CN103508940A - 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates - Google Patents

6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates Download PDF

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CN103508940A
CN103508940A CN201310250838.1A CN201310250838A CN103508940A CN 103508940 A CN103508940 A CN 103508940A CN 201310250838 A CN201310250838 A CN 201310250838A CN 103508940 A CN103508940 A CN 103508940A
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邱勇
范洪涛
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Abstract

The invention relates to a compound represented by formula (1). When R5 and R6 both represent H, then R7 and R8 are independently selected from C5-C30 nitrogen heterocyclic ring, substituted nitrogen heterocyclic ring or condensed heterocyclic aromatic hydrocarbon containing nitrogen; and R1 and R2 are independently selected from C1-C30 linear hydrocarbon or branched-chain hydrocarbon, C6-C30 substituted or unsubstituted benzene ring or polycyclic aromatic hydrocarbon; or R1 and R2 represent cyclic compounds formed by connection with other groups. Or when R7 and R8 both represent H, then R5 and R6 are independently selected from C5-C30 nitrogen heterocyclic ring, substituted nitrogen heterocyclic ring or condensed heterocyclic aromatic hydrocarbon containing nitrogen; and R1 and R2 are independently selected from C1-C30 linear hydrocarbon or branched-chain hydrocarbon, C6-C30 substituted or unsubstituted benzene ring or polycyclic aromatic hydrocarbon; or R1 and R2 represent cyclic compounds formed by connection with other groups. The invention also discloses applications of the 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates in organic light-emitting devices (OLED), and especially applications of the 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates as electron transport materials, and fluorescence or red phosphorescence host materials in OLED.

Description

A kind of 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, intermediate and preparation method and application
Technical field
The present invention relates to a kind of organic compound, relate in particular to a kind of compound for organic electroluminescence device and preparation method thereof and the application of this compound at organic electroluminescence device; The invention still further relates to the preparation method of intermediate and this intermediate of this compound.
Background technology
Electro optical phenomenon as far back as 20th century the '30s be found, initial luminescent material is ZnS powder, has developed thus LED technology, has been applied on energy-conserving light source widely now.And organic electroluminescent phenomenon is the people such as Pope in 1963, find the earliest, they find that the single layer crystal of anthracene is under the driving of the above voltage of 100V, can send faint blue light.Until the people such as doctor Deng Qingyun of Kodak in 1987 make bi-layer devices by organic fluorescent dye in vacuum evaporation mode, at driving voltage, be less than under the voltage of 10V, external quantum efficiency has reached 1%, make electroluminescent organic material and device there is the possibility of practicality, from then on greatly promoted the research of OLED material and device.
With respect to phosphor, electroluminescent organic material has the following advantages: 1. organic materials good processability, can by evaporation or spin coating method, film forming on any substrate; 2. the diversity of organic molecular structure makes to regulate thermostability, mechanical properties, the luminous and conductivity of organic materials by the method for Molecular Structure Design and modification, makes the material space that is significantly improved.
The principle of luminosity of organic electroluminescent diode is similar with inorganic light-emitting diode.When element is subject to the derivative forward bias voltage drop of direct current, in addition voltage energy will drive electronics (Electron) and hole (Hole) respectively by negative electrode and positive electrode injection element outward, when both meet in luminescent layer, combination, form the compound exciton of so-called electron-hole, exciton is got back to ground state by the form of luminous relaxation, thereby reaches luminous object.
The generation of organic electroluminescent is leaned on is the restructuring of the current carrier (electronics and hole) that transmits in organic semiconductor material, as everyone knows, the electroconductibility of organic materials is very poor, different from inorganic semiconductor is, in organic semiconductor, there is no being with of continuity, the conventional jump theory of transmission of current carrier is described, under the driving of an electric field, electronics is being excited or is being injected in the lumo energy of molecule, reaches the object of electric charge transmission via the lumo energy that jumps to another molecule.In order to make organic electroluminescence device reach breakthrough in application aspect, must overcome the poor difficulty of organic materials charge injection and transmittability.Scientists is by the adjustment of device architecture, for example increase the number of device organic material layer, and make different organic layers play the part of different roles, the functional materials for example having helps electronics to inject from anode from negative electrode and hole, some materials help the transmission of electric charge, some materials play the effect of block electrons and hole transport, certainly in organic electroluminescent, most important versicolor luminescent material also will reach the object matching with adjacent functional material, long organic electroluminescence device of excellent in efficiency life-span is the result of the optimization collocation of device architecture and various organic materialss normally, this is just for the functionalization material that chemists design and develop various structures provides great opportunities and challenges.
