CN106893581B - Organic electroluminescent compounds, organic electroluminescence device and its application - Google Patents

Organic electroluminescent compounds, organic electroluminescence device and its application Download PDF

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CN106893581B
CN106893581B CN201710095592.3A CN201710095592A CN106893581B CN 106893581 B CN106893581 B CN 106893581B CN 201710095592 A CN201710095592 A CN 201710095592A CN 106893581 B CN106893581 B CN 106893581B
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methyl
ethyl
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CN106893581A (en
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金振禹
钱超
高鹏惠
王晓维
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Nanjing Topto Materials Co Ltd
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Abstract

The present invention relates to field of light emitting materials, specifically, providing a kind of organic electroluminescent compounds, organic electroluminescence device and its application.The structural formula of the organic electroluminescent compounds is as follows:

Description

Organic electroluminescent compounds, organic electroluminescence device and its application
Technical field
The present invention relates to field of light emitting materials, send out in particular to a kind of organic electroluminescent compounds, organic electroluminescence Optical device and its application.
Background technique
So far, most of panel display screen is liquid crystal display (LCD, liquid crystal display), but It is while to have with liquid crystal display always actively hardy to develop more economy, performance more superior in worldwide Differentiated novel flat-plate display screen.Recently as next-generation panel display screen by the organic electroluminescence device attracted attention, Compared with liquid crystal display, there is low self-luminous, wide viewing angle, driving voltage, fast response time, Flexible Displays can be achieved etc. and is many Advantage.Since invention the 1980s, organic electroluminescence device is industrially applied, for example is used for phase Machine, computer, mobile phone, television display etc., due to the lasting investment and unremitting effort of all circles for many years, organic electroluminescent Technology has had great development.Nevertheless, the problems such as service life short, low efficiency still restrict organic electroluminescent device The development of part.
Organic electroluminescence device receives the hole injection layer in hole by substrate, anode, from anode, is used for transmission hole Hole transmission layer, electron-blocking layer, hole and the electronics for preventing electron emitting layer from entering hole transmission layer are combined and are shone Luminescent layer, tissue hole from luminescent layer enter electron transfer layer hole blocking layer, from cathode receive electronics electronics note Enter layer and cathode is constituted.
The driving principle of organic electroluminescence device is as follows: when applying voltage between Xiang Shangshu anode and cathode, from anode Injected holes will be moved to luminescent layer via hole injection layer and hole transmission layer.Meanwhile electronics from cathode via electronics Implanted layer and electron transfer layer, are injected into luminescent layer, in luminescent layer with carrier in conjunction with and form exciton.Exciton is in this shape Variation is ground state under state, as a result, the fluorescence mulecular luminescence of luminescent layer, forms portrait.At this point, excitation state passes through singlet excited Ground state is returned to, the light issued is called " fluorescence "；Ground state is returned to by triplet excited state, the light issued is called " phosphorus Light ".Returning to base probability of state by singlet excited is 25%, and returning to base probability of state by triplet excited state is 75%, because This, luminous efficiency is limited；If using phosphorescence, triplet 75% and singlet excited 25% may serve to shine, therefore, reason For upper, internal quantum can achieve 100%.The problem of this organic electroluminescence device maximum is that service life is short Low with luminous efficiency, larger in area with display screen, short become low with luminous efficiency of service life has to solve the problems, such as.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of organic electroluminescent compounds, which can As HTL, EBL, B-dopant, Host, EBL, ETL, CPL material, for can reduce driving in organic electroluminescence device Voltage improves luminous efficiency, brightness, thermal stability, color purity and device lifetime.
The second object of the present invention is to provide a kind of organic electroluminescence device, which includes upper Organic electroluminescent compounds are stated, so that the organic electroluminescence device has the excellent properties of high efficiency and long-life.
The third object of the present invention is to provide a kind of above-mentioned organic electroluminescent compounds in preparing luminescent device Using above-mentioned organic electroluminescent compounds are applied in luminescent device, can be improved the luminous efficiency and device of luminescent device The part service life.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the present invention provides a kind of organic electroluminescent compounds, the following institute of the structural formula of the compound Show:
Wherein, R1、R2And R3It is each independently hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, appoints The phenyl for choosing generation, the phenanthryl optionally replaced, the anthryl optionally replaced, the phenanthridinyl optionally replaced, is appointed at the naphthalene optionally replaced It chooses any one in the xenyl in generation, the pyridyl group optionally replaced, the pyrimidine radicals optionally replaced or the triazine radical optionally replaced Kind or at least two combination；
R4And R5It is each independently heavy hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, optionally replaces Phenyl, optionally replace naphthalene, optionally replace phenanthryl, optionally replace anthryl, optionally replace phenanthridinyl, optionally replace Xenyl, the pyridyl group optionally replaced, in the pyrimidine radicals optionally replaced or the triazine radical optionally replaced any one or extremely Few two kinds of combination；
R6For optionally replace phenyl, optionally replace naphthalene, optionally replace phenanthryl, optionally replace anthryl, optionally Substituted phenanthridinyl, the xenyl optionally replaced, pyridyl group, the pyrimidine radicals optionally replaced or optionally replace three optionally replaced In piperazine base any one or at least two combination；
R7And R8It is each independently the straight chained alkyl of C1~C20 for optionally replacing or branched alkyl and/or optionally replaces The aryl of C6~C30；
The integer that n is 1~4.
As further preferably technical solution, R7And R8It is interconnected to form aliphatic ring or aromatic ring.
As further preferably technical solution, R1、R2、R3、R4Or R5In phenyl, naphthalene, phenanthryl, anthryl, phenanthridinyl, In xenyl, pyridyl group, pyrimidine radicals or triazine radical, more than one hydrogen is independently by the straight chained alkyl of C1~C20 or branched alkane Base, the naphthenic base of C3~C24, the alkoxy of C1~C20, halogen ,-CN ,-CF3、-Si(CH3)3, naphthalene, anthryl, phenanthryl, benzo Replaced the heteroaryl of furyl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or annular atom number for 5~20.
As further preferably technical solution, the heteroaryl that annular atom number is 5~20 be 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 1- pyridyl group, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 1- indyl, 2- indyl, 3- indyl, 4- Yin Diindyl base, 5- indyl, 6- indyl, 7- indyl, 1- isoindolyl, 2- isoindolyl, 3- isoindolyl, 4- isoindolyl, 5- isoindolyl, 6- isoindolyl, 7- isoindolyl, 2- furyl, 3- furyl, 2- benzofuranyl, 3- benzofuranyl, The different benzo furan of 4- benzofuranyl, 5- benzofuranyl, 6- benzofuranyl, 7- benzofuranyl, 1- isobenzofuran-base, 3- It mutters base, 4- isobenzofuran-base, 5- isobenzofuran-base, 6- isobenzofuran-base, 7- isobenzofuran-base, 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, 2- quinoxalinyl, 5- quinoxalinyl, 6- Quinoxalinyl, 1- coffee piperidinyl, 2- coffee piperidinyl, 3- coffee piperidinyl, 4- coffee piperidinyl, 6- coffee piperidinyl, 7- coffee piperidinyl, 8- coffee piperidinyl, 9- coffee Piperidinyl, 10- coffee piperidinyl, 1,7- phenanthrene cough up beautiful jade -2- base, 1,7- phenanthrene coughs up beautiful jade -3- base, 1,7- phenanthrene coughs up beautiful jade -4- base, 1,7- phenanthrene coughs up beautiful jade -5- Base, 1,7- phenanthrene cough up beautiful jade -6- base, 1,7- phenanthrene coughs up beautiful jade -8- base, 1,7- phenanthrene coughs up beautiful jade -9- base, 1,7- phenanthrene coughs up beautiful jade -10- base, 1,8- phenanthrene is coughed up Beautiful jade -2- base, 1,8- phenanthrene cough up beautiful jade -3- base, 1,8- phenanthrene coughs up beautiful jade -4- base, 1,8- phenanthrene coughs up beautiful jade -5- base, 1,8- phenanthrene coughs up beautiful jade -6- base, 1,8- Phenanthrene coughs up beautiful jade -7- base, 1,8- phenanthrene coughs up beautiful jade -9- base, 1,8- phenanthrene coughs up beautiful jade -10- base, 1,9- phenanthrene coughs up beautiful jade -2- base, 1,9- phenanthrene coughs up beautiful jade -3- base, 1,9- phenanthrene coughs up beautiful jade -4- base, 1,9- phenanthrene coughs up beautiful jade -5- base, 1,9- phenanthrene coughs up beautiful jade -6- base, 1,9- phenanthrene coughs up beautiful jade -7- base, 1,9- phenanthrene coughs up beautiful jade -8- Base, 1,9- phenanthrene cough up beautiful jade -10- base, 1,10- phenanthrene coughs up beautiful jade -2- base, 1,10- phenanthrene coughs up beautiful jade -3- base, 1,10- phenanthrene coughs up beautiful jade -4- base, 1,10- Phenanthrene cough up beautiful jade -5- base, 2,9- phenanthrolines -1- base, 2,9- phenanthrene cough up beautiful jade -3- base, 2,9- phenanthrene coughs up beautiful jade -4- base, 2,9- phenanthrene coughs up beautiful jade -5- base, 2,9- phenanthrene coughs up beautiful jade -6- base, 2,9- phenanthrene coughs up beautiful jade -7- base, 2,9- phenanthrene coughs up beautiful jade -8- base, 2,9- phenanthrene coughs up beautiful jade -10- base, 2,8- phenanthrene coughs up beautiful jade - 1- base, 2,8- phenanthrene cough up beautiful jade -3- base, 2,8- phenanthrene coughs up beautiful jade -4- base, 2,8- phenanthrene coughs up beautiful jade -5- base, 2,8- phenanthrene coughs up beautiful jade -6- base, 2,8- phenanthrene is coughed up Beautiful jade -7- base, 2,8- phenanthrene cough up beautiful jade -9- base, 2,8- phenanthrene coughs up beautiful jade -10- base, 2,7- phenanthrene coughs up beautiful jade -1- base, 2,7- phenanthrene coughs up beautiful jade -3- base, 2,7- Phenanthrene coughs up beautiful jade -4- base, 2,7- phenanthrene coughs up beautiful jade -5- base, 2,7- phenanthrene coughs up beautiful jade -6- base, 2,7- phenanthrene coughs up beautiful jade -8- base, 2,7- phenanthrene coughs up beautiful jade -9- base, 2,7- phenanthrene cough up beautiful jade -10- base, 2- oxazolyl, 4- oxazolyl, 5- oxazolyl, 2- oxadiazoles base, 5- oxadiazoles base, 3- furazanyl, 2- Thienyl, 3- thienyl, 2- picoline -1- base, 2- methylpyrrole -3- base, 2- methylpyrrole -4- base, 2- methylpyrrole -5- Base, 3- methylpyrrole -1- base, 3- methylpyrrole -2- base, 3- methylpyrrole -4- base or 3- methylpyrrole -5- base.
As further preferably technical solution, R6Phenyl, naphthalene, phenanthryl, anthryl, phenanthridinyl, xenyl, pyridine In base, pyrimidine radicals or triazine radical, more than one hydrogen is independently by the straight chained alkyl of C1~C20 or branched alkyl, C3~C24 Naphthenic base, the alkoxy of C1~C20, halogen ,-CN ,-CF3、-Si(CH3)3Or replaced the aryl of C6~C50.
As further preferably technical solution, the straight chained alkyl or branched alkyl of C1~C20 be methyl, ethyl, propyl, Isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.
As further preferably technical solution, the aryl of C6~C30 is phenyl, 1- naphthalene, 2- naphthalene, 1- anthryl, 2- Anthryl, 9- anthryl, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacene base, 2- aphthacene base, 9- aphthacene Base, 1- pyrenyl, 2- pyrenyl, 4- pyrenyl, 2- xenyl, 3- xenyl, 4- xenyl, para-terpheny -4- base, para-terpheny -3- Base, para-terpheny -2- base, meta-terphenyl -4- base, meta-terphenyl -3- base, meta-terphenyl -2- base, o-tolyl, tolyl, P-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyl) phenyl, 3- methyl-2- naphthalene, 4- methyl-1-naphthalene, 4- methyl- 1- anthryl, 4'- methyl biphenyl or 4 "-tert-butyl-para-terpheny -4- base.
As further preferably technical solution, the compound is any one in following compounds:
Second aspect includes upper the present invention provides a kind of organic electroluminescence device, in the organic electroluminescence device The organic electroluminescent compounds stated.
The third aspect, the present invention provides a kind of above-mentioned organic electroluminescent compounds to prepare answering in luminescent device With.
