenyl of valency, (m+1) the difluorophenyl xenyl of valency, (m+1) the fluoro naphthyl of valency, (m+1) phenylbiphenylyl of valency, (m+1) phenyl napthyl of valency, (m+1) naphthylphenyl of valency, (m+1) the naphthyl xenyl of valency, (m+1) (these groups separately can have fluorine atom to the naphthyl naphthyl of valency, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement) etc.
As Ar 5when m=1, can enumerate: phenylene, methylphenylene, biphenylene, naphthylidene, anthrylene, sub-pyrenyl, terphenyl two base, fluoro substituted phenylen, difluorophenyl biphenylene, fluorine naphthylidene, phenyl biphenylene, phenyl naphthylidene, naphthylphenylene, naphthylbiphenylene, naphthyl naphthylidene etc.
When m=2, can separately enumerate: benzene three base, methylbenzene three base, xenyl three base, naphthalene three base, anthracene three base, pyrene three base, terphenyl three base, fluorobenzene three base, difluorophenyl xenyl three base, naphthalene fluoride three base, phenylbiphenylyl three base, phenylnaphthalene three base, naphthyl benzene three base, naphthyl xenyl three base, naphthyl naphthalene three base etc.
Good from the viewpoint of the performance as material for organic electroluminescence device, Ar 5be preferably the phenyl of (m+1) valency or (m+1) valency xenyl (these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4).It should be noted that, as (m+1) valency phenyl (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4), when m=1, preferred phenylene, methylphenylene, fluoro substituted phenylen, naphthylphenylene, more preferably phenylene.When m=2, preferred benzene three base, methylbenzene three base, fluorobenzene three base, naphthyl benzene three base, more preferably benzene three base.In addition, as (m+1) valency xenyl (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4), when m=1, preferred biphenylene, terphenyl two base, difluorophenyl biphenylene, naphthylbiphenylene, more preferably biphenylene.When m=2, preferred xenyl three base, terphenyl three base, difluorophenyl xenyl three base, naphthyl xenyl three base, more preferably xenyl three base.
In cyclic azine compound (1), as Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 (separately can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of carbonatoms 3 ~ 18 that the alkyl of carbonatoms 1 ~ 4 replaces) shown in substituting group, be not particularly limited, such as, can separately enumerate: pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, acridyl, thiazolyl, benzothiazolyl, quinazolyl, quinoxalinyl, naphthyridinyl, thianthrenyl, indolizine base, azepine indolizine base, fluorinated pyridine base, fluorinated pyrimidine base, fluoro pyrazinyl, fluoroquinolone base, fluoro isoquinolyl, fluoro acridyl, fluoro thiazolyl, fluorobenzene benzothiazolyl, fluoro quinazolyl, fluoroquinoxaline base, fluoro naphthyridinyl, fluoro thianthrenyl, fluoro indolizine base, fluorine azepine indolizine base, picolyl, methylpyrimidine base, methylpyrazine base, toluquinoline base, methylisoquinolinium base, methylacridine base, methylthiazol base, methylbenzothiazole base, methylquinazolin base, methyl-quinoxaline base, methyl naphthyridinyl, methyl thiazolium anthryl, methyl indolizine base, methyl azepine indolizine base, phenylpyridyl, phenyl pyrimidine base, phenyl pyrazines base, phenylquinoline base, phenyl isoquinolin quinoline base, phenylacridine base, phenyl thiazole base, phenylbenzothiazol base, phenylquinazoline base, phenyl quinoxalinyl, phenyl naphthyridinyl, phenyl thianthrenyl, phenyl indolizine base, phenyl azepine indolizine base, phenylpyridyl, phenyl pyrimidine base, phenyl pyrazines base, phenylquinoline base, phenyl isoquinolin quinoline base, phenylacridine base, phenyl thiazole base, phenylbenzothiazol base, phenylquinazoline base, phenyl quinoxalinyl, phenyl naphthyridinyl, phenyl thianthrenyl, phenyl indolizine base, phenyl azepine indolizine base, pyridinylphenyl, 1-(3,5-bipyridyl) phenyl, pyrimidyl phenyl, pyrazinylphenyl, pyridyl xenyl, pyrimidyl xenyl, pyrazinyl xenyl, quinolyl xenyl, isoquinolyl xenyl, acridyl xenyl, thiazolyl xenyl, benzothiazolyl xenyl, quinazolyl xenyl, quinoxalinyl xenyl, naphthyridinyl xenyl, thianthrenyl xenyl, indolizine base xenyl, azepine indolizine base xenyl etc.
Good from the viewpoint of the performance as material for organic electroluminescence device, Ar 4and Ar 6separately be preferably only by carbon, the nitrogen-containing hetero aryl of the carbonatoms 3 ~ 30 that hydrogen and nitrogen are formed (separately can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement), or only by carbon, hydrogen, the nitrogen-containing hetero aryl of the carbonatoms 3 ~ 30 that nitrogen and sulphur are formed (separately can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement).Wherein, be separately more preferably the carbonatoms 3 ~ 30 be only made up of carbon, hydrogen and nitrogen nitrogen-containing hetero aryl (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4).
And then from the viewpoint of synthesizing, easy and as material for organic electroluminescence device performance is good, Ar 4and Ar 6separately be preferably pyridyl, pyrimidyl, quinolyl, isoquinolyl, pyridinylphenyl, or 1-(3, 5-bipyridyl) (these groups separately can have fluorine atom to phenyl, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement), separately be more preferably pyridyl, pyrimidyl, quinolyl, isoquinolyl, pyridinylphenyl, or 1-(3, 5-bipyridyl) phenyl, more preferably pyridyl.
As above-mentioned only by carbon, the nitrogen-containing hetero aryl of the carbonatoms 3 ~ 30 that hydrogen and nitrogen are formed (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement), or only by carbon, hydrogen, the nitrogen-containing hetero aryl of the carbonatoms 3 ~ 30 that nitrogen and sulphur are formed (can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of carbonatoms 3 ~ 18 that the alkyl of carbonatoms 1 ~ 4 replaces) shown in substituting group, be not particularly limited, such as, can enumerate: pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, acridyl, thiazolyl, benzothiazolyl, quinazolyl, quinoxalinyl, naphthyridinyl, thianthrenyl, indolizine base, azepine indolizine base, fluorinated pyridine base, fluorinated pyrimidine base, fluoro pyrazinyl, fluoroquinolone base, fluoro isoquinolyl, fluoro acridyl, fluoro thiazolyl, fluorobenzene benzothiazolyl, fluoro quinazolyl, fluoroquinoxaline base, fluoro naphthyridinyl, fluoro thianthrenyl, fluoro indolizine base, fluorine azepine indolizine base, picolyl, methylpyrimidine base, methylpyrazine base, toluquinoline base, methylisoquinolinium base, methylacridine base, methylthiazol base, methylbenzothiazole base, methylquinazolin base, methyl-quinoxaline base, methyl naphthyridinyl, methyl thiazolium anthryl, methyl indolizine base, methyl azepine indolizine base, phenylpyridyl, phenyl pyrimidine base, phenyl pyrazines base, phenylquinoline base, phenyl isoquinolin quinoline base, phenylacridine base, phenyl thiazole base, phenylbenzothiazol base, phenylquinazoline base, phenyl quinoxalinyl, phenyl naphthyridinyl, phenyl thianthrenyl, phenyl indolizine base, phenyl azepine indolizine base, phenylpyridyl, phenyl pyrimidine base, phenyl pyrazines base, phenylquinoline base, phenyl isoquinolin quinoline base, phenylacridine base, phenyl thiazole base, phenylbenzothiazol base, phenylquinazoline base, phenyl quinoxalinyl, phenyl naphthyridinyl, phenyl thianthrenyl, phenyl indolizine base, phenyl azepine indolizine base, pyridinylphenyl, 1-(3,5-bipyridyl) phenyl, pyrimidyl phenyl, pyrazinylphenyl, pyridyl xenyl, pyrimidyl xenyl, pyrazinyl xenyl, quinolyl xenyl, isoquinolyl xenyl, acridyl xenyl, thiazolyl xenyl, benzothiazolyl xenyl, quinazolyl xenyl, quinoxalinyl xenyl, naphthyridinyl xenyl, thianthrenyl xenyl, indolizine base xenyl, azepine indolizine base xenyl etc.
As above-mentioned only by carbon, the nitrogen-containing hetero aryl of the carbonatoms 3 ~ 30 that hydrogen and nitrogen are formed (wherein, these groups can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of carbonatoms 3 ~ 18 that the alkyl of carbonatoms 1 ~ 4 replaces) shown in substituting group, be not particularly limited, such as can enumerate: pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, fluorinated pyridine base, fluorinated pyrimidine base, fluoro pyrazinyl, fluoroquinolone base, fluoro isoquinolyl, picolyl, methylpyrimidine base, methylpyrazine base, toluquinoline base, methylisoquinolinium base, phenylpyridyl, phenyl pyrimidine base, phenyl pyrazines base, phenylquinoline base, phenyl isoquinolin quinoline base, pyridinylphenyl, 1-(3, 5-bipyridyl) phenyl, pyrimidyl phenyl, pyrazinylphenyl, quinolyl phenyl, isoquinolyl phenyl.
Y and Z separately represents nitrogen-atoms or CH.Wherein, at least one in Y and Z is nitrogen-atoms.It should be noted that, good from the viewpoint of the performance as material for organic electroluminescence device, preferred Y and Z is that nitrogen-atoms or Y are CH and Z is nitrogen-atoms.
In addition, any hydrogen atom in cyclic azine compound (1) of the present invention can be replaced by D atom.
Then, the manufacture method of cyclic azine compound of the present invention is described.
The method manufacture shown in reaction formula (1), reaction formula (2), reaction formula (3) or reaction formula (4) below cyclic azine compound (1) of the present invention can utilize under the existence of metal catalyst or under the existence of alkali and metal catalyst.
In addition, the compound shown in general formula (2) is called compound (2) below.It should be noted that, compound (3) ~ compound (9) is defined similarly.
(in general formula (1), (2), (3), (4), (5), (6), (7), (8) and (9), Cz, Ar 1, Ar 2, Ar 3, Ar 4, n, Y and Z separately represent the definition identical with above-mentioned general formula (1).X 1, X 2, X 3, X 4, and M separately represent leavings group.H nrepresent the hydrogen atom on nitrogen-atoms in Cz.)
As X 1, X 2, X 3, and X 4shown leavings group, is not particularly limited, such as, can enumerate: chlorine atom, bromine atoms, triflate or atomic iodine.Wherein, good from the viewpoint of reaction yield, preferred bromine atoms or chlorine atom.
As the leavings group shown in M, be not particularly limited, such as, can illustrate: chlorine atom, bromine atoms, triflate, atomic iodine, metallic group are (such as: Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl 2, AlBr 2, Al (Me) 2, Al (Et) 2, Al ( ibu) 2, Sn (Me) 3, Sn (Bu) 3, SnF 3, ZnR 3(R 3represent halogen atom.) etc.), Si (R 4) 3, BF 3k, B (OR 1) 2, B (OR 2) 3deng.
As the containing metal group shown in M, can illustrate: B (OR 1) 2, B (OR 2) 3, ZnR 3, Si (R 4) 3deng, as ZnR 3, can illustrate: ZnCl, ZnBr, ZnI etc.In addition, the part such as ethers and amine can be coordinated in these containing metal groups, as the kind of part, as long as not hindering the material of reaction formula (1) just not limit.
In addition, as above-mentioned Si (R 4) 3, can illustrate: SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2oH etc.
In addition, as above-mentioned B (OR 1) 2, can illustrate: B (OH) 2, B (OMe) 2, B (O ipr) 2, B (OBu) 2, B (OPh) 2deng.
In addition, as 2 R 1b (OR when being integrated and forming ring containing Sauerstoffatom and boron atom 1) 2, the group shown in (I) to (VII) below can be illustrated, good from the viewpoint of yield, the preferably group shown in (II).
As above-mentioned B (OR 2) 3, the group shown in (I) to (III) below can be illustrated.
In these leavings groups, from the viewpoint of the easness etc. of the easiness of post-reaction treatment, material allocation, preferred chlorine atom, bromine atoms, triflate, atomic iodine, B (OR 1) 2, or B (OR 2) 3.
As shown in the reaction of reaction formula (1) and reaction formula (3), cyclic azine compound (1) of the present invention can be carried out linked reaction to synthesize by the mode recorded in using compound (2) and compound (3) or compound (6) and compound (7) with respective reaction formula under the existence of metal catalyst or under the existence of alkali and metal catalyst.
It should be noted that, excellent from the viewpoint of the efficiency of linked reaction etc., in the reaction of reaction formula (1) and reaction formula (3), metal catalyst is preferably palladium catalyst or copper catalyst.
It should be noted that, in the reaction of reaction formula (1) and reaction formula (3), also can add alkali and react, improve from the viewpoint of reaction yield, preferably add alkali.Particularly, be chlorine atom, bromine atoms, triflate, atomic iodine, B (OR at M 1) 2, or Si (R 4) 3situation, must alkali be added.
In addition, as shown in the reaction of reaction formula (2) and reaction formula (4), cyclic azine compound (1) of the present invention can be carried out linked reaction to synthesize by the mode recorded in using compound (4) and compound (5) or compound (8) and compound (9) with respective reaction formula under the existence of metal catalyst or under the existence of alkali and metal catalyst.
It should be noted that, excellent from the viewpoint of the efficiency of linked reaction etc., in the reaction of reaction formula (2) and reaction formula (4), metal catalyst is preferably palladium catalyst or nickel catalyzator.
It should be noted that, in the reaction of reaction formula (2) and reaction formula (4), also can add alkali and react, improve from the viewpoint of reaction yield, preferably add alkali.Particularly, be chlorine atom, bromine atoms, triflate, atomic iodine, B (OR at M 1) 2, or Si (R 4) 3situation, must alkali be added.
In addition, in the reaction of reaction formula (1) ~ (4), also phase-transfer catalyst can be added.As phase-transfer catalyst, be not particularly limited, such as, 18-can be used to be preced with-6-ether etc.It should be noted that, as its addition, be the not obvious arbitrary amount hindering the scope of reaction.
As the metal catalyst of the reaction for reaction formula (1) ~ (4), be not particularly limited, such as, can enumerate: palladium catalyst, copper catalyst, nickel catalyzator.
As palladium catalyst, be not particularly limited, such as, can illustrate: the salt such as Palladous chloride, palladium, trifluoracetic acid palladium, Palladous nitrate.And then, can illustrate: π-allyl palladium chloride dipolymer, palladium acetylacetonate, two (dibenzylideneacetone) palladium, three (dibenzylideneacetone) two palladium, two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium, three (tertiary butyl) phosphine palladium, (1,1 '-bis-(diphenylphosphine) ferrocene) palladium chloride etc.Wherein, good from the viewpoint of yield, preferably two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium, three (tertiary butyl) phosphine palladiums etc. have the palladium complex of tertiary phosphine as part, from the viewpoint of what easily obtain, preferred three (tertiary butyl) phosphine palladium further.
As copper catalyst, be not particularly limited, such as, can enumerate: cupric chloride, cupric bromide, cupric iodide, cupric oxide, copper trifluoromethanesulfcomposite.Wherein, excellent from the viewpoint of the efficiency of linked reaction etc., preferential oxidation copper, cupric iodide, from the viewpoint of what easily obtain, further preferential oxidation copper.
As nickel catalyzator, be not particularly limited, such as can enumerate: nickelous chloride, nickelous bromide, hydrated nickel chloride, (glycol dimethyl ether) Nickel Chloride, [1, two (diphenylphosphine) ethane of 2-] Nickel Chloride, [1, two (diphenylphosphine) propane of 3-] Nickel Chloride, [1, two (diphenylphosphine) butane of 4-] Nickel Chloride, [1, 1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride (above-mentioned 4 for having the example of tertiary phosphine as the nickel complex of part), (N, N, N ', N '-Tetramethyl Ethylene Diamine) Nickel Chloride.Wherein, excellent from the viewpoint of the efficiency of linked reaction etc., preferably (glycol dimethyl ether) Nickel Chloride, [1, two (diphenylphosphine) butane of 4-] Nickel Chloride, (N, N, N ', N '-Tetramethyl Ethylene Diamine) Nickel Chloride, from the viewpoint of what easily obtain, preferred (glycol dimethyl ether) Nickel Chloride, [Isosorbide-5-Nitrae-bis-(diphenylphosphine) butane] Nickel Chloride further.
It should be noted that to there is tertiary phosphine as the palladium complex of part and have the nickel complex of tertiary phosphine as part about above-mentioned, can in palladium salt, nickel salt or their complex compound, add tertiary phosphine and prepare.It should be noted that, this preparation joins in reaction system after also can reacting respectively, can also carry out in reaction system.