Common functionalization organic materials has: hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electron transport material, electronic blocking material and luminous material of main part and luminous object (dyestuff) etc.
Hole-injecting material (HIM) requires its HOMO energy level between anode and hole transmission layer, and the hole that is conducive to increase between interface is injected, and common hole-injecting material has CuPc, TNATA and PEDT:PSS etc.
Figure BDA00003388802900021
Hole mobile material (HTM), requires to have high thermostability (high Tg), has less potential barrier with anode or hole-injecting material, and higher cavity transmission ability can vacuum evaporation form free of pinholes film.Conventional HTM is aromatic multi-amine compounds, is mainly derivative of tri-arylamine group, as: NPB(T g=98 ℃, μ h=1 * 10 -3cm 2v -1s -1), TPD(T g=60 ℃, μ h=1 * 10 -3cm 2v -1s -1), TCTA(T g=151 ℃, μ h=1.5 * 10 -4cm 2v -1s -1, for blue phosphorescent OLED), DTASi(T g=106 ℃, μ h=1 * 10 -3cm 2v -1s -1, for blue phosphorescent OLED) etc.
Figure BDA00003388802900022
Figure BDA00003388802900031
Figure BDA00003388802900032
Electron transport material (Electron transport Material, ETM) requires ETM to have reversible and sufficiently high electrochemical reduction current potential, and suitable HOMO and LUMO can rank value can inject electronics better, and preferably have hole barrier ability; Higher electron transport ability, the film-forming properties having had and thermostability.ETM is generally the aromatic compound of the conjugate planes with electron deficiency structure.Common electron transport material has AlQ 3(μ e=5 * 10 -6cm 2v -1s -1), Bphen(μ e=4 * 10 -4cm 2v -1s -1), BCP (LUMO=3.0eV, μ e=1.1 * 10-3cm 2v -1s -1), PBD(μ e=1.9 * 10 -5cm 2v -1s -1) etc.
Figure BDA00003388802900033
Luminescent layer material of main part (host) need to possess following characteristics: reversible electrochemical redox current potential, the HOMO matching with adjacent hole and electron transfer layer and LUMO can rank, good and match hole and electron transport ability, good high thermostability and film-forming properties, and suitable singlet or triplet state energy gap be used for controlling exciton at luminescent layer, also have and corresponding fluorescence dye or phosphorescent coloring between good energy shift.
The feature that the luminescent material of luminescent layer need to have has: have high fluorescence or phosphorescence quantum yield; It is overlapping that the absorption spectrum of dyestuff and the emmission spectrum of main body have had, and main body and dyestuff energy are adaptive, transmission ofenergy effectively from main body to dyestuff; The emission peak of red, green, blue look narrow is as far as possible, with the purity of color obtaining; Good stability, can carry out evaporation etc.
Figure BDA00003388802900034
Figure BDA00003388802900035
Figure BDA00003388802900041
Summary of the invention
The object of the present invention is to provide a kind of electron transfer layer of organic electroluminescence device and organic materials of luminescent layer of can be used for, the scheme that the present invention takes is for this reason:
A kind of 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, have structure as the formula (1):
Figure BDA00003388802900051
Wherein:
Work as R 5, R 6while being H simultaneously, R 7, R 8respectively independently selected from C 5-C 30nitrogen heterocyclic ring, substituted azetidine or thick nitrogen heterocyclic ring aromatic hydrocarbons, and
R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound;
Or,
Work as R 7, R 8while being H simultaneously, R 5, R 6respectively independently selected from C 5-C 30nitrogen heterocyclic ring, substituted azetidine or thick nitrogen heterocyclic ring aromatic hydrocarbons, and
R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound.