Compared with prior art, the invention has the benefit that
Organic electroluminescent compounds provided by the invention can be used as HTL, EBL, B-dopant, Host, EBL, ETL, CPL material improves luminous efficiency, brightness, thermal stability, color for can reduce driving voltage in organic electroluminescence device Color purity and device lifetime.
Organic electroluminescence device provided by the invention includes above-mentioned organic electroluminescent compounds, so that the organic electroluminescence Luminescent device has the excellent properties of high efficiency and long-life.
Organic electroluminescent compounds provided by the invention, which are applied to, to be prepared in luminescent device, can be improved luminescent device Luminous efficiency and device lifetime.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.
Organic electroluminescent compounds structural formula provided by the invention is as follows:
Wherein, R1、R2And R3It is each independently hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, appoints The phenyl for choosing generation, the phenanthryl optionally replaced, the anthryl optionally replaced, the phenanthridinyl optionally replaced, is appointed at the naphthalene optionally replaced It chooses any one in the xenyl in generation, the pyridyl group optionally replaced, the pyrimidine radicals optionally replaced or the triazine radical optionally replaced Kind or at least two combination；
R4And R5It is each independently heavy hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, optionally replaces Phenyl, optionally replace naphthalene, optionally replace phenanthryl, optionally replace anthryl, optionally replace phenanthridinyl, optionally replace Xenyl, the pyridyl group optionally replaced, in the pyrimidine radicals optionally replaced or the triazine radical optionally replaced any one or extremely Few two kinds of combination；
R6For optionally replace phenyl, optionally replace naphthalene, optionally replace phenanthryl, optionally replace anthryl, optionally Substituted phenanthridinyl, the xenyl optionally replaced, pyridyl group, the pyrimidine radicals optionally replaced or optionally replace three optionally replaced In piperazine base any one or at least two combination；
R7And R8It is each independently the straight chained alkyl of C1~C20 for optionally replacing or branched alkyl and/or optionally replaces The aryl of C6~C30；
The integer that n is 1~4, such as 1,2,3 or 4.
The following are the typical but non-limiting optional embodiments of above compound: the aryl of C6~C30 is phenyl, 1- naphthalene Base, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthryl, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacene base, 2- aphthacene base, 9- aphthacene base, 1- pyrenyl, 2- pyrenyl, 4- pyrenyl, 2- xenyl, 3- xenyl, 4- xenyl, to three Benzene -4- base, para-terpheny -3- base, para-terpheny -2- base, meta-terphenyl -4- base, meta-terphenyl -3- base, meta-terphenyl -2- Base, o-tolyl, tolyl, p-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyl) phenyl, 3- methyl -2- naphthalene, 4- methyl-1-naphthalene, 4- methyl-1-anthryl, 4'- methyl biphenyl or 4 "-tert-butyl-para-terpheny-4- base；
The straight chained alkyl or branched alkyl of C1~C20 be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, The straight chained alkyl or branched alkyl of C13, C14, C15, C16, C17, C18, C19 or C20；Specifically, the straight chained alkyl of C1~C20 Or branched alkyl is typical but non-limiting any one in following alkyl: methyl, ethyl, propyl, isopropyl, positive fourth Base, sec-butyl, isobutyl group, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 1- methyl butyl, 2,2- dimethyl propylene Base, 1,2- dimethyl propyl, 1,1- dimethyl propyl, 1- ethyl propyl, n-hexyl, 4- methyl amyl, 3- methyl amyl, 2- first Base amyl, 1- methyl amyl, 2,3- dimethylbutyl, 1,3- dimethylbutyl, 3,3- dimethylbutyl, 2,2- dimethyl butyrate Base, 1,1- dimethylbutyl, 2- ethyl-butyl, 1- ethyl-butyl, 1- Ethyl-2-Methyl propyl, 1,1,2- thmethylpropyl, 1, 2,2- thmethylpropyl, 1- methyl-1-ethyl propyl, n-heptyl, 1- methylhexyl, 2- methylhexyl, 3- methylhexyl, 1,2- Methyl amyl, 1,3- dimethyl amyl group, 1,4- dimethyl amyl group, 2,3- dimethyl amyl group, 2,4- dimethyl amyl group, 1,1- diformazan Base amyl, 2,2- dimethyl amyl group, 3,3- dimethyl amyl group, 3,4- dimethyl amyl group, 1- ethylpentyl, 2- ethylpentyl, 3- Ethylpentyl, 1,2,3- trimethyl butyl, 1,1,2- trimethyl butyl, 1,1,3- trimethyl butyl, 1- ethyl 2- methyl butyl, 1- ethyl -3- methyl butyl, 2,2,3- trimethyl butyl, 2- ethyl -3- methyl butyl, 1,2- diethylpropyl, 1,1,2,2- Tetramethyl propyl, n-octyl, 1- methylheptyl, 2- methylheptyl, 3- methylheptyl, 4- methylheptyl, 1,1- dimethylhexanyl, 1,2- dimethylhexanyl, 1,3- dimethylhexanyl, 1,4- dimethylhexanyl, 1,5- dimethylhexanyl, 1- ethylhexyl, 2- ethyl Hexyl, 3- ethylhexyl, 1,2,3- tri-methyl-amyl, 1,2,4- tri-methyl-amyl, 2,3,4- tri-methyl-amyl, 1,1,2- front three Base amyl, 1,1,3- tri-methyl-amyl, 2,2,3- tri-methyl-amyl, 1- Ethyl-2-Methyl amyl, 1- ethyl -3- methyl amyl, 2- ethyl -3- methyl amyl, 1,1,2,2- tetramethyl butyl, 1,2- diethyl butyl, 1- ethyl -2,2- dimethylbutyl, 1, 1- dimethyl -2- ethyl-butyl, 1- propyl -2- methyl butyl, n-nonyl, 1- Methyl Octyl, 2- Methyl Octyl, 3- methyl are pungent Base, 4- Methyl Octyl, 5- Methyl Octyl, 1,1- dimethyl heptyl, 1,2- dimethyl heptyl, 1,3- dimethyl heptyl, 1,4- bis- Methylheptyl, 1- ethylheptyl, 2- ethylheptyl, 3- ethylheptyl, 4- ethylheptyl, 1,1,2- trimethyl, 1,1,3- Trimethyl, 2,2,3- trimethyl, 1,2,3- trimethyl, 1- Ethyl-2-Methyl hexyl, 1- ethyl -3- methyl Hexyl, 1- propyl hexyl, 2- propyl hexyl, 3- propyl hexyl, 1- isopropyl hexyl, 2- isopropyl hexyl, 3- isopropyl hexyl, 1,1,2,2- tetramethyl amyl, 1,1,3,3- tetramethyl amyl, 1,2,2,3- tetramethyl amyl, 1,2,3,3- tetramethyl amyl, 1- ethyl -2,2- dimethyl amyl group, 1- ethyl -2,3- dimethyl amyl group, 1,2- dimethyl -1- ethylpentyl, 1- propyl -2- first Base amyl, 1,1,2,2,3- trimethyl butyl, 3- methyl-1,2- diethyl butyl, positive decyl, 1- Nonyl, 2- methyl nonyl Base, 3- Nonyl, 4- Nonyl, 5- Nonyl, 1,1- dimethyl octyl, 1,3- dimethyl octyl, 1,4- dimethyl Octyl, 1,5- dimethyl octyl, 2,2- dimethyl octyl, 2,3- dimethyl octyl, 2,4- dimethyl octyl, 2,5- dimethyl-octa Base, 3,3- dimethyl octyl, 3,4- dimethyl octyl, 3,5- dimethyl octyl, 4,4- dimethyl octyl, 4,5- dimethyl-octa Base, 1- ethyloctanyl, 2- ethyloctanyl, 3- ethyloctanyl, 4- ethyloctanyl, 1,1,2- trimethyl heptyl, 1,1,3- trimethyl Heptyl, 1,1,4- trimethyl heptyl, 1- Ethyl-2-Methyl heptyl, 1- methyl -2- ethylheptyl, 1- propylheptyl, 2- propyl heptan Base, 3- propylheptyl, 1- isopropyl heptyl, 2- isopropyl heptyl, 3- isopropyl heptyl, 1,1,2,2- tetramethylhexyl, 1,1, 3,3- tetramethylhexyl, 1,2,2,3- tetramethylhexyl, 1,2,3,3- tetramethylhexyl, 1- ethyl -2,2- dimethylhexanyl, 1- Ethyl -2,3- dimethylhexanyl, 1,2- dimethyl -1- ethylhexyl, 1- propyl -2- methylhexyl, n-undecane base, 1- methyl Decyl, 2- methyldecyl, 3- methyldecyl, 4- methyldecyl, 5- methyldecyl, 1,1- dimethyl nonyl, 1,2- dimethyl nonyl Base, 1,3- dimethyl nonyl, 1,4- dimethyl nonyl, 1,5- dimethyl nonyl, 2,2- dimethyl nonyl, 2,3- dimethyl nonyl Base, 2,4- dimethyl nonyl, 2,5- dimethyl nonyl, 3,3- dimethyl nonyl, 3,4- dimethyl nonyl, 3,5- dimethyl nonyl Base, 1- ethylnonanyl, 2- ethylnonanyl, 3- ethylnonanyl, 4- ethylnonanyl, 5- ethylnonanyl, 1,1,2- trimethyloctyl, 1, 1,3- trimethyloctyl, 1,1,4- trimethyloctyl, 1,1,5- trimethyloctyl, 1- methyl-1-ethyloctanyl, 1- methyl-2- Ethyloctanyl, 1- methyl -3- ethyloctanyl, 1- methyl -4- ethyloctanyl, 2- methyl -2- ethyloctanyl, 2- methyl -3- ethyl Octyl, 3- methyl -4- ethyloctanyl, 1- propyl octyl, 2- propyl octyl, 3- propyl octyl, 4- propyl octyl, 1- isopropyl are pungent Base, 2- isopropyl octyl, 3- isopropyl octyl, 4- isopropyl octyl, 1,1,2,2- tetramethyl heptyl, 1,1,3,3- tetramethyl heptan Base, 1,2,2,3- tetramethyl heptyl, 1,2,3,3- tetramethyl heptyl, 1- ethyl -2,2- dimethyl heptyl, 1- ethyl -2,3- two Methylheptyl, 1,2- dimethyl -1- ethylheptyl, 1- propyl -2- methylheptyl, dodecyl, 1- methylundecyl, 2- Methylundecyl, 3- methylundecyl, 4- methylundecyl, 5- methylundecyl, 6- methylundecyl, 1,1- Dimethyl decyl, 1,2- dimethyl decyl, 1,3- dimethyl decyl, 1,4- dimethyl decyl, 1,5- dimethyl decyl, 1,6- bis- Methyldecyl, 2,2- dimethyl decyl, 2,3- dimethyl decyl, 2,4- dimethyl decyl, 2,5- dimethyl decyl, 3,3- diformazan Base decyl, 3,4- dimethyl decyl, 3,5- dimethyl decyl, 1- ethyl decyl, 2- ethyl decyl, 3- ethyl decyl, 4- ethyl Decyl, 5- ethyl decyl, 1,1,2- trimethyl nonyl, 1,1,3- trimethyl nonyl, 1,1,4- trimethyl nonyl, 1,1,5- front three Base nonyl, 1- methyl-1-ethylnonanyl, 1- methyl-2- ethylnonanyl, 1- methyl-3- ethylnonanyl, 1- methyl-4- ethyl nonyl Base, 2- methyl -2- ethylnonanyl, 2- methyl -3- ethylnonanyl, 3- methyl -4- ethylnonanyl, 1- propyl nonyl, 2- propyl nonyl Base, 3- propyl nonyl, 4- propyl nonyl, 1- isopropyl nonyl, 2- isopropyl nonyl, 3- isopropyl nonyl, 4- isopropyl nonyl, 1,1,2,2- tetramethyl octyl, 1,1,3,3- tetramethyl octyl, 1,2,2,3- tetramethyl octyl, 1,2,3,3- tetramethyl octyl, 1- ethyl -2,2- dimethyl octyl, 1- ethyl -2,3- dimethyl octyl, 1,2- dimethyl -1- ethyloctanyl, 