As tertiary phosphine, be not particularly limited, such as can illustrate: triphenylphosphine, trimethyl-phosphine, tributylphosphine, three (tertiary butyl) phosphine, tricyclohexyl phosphine, tert-butyl diphenyl phosphine, 9, 9-dimethyl-4, two (diphenylphosphine) xanthene of 5-, 2-(diphenylphosphine)-2 '-(N, N-dimethylamino) biphenyl, 2-(di-t-butyl phosphine) biphenyl, 2-(dicyclohexylphosphontetrafluoroborate) biphenyl, two (diphenylphosphine) methane, 1, two (diphenylphosphine) ethane of 2-, 1, two (diphenylphosphine) propane of 3-, 1, two (diphenylphosphine) butane of 4-, 1, 1 '-bis-(diphenylphosphine) ferrocene, three (2-furyl) phosphine, three (o-tolyl) phosphine, three (2, 5-xylyl) phosphine, (±)-2, 2 '-bis-(diphenylphosphine)-1, 1 '-dinaphthalene, 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl etc.Wherein, from the viewpoint of easily obtaining, yield is good, preferably (tertiary butyl) phosphine or 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl.
When interpolation tertiary phosphine is in palladium salt, nickel salt or their complex compound, the addition of tertiary phosphine is preferably 0.1 ~ 10 times mole relative to palladium salt, nickel salt or their complex compound 1 mole (palladium or nickle atom convert), good from the viewpoint of yield, more preferably 0.3 ~ 5 times mole.
It should be noted that, also can add part separately in above-mentioned copper catalyst.As the part added in copper catalyst, be not particularly limited, such as, can illustrate: 2,2 '-dipyridyl, 1,10-phenanthrolene, N, N, N ', N '-Tetramethyl Ethylene Diamine, triphenylphosphine, 2-(dicyclohexylphosphontetrafluoroborate) biphenyl etc.Wherein, from the viewpoint of easily obtaining, yield is good, preferably 1,10-phenanthrolene.
In the reaction of reaction formula (1) ~ (4), as operable alkali, be not particularly limited, such as, can illustrate: sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, Quilonum Retard, cesium carbonate, Potassium ethanoate, sodium-acetate, potassiumphosphate, sodium phosphate, Sodium Fluoride, Potassium monofluoride, cesium fluoride etc.Wherein, good from the viewpoint of yield, preferred salt of wormwood, potassiumphosphate or sodium hydroxide.
The reaction of reaction formula (1) ~ (4) is preferably implemented in a solvent.As solvent, be not particularly limited, such as, can enumerate: water, dimethyl sulfoxide (DMSO), dimethyl formamide, tetrahydrofuran (THF), toluene, benzene, diethyl ether, Isosorbide-5-Nitrae-two alkane, ethanol, butanols, dimethylbenzene etc., can use these materials by proper combination.Wherein, good from the viewpoint of yield, preferred Isosorbide-5-Nitrae-two the mixed solvent of the mixed solvent of alkane, dimethylbenzene, toluene and butanols or dimethylbenzene and butanols.
About cyclic azine compound (1) of the present invention, can by carry out after the reaction of reaction formula (1) ~ (4) terminates redeposition, concentrated, filter, the process such as refining improves purity.And then, in order to high purity, can refine with recrystallization, silica gel column chromatography, distillation etc. as required.
Below, the reaction of reaction formula (1) is described.
Compound (2) such as can use grand work in mountain " newly organized heterogeneous ring compound basis version ", talk society, the method manufacture disclosed in 2004.
Any hydrogen atom in compound (2) can be replaced by D atom.
As compound (3), be not particularly limited, such as can enumerate: 3-1 ~ 3-17 below (separately can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic hydrocarbyl of carbonatoms 6 ~ 18, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18, the aromatic hydrocarbyl of the carbonatoms 6 ~ 18 of the alkyl replacement of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement.It should be noted that, these substituting groups are identical with above-mentioned group.) shown in compound.
Compound (3) such as uses J.Tsuji work " Palladium Reagents and Catalysts ", JohnWiley & Sons, 2004, Journal of Organic Chemistry, 60 volumes, 7508-7510, nineteen ninety-five, Journal of Organic Chemistry, 65 volumes, 164-168,2000, Organic Letters, 10 volumes, 941-944,2008 or Chemistry of Materials, 20 volumes, 5951-5953, the method manufacture disclosed in 2008.
In addition, any hydrogen atom in compound (3) can be replaced by D atom.
Reaction formula (1) is as long as the amount of the middle palladium catalyst used just is not particularly limited for so-called catalytic amount, but good from the viewpoint of yield, be preferably 0.1 ~ 0.01 times mole (conversion of palladium atom) relative to compound (2) 1 moles.
The usage quantity of the alkali in reaction formula (1) is not particularly limited, but is preferably 1 ~ 10 times mole relative to compound (3) 1 moles, good from the viewpoint of yield, more preferably 1 ~ 3 times mole.
The mol ratio of the compound (2) used in reaction formula (1) and compound (3) is not particularly limited, but preferred is 0.2 ~ 5 times mole relative to compound (2) 1 moles, good from the viewpoint of yield, more preferably 1 ~ 3 times mole.
Below, reaction formula (2) is described.
Compound (4) such as can manufacture according to the method shown in the synthesis example-1 in embodiment.
In addition, any hydrogen atom in compound (4) can be replaced by D atom.
As compound (5), be not particularly limited, such as, can illustrate: 5-1 ~ 5-15 below (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.) compound.
(illustrate in formula (5-1) ~ (5-15), M defines identical with the M in above-mentioned general formula (5).)
Compound (5) such as can use J.Tsuji work " Palladium Reagents and Catalysts ", JohnWiley & Sons, 2004, Journal of Organic Chemistry, 60 volumes, 7508-7510, nineteen ninety-five, Journal of Organic Chemistry, 65 volumes, 164-168,2000, Organic Letters, 10 volumes, 941-944,2008 or Chemistry of Materials, 20 volumes, 5951-5953, the method manufacture disclosed in 2008.
In addition, any hydrogen atom in compound (5) can be replaced by D atom.
Reaction formula (2) is for making compound (4) according to circumstances in the presence of base, react with compound (5) under the existence of palladium catalyst, manufacture the method for cyclic azine compound (1) of the present invention, target compound can be obtained well by the reaction conditions yield of application Suzuki-Pu, palace reaction.
Reaction formula (2) is as long as the amount of the middle palladium catalyst used just is not particularly limited for so-called catalytic amount, but good from the viewpoint of yield, be preferably 0.1 ~ 0.01 times mole (conversion of palladium atom) relative to compound (5) 1 moles.
The usage quantity of alkali is not particularly limited, but is preferably 0.5 ~ 10 times mole relative to compound (5) 1 moles, good from the viewpoint of yield, more preferably 1 ~ 3 times mole.
The mol ratio of the compound (4) used in reaction formula (2) and compound (5) is not particularly limited, but preferred is 0.2 ~ 5 times mole relative to compound (2) 1 moles, good from the viewpoint of yield, more preferably 0.3 ~ 3 times mole.
Below, reaction formula (3) is described.
Compound (6) such as can according to the method manufacture shown in the synthesis example-2 in embodiment.
In addition, any hydrogen atom in compound (6) can be replaced by D atom.
As compound (7), be not particularly limited, such as, can illustrate: 7-1 ~ 7-21 below (can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.) compound.
(illustrate in formula (7-1) ~ (7-21), X 3with the X in above-mentioned general formula (7) 3define identical.)
Compound (7) such as can use J.Org.Chem.48 to roll up, 1064-1069, the method manufacture disclosed in nineteen eighty-three.
In addition, any hydrogen atom in compound (7) can be replaced by D atom.
Reaction formula (3) reacts with compound (7) under the existence of palladium catalyst and alkali for making compound (6), obtains the method for cyclic azine compound (1) of the present invention, can obtain target compound well by yield.
Reaction formula (3) is as long as the amount of the middle palladium catalyst used just is not particularly limited for so-called catalytic amount, but good from the viewpoint of yield, be preferably 0.01 ~ 0.1 times mole (conversion of palladium atom) relative to compound (6) 1 moles.As the usage quantity of alkali, be not particularly limited, but be preferably 0.5 ~ 10 times mole relative to compound (6) 1 moles, good from the viewpoint of yield, preferably 1 ~ 3 times mole further.
In addition, in reaction formula (3), the phase-transfer catalyst representated by 18-hat-6-ether can be added.
Good from the viewpoint of yield, the reaction of reaction formula (3) is preferably implemented in a solvent.
Below, reaction formula (4) is described.
Compound (8) such as can according to the method manufacture shown in the synthesis example-1 in embodiment.
In addition, any hydrogen atom in compound (8) can be replaced by D atom.
As compound (9), be not particularly limited, such as can enumerate: 9-1 ~ 9-12 below (separately can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, the aromatic hydrocarbyl of carbonatoms 6 ~ 18, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18, the aromatic hydrocarbyl of the carbonatoms 6 ~ 18 of the alkyl replacement of carbonatoms 1 ~ 4, the aromatic group of carbonatoms 3 ~ 18, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18, or by the aromatic group alternatively base of the carbonatoms 3 ~ 18 of the alkyl of carbonatoms 1 ~ 4 replacement.It should be noted that, these substituting groups are identical with above-mentioned group.) shown in compound.
(illustrate in formula (9-1) ~ (9-12), X 4with the X in above-mentioned general formula (7) 4define identical.)
Compound (9) such as can use J.Tsuji work " Palladium Reagents and Catalysts ", JohnWiley & Sons, 2004, Journal of Organic Chemistry, 60 volumes, 7508-7510, nineteen ninety-five, Journal of Organic Chemistry, 65 volumes, 164-168,2000, Organic Letters, 10 volumes, 941-944,2008 or Chemistry of Materials, 20 volumes, 5951-5953, the method manufacture disclosed in 2008.
In addition, any hydrogen atom in compound (9) can be replaced by D atom.
Reaction formula (4) reacts with compound (9) according to circumstances in the presence of base, under the existence of palladium catalyst for making compound (8), manufacture the method for cyclic azine compound (1) of the present invention, target compound can be obtained well by the reaction conditions yield of application Suzuki-Pu, palace reaction.
Reaction formula (4) is as long as the amount of the middle palladium catalyst used just is not particularly limited for so-called catalytic amount, but good from the viewpoint of yield, be preferably 0.1 ~ 0.01 times mole (conversion of palladium atom) relative to 1 mole of compound (9).
The usage quantity of alkali is not particularly limited, but is preferably 0.5 ~ 10 times mole relative to compound (9) 1 moles, good from the viewpoint of yield, more preferably 1 ~ 3 times mole.
The mol ratio of the compound (8) used in reaction formula (4) and compound (9) is not particularly limited, but preferred is 0.2 ~ 5 times mole relative to compound (8) 1 moles, good from the viewpoint of yield, more preferably 0.3 ~ 3 times mole.
The manufacture method of the organic electroluminescent device film be made up of cyclic azine compound (1) of the present invention is not particularly limited, but the film forming utilizing vacuum vapour deposition can be enumerated as preferred example.
Utilize the film forming of vacuum vapour deposition can be undertaken by using general vacuum deposition apparatus.For the vacuum tightness of vacuum tank when forming film with vacuum vapour deposition, manufacture pitch time in the making of organic electroluminescent device is short, have superiority from the viewpoint of manufacturing cost, preferably utilize usual used diffusion pump, turbomolecular pump, cryopump etc. accessible 1 × 10 -2~ 1 × 10 -6about Pa.
In addition, evaporation rate depends on the thickness of the film of formation, but preferred 0.005 ~ 10nm/ second.
In addition, the organic electroluminescent device film also can be made up of 1,3,5-triazines compound (1) by the manufacture of solution coat method.Such as also can for cyclic azine compound (1) be dissolved in chloroform, methylene dichloride, 1, in the organic solvents such as 2-ethylene dichloride, chlorobenzene, toluene, vinyl acetic monomer or tetrahydrofuran (THF), utilize the film forming employing the spin-coating method, ink jet method, teeming practice, pickling process etc. of general device.
[embodiment]
Below, enumerate synthesis example, embodiment, comparative example and reference example and the present invention is described in further detail, but the present invention is not limited to these makes an explanation.
Synthesis example-1
Under argon gas stream, by 2-(4-bromophenyl)-4,6-phenylbenzene-1,3, the toluene solution (96 μ L) of 5-triazine (621mg), 2-chlorine carbazole (339mg), palladium (7.2mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (332mg) and 18-are preced with-6-ether (84.6mg) and are suspended in dimethylbenzene (8.0mL), stir 21 hours at 120 DEG C.After being let cool by reaction mixture, add water.By the solid use water cleaning of separating out, then use washed with methanol, then with hexane cleaning, obtain the white powder (output 729mg, yield 90%) of the chloro-9-of 2-[4-(4, the 6-phenylbenzene triazine-2-base) phenyl] carbazole into target compound.
1H-NMR(CDCl 3)：
δ7.32(d,J＝8.4Hz,1H),7.37(t,J＝7.4Hz,1H),7.49(t,J＝7.6Hz,1H),7.55-7.57(m,2H),7.62-7.68(m,6H),7.82(d,J＝8.4Hz,2H),8.09(d,J＝8.4Hz,1H),8.16(d,J＝7.6Hz,1H),8.85(d,J＝6.4Hz,4H),9.06(d,J＝8.4Hz,2H).
Synthesis example-2
Under argon gas stream, by 2-[4-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) phenyl]-4,6-phenylbenzene-1,3,5-triazine (1.0g), 3-bromine carbazole (622mg) and tetrakis triphenylphosphine palladium (238mg) are suspended in Isosorbide-5-Nitrae-two in the mixed solvent of alkane (12mL) and 3M-aqueous potassium phosphate solution (1.1mL), reflux 20 hours.After being cooled to room temperature, add water.By the solid use water cleaning of separating out, then use washed with methanol, then with hexane cleaning, obtain the brown solid (output 794mg, yield 70%) of 3-[4-(4, the 6-phenylbenzene triazine-2-base) phenyl] carbazole into target compound.
1H-NMR(DMSO-d 6)：
δ7.23(t,J＝7.4Hz,1H),7.44(t,J＝7.6Hz,1H),7.54(d,J＝8.1Hz,1H),7.64(d,J＝8.4Hz,1H),7.63-7.75(m,6H),7.89(d,J＝8.5Hz,1H),8.10(d,J＝8.3Hz,2H),8.29(d,J＝7.8Hz,1H),8.65(s,1H),8.79(d,J＝7.0Hz,4H),8.85(d,J＝8.3Hz,2H),11.45(s,1H).
Synthesis example-3
Under argon gas stream, 3-bromine carbazole (4.92g), two tetramethyl ethylene ketone two boron (10.2g), Potassium ethanoate (7.85g) and bis-triphenylphosphipalladium palladium dichloride (281mg) are suspended in Isosorbide-5-Nitrae-two in alkane (100mL), reflux 2 hours.After being cooled to room temperature, leach nonsoluble.Secondly, filtrate is refined with silica gel chromatography (developing solvent: chloroform), obtains the white solid (output 3.94g, yield 67%) of 3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-carbazole.
1H-NMR(DMSO-d 6)：
δ1.17(s,12H),7.18(t,J＝7.4Hz,1H),7.40(t,J＝7.6Hz,1H),7.46-7.51(m,2H),7.70(d,J＝8.2Hz,1H),8.20(d,J＝7.8Hz,1H),8.46(s,1H),11.43(s,1H).
Synthesis example-4
Under argon gas stream, by 3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-carbazole (586mg), 2-bromopyridine (348mg) and tetrakis triphenylphosphine palladium (46mg) be suspended in the mixed solvent of THF (10mL) and 4N-aqueous sodium hydroxide solution (1.0mL), reflux 23 hours.After being cooled to room temperature, use chloroform extraction.Organic layer silica gel chromatography (developing solvent: toluene, then chloroform, then methyl alcohol) is refined, obtains the yellow solid (output 474mg, yield 97%) of 3-(2-pyridyl) carbazole.
1H-NMR(DMSO-d 6)：
δ7.20(t,J＝7.4Hz,1H),7.29(dd,J＝7.4,4.8Hz,1H),7.41(t,J＝7.6Hz,1H),7.50(d,J＝8.1Hz,1H),7.56(d,J＝8.5Hz,1H),7.87(t,J＝7.7Hz,1H),8.05(d,J＝8.1Hz,1H),8.18(d,J＝8.6Hz,1H),8.22(d,J＝7.8Hz,1H),8.66(d,J＝4.8Hz,1H),8.88(s,1H),11.41(s,1H).