Described R 1, R 2independent of one another is methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl ,-(CH 2) n-and n>=3, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, phenanthryl, anthryl, 9-replacement anthryl, pyrenyl, fluorenyl or replacement fluorenyl.
Described R 1, R 2directly be connected to form ring compound, or by-CH 2cH 2cH 2cH 2-or 2,2 '-xenyl connects into ring compound.
Described derivative has the structure shown in formula (2) or formula (3):
Figure BDA00003388802900052
Further R 5, R 6, R 7, R 8independent of each other is pyridyl, substituted pyridinyl, pyridyl phenyl, imidazoles, substituted imidazole, thiazole, substituted thiazole, oxazole, substituted oxazole, quinolyl or isoquinolyl.
More excellent, R 5with R 6identical, R 7with R 8identical.
Described 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, are selected from following structural formula:
Figure BDA00003388802900054
Figure BDA00003388802900061
Figure BDA00003388802900071
Figure BDA00003388802900091
Figure BDA00003388802900101
It is a kind of for the preparation of described 6 that the present invention also provides, the intermediate of two replacement-6-H-benzo [cd] pyrene derivatives of 6-, and described intermediate has the structure shown in formula (4) or formula (5):
Figure BDA00003388802900102
Figure BDA00003388802900103
Wherein, R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound.
Described intermediate is the structure shown in formula (A), formula (B), formula (C) or formula (D):
The present invention also provides a kind of method of preparing described intermediate A, comprises the steps:
(1), by 10 shown in formula A-I, 10-dimethyl anthrone and nitric acid generation nitration reaction, obtain the two nitro-compounds that replace shown in formula A-II;
(2) by compound and carbon tetrabromide shown in formula A-II, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula A-III, 1-dibromo olefin(e) compound;
(3) under nitrogen protection, by compound shown in formula A-III and trimethylsilyl acetylene at PdCl 2(PPh 3) 2under existing with CuI, there is Sonogashira reaction, then carry out catalysis and take off the trimethyl silicon based two alkine compounds shown in formula A-IV that obtain;
(4) under nitrogen protection, compound shown in formula A-IV is dissolved in dry toluene, add PtCl 2there is ring closure reaction, obtain the compound shown in formula A-V;
(5) compound shown in formula A-V is dissolved in the mixed solvent of ethanol and THF, under the existence of Pd/C, carries out catalytic hydrogenation nitroreduction is become to amido, then carry out diazotization-bromination reaction and obtain the intermediate shown in formula (A);
Figure BDA00003388802900112
The present invention also provides a kind of method of preparing described intermediate B, comprises the steps:
(1) under the condition as alkali, there are two alkyl cyclizations and obtain the compound shown in formula B-I in anthrone and Isosorbide-5-Nitrae-bis-butyl iodide at potassium tert.-butoxide;
(2) two replacement anthracyclinone derivatives and nitric acid shown in formula B-I are issued to raw nitration reaction in the existence of the vitriol oil, obtain the two nitro-compounds that replace shown in formula B-II;
(3) by compound and carbon tetrabromide shown in formula B-II, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula B-III, 1-dibromo olefin(e) compound;
(4) under nitrogen protection, by compound shown in formula B-III and trimethylsilyl acetylene at PdCl 2(PPh 3) 2under existing with CuI, there is Sonogashira reaction, then carry out catalysis and take off the trimethyl silicon based two alkine compounds shown in formula B-IV that obtain;
(5) under nitrogen protection, compound shown in formula B-IV is dissolved in dry toluene, add PtCl 2there is ring closure reaction, obtain the compound shown in formula B-V;
(6) compound shown in formula B-V is dissolved in the mixed solvent of ethanol and THF, under the existence of Pd/C, carries out catalytic hydrogenation nitroreduction is become to amido, then carry out diazotization-bromination reaction and obtain the intermediate shown in formula (B);