1- propyl -2- first Base octyl, n-tridecane base, 1- methyl dodecyl, 2- methyl dodecyl, 3- methyl dodecyl, 4- methyl dodecane Base, 5- methyl dodecyl, 6- methyl dodecyl, 1,1- dimethyl undecyl, 1,2- dimethyl undecyl, 1,3- bis- Methylundecyl, 1,4- dimethyl undecyl, 1,5- dimethyl undecyl, 1,6- dimethyl undecyl, 2,2- bis- Methylundecyl, 2,3- dimethyl undecyl, 2,4- dimethyl undecyl, 2,5- dimethyl undecyl, 2,6- bis- Methylundecyl, 3,3- dimethyl undecyl, 3,4- dimethyl undecyl, 3,5- dimethyl undecyl, 1- ethyl Undecyl, 2- ethyl undecyl, 3- ethyl undecyl, 4- ethyl undecyl, 5- ethyl undecyl, 1,1,2- tri- Methyldecyl, 1,1,3- trimethyldecylammonium, 1,1,4- trimethyldecylammonium, 1,1,5- trimethyldecylammonium, the 1- methyl-1-ethyl last of the ten Heavenly stems Base, 1- methyl -2- ethyl decyl, 1- methyl -3- ethyl decyl, 1- methyl -4- ethyl decyl, 2- methyl -2- ethyl decyl, 2- Methyl -3- ethyl decyl, 3- methyl -4- ethyl decyl, 1- propyl decyl, 2- propyl decyl, 3- propyl decyl, the 4- propyl last of the ten Heavenly stems Base, 1- isopropyl decyl, 2- isopropyl decyl, 3- isopropyl decyl, 4- isopropyl decyl, 1,1,2,2- tetramethyl nonyl, 1, 1,3,3- tetramethyl nonyl, 1,2,2,3- tetramethyl nonyl, 1,2,3,3- tetramethyl nonyl, 1- ethyl -2,2- dimethyl nonyl, 1- ethyl -2,3- dimethyl nonyl, 1,2- dimethyl -1- ethylnonanyl, 1- propyl -2- Nonyl, n-tetradecane base, 1- first Base tridecyl, 2- methyltridec base, 3- methyltridec base, 4- methyltridec base, 5- methyltridec base, 6- methyl Tridecyl, 7-- methyltridec base, 1,1- dimethyl dodecyl base, 1,2- dimethyl dodecyl base, 1,3- dimethyl 12 Alkyl, 1,4- dimethyl dodecyl base, 1,5- dimethyl dodecyl base, 1,6- dimethyl dodecyl base, 1,7- dimethyl 12 Alkyl, 2,2- dimethyl dodecyl base, 2,3- dimethyl dodecyl base, 2,4- dimethyl dodecyl base, 2,5- dimethyl 12 Alkyl, 2,6- dimethyl dodecyl base, 2,7- dimethyl dodecyl base, 3,3- dimethyl dodecyl base, 3,4- dimethyl 12 Alkyl, 3,5- dimethyl dodecyl base, 3,6- dimethyl dodecyl base, 3,7- dimethyl dodecyl base, 1- ethyl dodecyl, 2- ethyl dodecyl, 3- ethyl dodecyl, 4- ethyl dodecyl, 5- ethyl dodecyl, 6- ethyl dodecyl, 1, 1,2- norfarnesane base, 1,1,3- norfarnesane base, 1,1,4- norfarnesane base, 1,1,5- trimethyl 11 Alkyl, 1,1,6- norfarnesane base, 1- methyl-1-ethyl undecyl, 1- methyl-2- ethyl undecyl, 1- methyl- 3- ethyl undecyl, 1- methyl -4- ethyl undecyl, 2- methyl -2- ethyl undecyl, 2- methyl -3- ethyl 11 Alkyl, 3- methyl -4- ethyl undecyl, 1- propyl undecyl, 2- propyl undecyl, 3- propyl undecyl, 4- third Base undecyl, 1- isopropyl undecyl, 2- isopropyl undecyl, 3- isopropyl undecyl, 4- isopropyl hendecane Base, 1,1,2,2- tetramethyl decyl, 1,1,3,3- tetramethyl decyl, 1,2,2,3- tetramethyl decyl, the 1,2,3,3- tetramethyl last of the ten Heavenly stems Base, 1- ethyl -2,2- dimethyl decyl, 1- ethyl -2,3- dimethyl decyl, 1,2- dimethyl -1- ethyl decyl, 1- propyl - 2- methyldecyl, n-pentadecane base, 1- methyltetradecylphosphine base, 2- methyltetradecylphosphine base, 3- methyltetradecylphosphine base, 4- methyl 14 Alkyl, 5- methyltetradecylphosphine base, 6- methyltetradecylphosphine base, 7- methyltetradecylphosphine base, 1,1- dimethyltridecane base, 1,2- diformazan Base tridecyl, 1,3- dimethyltridecane base, 1,4- dimethyltridecane base, 1,5- dimethyltridecane base, 1,6- diformazan Base tridecyl, 1,7- dimethyltridecane base, 2,2- dimethyltridecane base, 2,3- dimethyltridecane base, 2,4- diformazan Base tridecyl, 2,5- dimethyltridecane base, 2,6- dimethyltridecane base, 2,7- dimethyltridecane base, 3,3- diformazan Base tridecyl, 3,4- dimethyltridecane base, 3,5- dimethyltridecane base, 3,6- dimethyltridecane base, 3,7- diformazan Base tridecyl, 1- ethyl tridecyl, 2- ethyl tridecyl, 3- ethyl tridecyl, 4- ethyl tridecyl, 5- ethyl Tridecyl, 6- ethyl tridecyl, 1,1,2- trimethyldodecane base, 1,1,3- trimethyldodecane base, 1,1,4- front three Base dodecyl, 1,1,5- trimethyldodecane base, 1,1,6- trimethyldodecane base, 1- methyl-1-ethyl dodecyl, 1- Methyl -2- ethyl dodecyl, 1- methyl -3- ethyl dodecyl, 1- methyl -4- ethyl dodecyl, 2- methyl -2- ethyl Dodecyl, 2- methyl -3- ethyl dodecyl, 3- methyl -4- ethyl dodecyl, 1- propyl dodecyl, 2- propyl ten Dialkyl group, 3- propyl dodecyl, 4- propyl dodecyl, 1- isopropyl dodecyl, 2- isopropyl dodecyl, 3- isopropyl Base dodecyl, 4- isopropyl dodecyl, 1,1,2,2- tetramethyl undecyl, 1,1,3,3- tetramethyl undecyl, 1, 2,2,3- tetramethyl undecyl, 1,2,3,3- tetramethyl undecyl, 1- ethyl -2,2- dimethyl undecyl, 1- ethyl - 2,3- dimethyl undecyl, 1,2- dimethyl -1- ethyl undecyl, 1- propyl -2- methylundecyl, hexadecane Base, 1- methyl pentadecyl, 2- methyl pentadecyl, 3- methyl pentadecyl, 4- methyl pentadecyl, 5- methyl pentadecane Base, 6- methyl pentadecyl, 7- methyl pentadecyl, 8- methyl pentadecyl, 1,1- dimethyl tetradecyl base, 1,2- dimethyl Myristyl, 1,3- dimethyl tetradecyl base, 1,4- dimethyl tetradecyl base, 1,5- dimethyl tetradecyl base, 1,6- dimethyl Myristyl, 1,7- dimethyl tetradecyl base, 1,8- dimethyl tetradecyl base, 2,2- dimethyl tetradecyl base, 2,3- dimethyl Myristyl, 2,4- dimethyl tetradecyl base, 2,5- dimethyl tetradecyl base, 2,6- dimethyl tetradecyl base, 2,7- dimethyl Myristyl, 3,3- dimethyl tetradecyl base, 3,4- dimethyl tetradecyl base, 3,5- dimethyl tetradecyl base, 3,6- dimethyl Myristyl, 3,7- dimethyl tetradecyl base, 1- ethyl myristyl, 2- ethyl myristyl, 3- ethyl myristyl, 4- second Base myristyl, 5- ethyl myristyl, 6- ethyl myristyl, 1,1,2- trimethyltridecvl, 1,1,3- trimethyl ten Trialkyl, 1,1,4- trimethyltridecvl, 1,1,5- trimethyltridecvl, 1,1,6- trimethyltridecvl, 1- methyl- 1- ethyl tridecyl, 1- methyl -2- ethyl tridecyl, 1- methyl -3- ethyl tridecyl, 1- methyl -4- ethyl 13 Alkyl, 2- methyl -2- ethyl tridecyl, 2- methyl -3- ethyl tridecyl, 3- methyl -4- ethyl tridecyl, 1- propyl Tridecyl, 2- propyl tridecyl, 3- propyl tridecyl, 4- propyl tridecyl, 1- isopropyl tridecyl, 2- isopropyl Base tridecyl, 3- isopropyl tridecyl, 4- isopropyl tridecyl, 1,1,2,2- tetramethyl dodecyl, 1,1,3,3- Tetramethyl dodecyl, 1,2,2,3- tetramethyl dodecyl, 1,2,3,3- tetramethyl dodecyl, 1- ethyl -2,2- diformazan Base dodecyl, 1- ethyl -2,3- dimethyl dodecyl base, 1,2- dimethyl -1- ethyl dodecyl, 1- propyl -2- methyl Dodecyl, n-heptadecane base, 1- methyl cetyl, 2- methyl cetyl, 3- methyl cetyl, 4- methyl hexadecane Base, 5- methyl cetyl, 6- methyl cetyl, 7- methyl cetyl, 8- methyl cetyl, 1,1- dimethyl 15 Alkyl, 1,2- dimethyl pentadecyl, 1,3- dimethyl pentadecyl, 1,4- dimethyl pentadecyl, 1,5- dimethyl 15 Alkyl, 1,6- dimethyl pentadecyl, 1,7- dimethyl pentadecyl, 1,8- dimethyl pentadecyl, 2,2- dimethyl 15 Alkyl, 2,3- dimethyl pentadecyl, 2,4- dimethyl pentadecyl, 2,5- dimethyl pentadecyl, 2,6- dimethyl 15 Alkyl, 2,7- dimethyl pentadecyl, 3,3- dimethyl pentadecyl, 3,4- dimethyl pentadecyl, 3,5- dimethyl 15 Alkyl, 3,6- dimethyl pentadecyl, 3,7- dimethyl pentadecyl, 1- ethyl pentadecyl, 2- ethyl pentadecyl, 3- second Base pentadecyl, 4- ethyl pentadecyl, 5- ethyl pentadecyl, 6- ethyl pentadecyl, 1,1,2- trimethyl tetradecyl base, 1,1,3- trimethyl tetradecyl base, 1,1,4- trimethyl tetradecyl base, 1,1,5- trimethyl tetradecyl base, 1,1,6- trimethyl ten Tetraalkyl, 1- methyl-1-ethyl myristyl, 1- methyl-2- ethyl myristyl, 1- methyl-3- ethyl myristyl, 1- first Base -4- ethyl myristyl, 2- methyl -2- ethyl myristyl, 2- methyl -3- ethyl myristyl, 3- methyl -4- ethyl ten Tetraalkyl, 1- propyl myristyl, 2- propyl myristyl, 3- propyl myristyl, 4- propyl myristyl, 1- isopropyl ten Tetraalkyl, 2- isopropyl myristyl, 3- isopropyl myristyl, 4- isopropyl myristyl, 1,1,2,2- tetramethyl 13 Alkyl, 1,1,3,3- tetramethyl tridecyl, 1,2,2,3- tetramethyl tridecyl, 1,2,3,3- tetramethyl tridecyl, 1- Ethyl -2,2- dimethyltridecane base, 1- ethyl -2,3- dimethyltridecane base, 1,2- dimethyl -1- ethyl tridecyl, 1- propyl -2- methyltridec base, n-octadecane base, 1- methyl heptadecyl, 2- methyl heptadecyl, 3- methyl heptadecane Base, 4- methyl heptadecyl, 5- methyl heptadecyl, 6- methyl heptadecyl, 7- methyl heptadecyl, 8- methyl heptadecane Base, 9- methyl heptadecyl, 1,1- dimethyl hexadecyl base, 1,2- dimethyl hexadecyl base, 1,3- dimethyl hexadecyl base, 1, 4- dimethyl hexadecyl base, 1,5- dimethyl hexadecyl base, 1,6- dimethyl hexadecyl base, 1,7- dimethyl hexadecyl base, 1, 8- dimethyl hexadecyl base, 2,2- dimethyl hexadecyl base, 2,3- dimethyl hexadecyl base, 2,4- dimethyl hexadecyl base, 2, 5- dimethyl hexadecyl base, 2,6- dimethyl hexadecyl base, 2,7- dimethyl hexadecyl base, 3,3- dimethyl hexadecyl base, 3, 4- dimethyl hexadecyl base, 3,5- dimethyl hexadecyl base, 3,6- dimethyl hexadecyl base, 3,7- dimethyl hexadecyl base, 1- Ethylhexadecyl, 2- ethylhexadecyl, 3- ethylhexadecyl, 4- ethylhexadecyl, 5- ethylhexadecyl, 6- second Base cetyl, 1,1,2- trimethylpentadecane base, 1,1,3- trimethylpentadecane base, 1,1,4- trimethylpentadecane base, 1, 1,5- trimethylpentadecane base, 1,1,6- trimethylpentadecane base, 1- methyl-1-ethyl pentadecyl, 1- methyl-2- ethyl ten Five alkyl, 1- methyl -3- ethyl pentadecyl, 1- methyl -4- ethyl pentadecyl, 2- methyl -2- ethyl pentadecyl, 2- first Base -3- ethyl pentadecyl, 3- methyl -4- ethyl pentadecyl, 1- propyl pentadecyl, 2- propyl pentadecyl, 3- propyl Pentadecyl, 4- propyl pentadecyl, 