Synthesis example-5
Under argon gas stream, by 2-(3-bromophenyl)-4,6-phenylbenzene-1,3,5-triazines (1.17g), 3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) carbazole (967mg) and tetrakis triphenylphosphine palladium (104mg) be suspended in Isosorbide-5-Nitrae-two in alkane (15mL), add 3M-wet chemical (2.5mL), reflux 17 hours.After being let cool by reaction mixture, add water.By the solid use water cleaning of separating out, then use washed with methanol, then clean with hexane, obtain 3-[3-(4, the 6-phenylbenzene-1,3 for target compound, 5-triazine-2-base) phenyl] white powder (output 1.37g, yield 96%) of carbazole.
1H-NMR(CDCl 3)：
δ,7.29(t,J＝7.0Hz,1H),7.43-7.50(m,2H),7.55-7.61(m,7H),7.66(t,J＝7.8Hz,1H),7.81(d,J＝8.4Hz,1H),7.94(d,J＝7.8Hz,1H),8.15(bs,1H),8.17(d,J＝7.8Hz,1H),8.41(s,1H),8.75(d,J＝7.8Hz,1H),8.80(d,J＝7.8Hz,4H),9.07(s,1H).
Synthesis example-6
Under argon gas stream, by 3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (2.00g), 2-bromopyridine (745mg), cupric oxide (56.23mg), 1,10-phenanthrolene (70.82mg), 18-are preced with-6-ether (207.76mg) and salt of wormwood (1358mg) is suspended in dimethylbenzene (20mL), reflux 16 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain N-(2-pyridyl)-3-[the chloro-5-(4 of 3-for target compound, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] yellow powder (output 2110mg, yield 92%) of carbazole.
1H-NMR(CDCl 3)：
δ7.33-7.39(m,2H),7.48(t,J＝7.2Hz,1H),7.56-7.64(m,6H),7.69(d,J＝8.0Hz,1H),7.80(d,J＝8.0Hz,1H),7.86(d,J＝7.6Hz,1H),7.92(s,1H),7.95-8.00(m,2H),8.22(d,J＝7.6Hz,1H),8.41(s,1H),8.71(s,1H),8.78-8.80(m,5H),8.97(s,1H).
Synthesis example-7
Under argon gas stream, by 3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl]-9-(2-pyridyl) carbazole (1.90g), two tetramethyl ethylene ketone two boron (0.90g), three (dibenzylideneacetone) two palladium (29.7mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (30.9mg) and Potassium ethanoate (0.95g) are suspended in Isosorbide-5-Nitrae-two in alkane (24mL), reflux 5 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol.Under reduced pressure, distillation, except desolventizing, obtains the 3-[3-(4,4 into target compound, 5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-5-(4,6-phenylbenzene-1,3,5-triazine-2-base) phenyl] white powder (output 1.98g, yield 90%) of-9-(2-pyridyl) carbazole.
1H-NMR(CDCl 3)：
δ,1.45(s,12H),7.31-7.37(m,2H),7.47(t,J＝7.4Hz,1H),7.56-7.61(m,6H),7.70(d,J＝8.2Hz,1H),7.85-7.89(m,2H),7.96(t,J＝8.2Hz,2H),8.24(d,J＝7.4Hz,1H),8.40(s,1H),8.48(s,1H)、8.75-8.83(m,5H),9.13(s,1H),9.18(s,1H).
Synthesis example-8
Under argon gas stream, by 2-[the chloro-5-(4 of 3-, 4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) phenyl]-4,6-phenylbenzene-1,3,5-triazine (93mg), the bromo-9-of 6-(2-pyridyl)-β-carboline (54mg), tetrakis triphenylphosphine palladium (5.7mg) and salt of wormwood (57mg) are suspended in Isosorbide-5-Nitrae-two in alkane (3.3mL), add water (150 μ L), reflux 14 hours.After being let cool by reaction mixture, add water.By the solid use water cleaning of separating out, then use washed with methanol, then with hexane cleaning, under reduced pressure, distillation is except desolventizing.Carry out utilizing the refining of silica gel column chromatography (elutriant: vinyl acetic monomer), obtain 9-(2-pyridyl)-6-[the chloro-5-(4 of 3-for target compound, 6-phenylbenzene triazine-2-base) phenyl] white powder (output 70mg, yield 71%) of-β-carboline.
1H-NMR(CDCl 3)：
δ,7.39(dd,J＝7.4,5.0Hz,1H),7.55-7.62(m,6H),7.72(d,J＝7.4Hz,1H),7.89(s,1H),7.92(d,J＝8.4Hz,1H),8.01(t,J＝7.8Hz,1H)，
8.06-8.09(m,2H),8.45(s,1H),8.60(d,J＝5.2Hz,1H),8.72(s,1H),8.76-8.78(m,5H),8.93(s,1H),9.32(s,1H).
Synthesis example-9
Under argon gas stream, by 2-[the chloro-5-(4 of 3-, 4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) phenyl]-4,6-phenylbenzene-1,3,5-triazine (706mg), the bromo-9-phenyl of 3--6-(2-pyridyl) carbazole (500mg), tetrakis triphenylphosphine palladium (28.9mg) and salt of wormwood (57mg) are suspended in Isosorbide-5-Nitrae-two in alkane (6.5mL), add water (1.3mL), reflux 20 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.Under reduced pressure, distillation, except desolventizing, obtains 3-[the chloro-5-(4 of 3-into target compound, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] white powder (output 754mg, yield 91%) of-9-phenyl-6-(2-pyridyl) carbazole.
1H-NMR(CDCl 3)：
δ,7.21(t,J＝7.4Hz,1H),7.52(t,J＝8.4Hz,2H),7.55-7.69(m,11H),7.76(t,J＝8.4Hz,2H),7.88(d,J＝8.4Hz,1H),7.92(s,1H),8.11(d,J＝8.4Hz,1H),8.54(s,1H),8.71-8.73(m,2H),8.75-8.80(m,4H),8.91(s,1H),8.96(s,1H).
Synthesis example-10
Under argon gas stream, by 2-(5-chlordiphenyl-3-base)-4,6-phenylbenzene-1,3,5-triazine (12.6g), two tetramethyl ethylene ketone two boron (8.4g), three (dibenzylideneacetone) two palladium (824mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (1.3g) and Potassium ethanoate (6.5g) are suspended in Isosorbide-5-Nitrae-two in alkane (150mL), reflux 3.5 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol.Under reduced pressure, distillation, except desolventizing, obtains the 2-[5-(4,4 into target compound, 5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-biphenyl-3-base-4,6-phenylbenzene-1, the white powder (output 14.8g, yield 96%) of 3,5-triazine (being compound (E-1) below).
1H-NMR(CDCl 3)：
δ,1.47(s,12H),7.45(t,J＝7.4Hz,1H),7.55(t,J＝7.4Hz,2H),7.60-7.68(m,6H),7.82(d,J＝8.1Hz,2H),8.33(s,1H),8.85(d,J＝7.9Hz,4H),9.12(s,1H),9.16(s,1H).
Synthesis example-11
Under argon gas stream, by 3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (4.00g), phenyl-boron dihydroxide (1.25g), palladium (53mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (225mg) is suspended in Isosorbide-5-Nitrae-two in alkane (80mL), add 3M-wet chemical (6.8mL), reflux 27 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.Under reduced pressure, distillation, except desolventizing, obtains the white powder (output 3.27g, yield 76%) of 3-[5-(4, the 6-phenylbenzene-1,3,5-triazines-2-base)-biphenyl-3-base] carbazole into target compound.
1H-NMR(CDCl 3)：
δ7.32(dd,J＝7.9,6.2Hz,1H),7.47-7.51(m,2H),7.59-7.68(m,10H),7.87-7.91(m,3H),8.18(s,1H),8.19(s,1H),8.22(d,J＝7.7Hz,1H),8.50(s,1H),8.84-8.87(m,4H),9.00(s,1H),9.09(s,1H).
Synthesis example-12
Under argon gas stream, 9-(2-pyridyl)-δ-carboline (700mg) and N-bromo-succinimide (559mg) are suspended in DMF (5.7mL), stir 10 hours at 30 DEG C.Then, add water, leach the solid of precipitation, with water cleaning, secondly clean with hexane.Under reduced pressure, distillation, except desolventizing, obtains the brown powder (output 761mg, yield 82%) into the bromo-9-of 6-(the 2-pyridyl)-δ-carboline of target compound.
1H-NMR(CDCl 3)：
δ,7.38(dd,J＝7.5,4.9Hz,1H),7.42(dd,J＝8.4,4.7Hz,1H),7.62(d,J＝8.2Hz,1H),7.65(d,J＝8.8Hz,1H),7.80(d,J＝8.8Hz,1H),7.80(t,J＝7.6Hz,1H),8.22(d,J＝8.4Hz,1H),8.59(s,1H),8.66(d,J＝4.7Hz,1H),8.75(d,J＝4.9Hz,1H).
Synthesis example-13
Under argon gas stream, 9-phenyl-3-(2-pyridyl) carbazole (757mg) and N-bromo-succinimide (463mg) are suspended in DMF (4.7mL), stir 7 hours at 30 DEG C.Then, add water, leach the solid of precipitation, with water cleaning, secondly clean with hexane.Under reduced pressure, distillation, except desolventizing, obtains the brown powder (output 852mg, yield 90%) into the bromo-9-phenyl of 3--6-(2-pyridyl) carbazole of target compound.
1H-NMR(CDCl 3)：
δ,7.27-7.30(m,1H),7.317.131(d,J＝8.5Hz,1H),7.49(d,J＝8.6Hz,1H),7.51-7.55(m,2H),7.57-7.60(m,2H),7.64-7.68(m,2H),7.84(t,J＝7.6Hz,1H),7.89(d,J＝8.0Hz,1H),8.14(d,J＝8.5Hz,1H),8.37(s,1H),8.77(d,J＝4.8Hz,1H),8.80(s,1H).
Synthesis example-14
Under argon gas stream, by 3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (2.55g), 4-(2-pyridyl) phenyl-boron dihydroxide (1.19g), palladium (22.5mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (143mg) is suspended in Isosorbide-5-Nitrae-two in alkane (25mL), then add 3M-wet chemical (4.0mL), reflux 14 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water, methyl alcohol, hexane cleaning.By obtained solid o-Xylol recrystallization, obtain the 3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-4 '-(2-pyridyl) biphenyl-3-base] white powder (output 2.31g, yield 74%) of carbazole (being compound (E-2) below).
1H-NMR(DMSO-d 6)：
δ7.21(t,J＝7.4Hz,1H),7.41(dd,J＝7.4,4.7Hz,1H),7.44(t,J＝7.6Hz,1H),7.55(d,J＝8.1Hz,1H),7.66-7.76(m,7H),7.92-7.97(m,2H),8.07-8.10(m,3H),8.30-8.32(m,3H),8.48(s,1H),8.71(s,1H),8.74(d,J＝4.7Hz,1H),8.77-8.80(m,4H),8.94(s,1H),9.00(s,1H),11.43(s,1H).
Synthesis example-15
Under argon gas stream, by 3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) carbazole (1.17g), 8-chloroquinoline (720mg), palladium (18.0mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (114mg) is suspended in THF (10mL), add 3M-wet chemical (2.7mL), reflux 15 hours.After being let cool by reaction mixture, add water, use chloroform extraction.After organic layer dried over mgso, filter.By underpressure distillation except desolventizing, the solid that leaching is separated out, obtains the yellow powder (output 780mg, yield 66%) of 3-(quinoline-8-yl) carbazole of target thus.
1H-NMR(CDCl 3)：
δ7.22(dd,J＝7.9,6.6Hz,1H),7.36(d,J＝8.0Hz,1H),7.40(dd,J＝8.1,6.6Hz,1H),7.44(dd,J＝8.4Hz,1H),7.46(dd,J＝8.3,4.2Hz,1H),7.67(dd,J＝8.2,7.0Hz,1H),7.76(d,8.3Hz,1H),7.86(d,J＝4.3Hz,1H),7.88(d,J＝4.3Hz,1H),8.05(d,J＝7.8Hz,1H),8.27(d,J＝8.3Hz,1H),8.35(s,1H),8.45(s,1H),9.02(d,J＝4.2Hz,1H).
Synthesis example-16
Under argon gas stream, by 3-(quinoline-8-yl) carbazole (736mg), 2-bromopyridine (474mg), cupric oxide (I) (17.9mg), 1,10-phenanthrolene (45mg), 18-are preced with-6-ether (132mg), salt of wormwood (691mg) is suspended in dimethylbenzene (6.2mL), reflux 15 hours.After reaction mixture is let cool, cross with Celite and filter unwanted material.Underpressure distillation removing filtrate, refines by column chromatography (developing solvent: chloroform), obtains the yellow powder (output 929mg, yield 100%) of 9-(2-pyridyl)-3-(quinoline-8-yl) carbazole of target thus.
1H-NMR(CDCl 3)：
δ7.32-7.36(m,2H),7.46-7.50(m,2H),7.69(dd,J＝8.1,7.1Hz,1H),7.74(d,J＝8.1Hz,1H),7.82(d,J＝8.5Hz,1H),7.87-7.92(m,2H),7.93(d,J＝8.4Hz,1H),7,97(dd,J＝8.0,7.5Hz,1H),7.97(d,J＝8.5Hz,1H),8,16(d,J＝7.7Hz,1H),8.29(d,J＝8.3Hz,1H),8.44(s,1H),8.78(d,J＝4.7Hz,1H),9.04(d,J＝4.1Hz,1H).
Synthesis example-17
Under argon gas stream, 9-(2-pyridyl)-3-(quinoline-8-yl) carbazole (929mg), N-bromo-succinimide (467mg) are suspended in DMF (10mL), stir 3 hours at 60 DEG C.Then, add water, leach the solid of precipitation, with water, hexane cleaning.Under reduced pressure, distillation, except desolventizing, obtains the brown powder (output 986mg, yield 88%) of the bromo-9-of 3-(2-pyridyl)-6-(quinoline-8-yl) carbazole of target.
1H-NMR(CDCl 3)：
δ,7.35(dd,J＝7.4,4.9Hz,1H),7.48(dd,J＝8.3,4.2Hz,1H),7.55(d,J＝8.8Hz,1H),7.69(dd,J＝7.8,7.5Hz,1H),7.70(d,J＝8.1Hz,1H),7.82(d,J＝8.5Hz,1H),7.83-7.90(m,3H),7.93(d,J＝8.5Hz,1H),7.98(dd,J＝8.0,7.5Hz,1H),8.27(s,1H),8.29(d,J＝8.3Hz,1H),8.40(s,1H),8.76(d,J＝4.9Hz,1H),9.02(d,J＝4.2Hz,1H).
Synthesis example-18
Under argon gas stream, by 3-[4-(2-pyridyl) phenyl] carbazole (3.20g), 2-bromopyridine (1.90g), cupric oxide (I) (71.5mg), 1,10-phenanthrolene (180mg), 18-are preced with-6-ether (529mg), salt of wormwood (2.76g) is suspended in dimethylbenzene (25mL), reflux 15 hours.After being let cool by reaction mixture, adding water and methyl alcohol, filtering unwanted material by crossing.By filtrate chloroform extraction, after organic layers with sodium sulfate drying, filter.Underpressure distillation is except desolventizing, refine by column chromatography (developing solvent: chloroform), obtain the yellow powder (output 3.62g, yield 91%) of 9-(2-pyridyl)-3-[4-(2-pyridyl) phenyl] carbazole of target thus.
1H-NMR(CDCl 3)：
δ7.26-7.30(m,1H),7.35(dd,J＝7.4,4.9Hz,1H),7.38(t,J＝7.5Hz,1H),7.50(t,J＝7.7Hz,1H),7.70(d,J＝8.1Hz,1H),7.78(d,J＝8.6Hz,1H),7.81-7.91(m,5H),7.95(d,J＝8.6Hz,1H),7.98(t,J＝7.8Hz,1H),8.16(d,J＝8.5Hz,2H),8.22(d,J＝7.5Hz,1H),8.42(s,1H),8.75-8.79(m,2H).
Synthesis example-19
Under argon gas stream, 9-(2-pyridyl)-3-[4-(2-pyridyl) phenyl] carbazole (1.99g), N-bromo-succinimide (979mg) are suspended in DMF (20mL), stir 4 hours at 60 DEG C.Then, add water, leach the solid of precipitation, with water, methyl alcohol, hexane cleaning, obtain the brown powder (output 2.12g, yield 89%) of the bromo-9-of 3-(2-pyridyl)-6-[4-(2-pyridyl) phenyl] carbazole of target thus.