The present invention also provides a kind of method of preparing described intermediate C, comprises the steps:
(1) by dimethyl anthrone and carbon tetrabromide shown in formula C-I, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula C-II, 1-dibromo olefin(e) compound;
(2) by Pd (PPh 3) 4the cross-coupling reaction of the C-II of catalysis and Reformasky reagent, obtains the di-ester-base compound shown in C-III;
(3) by compound shown in formula C-III through basic hydrolysis, chloride, obtain the compound shown in formula C-IV;
(4) by the compound process AlCl shown in formula C-IV 3the ring closure reaction of catalysis makes the bisphenol cpd shown in formula C-V;
(5) by compound shown in formula C-V through Br 2-PPh 3reagent effect, obtains the intermediate shown in formula (C);
Figure BDA00003388802900131
The present invention also provides a kind of method of preparing described intermediate D, comprises the steps:
(1) under the condition as alkali, there are two alkyl cyclizations and obtain the compound shown in formula D-I in anthrone and Isosorbide-5-Nitrae-bis-butyl iodide at potassium tert.-butoxide;
(2) by the compound shown in D-I and carbon tetrabromide, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula D-II, 1-dibromo olefin(e) compound;
(3) by Pd (PPh 3) 4the cross-coupling reaction of the D-II of catalysis and Reformasky reagent, obtains the di-ester-base compound shown in D-III;
(4) by compound shown in formula D-III through basic hydrolysis, chloride, obtain the compound shown in formula D-IV;
(5) by the compound process AlCl shown in formula D-IV 3the ring closure reaction of catalysis makes the bisphenol cpd shown in formula D-V;
(6) by compound shown in formula D-V through Br 2-PPh 3reagent effect, obtains the intermediate shown in formula (D);
Figure BDA00003388802900132
The present invention also provides a kind of and has prepared describedly 6, and the method for two replacements-6-H-benzo [cd] pyrene derivatives of 6-,, under nitrogen protection, passes through linked reaction by described intermediate and obtain.
The present invention also provides a kind of luminescent layer material of main part of organic electroluminescence device, and described material of main part is described 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
The present invention also provides a kind of organic electroluminescence device, comprises substrate, and is formed on successively anode layer, several luminescence unit layer and cathode layers on described substrate;
Described luminescence unit layer comprises hole transmission layer, organic luminous layer and electron transfer layer, and the material of main part of described luminescent layer is 6 described in one or more, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
Described luminescent layer comprises red phosphorescent luminescent layer, and described red phosphorescent luminescent layer material of main part is 6 described in one or more, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
It is a kind of described 6 that the present invention also provides, and two replacements-6-H-benzo [cd] pyrene derivatives of 6-are used for the application of organic electroluminescence device.
Compared with prior art, compound tool of the present invention has the following advantages:
(1) in the present invention, we have proposed with 2,10-and 3, disubstituted this class 6 of 9-, the novel material of two replacement-6-H benzo [cd] pyrene derivatives of 6-, the groups such as nitrogen heterocyclic ring such as pyridyl, thiazolyl, oxazolyl, imidazolyl or quinolyl, isoquinolyl in molecule with electron deficiency, these compounds have good electron transport ability, by regulating different substituted radicals can further regulate original just good high heat and chemical stability.
(2) this class novel material in the present invention can be used as electron transport material in efficient OLED device, can also be as fluorescence or red phosphorescent material of main part.