1- isopropyl pentadecyl, 2- isopropyl pentadecyl, 3- isopropyl pentadecyl, 4- Isopropyl pentadecyl, 1,1,2,2- tetramethyl myristyl, 1,1,3,3- tetramethyl myristyl, 1,2,2,3- tetramethyl ten Tetraalkyl, 1,2,3,3- tetramethyl myristyl, 1- ethyl -2,2- dimethyl tetradecyl base, 1- ethyl -2,3- dimethyl 14 Alkyl, 1,2- dimethyl -1- ethyl myristyl, 1- propyl -2- methyltetradecylphosphine base, NSC 77136 base, 1- methyl octadecane Base, 2- methyl octadecyl, 3- methyl octadecyl, 4- methyl octadecyl, 5- methyl octadecyl, 6- methyl octadecane Base, 7- methyl octadecyl, 8- methyl octadecyl, 9- methyl octadecyl, 1,1- dimethyl heptadecyl, 1,2- dimethyl Heptadecyl, 1,3- dimethyl heptadecyl, 1,4- dimethyl heptadecyl, 1,5- dimethyl heptadecyl, 1,6- dimethyl Heptadecyl, 1,7- dimethyl heptadecyl, 1,8- dimethyl heptadecyl, 2,2- dimethyl heptadecyl, 2,3- dimethyl Heptadecyl, 2,4- dimethyl heptadecyl, 2,5- dimethyl heptadecyl, 2,6- dimethyl heptadecyl, 2,7- dimethyl Heptadecyl, 3,3- dimethyl heptadecyl, 3,4- dimethyl heptadecyl, 3,5- dimethyl heptadecyl, 3,6- dimethyl Heptadecyl, 3,7- dimethyl heptadecyl, 1- ethyl heptadecyl, 2- ethyl heptadecyl, 3- ethyl heptadecyl, 4- second Base heptadecyl, 5- ethyl heptadecyl, 6- ethyl heptadecyl, 1,1,2- trimethyl cetyl, 1,1,3- trimethyl ten Six alkyl, 1,1,4- trimethyl cetyl, 1,1,5- trimethyl cetyl, 1,1,6- trimethyl cetyl, 1- methyl- 1- ethylhexadecyl, 1- methyl -2- ethylhexadecyl, 1- methyl -3- ethylhexadecyl, 1- methyl -4- ethyl 16 Alkyl, 2- methyl -2- ethylhexadecyl, 2- methyl -3- ethylhexadecyl, 3- methyl -4- ethylhexadecyl, 1- propyl Cetyl, 2- propyl cetyl, 3- propyl cetyl, 4- propyl cetyl, 1- isopropyl cetyl, 2- isopropyl Base cetyl, 3- isopropyl cetyl, 4- isopropyl cetyl, 1,1,2,2- tetramethyl-pentadecane base, 1,1,3,3- Tetramethyl-pentadecane base, 1,2,2,3- tetramethyl-pentadecane base, 1,2,3,3- tetramethyl-pentadecane base, 1- ethyl -2,2- diformazan Base pentadecyl, 1- ethyl -2,3- dimethyl pentadecyl, 1,2- dimethyl -1- ethyl pentadecyl, 1- propyl -2- methyl Pentadecyl, n-eicosane base, 1- methyl nonadecyl, 2- methyl nonadecyl, 3- methyl nonadecyl, 4- methyl nonadecane Base, 5- methyl nonadecyl, 6- methyl nonadecyl, 7- methyl nonadecyl, 8- methyl nonadecyl, 9- methyl nonadecane Base, 10- methyl nonadecyl, 1,1- dimethyl stearyl, 1,2- dimethyl stearyl, 1,3- dimethyl stearyl, 1,4- dimethyl stearyl, 1,5- dimethyl stearyl, 1,6- dimethyl stearyl, 1,7- dimethyl stearyl, 1,8- dimethyl stearyl, 1,9- dimethyl stearyl, 2,2- dimethyl stearyl, 2,3- dimethyl stearyl, 2,4- dimethyl stearyl, 2,5- dimethyl stearyl, 2,6- dimethyl stearyl, 2,7- dimethyl stearyl, 2,8- dimethyl stearyl, 2,9- dimethyl stearyl, 3,3- dimethyl stearyl, 3,4- dimethyl stearyl, 3,5- dimethyl stearyl, 3,6- dimethyl stearyl, 3,7- dimethyl stearyl, 1- ethyl octadecyl, 2- second Base octadecyl, 3- ethyl octadecyl, 4- ethyl octadecyl, 5- ethyl octadecyl, 6- ethyl octadecyl, 1,1,2- Trimethyl heptadecyl, 1,1,3- trimethyl heptadecyl, 1,1,4- trimethyl heptadecyl, 1,1,5- trimethyl heptadecane Base, 1,1,6- trimethyl heptadecyl, 1- methyl-1-ethyl heptadecyl, 1- methyl-2- ethyl heptadecyl, 1- methyl-3- Ethyl heptadecyl, 1- methyl -4- ethyl heptadecyl, 2- methyl -2- ethyl heptadecyl, 2- methyl -3- ethyl heptadecane Base, 3- methyl -4- ethyl heptadecyl, 1- propyl heptadecyl, 2- propyl heptadecyl, 3- propyl heptadecyl, 4- propyl Heptadecyl, 1- isopropyl heptadecyl, 2- isopropyl heptadecyl, 3- isopropyl heptadecyl, 4- isopropyl heptadecyl, 1,1,2,2- tetramethyl cetyl, 1,1,3,3- tetramethyl cetyl, 1,2,2,3- tetramethyl cetyl, 1,2,3,3- Tetramethyl cetyl, 1- ethyl -2,2- dimethyl hexadecyl base, 1- ethyl -2,3- dimethyl hexadecyl base, 1,2- diformazan Base -1- ethylhexadecyl or 1- propyl -2- methyl cetyl.
In a kind of preferred embodiment of organic electroluminescent compounds provided by the invention, R7And R8It is connected with each other shape At aliphatic ring or aromatic ring.
It is preferably carried out in mode in one kind, R1、R2、R3、R4Or R5In phenyl, naphthalene, phenanthryl, anthryl, phenanthridinyl, connection In phenyl, pyridyl group, pyrimidine radicals or triazine radical, more than one hydrogen independently by the straight chained alkyl of C1~C20 or branched alkyl, The naphthenic base of C3~C24, the alkoxy of C1~C20, halogen ,-CN ,-CF3、-Si(CH3)3, naphthalene, anthryl, phenanthryl, benzo furan It mutters replaced the heteroaryl of base, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or annular atom number for 5~20；
Wherein, the naphthenic base of C3~C24 is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
The alkoxy of C1~C20 are as follows: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, sec-butoxy, different Butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, positive oxygroup in heptan, n-octyloxy, positive nonyl epoxide, n-decyloxy, positive 11 Alkoxy, n-dodecane oxygroup, n-tridecane oxygroup, n-tetradecane oxygroup, n-pentadecane oxygroup, hexadecane oxygroup, positive ten Seven alkoxies, n-octadecane oxygroup, NSC 77136 oxygroup or n-eicosane oxygroup；
The heteroaryl that annular atom number is 5~20 is 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 1- pyridyl group, 2- pyridine Base, 3- pyridyl group, 4- pyridyl group, 1- indyl, 2- indyl, 3- indyl, 4- indyl, 5- indyl, 6- indyl, 7- Indyl, 1- isoindolyl, 2- isoindolyl, 3- isoindolyl, 4- isoindolyl, 5- isoindolyl, 6- isoindolyl, 7- are different Indyl, 2- furyl, 3- furyl, 2- benzofuranyl, 3- benzofuranyl, 4- benzofuranyl, 5- benzofuranyl, 6- benzofuranyl, 7- benzofuranyl, 1- isobenzofuran-base, 3- isobenzofuran-base, 4- isobenzofuran-base, the different benzene of 5- And furyl, 6- isobenzofuran-base, 7- isobenzofuran-base, 2- quinolyl, 3- quinolyl, 4- quinolyl, 5- quinolyl, 6- Quinolyl, 7- quinolyl, 8- quinolyl, 1- isoquinolyl, 3- isoquinolyl, 4- isoquinolyl, 5- isoquinolyl, 6- isoquinolin Base, 7- isoquinolyl, 8- isoquinolyl, 2- quinoxalinyl, 5- quinoxalinyl, 6- quinoxalinyl, 1- coffee piperidinyl, 2- coffee piperidinyl, 3- coffee piperidinyl, 4- coffee piperidinyl, 6- coffee piperidinyl, 7- coffee piperidinyl, 8- coffee piperidinyl, 9- coffee piperidinyl, 10- coffee piperidinyl, 1,7- phenanthrene cough up beautiful jade -2- Base, 1,7- phenanthrene cough up beautiful jade -3- base, 1,7- phenanthrene coughs up beautiful jade -4- base, 1,7- phenanthrene coughs up beautiful jade -5- base, 1,7- phenanthrene coughs up beautiful jade -6- base, 1,7- phenanthrene is coughed up Beautiful jade -8- base, 1,7- phenanthrene cough up beautiful jade -9- base, 1,7- phenanthrene coughs up beautiful jade -10- base, 1,8- phenanthrene coughs up beautiful jade -2- base, 1,8- phenanthrene coughs up beautiful jade -3- base, 1,8- Phenanthrene coughs up beautiful jade -4- base, 1,8- phenanthrene coughs up beautiful jade -5- base, 1,8- phenanthrene coughs up beautiful jade -6- base, 1,8- phenanthrene coughs up beautiful jade -7- base, 1,8- phenanthrene coughs up beautiful jade -9- base, 1,8- phenanthrene coughs up beautiful jade -10- base, 1,9- phenanthrene coughs up beautiful jade -2- base, 1,9- phenanthrene coughs up beautiful jade -3- base, 1,9- phenanthrene coughs up beautiful jade -4- base, 1,9- phenanthrene coughs up beautiful jade - 5- base, 1,9- phenanthrene cough up beautiful jade -6- base, 1,9- phenanthrene coughs up beautiful jade -7- base, 1,9- phenanthrene coughs up beautiful jade -8- base, 1,9- phenanthrene coughs up beautiful jade -10- base, 1,10- is luxuriant and rich with fragrance Cough up beautiful jade -2- base, 1,10- phenanthrene coughs up beautiful jade -3- base, 1,10- phenanthrene coughs up beautiful jade -4- base, 1,10- phenanthrene coughs up beautiful jade -5- base, 2,9- phenanthrolines -1- base, 2,9- phenanthrene coughs up beautiful jade -3- base, 2,9- phenanthrene coughs up beautiful jade -4- base, 2,9- phenanthrene coughs up beautiful jade -5- base, 2,9- phenanthrene coughs up beautiful jade -6- base, 2,9- phenanthrene coughs up beautiful jade -7- Base, 2,9- phenanthrene cough up beautiful jade -8- base, 2,9- phenanthrene coughs up beautiful jade -10- base, 2,8- phenanthrene coughs up beautiful jade -1- base, 2,8- phenanthrene coughs up beautiful jade -3- base, 2,8- phenanthrene is coughed up Beautiful jade -4- base, 2,8- phenanthrene cough up beautiful jade -5- base, 2,8- phenanthrene coughs up beautiful jade -6- base, 2,8- phenanthrene coughs up beautiful jade -7- base, 2,8- phenanthrene coughs up beautiful jade -9- base, 2,8- Phenanthrene coughs up beautiful jade -10- base, 2,7- phenanthrene coughs up beautiful jade -1- base, 2,7- phenanthrene coughs up beautiful jade -3- base, 2,7- phenanthrene coughs up beautiful jade -4- base, 2,7- phenanthrene coughs up beautiful jade -5- base, 2,7- phenanthrene coughs up beautiful jade -6- base, 2,7- phenanthrene coughs up beautiful jade -8- base, 2,7- phenanthrene coughs up beautiful jade -9- base, 2,7- phenanthrene coughs up beautiful jade -10- base, 2- oxazolyl, 4- Oxazolyl, 5- oxazolyl, 2- oxadiazoles base, 5- oxadiazoles base, 3- furazanyl, 2- thienyl, 3- thienyl, 2- picoline- 1- base, 2- methylpyrrole -3- base, 2- methylpyrrole -4- base, 2- methylpyrrole -5- base, 3- methylpyrrole -1- base, 3- methyl pyrrole Cough up -2- base, 3- methylpyrrole -4- base or 3- methylpyrrole -5- base.