1H-NMR(CDCl 3)：
δ7.26-7.30(m,1H),7.36(dd,J＝7.4,4.9Hz,1H),7.56(d,J＝8.8Hz,1H),7.66(d,J＝8.1Hz,1H),7.78-7.83(m,4H),7.85(d,J＝8.5Hz,2H),7.91(d,J＝8.5Hz,1H),7.98(dd,J＝8.0,7.5Hz,1H),8.15(d,J＝8.5Hz,2H),8.32(s,1H),8.35(s,1H),8.75-8.77(m,2H).
Synthesis example-20
Under argon gas stream, NSC 2020 (313mg), 1-(4-bromophenyl)-3-(1-naphthyl)-2-propylene-1-ketone (1.42g) are suspended in the ethanolic soln (2.0mL) of 2M-potassium hydroxide and the mixing solutions of ethanol (4.0mL), reflux 17 hours.After letting cool, add water, use chloroform extraction.Organic layer column chromatography (developing solvent: chloroform, hexane) is refined, obtains the yellow powder (output 459mg, yield 52%) of 4-(4-bromophenyl)-6-(1-the naphthyl)-2-phenyl pyrimidine of target thus.
1H-NMR(CDCl 3)：
δ7.53-7.61(m,5H),7.65(dd,J＝8.2,7.2Hz,1H),7.72(d,J＝8.6Hz,2H),7.82(d,J＝7.1Hz,1H),7.89(s,1H),7.98-8.00(m,1H),8.03(d,J＝8.2Hz,1H),8.21(d,J＝8.6Hz,2H),8.36-8.38(m,1H),8.69-8.72(m,2H).
Synthesis example-21
Under argon gas stream, by 3-[5-(4,6-phenylbenzene-1,3,5-triazine-2-base)-biphenyl-3-base] carbazole (1.10g), bromobenzene (377mg), palladium (9.0mg), three (tertiary butyl phosphine) 1M-toluene solution) (120 μ L), 18-is preced with-6-ether (106mg), salt of wormwood (553mg) is suspended in dimethylbenzene (10mL), reflux 15 hours.After being let cool by reaction mixture, add water.The solid use water of separating out, methyl alcohol, hexane are cleaned, obtain 9-phenyl-3-[5-(4, the 6-phenylbenzene-1,3 of target, 5-triazine-2-base)-biphenyl-3-base] yellow powder (output 1.21g, yield 97%) of carbazole (being ETL-4 below).
1H-NMR(CDCl 3)：
δ7.34-7.38(m,1H),7.47-7.56(m,4H),7.58-7.69(m,13H),7.87-7.89(m,3H),8.19(s,1H),8.29(d,J＝7.7Hz,1H),8.56(s,1H),8.84(d,J＝8.0Hz,4H),9.00(s,1H),9.10(s,1H).
Embodiment-1
Under argon gas stream, by 2-(3-bromophenyl)-4,6-phenylbenzene-1,3, the toluene solution (94 μ L) of 5-triazine (500mg), 3-[4-(2-pyridyl) phenyl] carbazole (606mg), palladium (7.0mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (431mg) and 18-are preced with-6-ether (82.5mg) and are suspended in dimethylbenzene (7.8mL), reflux 4 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain 3-[4-(2-pyridyl) phenyl]-9-[3-(4 for target compound, 6-phenylbenzene triazine-2-base) phenyl] yellow powder (output 867mg, yield 88%) of carbazole (A-1).
1H-NMR(DMSO-d 6)：
δ7.36-7.39(m,2H),7.48-7.53(m,2H),7.57(d,J＝8.8Hz,1H),7.64(t,J＝7.4Hz,4H),7.69-7.73(m,2H),7.88-7.94(m,2H),7.97(d,J＝8.5Hz,2H),8.01-8.06(m,3H),8.24(d,J＝8.4Hz,2H),8.45(d,J＝7.9Hz,1H),8.71(m,6H),8.91-8.93(m,2H).
Embodiment-2
Under argon gas stream, by 2-(4-bromophenyl)-4,6-phenylbenzene-1,3, the toluene solution (108 μ L) of 5-triazine (700mg), 3-[4-(2-pyridyl) phenyl] carbazole (635mg), palladium (8.1mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (498mg) and 18-are preced with-6 ethers (105mg) and are suspended in dimethylbenzene (9.0mL), reflux 2.5 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain 3-[4-(2-pyridyl) phenyl]-9-[4-(4 for target compound, 6-phenylbenzene triazine-2-base) phenyl] yellow powder (output 1108mg, yield 98%) of carbazole (A-2).
1H-NMR(CDCl 3)：
δ7.26-7.30(m,1H),7.40(t,J＝7.8Hz,1H),7.51(t,J＝7.7Hz,1H),7.61-7.68(m,8H),7.79-7.84(m,3H),7.87-7.91(m,4H),8.17(d,J＝8.4Hz,2H),8.27(d,J＝7.6Hz,1H),8.48(s,1H),8.76(d,J＝4.7Hz,1H),8.86(d,J＝6.4Hz,4H),9.08(d,J＝8.6Hz,2H).
Embodiment-3
Under argon gas stream, by 2-(5-chlordiphenyl-3-base)-4,6-phenylbenzene-1,3, the toluene solution (71 μ L) of 5-triazine (500mg), 3-[4-(2-pyridyl) phenyl] carbazole (420mg), palladium (5.3mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (329mg) and 18-are preced with-6 ethers (69mg) and are suspended in dimethylbenzene (6mL), reflux 21.5 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain 3-[4-(2-pyridyl) phenyl]-9-[5-(4 for target compound, 6-phenylbenzene triazine-2-base) biphenyl-3-base] yellow powder (output 800mg, yield 95%) of carbazole (A-3).
1H-NMR(CDCl 3)：
δ7.28(t,J＝6.2Hz,1H),7.41(t,J＝7.3Hz,1H),7.48-7.53(m,2H),7.57-7.66(m,10H),7.78-7.86(m,5H),7.90(d,J＝8.4Hz,2H),8.08(s,1H),8.17(d,J＝8.3Hz,2H),8.30(d,J＝7.7Hz,1H),8.51(s,1H),8.78(d,J＝4.7Hz,1H),8.81(d,J＝6.7Hz,4H),9.02(s,1H),9.14(s,1H).
Embodiment-4
Under argon gas stream, by 2-(4 '-chlordiphenyl-4-base)-4,6-phenylbenzene-1,3, the toluene solution (110 μ L) of 5-triazine (770mg), 3-[4-(2-pyridyl) phenyl] carbazole (646mg), palladium (8.2mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (507mg) and 18-are preced with-6 ethers (97mg) and are suspended in dimethylbenzene (9mL), reflux 4 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain 3-[4-(2-pyridyl) the phenyl]-9-[4 '-(4 for target compound, 6-phenylbenzene triazine-2-base) biphenyl-4-base] yellow powder (output 1140mg, yield 88%) of carbazole (A-4).
1H-NMR(CDCl 3)：
δ7.26-7.29(m,1H),7.38(t,J＝7.4Hz,1H),7.51(t,J＝7.1Hz,1H),7.57(d,J＝8.2Hz,1H),7.61-7.69(m,7H),7.76-7.86(m,5H),7.89(d,J＝8.4Hz,2H),7.95(d,J＝8.4Hz,2H),8.00(d,J＝8.4Hz,2H),8.17(d,J＝8.4Hz,2H),8.27(d,J＝7.7Hz,1H),8.48(s,1H),8.77(d,J＝4.7Hz,1H),8.86(d,J＝7.7Hz,4H),8.95(d,J＝8.4Hz,2H).
Embodiment-5
Under argon gas stream, by the chloro-9-of the 2-[4-(4 of synthesis in synthesis example-1,6-phenylbenzene triazine-2-base) phenyl] carbazole (715mg), 4-(2-pyridyl) phenyl-boron dihydroxide (336mg), palladium (6.3mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (40mg) is suspended in 3M-aqueous potassium phosphate solution (1.3mL) and Isosorbide-5-Nitrae-two in the mixing solutions of alkane (7mL), reflux 16 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, clean with water, then washed with methanol is used, then clean with hexane, obtain 2-[4-(2-pyridyl) phenyl]-9-[4-(4 for target compound, 6-phenylbenzene triazine-2-base) phenyl] white powder (output 842mg, yield 96%) of carbazole (A-5).
1H-NMR(CDCl 3)：
δ7.24-7.27(m,1H),7.38(t,J＝7.4Hz,1H),7.50(t,J＝7.4Hz,1H),7.59-7.69(m,8H),7.78-7.84(m,5H),7.90(d,J＝8.6Hz,2H),8.12(d,J＝8.5Hz,2H),8.23(d,J＝7.6Hz,1H),8.27(d,J＝8.1Hz,1H),8.74(d,J＝4.6Hz,1H),8.86(d,J＝8.0Hz,4H),9.09(d,J＝8.6Hz,2H).
Embodiment-6
Under argon gas stream, by chloro-for 4-9-[4-(4,6-phenylbenzene triazine-2-base) phenyl] carbazole (675mg), 4-(2-pyridyl) phenyl-boron dihydroxide (317mg), palladium (6.0mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (38mg) is suspended in 3M-aqueous potassium phosphate solution (1.1mL) and Isosorbide-5-Nitrae-two in the mixing solutions of alkane (13mL), reflux 18 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, clean with water, then washed with methanol is used, then clean with hexane, obtain 4-[4-(2-pyridyl) phenyl]-9-[4-(4 for target compound, 6-phenylbenzene triazine-2-base) phenyl] white powder (output 830mg, yield 100%) of carbazole (A-6).
1H-NMR(CDCl 3)：
δ7.10(t,J＝7.6Hz,1H),7.28(d,J＝7.5Hz,1H),7.31-7.34(m,1H),7.42(d,J＝7.7Hz,1H),7.51-7.71(m,10H),7.84-7.89(m,5H),7.93(d,J＝8.0Hz,1H),8.25(d,J＝8.3Hz,2H),8.81(d,J＝4.4Hz,1H),8.87(d,J＝8.0Hz,4H),9.08(d,J＝8.6Hz,2H).
Embodiment-7
Under argon gas stream, by 2-(4-bromophenyl)-4,6-bis-(biphenyl-4-base)-1,3, the toluene solution (56 μ L) of 5-triazine (500mg), 3-[4-(2-pyridyl) phenyl] carbazole (326mg), palladium (4.2mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (256mg) and 18-are preced with-6 ethers (49mg) and are suspended in dimethylbenzene (4.6mL), reflux 3 hours.After being let cool by reaction mixture, add water.The solid water of precipitation is cleaned, then washed with methanol is used, then clean with hexane, obtain 3-[4-(2-pyridyl) phenyl]-9-[4-(4 for target compound, 6-bis-(biphenyl-4-base) phenyl triazine-2-base) phenyl] yellow powder (output 673mg, yield 93%) of carbazole (A-7).
1H-NMR(CDCl 3)：
δ7.28(t,J＝5.9Hz,1H),7.40(t,J＝7.6Hz,1H),7.46(t,J＝7.4Hz,2H),7.51(d,J＝8.4Hz,1H),7.55(t,J＝7.5Hz,4H),7.63(d,J＝8.2Hz,1H),7.68(d,J＝8.5Hz,1H),7.77(d,J＝7.2Hz,4H),7.79-7.91(m,11H),8.17(d,J＝8.4Hz,2H),8.28(d,J＝7.7Hz,1H),8.48(s,1H),8.77(d,J＝4.6Hz,1H),8.94(d,J＝8.4Hz,4H),9.10(d,J＝8.5Hz,2H).
Embodiment-8
Under argon gas stream, by 2-(3,5-dibromo phenyl)-4,6-bis-(4-aminomethyl phenyl)-1,3,5-triazine (1000mg), 4-methyl isophthalic acid-naphthalene boronic acids (486mg) and tetrakis triphenylphosphine palladium (47mg) are suspended in the mixed solvent of 3M-aqueous potassium phosphate solution (1mL), THF (8mL) and ethanol (2mL), stir 72 hours at 40 DEG C.After being let cool by reaction mixture, filter the solid of separating out.Obtained solid use water is cleaned, then uses washed with methanol, then with hexane cleaning, obtain white-yellowish solid 978mg.
The toluene solution (103 μ L) of obtained white-yellowish solid (950mg), 3-[4-(2-pyridyl) phenyl] carbazole (602mg), palladium (7.7mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (473mg) and 18-are preced with-6-ether (90mg) to be suspended in dimethylbenzene (8.6mL), reflux 4.5 hours.After being let cool by reaction mixture, add water, leach the solid of precipitation.Secondly, by filtrate chloroform extraction, organic layer silica gel chromatography (developing solvent: chloroform) is refined, obtain 3-[4-(2-pyridyl) phenyl]-9-[3-(4 for target compound, 6-bis-(4-aminomethyl phenyl) triazine-2-base)-5-(4-methylnaphthalene-1-base)] yellow powder (output 640mg, yield 40%) of phenyl carbazole (A-8).
1H-NMR(CDCl 3)：
δ2.50(s,6H),2.85(s,3H),7.28(t,J＝6.0Hz,1H),7.35(d,J＝8.0Hz,4H),7.41(t,J＝7.5Hz,1H),7.52(d,J＝7.2Hz,1H),7.53(t,J＝7.7Hz,1H),7.51-7.68(m,3H),7.70(d,J＝8.2Hz,1H),7.75(d,J＝8.5Hz,1H),7.77-7.85(m,3H),7.91(d,J＝8.5Hz,2H),7.99(s,1H),8.18(d,J＝8.6Hz,4H),8.31(d,J＝7.6Hz,1H),8.52(s,1H),8.68(d,J＝8.2Hz,4H),8.79(d,J＝4.8Hz,1H),9.05(s,1H),9.13(s,1H).
Embodiment-9
Under argon gas stream, by the 3-[4-(4 of synthesis in synthesis example-2,6-phenylbenzene triazine-2-base) phenyl] carbazole (650mg), 3, the toluene solution (82 μ L) of 5-bis-(2-pyridyl) bromobenzene (469mg), palladium (6.2mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (379mg) and 18-are preced with-6-ether (72mg) and are suspended in dimethylbenzene (6.9mL), reflux 5.5 hours.After being let cool by reaction mixture, add water.Secondly, filter the solid of separating out, clean with water, then washed with methanol is used, then with hexane cleaning, 3-[4-(4,6-bis-(biphenyl-4-base) phenyl triazine-2-base) the phenyl]-9-[3 into target compound is obtained, 5-bis-(2-pyridyl) phenyl] brown solid (output 888mg, yield 92%) of carbazole (A-9).
1H-NMR(CDCl 3)：
δ7.32-7.36(m,2H),7.38(t,J＝7.4Hz,1H),7.50(t,J＝7.6Hz,1H),7.58(d,J＝8.2Hz,1H),7.60-7.68(m,7H),7.81-7.87(m,3H),7.95(d,J＝8.0Hz,2H),7.98(d,J＝8.6Hz,2H),8.29(d,J＝7.5Hz,1H),8.36(s,2H),8.53(s,1H),8.78(d,J＝4.8Hz,2H),8.84(s,1H),8.85(d,J＝7.8Hz,4H),8.91(d,J＝8.5Hz,2H).
Embodiment-10
Under argon gas stream, by 2-(4-bromophenyl)-4,6-phenylbenzene-1,3, the toluene solution (102 μ L) of 5-triazine (660mg), 3-(2-pyridyl) carbazole (457mg), palladium (7.6mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (470mg) and 18-are preced with-6-ether (90mg) and are suspended in dimethylbenzene (8.5mL), reflux 2 hours.After being let cool by reaction mixture, use chloroform extraction.After underpressure distillation removing organic layer, add methyl alcohol, solid is separated out.Filter the solid of separating out, by washed with methanol, secondly clean with hexane, obtain 3-(the 2-pyridyl)-9-[4-(4 for target compound, 6-phenylbenzene triazine-2-base) phenyl] yellow powder (output 917mg, yield 98%) of carbazole (A-10).
1H-NMR(CDCl 3)：
δ7.26(dd,J＝7.4,4.8Hz,1H),7.39(t,J＝7.4Hz,1H),7.50(t,J＝7.7Hz,1H),7.60-7.69(m,8H),7.81(t,J＝7.7Hz,1H),7.87(d,J＝8.7Hz,2H),7.90(d,J＝8.0Hz,1H),8.13(d,J＝8.7Hz,1H),8.28(d,J＝7.6Hz,1H),8.77(d,J＝4.8Hz,1H),8.84-8.696(m,5H),9.07(d,J＝8.6Hz,2H).