Accompanying drawing explanation
Fig. 1 be compd A in the embodiment of the present invention 1 nuclear magnetic spectrogram ( 1h);
Fig. 2 be compd B in the embodiment of the present invention 2 nuclear magnetic spectrogram ( 1h);
Fig. 3 be Compound C in the embodiment of the present invention 3 nuclear magnetic spectrogram ( 1h);
Fig. 4 be Compound D in the embodiment of the present invention 4 nuclear magnetic spectrogram ( 1h);
Fig. 5 be compound TM1 in the embodiment of the present invention 5 nuclear magnetic spectrogram ( 1h);
Fig. 6 be compound TM4 in the embodiment of the present invention 8 nuclear magnetic spectrogram ( 1h);
Fig. 7 be compound TM5 in the embodiment of the present invention 9 nuclear magnetic spectrogram ( 1h);
Fig. 8 be compound TM12 in the embodiment of the present invention 16 nuclear magnetic spectrogram ( 1h);
Fig. 9 be compound TM14 in the embodiment of the present invention 18 nuclear magnetic spectrogram ( 1h);
Figure 10 be compound TM19 in the embodiment of the present invention 23 nuclear magnetic spectrogram ( 1h);
Figure 11 be compound TM24 in the embodiment of the present invention 28 nuclear magnetic spectrogram ( 1h);
Figure 12 be compound TM27 in the embodiment of the present invention 31 nuclear magnetic spectrogram ( 1h);
Figure 13 be compound TM30 in the embodiment of the present invention 34 nuclear magnetic spectrogram ( 1h);
Figure 14 be compound TM33 in the embodiment of the present invention 37 nuclear magnetic spectrogram ( 1h);
Figure 15 be compound TM38 in the embodiment of the present invention 42 nuclear magnetic spectrogram ( 1h);
Figure 16 be compound TM42 in the embodiment of the present invention 46 nuclear magnetic spectrogram ( 1h);
Figure 17 be compound TM43 in the embodiment of the present invention 47 nuclear magnetic spectrogram ( 1h);
Figure 18 be compound TM45 in the embodiment of the present invention 49 nuclear magnetic spectrogram ( 1h);
Figure 19 be compound TM48 in the embodiment of the present invention 52 nuclear magnetic spectrogram ( 1h);
Figure 20 be compound TM49 in the embodiment of the present invention 53 nuclear magnetic spectrogram ( 1h);
Figure 21 be compound TM52 in the embodiment of the present invention 56 nuclear magnetic spectrogram ( 1h);
Figure 22 be compound TM53 in the embodiment of the present invention 57 nuclear magnetic spectrogram ( 1h);
Figure 23 be compound TM54 in the embodiment of the present invention 58 nuclear magnetic spectrogram ( 1h).
Embodiment
Nitric acid used in the present invention, sulfuric acid, carbon tetrabromide, triphenylphosphine, trimethylsilyl acetylene, cuprous iodide, two (triphenylphosphine) palladium chloride, tetrabutyl ammonium fluoride, platinum dichloride, 10% palladium/carbon, Sodium Nitrite, cuprous bromide, 48% Hydrogen bromide, zinc powder, ethyl bromoacetate, four (triphenyl phosphorus) palladium, lithium hydroxide, sulfur oxychloride, aluminum chloride, bromine, 1, 4-bis-butyl iodides, anthrone, tertiary butyl potassium alcoholate, the chemical productss such as carbazole are all bought from domestication chemical product market, 9, 9-dimethyl anthrone is pressed the synthetic (J.Am.Chem.Soc.1975 of literature method, 97, 6790), final step linked reaction boric acid used can be by buying, or according to literature method (D.J.Hall, Boronic Acids:Preparation and Applications in Organic Synthesis and Medicine, Wiley-Vch, 2005) preparation.