It is preferably carried out in mode in one kind, R6Phenyl, naphthalene, phenanthryl, anthryl, phenanthridinyl, xenyl, pyridyl group, In pyrimidine radicals or triazine radical, more than one hydrogen is independently by the straight chained alkyl of C1~C20 or the ring of branched alkyl, C3~C24 Alkyl, the alkoxy of C1~C20, halogen ,-CN ,-CF3、-Si(CH3)3Or replaced the aryl of C6~C50；
Wherein, the naphthenic base of C3~C24 is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
The alkoxy of C1~C20 are as follows: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, sec-butoxy, different Butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, positive oxygroup in heptan, n-octyloxy, positive nonyl epoxide, n-decyloxy, positive 11 Alkoxy, n-dodecane oxygroup, n-tridecane oxygroup, n-tetradecane oxygroup, n-pentadecane oxygroup, hexadecane oxygroup, positive ten Seven alkoxies, n-octadecane oxygroup, NSC 77136 oxygroup or n-eicosane oxygroup；
The aryl of C6~C50 be phenyl, 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthryl, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacene base, 2- aphthacene base, 9- aphthacene base, 1- pyrenyl, 2- pyrenyl, 4- pyrenyl, 2- Xenyl, 3- xenyl, 4- xenyl, para-terpheny -4- base, para-terpheny -3- base, para-terpheny -2- base, meta-terphenyl - 4- base, meta-terphenyl -3- base, meta-terphenyl -2- base, o-tolyl, tolyl, p-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyl) phenyl, 3- methyl-2- naphthalene, 4- methyl-1-naphthalene, 4- methyl-1-anthryl, 4'- methyl biphenyl or 4 "- Tert-butyl-para-terpheny -4- base.
It is preferably carried out in mode in one kind, the aryl of C6~C30 is phenyl, 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthracene Base, 9- anthryl, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacene base, 2- aphthacene base, 9- aphthacene Base, 1- pyrenyl, 2- pyrenyl, 4- pyrenyl, 2- xenyl, 3- xenyl, 4- xenyl, para-terpheny -4- base, para-terpheny -3- Base, para-terpheny -2- base, meta-terphenyl -4- base, meta-terphenyl -3- base, meta-terphenyl -2- base, o-tolyl, tolyl, P-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyl) phenyl, 3- methyl-2- naphthalene, 4- methyl-1-naphthalene, 4- methyl- 1- anthryl, 4'- methyl biphenyl or 4 "-tert-butyl-para-terpheny -4- base.
Organic electroluminescent compounds provided by the invention are further described in detail below with reference to embodiment 1-6.
Embodiment 1
Organic electroluminescent compounds 15, structural formula is as follows:
The synthetic method of compound 15 is as follows:
The synthesis of intermediate (1)
[reaction equation 1]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 18.0g (100mmol, 1.0eq.) 9- fluorenes is added dropwise at such a temperature Ketone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase is used Saturated common salt is washed to neutrality, dry, and rotation removes solvent, sufficiently dry, then is dosed into the drying three-necked flask of 2L, is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 28.9g intermediate (1), yield 79%.
The synthesis of intermediate (2)
[reaction equation 2]
Feed intake intermediate (1) 28.9g (79mmol) that [reaction equation 1] obtain in the three-necked flask of 2L, uses trifluoroacetic acid Make solvent 600ml, add 6.0g (94.8mmol, 1.2eq.) concentrated nitric acid, be heated to 80 DEG C, flows back 12 hours.Wait react knot Beam is cooled to room temperature, and 1L water is added, has solid generation, lowers to temperature, is filtered, and obtained filter cake is repeatedly washed, and uses ethyl alcohol Recrystallization, it is dry, obtain 29.6g intermediate (2), yield 91%.
The synthesis of intermediate (3)
[reaction equation 3]
Intermediate (2) 29.6g (71.9mmol) that [reaction equation 2] obtains is added in the three-necked flask of 2L, with threeway, Extraction nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% later Palladium carbon 1.5g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), being careful not to drain (can suitably add Water), to last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains among 25.2g Body (3), yield 92%.
The synthesis of intermediate (4)
[reaction equation 4]
In the three-necked flask of 2L, the product 25.2g (66.1mmol) that investment [reaction equation 3] obtains is made with 300ml acetic acid Solvent divides 3 batches of dropwise addition 15.8g (99.2mmol, 1.5eq.) bromines at room temperature, drips and is warming up to 120 DEG C, reaction 18 is small When.After reaction, it is cooled to room temperature, 500ml water is added, a large amount of solids are precipitated, stir 1 hour, filter, repeatedly wash, do Toluene and ethyl alcohol recrystallization are used after dry, obtain 23.7g intermediate (4), yield 78%.
The synthesis of intermediate (5)
[reaction equation 5]
By the bromo- 5- iodine naphthalene of 33.3g (100mmol) 1- and 23.5g (110mmol) dibenzofurans -4- boric acid, it is added to 2L Three-necked flask in, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 150ml K2CO3 The aqueous solution of (300mmol, 2M) is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 30.8g intermediate (5), yield It is 82%.
The synthesis of intermediate (6)
[reaction equation 6]
In dry 2L three-necked flask, feed intake the product 30.8g (82mmol) and 22.9g that [reaction equation 5] obtains (90.2mmol) joins pinacol borate, makees solvent with 600ml Isosorbide-5-Nitrae-dioxane, leads to nitrogen 15 minutes, adds 1.2g (2%mol) Pd (dppf) Cl2With 24.1g (246mmol) potassium acetate, 120 DEG C are warming up to, back flow reaction 6 hours, reaction terminated, It is down to room temperature, adds active carbon, crosses short column of silica gel, is filtered, filtrate is spin-dried for, and crosses chromatographic column, obtains product 31.5g intermediate (6), produces Rate is 91%.
The synthesis of intermediate (7)
[reaction equation 7]
The obtained product of 23.7g (51.5mmol) [reaction equation 4] and 23.9g (56.6mmol) [reaction equation 6] are obtained Product is added in the three-necked flask of 2L, and 600ml toluene and the dissolution of 150ml ethyl alcohol is added, and is led to nitrogen 15 minutes, is added 150ml K2CO3The aqueous solution of (300mmol, 2M) is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, instead Answering 12 hours terminates.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 29.6g product Intermediate (7), yield 85%.
The synthesis of intermediate (8)
[reaction equation 8]
By the fluoro- 2- iodobenzene of the bromo- 4- of 30.1g (100mmol) 1- and 27.6g (110mmol) 6- bromonaphthalene -2- boric acid, it is added to In the three-necked flask of 2L, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 150ml K2CO3 The aqueous solution of (300mmol, 2M) is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 31.2g intermediate (8), yield It is 82%.
The synthesis of intermediate (9)
[reaction equation 9]
By the obtained product of 31.2g (82mmol) [reaction equation 8] and 52.6g (410mmol) trifluoro-acetate (MTFA, 410.5mmol), 31.2g cesium fluoride (CsF, 205.3mmol), 15.6g cuprous iodide (CuI, 82.1mmol), 600ml DMF, 180 DEG C are warming up to, 8h is reacted.To after, near room temperature, active carbon depigmentation is filtered, is extracted with dichloromethane, and is washed more Secondary, dry, rotation removes solvent, and dress silica gel crosses column, obtains product 28.2g intermediate (9), yield 93%.
The synthesis of intermediate (10)
[reaction equation 10]
In dry 2L three-necked flask, feed intake the product 28.2g (76.3mmol) and 22.9g that [reaction equation 9] obtains (83.9mmol) joins pinacol borate, makees solvent with 600ml Isosorbide-5-Nitrae-dioxane, leads to nitrogen 15 minutes, adds 1.1g (2%mol) Pd (dppf) Cl2With 22.5g (228.9mmol) potassium acetate, 120 DEG C are warming up to, back flow reaction 6 hours, reaction was tied Beam is down to room temperature, adds active carbon, crosses short column of silica gel, filters, and filtrate is spin-dried for, and crosses chromatographic column, obtains product 27.9g intermediate (10), yield 88%.
The synthesis of intermediate (11)
[reaction equation 11]
The bromo- 6- phenylnaphthalene of 28.3g (100mmol) 2- and 10.2g (110mmol) benzene are added in dry 2L three-necked flask Amine adds dry and degasification 600ml toluene and makees solvent.28.8g (300mmol) sodium tert-butoxide, 0.45g catalyst is added Palladium acetate (2%mol) and 2.5g ligand 1, the bis- diphenyl phosphines of 1'- dinaphthalene -2,2'- (BINAP, 4%mol).110 DEG C are warming up to, instead It answers 15 hours.It to the end of reacting, being cooled to room temperature, adds activated carbon adsorption, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, Obtain 25.1g intermediate (11), yield 85%.
The synthesis of intermediate (12)
[reaction equation 12]
Product and 27.9g that 25.1g (85.0mmol) [reaction equation 11] obtains are added in dry 2L three-necked flask The bromo- 5- iodobenzene of (77.3mmol) 1,3- bis- adds dry and degasification 600ml toluene and makees solvent, leads to nitrogen 15 minutes.Add Enter 22.3g (231.9mmol) sodium tert-butoxide, 1.4g (2%mol) catalyst Pd2(dba)3With 6.3ml (4%mol) P (t-bu)3 Toluene solution (m/v, 10%).110 DEG C are warming up to, is reacted 16 hours.It to the end of reacting, is cooled to room temperature, active carbon is added to inhale It is attached, it filters, rotation removes solvent and obtains 32.3g intermediate (12), yield 79% with toluene and ethyl alcohol recrystallization.
The synthesis of intermediate (13)
[reaction equation 13]
The obtained product of 27.9g (67mmol) [reaction equation 10] and 32.3g (60.9mmol) [reaction equation 12] are obtained Product is added in the three-necked flask of 2L, and 600ml toluene and the dissolution of 150ml ethyl alcohol is added, and is led to nitrogen 15 minutes, is added 91.4ml K2CO3The aqueous solution of (182.7mmol, 2M) is eventually adding 1.4g Pd (PPh3)4(2mol%).110 DEG C are warming up to, Reaction terminates for 12 hours.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain in 32.8g Mesosome (13), yield 73%.
The synthesis of intermediate (14)
[reaction equation 14]
By the obtained product of 32.8g (44.5mmol) [reaction equation 13] and 12.3g (48.9mmol) 6- bromonaphthalene -2- boric acid, It is added in the three-necked flask of 2L, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, lead to nitrogen 15 minutes, add 66.8ml K2CO3The aqueous solution of (133.5mmol, 2M) is eventually adding 1.0g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction 12 Hour terminates.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 29.2g intermediate (14), yield 76%.
The synthesis of intermediate (15)
[reaction equation 15]
29.2g (33.8mmol) [reaction equation 14] is added in dry 1L three-necked flask, 21.6g trifluoro-acetate (MTFA, 168.8mmol), 12.8g cesium fluoride (CsF, 84.5mmol), 6.4g cuprous iodide (CuI, 33.8mmol), 600ml DMF is warming up to 180 DEG C, reacts 8h.To after, near room temperature, active carbon depigmentation is filtered, is extracted with dichloromethane, water It washes repeatedly, dry, rotation removes solvent, and dress silica gel crosses column, obtains intermediate (15) 26.3g, yield 91%.
The synthesis of intermediate (16)
[reaction equation 16]
The product and [reaction equation that 20.8g (30.8mmol) [reaction equation 7] obtains are added in dry 2L three-necked flask 15] the product 26.3g (30.8mmol) obtained adds dry and degasification 500ml DMF and makees solvent, is slow added into 30.1g (92.4mmol) cesium carbonate.160 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, adds water and stirs 1 Hour, there is solid generation, filter, a small amount of ethyl alcohol is added to rinse, it is dry, with toluene and ethyl alcohol recrystallization, obtain 33.5g intermediate (16), yield 72%.
The synthesis of compound 15
[reaction equation 17]
Experimental provision is sufficiently dry, 33.5g (22.2mmol, 1.1eq.) [reaction equation 16] is added in 2L three-necked flask Obtained reaction product is added the dried tetrahydrofuran of 800ml, -78 DEG C is cooled to after dissolution, 9.7ml 2.5M is added dropwise The n-BuLi of (24.2mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 4.7g is added dropwise at such a temperature (20.2mmol, 1.0eq.) 2- Benzophenone base naphthalene, is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid is added Solution is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dry, and rotation removes solvent, sufficiently dry, then feeds intake Into the drying three-necked flask of 2L, 400ml acetic anhydride is added, is warming up to 120 DEG C, flows back 5 hours, reaction was completed.It is cooled to room Temperature, rotation remove solvent, are dissolved with methylene chloride, are added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, are tied again with toluene and ethyl alcohol Crystalline substance obtains 21.6g compound 15, yield 62%.