Embodiment-11
Under argon gas stream, by 3-[3-(4,6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (1.19g), 2-bromopyridine (474mg), cupric oxide (36mg), 1,10-phenanthrolene (45mg), 18-are preced with-6-ether (132mg) and salt of wormwood (864mg) is suspended in dimethylbenzene (12.5mL), reflux 15 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(2-pyridyl)-3-[3-(4, the 6-phenylbenzene-1,3 for target compound, 5-triazine-2-base) phenyl] yellow powder (output 1.29g, yield 93%) of carbazole (A-11).
1H-NMR(CDCl 3)：
δ7.32-7.37(m,2H),7.48(t,J＝7.6Hz,1H),7.58-7.61(m,6H),7.66-7.71(m,2H),7.83(d,J＝8.0Hz,1H),7.87(d,J＝8.0Hz,1H),7.94-7.99(m,3H),8.21(d,J＝7.6Hz,1H),8.44(s,1H),8.75-8.81(m,2H),8.80(d,J＝7.8Hz,4H),9.08(s,1H).
Embodiment-12
Under argon gas stream, by 2-[5-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) xenyl]-4,6-phenylbenzene-1,3,5-triazine (1.08g), the bromo-9-of 3-(2-pyridyl) carbazole (570mg) and tetrakis triphenylphosphine palladium (102mg) are suspended in Isosorbide-5-Nitrae-two in alkane (9.0mL), and then add 3M-aqueous potassium phosphate solution (1.8mL), reflux 27 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(2-pyridyl)-3-[5-(4, the 6-phenylbenzene-1,3 for target compound, 5-triazine-2-base) biphenyl-3-base] the grey powder (output 800mg, yield 60%) of carbazole (A-12).
1H-NMR(CDCl 3)：
δ7.32-7.35(m,2H),7.44-7.50(m,2H),7.54-7.62(m,8H),7.71(d,J＝8.0Hz,1H),7.84(d,J＝8.4,2H),7.87(d,J＝8.4,2H),7.96(t,J＝7.8,1H),8.00(d,J＝8.4Hz,1H),8.16(s,1H),8.22(d,J＝7.6Hz,1H),8.49(s,1H),8.76(d,J＝6.0Hz,1H),8.81(d,J＝8.0Hz,4H),8.97(s,1H),9.07(s,1H).
Embodiment-13
Under argon gas stream, by 3-[the chloro-5-(4 of 1-, 6-phenylbenzene-1,3,5-triazine-2-base)-3-base]-9-(2-pyridyl) carbazole (1.47g), 4-(2-pyridyl) phenyl-boron dihydroxide (597mg), palladium (11mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (72mg) is suspended in the mixed solvent of dimethylbenzene (22.5mL) and n-butyl alcohol (2.5mL), and then add 3M-wet chemical (2.5mL), reflux 24 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(2-pyridyl)-3-[5-(4, the 6-phenylbenzene-1,3 for target compound, 5-triazine-2-base)-4 '-(2-pyridyl) biphenyl-3-base] the grey powder (output 1.50g, yield 60%) of carbazole (A-13).
1H-NMR(CDCl 3)：
δ7.26-7.28(m,1H),7.33-7.38(m,2H),7.48(t,J＝7.2Hz,1H),7.57-7.63(m,6H),7.71(d,J＝8.0Hz,1H),7.77-7.85(m,2H),7.88-7.91(m,2H),7.96-8.00(m,3H),8.02(d,J＝8.0Hz,1H),8.18-8.24(m,3H),8.24(d,J＝7.4Hz,1H),8.50(s,1H),8.75(d,J＝4.6Hz,1H),8.77(d,J＝4.6Hz,1H),8.82(d,J＝8.0Hz,4H),9.04(s,1H),9.08(s,1H).
Embodiment-14
Under argon gas stream, by 6-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl]-9-(2-pyridyl)-β-carboline (845mg), 4-(2-pyridyl) phenyl-boron dihydroxide (873mg), palladium (9.7mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (61.7mg) is suspended in THF (30mL), and then add 3M-wet chemical (1.5mL), reflux 60 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, with water cleaning, then use washed with methanol, then with hexane cleaning, and then under reduced pressure, distillation is except desolventizing.Then, carry out utilizing the refining of silica gel column chromatography (elutriant: vinyl acetic monomer), obtain the 6-[5-(4 for target compound, 6-phenylbenzene-1,3,5-triazine-2-base)-4 '-(2-pyridyl) biphenyl-3-base] white powder (output 834mg, yield 82%) of-9-(2-pyridyl)-β-carboline (A-14).
1H-NMR(CDCl 3)：
δ7.27-7.29(m,1H),7.39(dd,J＝7.4,5.0Hz,1H),7.57-7.74(m,6H),7.74-7.85(m,3H),7.96(d,J＝8.4Hz,2H),8.00-8.06(m,2H),8.10-8.12(m,2H),8.19-8.21(m,3H),8.56(s,1H),8.60(d,J＝5.2Hz,1H),8.75(d,J＝4.8Hz,1H),8.79(d,J＝4.8Hz,1H),8.83(d,J＝8.0Hz,4H),9.06(s,2H),9.35(s,1H).
Embodiment-15
Under argon gas stream, by 3-[3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-5-(4,6-phenylbenzene-1,3,5-triazine-2-base) phenyl]-9-(2-pyridyl) carbazole (1.98g) and 2-bromopyridine (0.56g), tetrakis triphenylphosphine palladium (101.5mg) be suspended in Isosorbide-5-Nitrae-two in alkane (15mL), and then add 3M-wet chemical (3mL), reflux 17 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.And then, under reduced pressure, distillation is except desolventizing, obtain 3-[3-(2-the pyridyl)-5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] the grey powder (output 1.72g, yield 93%) of-9-(2-pyridyl) carbazole (A-15).
1H-NMR(CDCl 3)：
δ7.32-7.38(m,3H),7.50(t,J＝7.4Hz,1H),7.56-7.62(m,6H),7.71(d,J＝8.4Hz,1H),7.87-7.89(m,2H),7.92(d,J＝8.4Hz,1H),7.97(t,J＝7.4Hz,1H),8.03(t,J＝7.4Hz,2H),8.24(d,J＝8.4Hz,1H),8.54(s,1H),8.64(s,1H),8.77(d,J＝4.4Hz,1H),8.81-8.8(m,5H),9.15(s,1H),9.30(s,1H).
Embodiment-16
Under argon gas stream, by 3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl]-9-phenyl-6-(2-pyridyl) carbazole (754mg), phenyl-boron dihydroxide (167mg), palladium (5.1mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (32.6mg) is suspended in dimethylbenzene (9mL), and then add 3M-wet chemical (1.2mL), reflux 48 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.And then, under reduced pressure, distillation is except desolventizing, obtain the 3-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the yellow-white powder (output 297.9mg, yield 37%) of-9-phenyl-6-(2-pyridyl) carbazole (A-16).
The results verification that mass spectrum (mass analysis) measures: molecular weight is 703, the compound obtained is A-16.
Embodiment-17
Under argon gas stream, by 3-[5-(4,6-phenylbenzene-1,3,5-triazine-2-base)-biphenyl-3-base] carbazole (1.50g), 2-bromopyridine (515mg), cupric oxide (I) (20mg), 1,10-phenanthrolene (49mg), 18-are preced with-6-ether (143mg) and salt of wormwood (752mg) is suspended in dimethylbenzene (14mL), reflux 15 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(2-pyridyl)-3-[5-(4, the 6-phenylbenzene-1,3 for target compound, 5-triazine-2-base)-biphenyl-3-base] yellow powder (output 1.28g, yield 96%) of carbazole (A-12).
1H-NMR(CDCl 3)：
δ7.32-7.35(m,2H),7.44-7.50(m,2H),7.54-7.62(m,8H),7.71(d,J＝8.0Hz,1H),7.84(d,J＝8.4,2H),7.87(d,J＝8.4,2H),7.96(t,J＝7.8,1H),8.00(d,J＝8.4Hz,1H),8.16(s,1H),8.22(d,J＝7.6Hz,1H),8.49(s,1H),8.76(d,J＝6.0Hz,1H),8.81(d,J＝8.0Hz,4H),8.97(s,1H),9.07(s,1H).
Embodiment-18
Under argon gas stream, compound (E-1) (1.13g), the bromo-9-of 6-(2-pyridyl)-δ-carboline (749mg) and two (triphenylphosphine) palladium chloride (31mg) are suspended in Isosorbide-5-Nitrae-two in alkane (11mL), and then add 3M-wet chemical (1.5mL), reflux 18 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.
And then, under reduced pressure, distillation is except desolventizing, obtain the 6-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 1.30g, yield 94%) of-9-(2-pyridyl)-δ-carboline (A-17).
1H-NMR(CDCl 3)：
δ7.39(dd,J＝7.4,4.9Hz,1H),7.45(dd,J＝8.4,4.7Hz,1H),7.48(t,J＝7.4Hz,1H),7.55-7.67(m,8H),7.73(d,J＝8.1Hz,1H),7.87(d,J＝7.7Hz,2H),8.01(t,J＝7.7Hz,1H),8.05-8.06(m,2H),8.24(s,1H),8.32(d,J＝8.4Hz,1H),8.70(d,J＝4.7Hz,1H),8.78(d,J＝4.9Hz,1H),8.84(d,J＝7.9Hz,4H),8.95(s,1H),9.01(s,1H),9.11(s,1H).
Embodiment-19
Under argon gas stream, by compound (E-1) (418mg), the chloro-9-of 3-(2-pyridyl)-δ-carboline (240mg), palladium (3.7mg) and 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (22.9mg) is suspended in Isosorbide-5-Nitrae-two in alkane (4.1mL), and then add 3M-wet chemical (0.54mL), reflux 2 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.And then, under reduced pressure, distillation is except desolventizing, obtain the 3-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 447mg, yield 87%) of-9-(2-pyridyl)-δ-carboline (A-18).
1H-NMR(CDCl 3)：
δ7.39(dd,J＝7.4,4.9Hz,1H),7.46-7.52(m,2H),7.59-7.68(m,9H),7.74(d,J＝8.1Hz,1H),7.93-7.97(m,3H),8.02(t,J＝7.6Hz,1H),8.10(d,J＝8.7Hz,1H),8.42(d,J＝8.6Hz,1H),8.66(d,J＝4.3Hz,1H),8.78(s,1H),8.79(d,J＝4.9Hz,1H),8.87(d,J＝7.9Hz,4H),9.07(s,1H),9.46(s,1H).
Embodiment-20
Under argon gas stream, compound (E-1) (1.02g), 3-bromo-6-phenyl-9-(2-pyridyl) carbazole (839g) and two (triphenylphosphine) palladium chloride (28mg) are suspended in Isosorbide-5-Nitrae-two in alkane (10mL), and then add 3M-wet chemical (1.3mL), reflux 5 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then clean with hexane.And then, under reduced pressure, distillation is except desolventizing, obtain the 3-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 1.34g, yield 95%) of-6-phenyl-9-(2-pyridyl) carbazole (A-19).
1H-NMR(CDCl 3)：
δ7.39(t,J＝7.4Hz,1H),7.40-7.43(m,1H),7.47-7.54(m,3H),7.58-7.68(m,8H),7.77-7.81(m,4H),7.89(d,J＝8.2Hz,2H),7.95(d,J＝8.6Hz,1H),7.98(d,J＝8.6Hz,1H),8.04-8.08(m,2H),8.21(s,1H),8.48(s,1H),8.58(s,1H),8.83-8.87(m,5H),9.02(s,1H),9.12(s,1H).
Embodiment-21
Under argon gas stream, compound (E-1) (1.34g), 6-bromo-3-phenyl-9-(2-pyridyl)-δ-carboline (1.00g) and two (triphenylphosphine) palladium chloride (35.1mg) are suspended in Isosorbide-5-Nitrae-two in alkane (16.7mL), and then add 3M-wet chemical (1.8mL), reflux 19 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then with hexane cleaning, and then under reduced pressure, distillation is except desolventizing.By obtained solid o-Xylol recrystallization, obtain the 6-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 1.7g, yield 97%) of-3-phenyl-9-(2-pyridyl)-δ-carboline (A-20).
1H-NMR(CDCl 3)：
δ7.39(dd,J＝7.4,4.9Hz,1H),7.45(t,J＝7.3Hz,1H),7.49(t,J＝7.4Hz,1H),7.54-7.68(m,10H),7.76(d,J＝8.1Hz,1H),7.89(d,J＝8.6Hz,1H),7.90(d,J＝8.0Hz,2H),8.01-8.06(m,2H),8.10(d,J＝8.6Hz,1H),8.24(d,J＝8.1Hz,2H),8.27(s,1H),8.35(d,J＝8.7Hz,1H),8.80(d,J＝4.9Hz,1H),8.86(d,J＝8.1Hz,4H),8.98(s,1H),9.02(s,1H),9.15(s,1H).
Embodiment-22
Under argon gas stream, compound (E-1) (701mg), 6-bromo-9-phenyl-3-(2-pyridyl)-δ-carboline (550mg) and two (triphenylphosphine) palladium chloride (19mg) are suspended in Isosorbide-5-Nitrae-two in alkane (7mL), and then add 3M-wet chemical (1mL), reflux 40 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then with hexane cleaning, and then under reduced pressure, distillation is except desolventizing.By obtained solid re crystallization from toluene, obtain the 6-[5-(4 into target compound thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 400mg, yield 41%) of-9-phenyl-3-(2-pyridyl)-δ-carboline (A-21).
1H-NMR(CDCl 3)：
δ7.32(dd,J＝7.4,4.8Hz,1H),7.50(t,J＝7.4Hz,1H),7.55-7.73(m,14H),7.86-7.91(m,4H),8.00(d,J＝8.6Hz,1H),8.26(s,1H),8.58(d,J＝8.7Hz,1H),8.73(d,J＝4.8Hz,1H),8.79(d,8.0Hz,1H),8.84-8.86(m,4H),8.96(s,1H),9.02(s,1H),9.14(s,1H).
Embodiment-23
Under argon gas stream, compound (E-1) (1.02g), 3-bromo-9-phenyl-6-(2-pyridyl) carbazole (839g) and two (triphenylphosphine) palladium chloride (28mg) are suspended in Isosorbide-5-Nitrae-two in alkane (10mL), and then add 3M-wet chemical (1.3mL), reflux 5 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then with hexane cleaning, and then under reduced pressure, distillation is except desolventizing.Obtained solid is carried out utilize silica gel column chromatography (elutriant: chloroform) to refine, obtain the 3-[5-(4 for target compound, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 1.06g, yield 75%) of-9-phenyl-6-(2-pyridyl) carbazole (A-16).
1H-NMR(CDCl 3)：
δ7.26-7.30(m,1H),7.50(t,J＝7.4Hz,1H),7.54-7.71(m,15H),7.85(t,J＝7.6Hz,1H),7.89-7.93(m,3H),7.95(d,J＝8.0Hz,1H),8.18(d,J＝8.7Hz,1H),8.21(s,1H),8.66(s,1H),8.78(d,J＝4.8Hz,1H),8.85(d,J＝7.9Hz,4H),8.98(s,1H),9.02(s,1H),9.11(s,1H).
Embodiment-24
Under argon gas stream, compound (E-1) (1.53g), 3-bromo-9-phenyl-6-(pyrazinyl) carbazole (1.20g) and two (triphenylphosphine) palladium chloride (42.1mg) are suspended in Isosorbide-5-Nitrae-two in alkane (15mL), and then add 3M-wet chemical (2.0mL), reflux 7 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water cleaning, then use washed with methanol, then with hexane cleaning, and then under reduced pressure, distillation is except desolventizing.Obtained solid is carried out utilize silica gel column chromatography (elutriant: chloroform) to refine, obtain the 3-[5-(4 for target compound, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 1.59g, yield 75%) of-9-phenyl-6-(pyrazinyl) carbazole (A-22).
1H-NMR(CDCl 3)：
δ7.50(t,J＝7.4Hz,1H),7.56-7.72(m,15H),7.89(d,J＝8.3Hz,2H),7.92(d,J＝8.6Hz,1H),8.15(d,J＝8.7Hz,1H),8.20(s,1H),8.51(d,J＝2.5Hz,1H),8.65(s,1H),8.68(d,J＝2.5Hz,1H),8.84(d,J＝8.0Hz,4H),8.99(s,1H),9.00(s,1H),9.10(s,1H),9.21(s,1H).
Embodiment-25
Under argon gas stream, by above-claimed cpd (E-2) (628mg), iodine pyrazine (309mg), cupric oxide (I) (7.2mg), 1,10-phenanthrolene (18mg), 18-are preced with-6-ether (53mg), salt of wormwood (276mg) is suspended in dimethylbenzene (5.0mL), reflux 18 hours.After being let cool by reaction mixture, add water and methyl alcohol.After the solid use water of separating out, methyl alcohol, hexane are cleaned, use dimethylbenzene recrystallization, obtain the 9-pyrazinyl-3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-4 '-(2-pyridyl) biphenyl-3-base] brown powder (output 691mg, yield 98%) of carbazole (A-23).