Embodiment 1-4 is the Preparation Example of intermediate of the present invention:
Embodiment 1
Intermediate 3 shown in the present embodiment preparation formula (A), 9-bis-is bromo-6,6-dimethyl-6-H benzo [cd] pyrene:
Figure BDA00003388802900151
Synthetic route is as follows:
Figure BDA00003388802900152
Preparation method is:
(1) A-II's is synthetic
In 500mL there-necked flask, add 150mL nitrosonitric acid, with ice-water bath, be cooled to approximately 5 ℃, under stirring, add 22.2g10 in batches, 10-dimethyl anthrone A-I (0.1mol), controlling feed rate makes reacting liquid temperature not higher than 10 ℃, after reactant adds, keep reacting liquid temperature at 5 ℃ of about 30min.Reactant is poured in 400mL frozen water into vigorous stirring, then suction filtration.Filter cake is through washing, dry, with ethanol-sherwood oil mixed solvent recrystallization, obtains 25g faint yellow solid A-II, yield 80%;
(2) A-III's is synthetic
In the dry voltage-resistant reactor of Corey-Fuchs dibromo olefination: 500mL, add 25gA-II(80mmol), 53g carbon tetrabromide (160mmol), reaction system is after three find time-nitrogen circulation, add 250mL dry benzene, mixture stirs 5min, adds 83.7g triphenylphosphine (320mmol).Reaction mixture is vigorous stirring reaction 48h at 150 ℃, etc. system, cools to room temperature, adds enough CH 2cl 2solubilizing reaction mixture.Crude product obtains 22.5g faint yellow solid A-III, yield 60% through column chromatography for separation (pure sherwood oil);
(3) A-IV's is synthetic
Under nitrogen protection, in the withstand voltage reaction flask of 250mL, the triethylamine solution that adds 100mL to contain 5.7mL trimethylsilyl acetylene (40mmol), then add 4.7g dibromo compound A-III(10mmol), 0.7g PdCl 2(PPh 3) 2(1mmol) with 0.38g CuI(2mmol), reaction mixture is heated to 100 ℃, and reacts 20h at this temperature.After system cool to room temperature, add 100mL CH 2cl 2, more successively by saturated ammonium chloride solution and water difference washed twice, dry.Thick product obtains 3.77g light brown solid, yield 75% by column chromatography separation;
Above-mentioned light brown solid is dissolved in to 30mL CH 2cl 2, slowly drip the CH that 15mL contains 10g 4-butyl ammonium fluoride trihydrate 2cl 2solution, the about 1h of stirring reaction at room temperature after adding, TLC detection reaction completes.Reaction soln is filtered by a silica gel short column, drain solvent and obtain 2.7g white solid A-IV, yield approaches 100%;
(4) A-V's is synthetic
Under nitrogen protection, 2.7g(7.5mmol) compd A-IV is dissolved in the toluene that 50mL is dry, adds 0.1gPtCl 2(0.38m mol, 5%eq.).Back flow reaction 6h, reaction solution, without precipitation, with short silicagel column decolouring, obtains 1.35g orange solids compd A-V, productive rate 50%;
(5) intermediate 3 shown in formula A, 9-bis-is bromo-6,6-dimethyl-6-H benzo [cd] pyrene synthetic
1.35g A-V is dissolved in the 1:1 mixed solvent of 10mL ethanol and THF, add 1g10%Pd/C, by find time-replacing hydrogen, make system become hydrogen atmosphere, and be positive hydrogen pressure by hydrogen balloon holder, mixture is stirring reaction 10h at room temperature, and raw material disappears, and removes by filter palladium-carbon catalyst, filtrate obtains 1.3g faint yellow solid, yield 95% after draining;
By 2.98g(10mmol) above-mentioned faint yellow solid is dissolved in 15mL48% Hydrogen bromide, with ice-water bath, reaction system is cooled to below 5 ℃, slowly drips 10mL containing 2.1g NaNO 2(30mmol) the aqueous solution, keeps system temperature not higher than 10 ℃ in dropping process, drip off rear continuation and stir 0.5h at 5 ℃.Then add 5g CuBr-48%HBr(10mL) solution, this system is heated to 80 ℃ and stir 3h at this temperature, adopts CH 2cl 2the product that extraction generates, and separatory is dry, separated 3.2g white solid A, the yield 75% of obtaining of column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compd A refer to table 1, the nuclear-magnetism detection spectrogram of compd A ( 1h) refer to accompanying drawing 1.