The following are the nuclear magnetic resonance spectroscopies of compound 15:1H NMR (DMSO, 300Hz): δ (ppm)=8.58-8.47 (m, 2H),8.45-8.38(m,2H),8.35-8.28(m,3H)8.26-8.08(m,3H),8.05-7.56(m,23H),7.54-7.10 (m,30H),7.08-7.01(s,1H),6.98-6.86(m,3H),6.84-6.73(m,3H),6.71-6.58(m,3H),6.47- 6.32(s,1H)。
MS(FAB):1721(M+)。
Embodiment 2
Organic electroluminescent compounds 32, structural formula is as follows:
The synthetic method of compound 32 is as follows:
The synthesis of intermediate (17)
[reaction equation 18]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 25.9g (100mmol, 1.0eq.) 2- bromine is added dropwise at such a temperature Fluorenone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase It is washed to neutrality with saturated common salt, dry, rotation removes solvent, and it is sufficiently dry, then be dosed into the drying three-necked flask of 2L, it is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 34.7g intermediate (17), yield 78%.
The synthesis of intermediate (18)
[reaction equation 19]
Feed intake intermediate (17) 34.7g (78mmol) that [reaction equation 18] obtain in the three-necked flask of 2L, with trifluoro second Acid makees solvent 600ml, adds 5.9g (93.6mmol, 1.2eq.) concentrated nitric acid, is heated to 80 DEG C, flows back 12 hours.Wait react Terminate, be cooled to room temperature, 1L water is added, has solid generation, lowers to temperature, filter, obtained filter cake is repeatedly washed, and second is used Alcohol recrystallization, it is dry, obtain 34.8g intermediate (18), yield 91%.
The synthesis of intermediate (19)
[reaction equation 20]
By the obtained product of 34.8g (71mmol) [reaction equation 19] and 9.5g (78.1mmol) phenyl boric acid, it is added to 2L's In three-necked flask, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 107ml K2CO3 The aqueous solution of (213mmol, 2M) is eventually adding 1.6g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, it with toluene and ethyl alcohol recrystallization, obtains 38.2g intermediate (19), produces Rate is 81%.
The synthesis of intermediate (20)
[reaction equation 21]
The product 31.5g (64.6mmol) that [reaction equation 20] obtains is added in the three-necked flask of 2L, with threeway, extraction Nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% palladium later Carbon 1.6g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), be careful not to drain and (can suitably add a little water), To last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains 27.5g intermediate (20), yield 93%.
The synthesis of intermediate (21)
[reaction equation 22]
Product and 21.9g that 27.5g (60.1mmol) [reaction equation 21] obtains are added in dry 2L three-necked flask (54.6mmol) N- (4- bromophenyl -)-N- phenyl-benzidine adds dry and degasification 600ml toluene and makees solvent.Add Enter 15.7g (163.8mmol) sodium tert-butoxide, 0.25g catalyst acetic acid palladium (2%mol) and 1.4g ligand 1,1'- dinaphthalene -2,2'- Double diphenyl phosphines (BINAP, 4%mol).110 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, adds active carbon Absorption filters, and rotation removes solvent and obtains 37.8g intermediate (21), yield 89% with toluene and ethyl alcohol recrystallization.
The synthesis of compound 32
[reaction equation 23]
Experimental provision is sufficiently dry, 37.8g (48.6mmol, 1.1eq.) [reaction equation 22] is added in 2L three-necked flask Obtained reaction product is added the dried tetrahydrofuran of 600ml, -78 DEG C is cooled to after dissolution, 21.2ml 2.5M is added dropwise The n-BuLi of (53.0mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 8.1g is added dropwise at such a temperature (44.2mmol, 1.0eq.) benzophenone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, It being extracted with dichloromethane, organic phase is washed to neutrality with saturated common salt, and dry, rotation removes solvent, and it is sufficiently dry, then it is dosed into 2L's In dry three-necked flask, 400ml acetic anhydride is added, is warming up to 120 DEG C, flows back 5 hours, reaction was completed.It is cooled to room temperature, rotation removes Solvent is dissolved with methylene chloride, is added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, with toluene and ethyl alcohol recrystallization, is obtained 31.2g compound 32, yield 75%.
The following are the nuclear magnetic resonance spectroscopies of compound 32:1H NMR (DMSO, 300Hz): δ (ppm)=8.37-8.23 (d, 1H),8.17-8.02(d,1H),7.88-7.69(m,2H),7.66-7.04(m,33H),6.98-6.87(d,1H),6.84- 6.76(t,1H),6.72-6.54(m,4H),6.49-6.26(m,5H)。
MS(FAB):941(M+)。
Embodiment 3
Organic electroluminescent compounds 44, structural formula is as follows:
The synthetic method of compound 44 is as follows:
The synthesis of intermediate (22)
[reaction equation 24]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 18.0g (100mmol, 1.0eq.) 9- fluorenes is added dropwise at such a temperature Ketone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase is used Saturated common salt is washed to neutrality, dry, and rotation removes solvent, sufficiently dry, then is dosed into the drying three-necked flask of 2L, is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 28.9g intermediate (22), yield 79%.
The synthesis of intermediate (23)
[reaction equation 25]
Feed intake the product 28.9g (79mmol) that [reaction equation 24] obtain in the three-necked flask of 2L, is made with trifluoroacetic acid molten Agent 600ml adds 6.0g (94.8mmol, 1.2eq.) concentrated nitric acid, is heated to 80 DEG C, flows back 12 hours.It is cold to the end of reacting But to room temperature, 1L water is added, has solid generation, lowers to temperature, filter, obtained filter cake is repeatedly washed, tied again with ethyl alcohol Crystalline substance, it is dry, obtain 29.6g intermediate (23), yield 91%.
The synthesis of intermediate (24)
[reaction equation 26]
The product 29.6g (71.9mmol) that [reaction equation 25] obtains is added in the three-necked flask of 2L, with threeway, extraction Nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% palladium later Carbon 1.5g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), be careful not to drain and (can suitably add a little water), To last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains 25.2g intermediate (24), yield 92%.
The synthesis of intermediate (25)
[reaction equation 27]
By the fluoro- 2- iodobenzene of the bromo- 1- of 30.1g (100mmol) 4- and 13.4g (110mmol) phenyl boric acid, it is added to three mouthfuls of 2L In flask, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol,2M) Aqueous solution, be eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Active carbon is added to inhale It is attached, it filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 22.3g intermediate (25), yield 89%.
The synthesis of intermediate (26)
[reaction equation 28]
Be added in dry 2L three-necked flask [reaction equation 27] obtained intermediate (25) 22.3g (89mmol) and 19.5g (89mmol) N- phenyl-2-naphthylamine adds dry and degasification 400ml DMF and makees solvent, is slow added into 87.0g (267mmol) cesium carbonate.160 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, it is small to add water and stir 1 When, there is solid generation, filter, a small amount of ethyl alcohol is added to rinse, it is dry, with toluene and ethyl alcohol recrystallization, obtain 34.1g intermediate (26), yield 85%.
The synthesis of intermediate (27)
[reaction equation 29]
Be added in dry 2L three-necked flask 25.2g (66.1mmol) [reaction equation 27] obtained intermediate (24) and The intermediate (26) that 27.0g (60.1mmol) [reaction equation 28] is obtained, add dry and degasification 600ml toluene make it is molten Agent.17.3g (180.3mmol) sodium tert-butoxide, 0.39g catalyst acetic acid palladium (2%mol) and 1.5g ligand 1,1'- dinaphthalene-is added 2,2'- bis- diphenyl phosphines (BINAP, 4%mol).110 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, adds work Property charcoal absorption, filter, rotation is obtained 37.0g intermediate (27) with toluene and ethyl alcohol recrystallization except solvent, yield 82%.
The synthesis of compound 44
[reaction equation 30]
Experimental provision is sufficiently dry, 37.0g (49.3mmol, 1.1eq.) [reaction equation 29] is added in 2L three-necked flask Obtained intermediate (27) is added the dried tetrahydrofuran of 800ml, -78 DEG C is cooled to after dissolution, 21.5ml 2.5M is added dropwise The n-BuLi of (53.8mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 10.4g is added dropwise at such a temperature (44.8mmol, 1.0eq.) benzophenone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, It being extracted with dichloromethane, organic phase is washed to neutrality with saturated common salt, and dry, rotation removes solvent, and it is sufficiently dry, then it is dosed into 2L's In dry three-necked flask, 400ml acetic anhydride is added, is warming up to 120 DEG C, flows back 5 hours, reaction was completed.It is cooled to room temperature, rotation removes Solvent is dissolved with methylene chloride, is added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, with toluene and ethyl alcohol recrystallization, is obtained 28.5g compound 44, yield 66%.
The following are the nuclear magnetic resonance spectroscopies of compound 44:1H NMR (DMSO, 300Hz): δ (ppm)=8.43-8.25 (d, 1H),8.21-8.07(d,1H),8.05-7.71(m,9H),7.68-7.01(m,29H),6.97-6.88(d,1H),6.86- 6.77(t,1H),6.71-6.58(m,3H),6.51-6.38(m,2H),6.36-6.24(d,1H)。
MS(FAB):965(M+)。
Embodiment 4
Organic electroluminescent compounds 73, structural formula is as follows:
The synthetic method of compound 73 is as follows:
The synthesis of intermediate (28)
[reaction equation 31]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 25.9g (100mmol, 1.0eq.) 4- bromine is added dropwise at such a temperature Fluorenone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase It is washed to neutrality with saturated common salt, dry, rotation removes solvent, and it is sufficiently dry, then be dosed into the drying three-necked flask of 2L, it is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 33.4g intermediate (28), yield 75%.
The synthesis of intermediate (29)
[reaction equation 32]
Feed intake the product 33.4g (75mmol) that [reaction equation 31] obtain in the three-necked flask of 2L, is made with trifluoroacetic acid molten Agent 600ml adds 5.7g (90.0mmol, 1.2eq.) concentrated nitric acid, is heated to 80 DEG C, flows back 12 hours.It is cold to the end of reacting But to room temperature, 1L water is added, has solid generation, lowers to temperature, filter, obtained filter cake is repeatedly washed, tied again with ethyl alcohol Crystalline substance, it is dry, obtain 33.1g intermediate (29), yield 90%.
The synthesis of intermediate (30)
[reaction equation 33]
By the obtained product of 33.1g (67.5mmol, 1.0eq.) [reaction equation 32] and 4.9g (101.3mmol, 1.5eq.) Cymag is put into the three-necked flask of 2L, and with 600ml N, N '-dimethyl formamide (DMF) makees solvent, is heated to 120 DEG C, instead It answers 15 hours.To the end of reacting, it is down to room temperature, water is added, a large amount of solids is had and is precipitated, stir 1 hour, filter, repeatedly wash, It is dry, with ethyl alcohol recrystallization, obtain intermediate (30) 26.8g, yield 91%.
The synthesis of intermediate (31)
[reaction equation 34]
The product 26.8g (61.4mmol) that [reaction equation 33] obtains is added in the three-necked flask of 2L, with threeway, extraction Nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% palladium later Carbon 1.3g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), be careful not to drain and (can suitably add a little water), To last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains 23.0g intermediate (31), yield 92%.
The synthesis of intermediate (32)
[reaction equation 35]
28.0g (100mmol) 3- iodine biphenyl and 18.6g (110mmol) are added in dry 2L three-necked flask to phenyl Aniline adds dry and degasification 600ml toluene and makees solvent.28.8g (300mmol) sodium tert-butoxide, 0.45g catalysis is added Agent palladium acetate (2%mol) and 2.5g ligand 1, the bis- diphenyl phosphines of 1'- dinaphthalene -2,2'- (BINAP, 4%mol).110 DEG C are warming up to, Reaction 15 hours.It to the end of reacting, is cooled to room temperature, adds activated carbon adsorption, filter, rotation removes solvent, is tied again with toluene and ethyl alcohol Crystalline substance obtains 28.6g intermediate (32), yield 89%.