1H-NMR(CDCl 3)：
δ7.31-7.35(m,1H),7.45(t,J＝7.4Hz,1H),7.56(t,J＝7.7Hz,1H),7.61-7.68(m,6H),7.86-7.89(m,2H),7.94-7.98(m,2H),8.00(d,J＝8.3Hz,2H),8.10(d,J＝8.6Hz,1H),8.22(d,J＝8.5Hz,2H),8.24(s,1H),8.28(d,J＝7.6Hz,1H),8.54(s,1H),8.63(s,1H),8.76(s,1H),8.81(d,J＝4.3Hz,1H),8.85(d,J＝7.8Hz,4H),9.08(s,1H).
Embodiment-26
Under argon gas stream, by above-claimed cpd (E-2) (628mg), 2-bromo pyrimi piperidine (238mg), cupric oxide (I) (7.2mg), 1,10-phenanthrolene (18.0mg), salt of wormwood (276mg), 18-are preced with-6 ethers (52.9mg) and are suspended in dimethylbenzene (5.0mL), heat 60 hours at 150 DEG C.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, with toluene 30ml recrystallization, obtain the 3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-4 '-(2-pyridyl) biphenyl-3-base] the grey powder (output 636mg, yield 90%) of-9-(2-pyrimidyl) carbazole (A-24).
1H-NMR(CDCl 3)：
δ7.16(t,J＝5.0Hz,1H),7.31(m,1H),7.41(t,J＝7.0Hz,1H),7.54-7.66(m,7H),7.82-7.89(m,2H),7.95-8.00(m,3H),8.20-8.23(m,4H),8.64(d,J＝18Hz,1H),8.78-8.84(m,5H),8.89-8.94(m,3H),9.02-9.06(m,2H),9.11(s,1H).
Embodiment-27
Under argon gas stream, by 9-pyrazinyl-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (2.00g), 4-biphenylboronic (875mg), palladium (23mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (97mg) is suspended in the mixed solvent of toluene (34mL) and n-butyl alcohol (3.0mL), add 3M-wet chemical (3.0mL), reflux 24 hours.After being let cool by reaction mixture, add water.The solid use water of separating out, methyl alcohol, hexane are cleaned.After obtained solid re crystallization from toluene, sublimation purifying, obtain the 9-pyrazinyl-3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-1,1 ': 4 '; 1 "-terphenyl-3-base] pale yellow powder (output 329mg, yield 14%) of carbazole (A-25).
1H-NMR(CDCl 3)：
δ7.43(t,J＝7.6Hz,1H),7.46(d,J＝7.8Hz,1H),7.52(d,J＝7.8Hz,1H),7.54-7.58(m,2H),7.61-7.67(m,6H),7.74(d,J＝8.0Hz,2H),7.83(d,J＝8.4Hz,2H),7.94-7.99(m,4H),8.10(d,J＝8.6Hz,1H),8.23(s,1H),8.27(d,J＝7.4Hz,1H),8.53(s,1H),8.63(s,1H),8.77(s,1H),8.85(d,J＝8.0Hz,4H),9.07(s,1H),9.10(s,1H),9.16(s,1H).
Embodiment-28
Under argon gas stream, by above-mentioned N-(2-pyridyl)-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (586mg), 4-biphenylboronic (257mg), palladium (4.5mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (28.6mg) is suspended in the mixed solvent of toluene (20mL) and n-butyl alcohol (0.9mL), add 3M-wet chemical (0.9mL), reflux 18 hours.After being let cool by reaction mixture, add water.The solid use water of separating out, methyl alcohol, hexane are cleaned.After obtained solid re crystallization from toluene, sublimation purifying, obtain 9-(the 2-pyridyl)-3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-1,1 ': 4 '; 1 "-terphenyl-3-base] pale yellow powder (output 171mg, yield 24%) of carbazole (A-26).
1H-NMR(CDCl 3)：
δ7.38-7.45(m,3H),7.51-7.55(m,3H),7.60-7.67(m,6H),7.74(d,J＝8.2Hz,2H),7.76(d,J＝7.1Hz,1H),7.83(d,J＝8.4Hz,2H),7.92(d,J＝8.3Hz,1H),7.93(d,J＝8.5Hz,1H),7.97(d,J＝8.4Hz,2H),8.00-8.04(m,1H),8.05(d,J＝8.5Hz,1H),8.24(s,1H),8.27(d,J＝7,1Hz,1H),8.54(s,1H),8.81-8.82(m,1H),8.85(d,J＝7.9Hz,4H),9.06(s,1H),9.11(s,1H).
Embodiment-29
Under argon gas stream, by above-mentioned N-(2-pyridyl)-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (586mg), the luxuriant and rich with fragrance boric acid (267mg) of 9-, palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), add 3M-wet chemical (0.6mL), reflux 5 hours.Then, add the luxuriant and rich with fragrance boric acid (267mg) of 9-, palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg), and then, reflux 5 hours.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, refine with silica gel chromatography (developing solvent chloroform: hexane=1:9).Used re crystallization from toluene, obtain 3-[5-(9-the phenanthryl)-3-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] the grey powder (output 119mg, yield 16%) of-9-(2-pyridyl) carbazole (A-27).
1H-NMR(CDCl 3)：
δ7.35-7.42(m,2H),7.50(t,J＝7.5Hz,1H),7.54-7.63(m,6H),7.66-7.77(m,4H),7.87(d,J＝8.3Hz,1H),7.94-8.10(m,6H),8.15(t,J＝1.9Hz,1H),8.20(d,J＝7.7Hz,1H),8.52(d,J＝1.3Hz,1H),8.79-8.87(m,8H),8.94(t,J＝1.5Hz,1H),9.22(t,J＝1.7Hz,1H).
Embodiment-30
Under argon gas stream, by above-mentioned N-(2-pyridyl)-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (586mg), 9-anthracene boric acid (666mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), add 3M-wet chemical (0.6mL), reflux 3.5 hours.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, secondly with re crystallization from toluene, obtain 3-[5-(9-the anthryl)-3-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] the grey powder (output 575mg, yield 79%) of-9-(2-pyridyl) carbazole (A-28).
1H-NMR(CDCl 3)：
δ7.35(t,J＝7.1Hz,1H),7.40-7.61(m,13H),7.89(d,J＝8.4Hz,3H),7.97-8.07(m,4H),8.13(d,J＝8.9Hz,2H),8.18(d,J＝8.2Hz,1H),8.52(s,1H),8.61(s,1H),8.76-8.78(m,5H),8.84(s,1H),9.31(s,1H).
Embodiment-31
Under argon gas stream, by above-mentioned N-(2-pyridyl)-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (586mg), 4-dibenzothiophene boric acid (274mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), add 3M-wet chemical (0.6mL), reflux 5 hours.Then, add 4-dibenzothiophene boric acid (274mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg), and then, reflux 5 hours.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, then chloroform heat filtering is used, obtain 3-[5-(dibenzothiophene-4-the base)-3-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] the grey powder (output 213mg, yield 29%) of-9-(2-pyridyl) carbazole (A-29).
1H-NMR(CDCl 3)：
δ7.38(t,J＝7.9Hz,1H),7.48-7.52(m,3H),7.56-7.63(m,6H),7.67(t,J＝7.2Hz,1H),7.74-7.77(m,2H),7.88(d,J＝8.3Hz,2H),7.94-8.04(m,3H),8.23-8.28(m,3H),8.35(d,J＝1.6Hz,1H),8.54(d,J＝1.4Hz,1H),8.80-8.84(m,6H),9.17(d,J＝7.3Hz,2H).
Embodiment-32
Under argon gas stream, by above-mentioned N-(2-pyridyl)-3-[the chloro-5-(4 of 3-, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] carbazole (586mg), 3-quinoline boronic acid (346mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), add 3M-wet chemical (0.6mL), reflux 9 hours.Reaction mixture is let cool, adds methyl alcohol, the solid that leaching is separated out.By obtained solid and 3-quinoline boronic acid (346mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), add 3M-wet chemical (0.6mL), reflux 3 hours again.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, then re crystallization from toluene is used, obtain the 3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base)-3-(3-quinolyl) phenyl] the grey powder (output 541mg, yield 80%) of-9-(2-pyridyl) carbazole (A-30).
1H-NMR(CDCl 3)：
δ7.35-7.41(m,2H),7.50(t,J＝7.4Hz,1H),7.58-7.74(m,8H),7.83(t,J＝6.9Hz,1H),7.91(t,J＝8.5Hz,2H),7.98-8.06(m,3H),8.26-8.33(m,3H),8.53(s,1H),8.65(s,1H),8.79-8.83(m,5H),9.10(s,1H),9.18(s,1H),9.48(s,1H).
Embodiment-33
Under argon gas stream, by above-mentioned 3-[3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-5-(4,6-phenylbenzene-1,3,5-triazine-2-base) phenyl]-9-(2-pyridyl) carbazole (339mg), the bromo-6-phenylpyridine (129mg) of 3-, tetrakis triphenylphosphine palladium (11.6mg) be suspended in Isosorbide-5-Nitrae-two in alkane (2.5mL), add 3M-wet chemical (0.33mL), reflux 20 hours.After being let cool by reaction mixture, add water.Leach the solid of precipitation, with water, methyl alcohol, hexane cleaning, under reduced pressure, heat drying.Used re crystallization from toluene, obtain 3-[5-(6-phenylpyridine-3-the base)-3-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] brown powder (output 207mg, yield 59%) of-9-(2-pyridyl) carbazole (A-31).
1H-NMR(CDCl 3)：
δ7.37-7.43(m,2H),7.49-7.69(m,10H),7.75(d,J＝7.8Hz,1H),7.91-7.93(m,2H),7.99(d,J＝8.3Hz,1H),8.02(t,J＝7.7Hz,1H),8.06(d,J＝8.4Hz,1H),8.16(d,J＝7.3Hz,2H),8.23(s,1H),8.27-8,31(m,2H),8.54(s,1H),8.81-8.86(m,5H),9.07(s,1H),9.17(s,1H),9.27(s,1H).
Embodiment-34
Under argon gas stream, by above-mentioned 3-[3-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base)-5-(4,6-phenylbenzene-1,3,5-triazines-2-base) phenyl]-9-(2-pyridyl) carbazole (678mg), 2-bromine dibenzothiophene (316mg), palladium (2.3mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (9.5mg) is suspended in the mixed solvent of toluene (20.0mL) and n-butyl alcohol (0.6mL), adds 3M-wet chemical (0.6mL), reflux 24 hours.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, then re crystallization from toluene is used, obtain 3-[5-(dibenzothiophene-2-the base)-3-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] the grey powder (output 640mg, yield 87%) of-9-(2-pyridyl) carbazole (A-32).
1H-NMR(CDCl 3)：
δ7.38-7.41(m,2H),7.50-7.53(m,3H),7.58-7.64(m,6H),7.89-7.97(m,4H),8.00-8.06(m,3H),8.22-8.28(m,2H),8.34(t,J＝5.8Hz,1H),8.50-8.59(m,2H),8.78-8.85(m,6H),9.08-9.13(m,2H).
Embodiment-35
Under argon gas stream, the bromo-9-of 3-(2-pyridyl)-6-(quinoline-8-yl) carbazole (946mg) of synthesis in above-claimed cpd (E-1) (1.02g), synthesis example-17, tetrakis triphenylphosphine palladium (46.2mg) are suspended in Isosorbide-5-Nitrae-two in alkane (10mL), add 3M-wet chemical (1.3mL), reflux 13 hours.After being let cool by reaction mixture, add water and methyl alcohol.Leach the solid of precipitation, with water, methyl alcohol, hexane cleaning, by leaching thing under reduced pressure heat drying.By obtained solid dimethylbenzene recrystallization, obtain the 3-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the tawny powder (output 1.08g, yield 72%) of-9-(2-pyridyl)-6-(quinoline-8-yl) carbazole (A-33).
1H-NMR(CDCl 3)：
δ7.39(dd,J＝7.4,4.9Hz,1H),7.45-7.51(m,2H),7.56-7.65(m,8H),7.71(t,J＝7.3Hz,1H),7.83(d,J＝8.1Hz,1H),7.86-7.91(m,4H),7.93-7.96(m,2H),8.00-8.05(m,1H),8.03(d,J＝8.6Hz,1H),8.11(d,J＝8.6Hz,1H),8.20(s,1H),8.31(d,J＝8.1Hz,1H),8.56(s,1H),8.58(s,1H),8.82-8.85(m,5H),9.00(s,1H),9.06-9.07(m,1H),9.11(s,1H).
Embodiment-36
Under argon gas stream, by 2-[4-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) phenyl]-4,6-phenylbenzene-1,3,5-triazine (1.31g), the bromo-9-of 3-(2-pyridyl)-6-[4-(2-pyridyl) phenyl] carbazole (1.57g), tetrakis triphenylphosphine palladium (69.3mg) are suspended in Isosorbide-5-Nitrae-two in the mixed solvent of alkane (20mL) and 3M-wet chemical (2.0mL), reflux 13 hours.After being cooled to room temperature, add water and methyl alcohol.The solid use water of separating out, methyl alcohol, hexane are cleaned, by leaching thing dimethylbenzene recrystallization, obtain the 3-[4-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) phenyl] brown solid (output 1.33g, yield 63%) of-9-(2-pyridyl)-6-[4-(2-pyridyl) phenyl] carbazole (A-34).
1H-NMR(DMSO-d 6)：
δ7.26-7.29(m,1H),7.38(dd,J＝7.5Hz,4.9Hz,1H),7.60-7.68(m,6H),7.74(d,J＝8.0Hz,1H),7.81(d,J＝8.7Hz,2H),7.83-7.86(m,2H),7.90(d,J＝8.5Hz,2H),7.96-8.03(m,5H),8.16(d,J＝8.5Hz,2H),8.51(s,1H),8.54(s,1H),8.76(d,J＝4.6Hz,1H),8.80(d,J＝4.9Hz,1H),8.83(d,J＝7.9Hz,4H),8.91(d,J＝8.5Hz,2H).
Embodiment-37
Under argon gas stream, by above-claimed cpd (E-1) (1.02g), 3-bromo-6,9-bis-(2-pyridyl) carbazole (961mg), palladium (4.5mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (19.0mg) is suspended in Isosorbide-5-Nitrae-two in alkane (40.0mL), add 3M-wet chemical (1.3mL), heat 4 hours at 95 DEG C.After being let cool by reaction mixture, add methyl alcohol, the solid that leaching is separated out.By obtained solid use water, methyl alcohol, hexane cleaning, then re crystallization from toluene is used, obtain the 6-[5-(4 of target thus, 6-phenylbenzene-1,3,5-triazine-2-base) biphenyl-3-base] the grey powder (output 492mg, yield 35%) of-3,9-bis-(2-pyridyl) carbazole (A-35).
1H-NMR(CDCl 3)：
δ7.26-7.29(m,1H),7.41(dd,J＝7.4,4.9Hz,1H),7.50(t,J＝7.4Hz,1H),7.58-7.66(m,8H),7.78(d,J＝8.0Hz,1H),7.84(t,J＝7.7Hz,1H),7.88-7.92(m,2H),7.95(d,J＝8.6Hz,2H),8.00(d,J＝8.6Hz,1H),8.04(t,J＝7.7Hz,1H),8.06(d,J＝8.6Hz,1H),8.18-8.23(m,2H),8.64(s,1H),8.78(d,J＝4.8Hz,1H),8.83(d,J＝4.9Hz,1H),8.85(d,J＝7.8Hz,4H),8.95(s,1H),9.02(s,1H),9.11(s,1H).
Embodiment-38
Under argon gas stream, by 2-(3,5-dibromo phenyl)-4,6-diphenylpyrimidin (466mg), 9-anthracene boric acid (233mg) and tetrakis triphenylphosphine palladium (23mg) are suspended in the mixed solvent of 4N-aqueous sodium hydroxide solution (0.5mL) and THF (2.0mL), stir 3 hours at 30 DEG C.Then, add water, filter the solid of separating out, with water cleaning, then use washed with methanol, then with hexane cleaning, obtain white-yellowish solid 500mg.
The toluene solution (53 μ L) of obtained white-yellowish solid (500mg), 3-[4-(2-pyridyl) phenyl] carbazole (285mg), palladium (4mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (246mg) and 18-are preced with-6-ether (47mg) to be suspended in dimethylbenzene (4.4mL), reflux 5 hours.After being let cool by reaction mixture, use chloroform extraction.Organic layer silica gel chromatography (developing solvent: chloroform) is refined, obtain 3-[4-(2-pyridyl) phenyl]-9-[3-(4,6-diphenylpyrimidin-2-base)-5-(anthracene-9-base)] yellow solid (output 580mg, yield 72%) of phenyl carbazole (B-1).
1H-NMR(CDCl 3)：
δ7.29(t,J＝5.9Hz,1H),7.48(t,J＝7.4Hz,1H),7.54-7.64(m,11H),7.79(t,J＝8.0Hz,1H),7.83(d,J＝7.9Hz,1H),7.86-7.07(m,6H),8.12(d,J＝7.5Hz,2H),8.16(s,1H),8.19-8.24(m,4H),8.33-8.38(m,5H),8.58(s,1H),8.67(s,1H),8.84(d,J＝4.8Hz,1H),9.13(s,1H),9.38(s,1H).
Embodiment-39
Under argon gas stream, by 2-(5-chlordiphenyl-3-base)-4, the toluene solution (465 μ L) of 6-diphenylpyrimidin (3.25g), 3-[4-(2-pyridyl) phenyl] carbazole (2.73g), palladium (34.8mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (2.14g) and 18-are preced with-6-ether (410mg) and are suspended in dimethylbenzene (39mL), reflux 18 hours.After being let cool by reaction mixture, use chloroform extraction.Organic layer silica gel chromatography (developing solvent: chloroform) is refined, obtain 3-[4-(2-pyridyl) phenyl]-9-[5-(4 for target compound, 6-diphenylpyrimidin-2-base) biphenyl-3-base] brown powder (output 5.03g, yield 92%) of carbazole (B-2).
1H-NMR(CDCl 3)：
δ7.28(dd,J＝7.0,4.8Hz,1H),7.39(t,J＝7.4Hz,1H),7.47(t,J＝7.4Hz,1H),7.51(t,J＝7.7Hz,1H),7.55-7.64(m,9H),7.68(d,J＝8.6Hz,1H),7.78-7.87(m,5H),7.90(d,J＝8.5Hz,2H),8.00(s,1H),8.13(s,1H),8.17(d,J＝8.5Hz,2H),8.329-8.35(m,5H),8.51(s,1H),8.76(d,J＝4.8Hz,1H),8.97(s,1H),9.12(s,1H).
Embodiment-40
Under argon gas stream, by 2-(5-chlordiphenyl-3-base)-4, the toluene solution (172 μ L) of 6-diphenylpyrimidin (1.20g), 3-(2-pyridyl) carbazole (770mg), palladium (12.8mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (791mg) and 18-are preced with-6-ether (151mg) and are suspended in dimethylbenzene (14mL), reflux 44 hours.After being let cool by reaction mixture, use chloroform extraction.Organic layer silica gel chromatography (developing solvent: chloroform) is refined, obtain 3-(the 2-pyridyl)-9-[5-(4 for target compound, 6-diphenylpyrimidin-2-base) biphenyl-3-base] brown powder (output 949mg, yield 53%) of carbazole (B-3).
1H-NMR(CDCl 3)：
δ7.25(dd,J＝7.2,4.8Hz,1H),7.38(t,J＝7.4Hz,1H),7.47(t,J＝7.4Hz,1H),7.50(t,J＝7.7Hz,1H),7.54-7.62(m,9H),7.66(d,J＝8.8Hz,1H),7.81(t,J＝7.7Hz,1H),7.84(d,J＝8.0Hz,2H),7.90(d,J＝8.0Hz,1H),7.99(s,1H),8.12(d,J＝8.6Hz,1H),8.13(s,1H),8.29-8.33(m,5H),8.77(d,J＝4.8Hz,1H),8.91(s,1H),8.96(s,1H),9.11(s,1H).
Embodiment-41
Under argon gas stream, by 9-(2-pyridyl)-9-[the chloro-5-(4 of 3-, 6-diphenylpyrimidin-2-base) phenyl] carbazole (1.17g), phenyl-boron dihydroxide (293mg), palladium (9.0mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (57mg) and 3M-wet chemical (1.6mL) are suspended in the mixed solvent of toluene (9.0mL) and propyl carbinol (1.0mL), reflux 3 hours.After being let cool by reaction mixture, add water, use chloroform extraction.Then, after organic layer dried over mgso, filter, underpressure distillation is except desolventizing.Then, hexane is added in concentrated organic layer, make solid redeposition, obtain 9-(the 2-pyridyl)-3-[5-(4 into target compound thus, 6-diphenylpyrimidin-2-base) biphenyl-3-base] brown powder (output 900mg, yield 72%) of carbazole (B-4).
1H-NMR(CDCl 3)：
δ7.28(dd,J＝7.4,4.9Hz,1H),7.40(t,J＝7.4Hz,1H),7.47-7.54(m,2H),7.57-7.64(m,8H),7.73(d,J＝8.1Hz,1H),7.89-7.94(m,4H),7.98(t,J＝7.7Hz,1H),8.02(d,J＝8.5Hz,1H),8.07(s,1H),8.12(s,1H),8.25(d,J＝7.4Hz,1H),8.349-8.37(m,4H),8.54(s,1H),8.81(d,J＝4.9Hz,1H),8.99(s,1H),9.08(s,1H).
Embodiment-42
Under argon gas stream, by 9-(2-pyridyl)-9-[the chloro-5-(4 of 3-, 6-diphenylpyrimidin-2-base) phenyl] carbazole (585mg), 4-(2-pyridyl) phenyl-boron dihydroxide (239mg), palladium (4.5mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (29mg) and 3M-wet chemical (0.8mL) are suspended in the mixed solvent of toluene (4.5mL) and propyl carbinol (0.5mL), reflux 3 hours.After reaction mixture is let cool, add water and Methanol form slurry, solid is separated out.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(the 2-pyridyl)-3-[5-(4 for target compound, 6-diphenylpyrimidin-2-base)-4 '-(2-pyridyl) biphenyl-3-base] brown powder (output 676mg, yield 96%) of carbazole (B-5).
1H-NMR(CDCl 3)：
δ7.28(t,J＝6.0Hz,1H),7.34(dd,J＝7.2,5.0Hz,1H),7.39(t,J＝7.5Hz,1H),7.52(t,J＝7.5Hz,1H),7.56-7.63(m,6H),7.71(d,J＝8.0Hz,1H),7.78-7.85(m,2H),7.91-8.02(m,6H),8.05(s,1H),8.15(s,1H),8.21(d,J＝8.3Hz,2H),8.25(d,J＝7.7Hz,1H),8.35(d,J＝7.8Hz,4H),8.53(s,1H),8.78(d,J＝4.8Hz,1H),8.80(d＝4.4Hz,1H),9.03(s,1H),9.08(s,1H).
Embodiment-43
Under argon gas stream, by 9-(2-pyridyl)-9-[the chloro-5-(4 of 3-, 6-diphenylpyrimidin-2-base) phenyl] carbazole (1.17g), 4-(2-pyrazinyl) phenyl-boron dihydroxide (480mg), palladium (9.0mg), 2-dicyclohexylphosphontetrafluoroborate-2 ', 4 ', 6 '-tri isopropyl biphenyl (57mg) and 3M-wet chemical (1.6mL) are suspended in the mixed solvent of toluene (9.0mL) and propyl carbinol (1.0mL), reflux 2 hours.After being let cool by reaction mixture, add water.Filter the solid of separating out, clean with water, then washed with methanol is used, then clean with hexane, obtain 9-(the 2-pyridyl)-3-[5-(4 for target compound, 6-diphenylpyrimidin-2-base)-4 '-(2-pyrazinyl) biphenyl-3-base] brown powder (output 1.25g, yield 89%) of carbazole (B-6).
1H-NMR(CDCl 3)：
δ7.34-7.40(m,2H),7.51(t,J＝7.7Hz,1H),7.56-7.63(m,6H),7.72(d,J＝8.0Hz,1H),7.91(d,J＝8.5Hz,1H),7.92(d,J＝8.2Hz,1H),7.96-8.03(m,4H),8.06(s,1H),8.13(s,1H),8.21-8.25(m,3H),8.33-8.35(m,4H),8.52(s,1H),8.56(s,1H),8.70(s,1H),8.80(d,J＝4.8Hz,1H),9.01(s,1H),9.08(s,1H),9.15(s,1H).
Embodiment-44
Under argon gas stream, the toluene solution (30 μ L) of 3-(quinoline-8-yl) carbazole (162mg) of synthesis in 4-(4-bromophenyl)-6-(1-the naphthyl)-2-phenyl pyrimidine (219mg) of synthesis in synthesis example-20, synthesis example-15, palladium (2.2mg), 1M-tri-(tertiary butyl) phosphine, salt of wormwood (152mg), 18-are preced with-6-ether (26mg) and are suspended in dimethylbenzene (2.5mL), reflux 20 hours.After being let cool by reaction mixture, filter unwanted material by crossing.Filtrate is refined with silica gel chromatography (developing solvent chloroform), obtain the yellow powder (output 297mg, yield 91%) of 9-[4-(6-naphthyl-2-phenyl pyrimidine-4-base) phenyl]-3-(quinoline-8-yl) carbazole (B-7) of target.
1H-NMR(CDCl 3)：
δ7.35(t,J＝7.4Hz,1H),7.47(d,J＝8.0Hz,1H),7.47-7.50(m,1H),7.56-7.63(m,6H),7.66-7.72(m,3H),7.85(d,J＝8.5Hz,1H),7.88(d,J＝8.6Hz,2H),7.86-7.93(m,3H),8.00-8.02(m,1H),8.04(s,1H),8.06(d,J＝8.2Hz,1H),8.21(d,J＝7.6Hz,1H),8.29(d,J＝8.3Hz,1H),8.43-8.46(m,1H),8.48(s,1H),8.60(d,J＝8.6Hz,2H),8.76-8.79(m,2H),9.04(d,J＝4.1Hz,1H).
< take cyclic azine as making and the performance evaluation > of the organic electroluminescent device of constituent
Following embodiment, reference example and comparative example include making and the performance evaluation of electro-luminescence element.
The structural formula of the compound used is as follows.
Embodiment-45
With regard to substrate, wide Indium sesquioxide-Xi (ITO) film patterning of 2mm is used to be the glass substrate of the band ito transparent electrode of striated.By this substrate with after Virahol cleaning, carry out surface treatment with oxygen plasma cleaning.With vacuum vapour deposition, the substrate after cleaning is carried out to the vacuum evaporation of each layer, make sectional view light-emitting area 4mm as shown in Figure 1 2organic electroluminescent device.
First, in vacuum evaporation groove, import above-mentioned glass substrate, be decompressed to 1.0 × 10 -4pa.Then, on the glass substrate of the band ito transparent electrode shown in 1 of Fig. 1 successively film forming as the hole injection layer 2 of organic compound layer, hole transmission layer 3, luminescent layer 4 and electron transfer layer 5, then, film forming cathode layer 6.It should be noted that, be formed with the material use resistance heating manner vacuum evaporation of each layer of electro-luminescence element.
As hole injection layer 2, by the CuPc of sublimation purifying with the film forming speed of 0.06nm/ second with the thickness vacuum evaporation of 25nm.
As hole transmission layer 3, by NPD with the film forming speed of 0.30nm/ second with the thickness vacuum evaporation of 45nm.
As luminescent layer 4, by EML-1 and EML-2 with the film forming speed of 0.18nm/ second with the thickness of 40nm (the common evaporation of EML-1/EML-2=95/5 (weight ratio)) vacuum evaporation.
As electron transfer layer 5, by the A-1 of synthesis in embodiments of the invention 1 with the film forming speed of 0.25nm/ second with the thickness vacuum evaporation of 20nm.
Finally, configure metal mask in the mode vertical with ITO striped, film forming cathode layer 6.Anticathode layer 6, by lithium fluoride and aluminium successively respectively with the film forming speed of 0.1nm/ second and 0.25nm/ second with the thickness vacuum evaporation of 1.0nm and 100nm, make 2 Rotating fields.
Respective thickness measures with contact pin type elcometer (DEKTAK, Veeco Inc.).
And then, this element is sealed in the nitrogen atmosphere glove box of oxygen and below moisture concentration 1ppm.Sealing uses seal cap and the above-mentioned substrate for film deposition epoxy type ultraviolet curable resin (Nagasechemtex Inc.) of glass.
Embodiment-46
In the electron transfer layer 5 of embodiment-45, use the A-3 of synthesis in embodiment 3 to replace A-1, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-45.
Embodiment-47
In the electron transfer layer 5 of embodiment-45, use the A-6 of synthesis in embodiment 6 to replace A-1, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-45.
Reference example-1
In the electron transfer layer 5 of embodiment-31, be used as the ETL-1 of known electron transport material to replace A-1, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-45.
Galvanic current is applied to the organic electroluminescent device made, uses the luminance meter of the LUMINANCE METER (BM-9) of TOPCON Inc. to evaluate the characteristics of luminescence.As life characteristic, to circulating current density 20mA/cm 2time, brightness decay time when lighting continuously measures.By brightness (cd/m 2) time when reducing 20% is shown in following.
[table 1]
As shown in Table 1, compared with reference example, the life characteristic employing the organic electroluminescent device of cyclic azine derivative of the present invention is excellent.
Embodiment-48
In the luminescent layer 4 of embodiment-45, TBADN and EML-2 is carried out vacuum evaporation with the film forming speed of 0.18nm/ second with the thickness of 40nm (the common evaporation of TBADN/EML-2=95/5 (weight ratio)), replaces EML-1 and EML-2 to carry out vacuum evaporation with the film forming speed of 0.18nm/ second with the thickness of 40nm (the common evaporation of EML-1/EML-2=95/5 (weight ratio)).
In addition, in electron transfer layer 5, replace A-1 to carry out vacuum evaporation with the film forming speed of 0.25nm/ second with the thickness of 20nm with A-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-45.
Embodiment-49
In the electron transfer layer 5 of embodiment-48, use the A-10 of synthesis in embodiment 10 to replace A-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-48.
Comparative example-1
In the electron transfer layer 5 of embodiment-48, use the ETL-2 recorded in patent documentation 4 to replace A-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-48.
Galvanic current is applied to the organic electroluminescent device made, uses the luminance meter of the LUMINANCE METER (BM-9) of TOPCON Inc. to evaluate the characteristics of luminescence.By brightness (cd/m 2) time when reducing 20% and in the component with 20mA/cm 2density flow galvanization time voltage and efficiency be shown in following.
[table 2]
By table 2 illustrate, cyclic azine compound (1) of the present invention and existing known Compound Phase ratio, the electron injection of organic electroluminescent device, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [cd/A]) and component life significantly improve.
Embodiment-50
For substrate, wide Indium sesquioxide-Xi (ITO) film patterning of 2mm is used to be the glass substrate of the band ito transparent electrode of striated.By this substrate with after Virahol cleaning, with oxygen plasma cleaning, carry out surface treatment.With vacuum vapour deposition, the substrate after cleaning is carried out to the vacuum evaporation of each layer, make sectional view light-emitting area 4mm as shown in Figure 2 2organic electroluminescent device.
First, in vacuum evaporation groove, import above-mentioned glass substrate, be decompressed to 1.0 × 10 -4pa.Then, on the glass substrate of the band ito transparent electrode shown in 11 of Fig. 2 successively film forming as hole injection layer 12, first hole transmission layer 13, second hole transmission layer 14 of organic compound layer, luminescent layer 15 and electron transfer layer 16, then, film forming cathode layer 17.It should be noted that, be formed with the material use resistance heating manner vacuum evaporation of each layer of electro-luminescence element.
As hole injection layer 12, HTL-1 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 40nm.
As the first hole transmission layer 13, HAT-CN is carried out vacuum evaporation with the film forming speed of 0.025nm/ second with the thickness of 5nm.
As the second hole transmission layer 14, HTL-2 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 25nm.
As luminescent layer 15, EML-1 and EML-2 is carried out vacuum evaporation with the film forming speed of 0.18nm/ second with the thickness of 40nm (the common evaporation of EML-1/EML-2=95/5 (weight ratio)).
As electron transfer layer 16, the B-2 of synthesis in embodiments of the invention 39 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 30nm.
Finally, configure metal mask in the mode vertical with ITO striped, film forming cathode layer 17.Anticathode layer 17, by Liq, magnesium/silver (weight ratio 80/20), silver successively respectively with the film forming speed of 0.005nm/ second, 0.5nm/ second, 0.2nm/ second with the thickness vacuum evaporation of 0.5nm, 80nm, 20nm, make 3-tier architecture.