The synthesis of intermediate (33)
[reaction equation 36]
Product and 29.0g that 28.6g (89mmol) [reaction equation 35] obtains are added in dry 2L three-necked flask The iodo- 4 '-bromo biphenyl of (80.9mmol) 4- adds dry and degasification 600ml toluene and makees solvent, leads to nitrogen 15 minutes.Add Enter 23.3g (242.7mmol) sodium tert-butoxide, 1.48g (2%mol) catalyst Pd2(dba)3With 6.5ml (4%mol) P (t-bu)3 Toluene solution (m/v, 10%).110 DEG C are warming up to, is reacted 16 hours.It to the end of reacting, is cooled to room temperature, active carbon is added to inhale It is attached, it filters, rotation removes solvent and obtains 36.7g intermediate (33), yield 82% with toluene and ethyl alcohol recrystallization.
The synthesis of intermediate (34)
[reaction equation 37]
Product and 28.4g that 23.0g (56.6mmol) [reaction equation 34] obtains are added in dry 2L three-necked flask The product that (51.4mmol) [reaction equation 36] obtains adds dry and degasification 600ml toluene and makees solvent.14.8g is added (154.2mmol) sodium tert-butoxide, 0.23g catalyst acetic acid palladium (2%mol) and 1.3g ligand 1, the bis- hexichol of 1'- dinaphthalene -2,2'- Phosphine (BINAP, 4%mol).110 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, adds activated carbon adsorption, take out Filter, rotation remove solvent and obtain 39.7g intermediate (34), yield 88% with toluene and ethyl alcohol recrystallization.
The synthesis of compound 73
[reaction equation 38]
Experimental provision is sufficiently dry, 39.7g (45.2mmol, 1.1eq.) [reaction equation 37] is added in 2L three-necked flask Obtained reaction product is added the dried tetrahydrofuran of 800ml, -78 DEG C is cooled to after dissolution, 19.7ml 2.5M is added dropwise The n-BuLi of (49.3mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 10.6g is added dropwise at such a temperature (41.1mmol, 1.0eq.) biphenyl -4- Benzophenone, is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid is added Solution is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dry, and rotation removes solvent, sufficiently dry, then feeds intake Into the drying three-necked flask of 2L, 400ml acetic anhydride is added, is warming up to 120 DEG C, flows back 5 hours, reaction was completed.It is cooled to room Temperature, rotation remove solvent, are dissolved with methylene chloride, are added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, are tied again with toluene and ethyl alcohol Crystalline substance obtains 29.9g compound 73, yield 65%.
The following are the nuclear magnetic resonance spectroscopies of compound 73:1H NMR (DMSO, 300Hz): δ (ppm)=8.41-8.26 (d, 1H),8.22-8.07(d,1H),7.84-7.69(d,1H),7.66-7.49(m,14H),7.47-7.02(m,27H),6.98- 6.93(d,1H),6.91-6.76(m,2H),6.72-6.53(m,7H),6.50-6.36(s,1H)。
MS(FAB):1118(M+)。
Embodiment 5
Organic electroluminescent compounds 93, structural formula is as follows:
The synthetic method of compound 93 is as follows:
The synthesis of intermediate (35)
[reaction equation 39]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 18.0g (100mmol, 1.0eq.) 9- fluorenes is added dropwise at such a temperature Ketone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase is used Saturated common salt is washed to neutrality, dry, and rotation removes solvent, sufficiently dry, then is dosed into the drying three-necked flask of 2L, is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 28.9g intermediate (35), yield 79%.
The synthesis of intermediate (36)
[reaction equation 40]
Feed intake the product 28.9g (79mmol) that [reaction equation 39] obtain in the three-necked flask of 2L, is made with trifluoroacetic acid molten Agent 600ml adds 6.0g (94.8mmol, 1.2eq.) concentrated nitric acid, is heated to 80 DEG C, flows back 12 hours.It is cold to the end of reacting But to room temperature, 1L water is added, has solid generation, lowers to temperature, filter, obtained filter cake is repeatedly washed, tied again with ethyl alcohol Crystalline substance, it is dry, obtain 29.6g intermediate (36), yield 91%.
The synthesis of intermediate (37)
[reaction equation 41]
In the three-necked flask of 2L, the product 29.6g (71.9mmol) that investment [reaction equation 40] obtains, with 300ml acetic acid Make solvent, divide 3 batches of dropwise addition 17.2g (107.9mmol, 1.5eq.) bromines at room temperature, drips and be warming up to 120 DEG C, reaction 18 Hour.After reaction, it is cooled to room temperature, 500ml water is added, a large amount of solids are precipitated, stir 1 hour, filter, repeatedly wash, Toluene and ethyl alcohol recrystallization are used after drying, obtain 27.9g intermediate (37), yield 79%.
The synthesis of intermediate (38)
[reaction equation 42]
By 3,3 '-'-dibromobiphenyl of 31.2g (100mmol) and 13.4g (110mmol) phenyl boric acid, it is added to three mouthfuls of burnings of 2L In bottle, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol, 2M's) Aqueous solution is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add activated carbon adsorption, It filtering, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain 25.4g intermediate (38), yield 82%.
The synthesis of intermediate (39)
[reaction equation 43]
In dry 2L three-necked flask, product and 22.9g that investment 25.4g (82mmol) [reaction equation 42] obtains (90.2mmol) joins pinacol borate, makees solvent with 600ml Isosorbide-5-Nitrae-dioxane, leads to nitrogen 15 minutes, adds 1.5g (2%mol) Pd (dppf) Cl2With 29.4g (300mmol) potassium acetate, 120 DEG C are warming up to, back flow reaction 6 hours, reaction terminated, It is down to room temperature, adds active carbon, crosses short column of silica gel, is filtered, filtrate is spin-dried for, and crosses chromatographic column, obtains intermediate (39) 33.8g, yield It is 89%.
The synthesis of intermediate (40)
[reaction equation 44]
The obtained product of 27.9g (56.9mmol) [reaction equation 41] and 22.3g (62.6mmol) [reaction equation 43] are obtained Product, be added in the three-necked flask of 2L, 600ml toluene and the dissolution of 150ml ethyl alcohol be added, leads to nitrogen 15 minutes, adds 85.4ml K2CO3The aqueous solution of (170.7mmol, 2M) is eventually adding 1.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, Reaction terminates for 12 hours.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, obtain in 33.1g Mesosome (40), yield 91%.
The synthesis of intermediate (41)
[reaction equation 45]
The product 33.1g (71.9mmol) that [reaction equation 44] obtains is added in the three-necked flask of 2L, with threeway, extraction Nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% palladium later Carbon 1.7g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), be careful not to drain and (can suitably add a little water), To last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains 39.5g intermediate (41), yield 90%.
The synthesis of intermediate (42)
[reaction equation 46]
Product and 16.6g that 39.5g (64.7mmol) [reaction equation 45] obtains are added in dry 2L three-necked flask (58.8mmol) adds dry and degasification 400ml toluene and makees solvent to bromo-iodobenzene.17.0g (176.4mmol) uncle is added Sodium butoxide, 0.26g catalyst acetic acid palladium (2%mol) and 1.5g ligand 1, and the bis- diphenyl phosphines of 1'- dinaphthalene -2,2'- (BINAP, 4% mol).110 DEG C are warming up to, is reacted 6 hours.It to the end of reacting, being cooled to room temperature, adds activated carbon adsorption, filter, rotation removes solvent, With toluene and ethyl alcohol recrystallization, 40.0g intermediate (42), yield 89% are obtained.
The synthesis of intermediate (43)
[reaction equation 47]
By 39.5g (100mmol) 3- bromo- 9,9 '-spiral shell, two fluorenes and 15.0g (110mmol) phenyl boric acid are added to three mouthfuls of 2L In flask, 800ml toluene and the dissolution of 200ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol,2M) Aqueous solution, be eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Active carbon is added to inhale It is attached, it filters, rotation removes solvent, and it is dry, with toluene and ethyl alcohol recrystallization, 34.1g intermediate (43) are obtained, yield is 83%.
The synthesis of intermediate (44)
[reaction equation 48]
3.6g Mg (150mmol, 1.5eq.) is added in the three-necked flask of dry 2L, 15ml THF, 0.36g I2, Initiation reaction is heated, then the bromo- 1- amido naphthalene of 24.4g (110mmol, 1.1eq.) 6- and 300ml THF are added dropwise at room temperature Mixed solution, reacted 2 hours at 51 DEG C again after completion of dropwise addition, stand 5 minutes, supernatant is added drop-wise to 10.9g In (100mmol, 1.0eq.) trimethylsilyl chloride and 100ml THF solution, it is warming up to 51 DEG C later, reacts 15 hours.To anti- It should terminate, be cooled to room temperature, water quenching is added dropwise and goes out, is extracted with methylene chloride and water, washes, dry, rotation removes solvent, is mentioned with chromatographic column It is pure, obtain intermediate (44) 18.3g, yield 85%.
The synthesis of intermediate (45)
[reaction equation 49]
Product 31.7g (77.2mmol) and 18.3g that [reaction equation 47] obtains are added in dry 2L three-necked flask The product that (85mmol) [reaction equation 48] obtains adds dry and degasification 600ml DMF and makees solvent, is slow added into 75.5g (231.6mmol) cesium carbonate.160 DEG C are warming up to, is reacted 16 hours.It to the end of reacting, is cooled to room temperature, adds water and stirs 1 Hour, there is solid generation, filter, a small amount of ethyl alcohol is added to rinse, it is dry, with toluene and ethyl alcohol recrystallization, obtain 38.8g intermediate (45), yield 83%.
The synthesis of intermediate (46)
[reaction equation 50]
Product and 31.7g that 40g (52.3mmol) [reaction equation 46] obtains are added in dry 2L three-necked flask The product that (52.3mmol) [reaction equation 49] obtains adds dry and degasification 800ml toluene and makees solvent, and logical nitrogen 15 divides Clock.15.1g (156.9mmol) sodium tert-butoxide, 0.96g (2%mol) catalyst Pd is added2(dba)3With 4.2ml (4%mol) P (t-bu)3Toluene solution (m/v, 10%).110 DEG C are warming up to, is reacted 16 hours.It to the end of reacting, is cooled to room temperature, adds work Property charcoal absorption, filter, rotation is obtained 54g intermediate (46) with toluene and ethyl alcohol recrystallization except solvent, yield 80%.
The synthesis of compound 93
[reaction equation 51]
Experimental provision is sufficiently dry, 54.0g (41.8mmol, 1.1eq.) [reaction equation 50] is added in 2L three-necked flask Obtained reaction product is added the dried tetrahydrofuran of 1000ml, -78 DEG C is cooled to after dissolution, 18.2ml 2.5M is added dropwise The n-BuLi of (45.6mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 8.8g is added dropwise at such a temperature (38.0mmol, 1.0eq.) 2- Benzophenone naphthalene, is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, it is molten that 4M hydrochloric acid is added Liquid is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dry, and rotation removes solvent, sufficiently dry, then is dosed into In the drying three-necked flask of 2L, 500ml acetic anhydride is added, is warming up to 120 DEG C, flows back 5 hours, reaction was completed.It is cooled to room temperature, Rotation removes solvent, is dissolved with methylene chloride, is added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, with toluene and ethyl alcohol recrystallization, Obtain 38.3g compound 93, yield 67%.
The following are the nuclear magnetic resonance spectroscopies of compound 93:1H NMR (DMSO, 300Hz): δ (ppm)=8.41-8.26 (d, 1H),8.12-7.89(m,7H),7.87-7.80(m,2H),7.78-7.68(m,5H),7.66-7.47(m,16H),7.45- 6.96(m,38H),6.92-6.76(m,2H),6.72-6.58(m,2H)6.54-6.36(m,5H)。
MS(FAB):1503(M+)。
Embodiment 6
Organic electroluminescent compounds 109, structural formula is as follows:
The synthetic method of compound 109 is as follows:
The synthesis of intermediate (47)
[reaction equation 52]
Experimental provision is sufficiently dry, 31.1g (110mmol) 1- (2- bromobenzene) naphthalene is added in 2L three-necked flask, is added 600ml dried tetrahydrofuran is cooled to -78 DEG C after dissolution, the n- of 48ml 2.5M (120mmol, 1.2eq.) is added dropwise BuLi.It is stirred at such a temperature after completion of dropwise addition 1 hour, then 18.0g (100mmol, 1.0eq.) 9- fluorenes is added dropwise at such a temperature Ketone is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, 4M hydrochloric acid solution is added, is extracted with dichloromethane, organic phase is used Saturated common salt is washed to neutrality, dry, and rotation removes solvent, sufficiently dry, then is dosed into the drying three-necked flask of 2L, is added 600ml acetic acid and 150ml HCl are warming up to 120 DEG C, flow back 5 hours, reaction was completed.It is cooled to room temperature, 500ml water, analysis is added Solid out is washed with water 4 times, dry, dry, with toluene and ethyl alcohol recrystallization, obtains 28.9g intermediate (47), yield 79%.