Respective thickness measures with contact pin type elcometer (DEKTAK, Veeco Inc.).
And then, this element is sealed in the nitrogen atmosphere glove box of oxygen and below moisture concentration 1ppm.Sealing uses seal cap and the above-mentioned substrate for film deposition epoxy type ultraviolet curable resin (Nagasechemtex Inc.) of glass.
Embodiment-51
In the electron transfer layer 16 of embodiment-50, use the B-3 of synthesis in embodiment 40 to replace B-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-50.
Embodiment-52
In the electron transfer layer 16 of embodiment-50, use the B-4 of synthesis in embodiment 41 to replace B-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-50.
Embodiment-53
In the electron transfer layer 16 of embodiment-50, use the B-5 of synthesis in embodiment 42 to replace B-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 50.
Embodiment-54
In the electron transfer layer 16 of embodiment-50, use the B-6 of synthesis in embodiment 43 to replace B-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-50.
Comparative example-2
In the electron transfer layer 16 of embodiment-50, use ETL-3 to replace B-2, in addition, be manufactured with electro-luminescence element with the method identical with embodiment-50.
Galvanic current is applied to the organic electroluminescent device made, uses the luminance meter of the LUMINANCE METER (BM-9) of TOPCON Inc. to evaluate the characteristics of luminescence.As life characteristic, to circulating current density 20mA/cm 2time, brightness decay time when lighting continuously measures.By brightness (cd/m 2) time when reducing 10% and in the component with 20mA/cm 2density flow galvanization time voltage and efficiency be shown in following.
[table 3]
By table 3 illustrate, cyclic azine compound (1) of the present invention and existing known Compound Phase ratio, the electron injection of organic electroluminescent device, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [cd/A]) and component life significantly improve.
Embodiment-55
With regard to substrate, wide Indium sesquioxide-Xi (ITO) film patterning of 2mm is used to be the glass substrate of the band ito transparent electrode of striated.By this substrate with after Virahol cleaning, with oxygen plasma cleaning, carry out surface treatment.With vacuum vapour deposition, the substrate after cleaning is carried out to the vacuum evaporation of each layer, make sectional view light-emitting area 4mm as shown in Figure 2 2organic electroluminescent device.
First, in vacuum evaporation groove, import above-mentioned glass substrate, be decompressed to 1.0 × 10 -4pa.Then, on the glass substrate of the band ito transparent electrode shown in 11 of Fig. 2 successively film forming as hole injection layer 12, first hole transmission layer 13, second hole transmission layer 14 of organic compound layer, luminescent layer 15 and electron transfer layer 16, then, film forming cathode layer 17.It should be noted that, be formed with the material use resistance heating manner vacuum evaporation of each layer of electro-luminescence element.
As hole injection layer 12, by HTL-1 with the film forming speed of 0.15nm/ second with the thickness vacuum evaporation of 45nm.
As the first hole transmission layer 13, HAT-CN is carried out vacuum evaporation with the film forming speed of 0.025nm/ second with the thickness of 5nm.
As the second hole transmission layer 14, HTL-2 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 30nm.
As luminescent layer 15, EML-1 and EML-2 is carried out vacuum evaporation with the film forming speed of 0.18nm/ second with the thickness of 20nm (the common evaporation of EML-1/EML-2=96/4 (weight ratio)).
As electron transfer layer 16, the A-3 of synthesis in embodiments of the invention 3 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 30nm.
Finally, configure metal mask in the mode vertical with ITO striped, film forming cathode layer 17.Anticathode layer 17, carries out vacuum evaporation with the film forming speed of 0.005nm/ second, 0.5nm/ second, 0.2nm/ second with the thickness of 0.5nm, 80nm, 20nm respectively successively by lithium fluoride, magnesium/silver (weight ratio 80/20), silver, makes 3-tier architecture.
Respective thickness measures with contact pin type elcometer (DEKTAK, Veeco Inc.).
And then, this element is sealed in the nitrogen atmosphere glove box of oxygen and below moisture concentration 1ppm.Sealing uses seal cap and the above-mentioned substrate for film deposition epoxy type ultraviolet curable resin (Nagasechemtex Inc.) of glass.
Embodiment-56
In the electron transfer layer 16 of embodiment-55, use the A-13 of synthesis in embodiment 13 to replace A-3, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 55.
Embodiment-57
In the electron transfer layer 16 of embodiment-55, use the B-5 of synthesis in embodiment 42 to replace A-3, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 55.
Reference example-2
In the electron transfer layer 16 of embodiment-55, use ETL-1 to replace A-3, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 55.
Galvanic current is applied to the organic electroluminescent device made, uses the luminance meter of the LUMINANCE METER (BM-9) of TOPCON Inc. to evaluate the characteristics of luminescence.As life characteristic, to circulating current density 20mA/cm 2time, brightness decay time when lighting continuously measures.By brightness (cd/m 2) time when reducing 20% and in the component with 10mA/cm 2density flow galvanization time voltage and efficiency be shown in following.
[table 4]
By table 4 illustrate, cyclic azine compound (1) of the present invention and existing known Compound Phase ratio, the driving voltage (voltage [V]) of organic electroluminescent device, current efficiency (efficiency [cd/A]) and life characteristic are excellent.
Embodiment-58
With regard to substrate, wide Indium sesquioxide-Xi (ITO) film patterning of 2mm is used to be the glass substrate of the band ito transparent electrode of striated.By this substrate with after Virahol cleaning, with oxygen plasma cleaning, carry out surface treatment.With vacuum vapour deposition, the substrate after cleaning is carried out to the vacuum evaporation of each layer, make sectional view light-emitting area 4mm as shown in Figure 2 2organic electroluminescent device.
First, in vacuum evaporation groove, import above-mentioned glass substrate, be decompressed to 1.0 × 10 -4pa.Then, on the glass substrate of the band ito transparent electrode shown in 11 of Fig. 2 successively film forming as hole injection layer 12, first hole transmission layer 13, second hole transmission layer 14 of organic compound layer, luminescent layer 15 and electron transfer layer 16, then, film forming cathode layer 17.It should be noted that, the material use resistance heating manner being formed with each layer of electro-luminescence element carries out vacuum evaporation.
As hole injection layer 12, HTL-1 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 65nm.
As the first hole transmission layer 13, HAT-CN is carried out vacuum evaporation with the film forming speed of 0.025nm/ second with the thickness of 5nm.
As the second hole transmission layer 14, HTL-2 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 10nm.
As luminescent layer 15, EML-1 and EML-2 is carried out vacuum evaporation with the film forming speed of 0.18nm/ second with the thickness of 25nm (the common evaporation of EML-1/EML-2=96/4 (weight ratio)).
As electron transfer layer 16, the A-12 of synthesis in embodiments of the invention 12 is carried out vacuum evaporation with the film forming speed of 0.15nm/ second with the thickness of 30nm.
It should be noted that, each organic materials utilizes resistance heating manner film forming, and the compound of heating is carried out vacuum evaporation with the film forming speed of 0.3 ~ 0.5nm/ second.
Finally, metal mask is configured in the mode of vertical with ITO striped (craspedodrome), film forming cathode layer 17.Anticathode layer 7, carries out vacuum evaporation with the film forming speed of 0.005nm/ second, 0.5nm/ second, 0.2nm/ second with the thickness of 0.5nm, 80nm, 20nm respectively successively by Liq, magnesium/silver (weight ratio 80/20), silver, makes 3-tier architecture.
Respective thickness measures with contact pin type elcometer (DEKTAK, Veeco Inc.).And then, this element is sealed in the nitrogen atmosphere glove box that oxygen and moisture concentration are below 1ppm.Sealing uses seal cap and the above-mentioned substrate for film deposition epoxy type ultraviolet curable resin (Nagasechemtex Inc.) of glass.
Embodiment-59
In the electron transfer layer 16 of embodiment-58, use the A-16 of synthesis in embodiment 16 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Embodiment-60
In the electron transfer layer 16 of embodiment-58, use the A-17 of synthesis in embodiment 18 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Embodiment-61
In the electron transfer layer 16 of embodiment-58, use the A-18 of synthesis in embodiment 19 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Embodiment-62
In the electron transfer layer 16 of embodiment-58, use the A-19 of synthesis in embodiment 20 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Embodiment-63
In the electron transfer layer 16 of embodiment-58, use the A-20 of synthesis in embodiment 21 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Embodiment-64
In the electron transfer layer 16 of embodiment-58, use the A-22 of synthesis in embodiment 24 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Comparative example-3
In the electron transfer layer 16 of embodiment-58, use the ETL-4 of synthesis in synthesis example-21 to replace A-12, in addition, be manufactured with electro-luminescence element with the method identical with embodiment 58.
Galvanic current is applied to the organic electroluminescent device made, uses the luminance meter of the LUMINANCE METER (BM-9) of TOPCON Inc. to evaluate the characteristics of luminescence.As life characteristic, to circulating current density 20mA/cm 2time, brightness decay time when lighting continuously measures.By brightness (cd/m 2) time when reducing 10% and in the component with 10mA/cm 2density flow galvanization time voltage be shown in following.
[table 5]
By table 5 illustrate, cyclic azine compound (1) of the present invention and existing known Compound Phase ratio, the driving voltage (voltage [V]) of organic electroluminescent device and life characteristic excellence.
So known, employ the organic electroluminescent device of cyclic azine compound (1) of the present invention and existing known Compound Phase ratio, the element characteristic such as driving voltage, current efficiency, component life of organic electroluminescent device is significantly excellent.
Industrial applicibility
Employ the organic electroluminescent device of cyclic azine compound of the present invention compared with the organic electroluminescent device employing current material, can drive for a long time, be not only applicable to the element employing fluorescence luminescent material, also can be applicable to the various organic electroluminescent devices etc. employing phosphorescent light-emitting materials, industrially very useful.
In addition, the solubleness of cyclic azine compound of the present invention is also better, not only vacuum vapour deposition can be adopted, also coating method can be adopted to make element, except electron transfer layer, also can be used as the application such as luminous main stor(e)y, and then, except the purposes such as flat-faced screen, also useful in lighting use seeking low power consumption etc.
It should be noted that, quote at this No. 2012-136711, Japanese patent application applied on June 18th, 2012, the full content of the specification sheets of No. 2012-247767, Japanese patent application that on November 9th, 2012 applies for and No. 2012-279641, Japanese patent application applying on December 21st, 2012, claims, accompanying drawing and summary, the disclosure received as specification sheets of the present invention.

Claims (22)

1. a cyclic azine compound, it is represented by general formula (1),
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5separately represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M separately represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
2. cyclic azine compound as claimed in claim 1, wherein, general formula (1) is represented by general formula (B), (C) or (D),
In formula (D), the carbolinyl of Cb represents (n+1) valency,
In formula (B), (C) and (D),
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
Ar 3separately represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
N separately represents the integer of 1 ~ 7,
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
3. as cyclic azine compound according to claim 1 or claim 2, wherein,
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4, and
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 is separately the nitrogen-containing hetero aryl of the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 be only made up of carbon, hydrogen and nitrogen or the carbonatoms 3 ~ 30 be only made up of carbon, hydrogen, nitrogen and sulphur,
Wherein, the nitrogen-containing hetero aryl of the described carbonatoms 3 ~ 30 be only made up of carbon, hydrogen and nitrogen can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
The nitrogen-containing hetero aryl of the described carbonatoms 3 ~ 30 be only made up of carbon, hydrogen, nitrogen and sulphur can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
4. the cyclic azine compound according to any one of claim 1 to claim 3, wherein,
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4, and
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 separately for being only made up of carbon, hydrogen and nitrogen, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
5. the cyclic azine compound according to any one of claim 1 to claim 4, wherein,
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4, and
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 is separately pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, pyridinylphenyl or 1-(3,5-bipyridyl) phenyl, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
6. the cyclic azine compound according to any one of claim 1 to claim 5, wherein,
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4, and
Ar 4and Ar 6the nitrogen-containing hetero aryl of shown carbonatoms 3 ~ 30 is separately pyridyl, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
7. the cyclic azine compound according to any one of claim 1 to claim 6, wherein, Ar 1and Ar 2be separately phenyl, xenyl, naphthyl, anthryl, pyrenyl, terphenyl or phenanthryl, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
8. the cyclic azine compound according to any one of claim 1 to claim 7, wherein, Ar 1and Ar 2be separately phenyl or xenyl, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
9. the cyclic azine compound according to any one of claim 1 to claim 8, wherein, Ar 1and Ar 2be separately phenyl, aminomethyl phenyl or xenyl.
10. the cyclic azine compound according to any one of claim 1 to claim 9, wherein, Ar 3for phenylene or biphenylene, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
11. cyclic azine compounds according to any one of claim 1 to claim 10, wherein, Ar 5for the phenyl of (m+1) valency or the xenyl of (m+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4.
12. cyclic azine compounds according to any one of claim 1 to claim 11, wherein, Y and Z is nitrogen-atoms, or Y be CH, Z is nitrogen-atoms.
13. cyclic azine compounds according to any one of claim 1 to 12, wherein, n is 1,2 or 3.
14. cyclic azine compounds according to any one of claim 1 to 13, wherein, m is 1 or 2.
The manufacture method of the cyclic azine compound shown in 15. 1 kinds of general formulas (1), the method comprises: make the compound shown in the compound shown in general formula (2) and general formula (3) carry out linked reaction under the existence of metal catalyst or under the existence of alkali and metal catalyst
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
H nrepresent the hydrogen atom on nitrogen-atoms in Cz,
X 1represent leavings group,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
The manufacture method of the cyclic azine compound shown in 16. 1 kinds of general formulas (1), the method comprises: make the compound shown in the compound shown in general formula (4) and general formula (5) under the existence of metal catalyst or carry out linked reaction under the existence of alkali and metal catalyst
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
M and X 2represent leavings group,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
The manufacture method of the cyclic azine compound shown in 17. 1 kinds of general formulas (1), the method comprises: make the compound shown in the compound shown in general formula (6) and general formula (7) under the existence of metal catalyst or carry out linked reaction under the existence of alkali and metal catalyst
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
H nrepresent the hydrogen atom on the nitrogen-atoms in Cz,
X 3represent leavings group,
N is 1,
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
The manufacture method of the cyclic azine compound shown in 18. 1 kinds of general formulas (1), the method comprises: make the compound shown in the compound shown in general formula (8) and general formula (9) under the existence of metal catalyst or carry out linked reaction under the existence of alkali and metal catalyst
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
M and X 4represent leavings group,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
19. 1 kinds of organic electroluminescent devices, it contains the cyclic azine compound shown in general formula (1),
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
20. organic electroluminescent devices as claimed in claim 19, wherein, containing the cyclic azine compound shown in general formula (1) in any layer in hole blocking layer, electron transfer layer or electron injecting layer.
The life method of 21. 1 kinds of organic electroluminescent devices, the method comprises: the cyclic azine compound shown in general formula (1) is used for electron transfer layer,
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), wherein, the nitrogen-containing hetero aryl of described carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
22. 1 kinds make organic electroluminescent device current consumption reduction method, and the method comprises: the cyclic azine compound shown in general formula (1) is used for electron transfer layer,
In formula, Cz represents (n+1) carbazyl of valency or the carbolinyl of (n+1) valency, these groups can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 6 ~ 18 aromatic hydrocarbyl, there is fluorine atom and the aromatic hydrocarbyl of carbonatoms 6 ~ 18 or replaced and the aromatic hydrocarbyl alternatively base of carbonatoms 6 ~ 18 by the alkyl of carbonatoms 1 ~ 4
Ar 1and Ar 2separately represent the aromatic hydrocarbyl of carbonatoms 6 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 3represent the arylidene of carbonatoms 6 ~ 30, they can have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 4separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30 or the substituting group shown in general formula (A), the nitrogen-containing hetero aryl of wherein said carbonatoms 3 ~ 30 can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Y and Z separately represents nitrogen-atoms or CH, and wherein, at least one in Y and Z is nitrogen-atoms,
N represents the integer of 1 ~ [the upper maximum bonding number-1 formed of Cz],
-Ar 5-(Ar 6) m(A)
In formula, Ar 5represent the aryl of the carbonatoms 6 ~ 30 of (m+1) valency, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
Ar 6separately represent the nitrogen-containing hetero aryl of carbonatoms 3 ~ 30, they can separately have fluorine atom, the alkyl of carbonatoms 1 ~ 4, carbonatoms 3 ~ 18 aromatic group, there is fluorine atom and the aromatic group of carbonatoms 3 ~ 18 or the aromatic group alternatively base of carbonatoms 3 ~ 18 that replaced by the alkyl of carbonatoms 1 ~ 4
M represents 1 ~ [Ar 5on the maximum bonding number-1 that can be formed] integer.
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