The synthesis of intermediate (48)
[reaction equation 53]
Feed intake the product 28.9g (79mmol) that [reaction equation 52] obtain in the three-necked flask of 2L, is made with trifluoroacetic acid molten Agent 600ml adds 6.0g (94.8mmol, 1.2eq.) concentrated nitric acid, is heated to 80 DEG C, flows back 12 hours.It is cold to the end of reacting But to room temperature, 1L water is added, has solid generation, lowers to temperature, filter, obtained filter cake is repeatedly washed, tied again with ethyl alcohol Crystalline substance, it is dry, obtain 29.6g intermediate (48), yield 91%.
The synthesis of intermediate (49)
[reaction equation 54]
The product 29.6g (71.9mmol) that [reaction equation 53] obtains is added in the three-necked flask of 2L, with threeway, extraction Nitrogen makees solvent three times, with ethyl alcohol/THF=600ml/120ml, and extraction nitrogen three times, then leads to hydrogen, weighs 5% palladium later Carbon 1.5g, normal-temperature reaction 8 hours.It is completed wait react, prepares to filter (diatomite), be careful not to drain and (can suitably add a little water), To last time, wet palladium carbon is filled with water seal.Filtrate is spin-dried for, dry, with ethyl alcohol recrystallization, obtains 25.2g intermediate (49), yield 92%.
The synthesis of intermediate (50)
[reaction equation 55]
The fluoro- 1- iodobenzene of the bromo- 4- of 30.1g (100mmol) 2- and 29.6g are added in dry 2L three-necked flask (110mmol) 2- anilino- is luxuriant and rich with fragrance, adds dry and degasification 600ml toluene and makees solvent, leads to nitrogen 15 minutes.It is added 28.8g (300mmol) sodium tert-butoxide, 1.8g (2%mol) catalyst Pd2(dba)3With 8.1ml (4%mol) P (t-bu)3First Benzole soln (m/v, 10%).110 DEG C are warming up to, is reacted 16 hours.It to the end of reacting, is cooled to room temperature, adds activated carbon adsorption, take out Filter, rotation remove solvent and obtain 39.8g intermediate (50), yield 90% with toluene and ethyl alcohol recrystallization.
The synthesis of intermediate (51)
[reaction equation 56]
By the obtained product of 39.8g (90mmol) [reaction equation 55] and 17.0g (99mmol) 1- naphthalene boronic acids, it is added to 2L's In three-necked flask, 600ml toluene and the dissolution of 150ml ethyl alcohol is added, leads to nitrogen 15 minutes, adds 135ml K2CO3 The aqueous solution of (270mmol, 2M) is eventually adding 2.1g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Adding activated carbon adsorption, filters, rotation removes solvent, and it is dry, it with toluene and ethyl alcohol recrystallization, obtains 39.2g intermediate (51), produces Rate is 89%.
The synthesis of intermediate (52)
[reaction equation 57]
Product 25.2g (66.1mmol) and 32.3g that [reaction equation 54] obtains are added in dry 2L three-necked flask The product that (66.1mmol) [reaction equation 56] obtains adds dry and degasification 500ml DMF and makees solvent, is slow added into 64.6g (198.3mmol) cesium carbonate.160 DEG C are warming up to, is reacted 15 hours.It to the end of reacting, is cooled to room temperature, adds water and stirs 1 Hour, there is solid generation, filter, a small amount of ethyl alcohol is added to rinse, it is dry, with toluene and ethyl alcohol recrystallization, obtain 49.5g intermediate (52), yield 88%.
The synthesis of compound 109
[reaction equation 57]
Experimental provision is sufficiently dry, 49.5g (58.2mmol, 1.1eq.) [reaction equation 57] is added in 2L three-necked flask Obtained reaction product is added the dried tetrahydrofuran of 1000ml, -78 DEG C is cooled to after dissolution, 25.4ml 2.5M is added dropwise The n-BuLi of (63.5mmol, 1.2eq.).It is stirred at such a temperature after completion of dropwise addition 1 hour, then 10.4g is added dropwise at such a temperature (52.9mmol, 1.0eq.) 4,4 '-diphenylbenzophenone, is stirred at room temperature 12 hours after completion of dropwise addition.To the end of reacting, it is added 4M hydrochloric acid solution, is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dry, and rotation removes solvent, sufficiently dry, It is dosed into the drying three-necked flask of 2L again, 600ml acetic anhydride is added, be warming up to 120 DEG C, flowed back 5 hours, reaction was completed.It is cold But to room temperature, rotation removes solvent, is dissolved with methylene chloride, is added suitable quantity of water 3 times, dry, and rotation removes solvent, dry, with toluene and second Alcohol recrystallization, obtains 40.1g compound 109, yield 65%.
The following are the nuclear magnetic resonance spectroscopies of compound 109:1H NMR (DMSO, 300Hz): δ (ppm)=9.03-8.86 (d, 1H),8.71-8.62(d,1H),8.59-8.48(d,1H),8.46-8.37(d,1H),8.33-8.26(d,1H),8.24-8.04 (m,4H),7.97-7.68(m,5H),7.66-7.53(m,13H)7.51-7.01(m,23H),6.98-6.89(d,1H),6.87- 6.76(t,1H),6.71-6.58(m,3H),6.53-6.38(m,2H),6.36-6.24(d,1H)。
MS(FAB):1167(M+)。
" room temperature " or " room temperature " in the various embodiments described above refers to 18 DEG C -28 DEG C.
All organic electroluminescent chemical combination provided by the present invention can be synthesized by the method for above-mentioned reaction equation 1~57 Object.
The structure of organic electroluminescence device of the invention is typical but is not limited to following several:
(1) anode/luminescent layer/cathode；
(2) anode/hole injection layer/luminescent layer/cathode；
(3) anode/hole injection layer/hole transmission layer/luminescent layer/cathode；
(4) anode/hole injection layer/hole transmission layer/electron-blocking layer/luminescent layer/cathode；
(5) anode/luminescent layer/electron injecting layer/cathode；
(6) anode/luminescent layer/electron transfer layer/electron injecting layer/cathode；
(7) anode/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode；
(8) anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/cathode；
(9) anode/hole injection layer/hole transmission layer/electron-blocking layer/luminescent layer/hole blocking layer/electron-transport Layer/electron injecting layer/cathode/coating.
For the manufacturing method for the organic electroluminescence device that structure is (8), comprising the following steps:
Step 1, anode material is crossed into modeling and forms anode in substrate surface, used substrate selection has good clear Property, surface smoothness, operability and waterproofness glass substrate or transparent plastic substrate, anode material can be used it is transparent and pass The property led superior ITO, IZO, SnO2, ZnO etc..
Step 2, by hole injection layer material (HIL) vacuum heat deposition or it is spin-coated on anode surface, hole injection layer material It can be CuPc, m-MTDATA, m-MTDAPB, TCTA, 2-TNATA of star-like amine or from Japanese Idemitsu Kosen Co., Ltd.'s energy The IDE406 etc. enough bought.
Step 3, by hole transport layer material (HTL) vacuum heat deposition or be spin-coated on hole injection layer surface formed hole pass Defeated layer.
Step 4, by emitting layer material (EML) vacuum heat deposition or it is spin-coated on hole transport layer surface, forms luminescent layer.
Step 5, it by electron transport layer materials (ETL) vacuum heat deposition or is spin-coated on luminous layer surface and forms electron-transport Layer.There is no particular limitation for electron transport layer materials, it is preferable to use Alq3。
Step 6, by electron injecting layer material (EIL) vacuum heat deposition or it is spin-coated on electron-transport layer surface, forms electronics Implanted layer.Electron injecting layer substance can be LiF, Liq, Li2O, BaO, NaCl, CsF etc..
Step 7, by cathode material vacuum heat deposition or it is spin-coated on electron injecting layer, forms cathode.Cathode material, Ke Yiwei Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag etc..Alternatively, it is also possible to use tin indium oxide (ITO) or indium zinc oxide (IZO) to make At light transmissive transparent cathode.
Further, it can also add hole blocking layer (HBL), while shine between the light emitting layer and the electron transport layer Layer is used together phosphorescence doping, and the effect for preventing triplet excitons or hole to be diffused into electron transfer layer may be implemented.Using normal Rule method is by hole blocking layer material (HBL) vacuum heat deposition or is spin-coated on luminous layer surface, forms hole blocking layer.Hole resistance There is no particular limitation for interlayer material, organic compound preferably of the invention, Liq, 2- methyl -8-hydroxyquinoline parazon Close aluminium, BCP and LiF etc..
Organic electroluminescence device provided by the invention is done further in detail below with reference to embodiment 7-18 and reference examples 1 Explanation.
Embodiment 7
A kind of organic electroluminescence device uses ITO as reflecting layer anode grid substrate material, and uses N2Plasma or UV-Ozone is surface-treated it.Above anode grid substrate, deposited to hole injection layerThe HAT-CN of thickness.Upper It states above hole injection layer, selects 15 vacuum evaporation of above compoundForm hole transmission layer.In above-mentioned hole transmission layer Upper vacuum evaporation TCTA is formedElectron-blocking layer, above-mentioned electron-blocking layer vapor deposition be capable of forming blue EML main body material 9,10-Bis (2-naphthyl) anthraces (ADN) of materialWith the T-Bu- as dopant doping about 5% Perylene is formedLuminescent layer.Anthracene derivant and Liq are mixed into vapor deposition with the ratio of 1:1 above itThickness Electron transfer layer is spent, is deposited on electron transfer layerLiq as electron injecting layer.In cathode evaporationThickness Silver.Finally it is depositedThe DNTPD of thickness is as coating.It is inhaled in addition, being used in cathode surface containing UV curable adhesive Water material sealing, with protect organic electroluminescence device not by atmosphere oxygen or moisture influence.
The structural formula of involved compound is as follows in the present embodiment:
Embodiment 8~18
Respectively using compound 3,18,19,29,32,44,56,73,93,100 and 109 as hole transmission layer (HTL) object Matter, other parts and embodiment 7 are consistent, produce the organic electroluminescence device of embodiment 8~18 accordingly.
Reference examples 1
Difference with embodiment 7 is, NPD is used to replace organic electroluminescent compounds of the invention as hole transport Layer substance, remaining is same as Example 7.
The organic electroluminescence device that embodiment 7~18 and reference examples 1 are prepared is in current density 10mA/cm2's Under the conditions of be tested for the property, as a result as shown in the table.
As can be known from the above table, had using organic electroluminescent compounds of the invention as prepared by the substance of hole transmission layer The embodiment 7~18 of organic electroluminescence devices is compared with reference examples 1, and luminous efficiency significantly improves, and driving voltage is substantially reduced.
In addition, from above-mentioned experimental result it is found that using organic compound of the invention as hole transporting material, Organic Electricity The luminous efficiency of electroluminescence device is improved.Therefore, organic matter of the invention can be such that the driving voltage of device reduces, and then subtract Few power consumption.Additionally by low voltage drive, the service life of organic electroluminescence device also increases.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (3)

1. a kind of organic electroluminescent compounds, which is characterized in that the structural formula of the compound is as follows:
Wherein, R1、R2And R3It is each independently hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, optionally takes The phenyl in generation, the phenanthryl optionally replaced, the anthryl optionally replaced, the phenanthridinyl optionally replaced, optionally takes the naphthalene optionally replaced In the xenyl in generation, the pyridyl group optionally replaced, the pyrimidine radicals optionally replaced or the triazine radical optionally replaced any one or At least two combination；
R4And R5It is each independently heavy hydrogen, the straight chained alkyl of C1~C20 that optionally replaces or branched alkyl, the benzene optionally replaced Base, the naphthalene optionally replaced, the phenanthryl optionally replaced, the anthryl optionally replaced, the phenanthridinyl optionally replaced, the connection optionally replaced Any one in phenyl, the pyridyl group optionally replaced, the pyrimidine radicals optionally replaced or the triazine radical optionally replaced or at least two The combination of kind；
R6For optionally replace phenyl, optionally replace naphthalene, optionally replace phenanthryl, optionally replace anthryl, optionally replace In phenanthridinyl, the xenyl optionally replaced, the pyridyl group optionally replaced, the pyrimidine radicals optionally replaced or the triazine radical optionally replaced Any one or at least two combination；
R7And R8Be each independently the C1~C20 optionally replaced straight chained alkyl or branched alkyl and/or the C6 optionally replaced~ The aryl of C30；
The integer that n is 1~4；
R7And R8It is mutually not connected to or R7And R8It is interconnected to form aliphatic ring or aromatic ring；
The compound is any one in following compounds:
2. a kind of organic electroluminescence device including organic electroluminescent compounds described in claim 1.
3. organic electroluminescent compounds described in claim 1 are preparing the application in luminescent device.
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