Embodiment 2
Intermediate 3 shown in the present embodiment preparation formula B, 9-bis-is bromo-6,6-cyclobutyl-6-H benzo [cd] pyrene:
Figure BDA00003388802900171
Synthetic route is as follows:
Preparation method:
(1) B-I's is synthetic
In 250mL there-necked flask, add 19.4g anthrone (0.1mol), the THF that 150mL is dry, under agitation adds 34.1g1,4-bis-butyl iodides (0.11mol) and 26.8g potassium tert.-butoxide (0.24mol), and reaction system at room temperature stirs 3h, then back flow reaction 3h.Add saturated ammonium chloride solution cancellation reaction, adopt ethyl acetate to extract, separatory is dry, and column chromatography for separation obtains 13.6g white solid B-I, yield 55%;
(2) B-II's is synthetic
This step is basically identical with the step (1) in embodiment 1, and difference is to use B-I as starting raw material (add-on is 24.6g (0.1mol)), and the faint yellow solid B-II obtaining is 26.4g, yield 78%;
(3) B-III's is synthetic
This step is basically identical with the step (2) in embodiment 1, and difference is to use B-II for starting raw material (add-on is 27g(80mmol)), obtaining faint yellow solid B-III is 31.9g(yield 65%);
(4) B-IV's is synthetic
Step (3) in this step and embodiment 1 is basically identical, and difference is, dibromo compound B-III add-on is 4.8g(10mmol), the white solid B-IV finally obtaining is 2.4g, two step total recoverys are about 67%;
(5) B-V's is synthetic
Step (4) in this step and embodiment 1 is basically identical, and difference is, compd B-IV add-on is 2.4g(6.7mmol), the orange solids compd B-V obtaining is 1.2g, productive rate 50%;
(6) intermediate (B) is synthetic
Step (5) in this step and embodiment 1 is basically identical, and difference is, the add-on of B-V is 1.2g, and the faint yellow solid obtaining is 1.15g, yield 94%; Described faint yellow solid add-on in the process of synthetic intermediate (B) is 3.24g(10mmol) the white solid B that obtains is 3.5g, yield 78%.Mass spectrometric detection data and the ultimate analysis data of gained compd B refer to table 1, the nuclear-magnetism detection spectrogram of compd B ( 1h) refer to accompanying drawing 2.
Embodiment 3
Intermediate 2 shown in the present embodiment preparation formula C, 10-bis-is bromo-6,6-dimethyl-6-H benzo [cd] pyrene:
Figure BDA00003388802900181
Synthetic route is:
Figure BDA00003388802900182
Preparation method:
(1) C-II's is synthetic
Step (2) in this step and embodiment 1 is basically identical, and difference is, the add-on of dimethyl anthrone C-I is 22.2g(80mmol), obtaining white solid C-II is 24.5g, yield 65%;
(2) preparation of C-III
N 2under protection, in 250mL there-necked flask, add 2.6g zinc powder (0.04mol), a small amount of iodine; with the dry DMF of 100mL, be stirred to red disappearance, add 5g ethyl bromoacetate (30mmol); be heated to 60 ℃, stir 3h, by the solution filter generating to another dry 250mL there-necked flask.The C-II(10mmol that adds 3.78g to obtain) and 0.55g Pd (PPh 3) 4(0.5mmol, 5%eq.), is heated to 120 ℃, and at this temperature stirring reaction 15h.Add saturated ammonium chloride solution cancellation reaction, profit is extracted with ethyl acetate, and separatory is dry, separated 2g white solid C-III, the yield 55% of obtaining of column chromatography;
(3) preparation of C-IV
By 36.4g C-III(0.1mol) be dissolved in 100mL THF, add 100mL to contain 12g LiOH(0.5mol) the aqueous solution, the system that is at room temperature stirred to becomes homogeneous phase settled solution.Concentrating under reduced pressure reaction solution volume is to 50mL left and right, cooling.Under ice bath, with dilute hydrochloric acid, regulating pH is 1, separates out a large amount of white solids, filters, and washing, is dried to obtain 32g white solid, yield 97%;
The above-mentioned white solid of 32g is dissolved in to 100mL methylene dichloride, adds 40mL SOCl 2, reflux 3h.Removal of solvent under reduced pressure and unreacted sulfur oxychloride, obtain weak yellow liquid C-IV;
(4) preparation of C-V
37.3g C-IV (0.1mol) is dissolved in to 200mL CCl 4in, reaction system is cooled to 0 ℃, then slowly add the powdery AlCl of the new distillation of 40g 3(0.3mol), control temperature of reaction not higher than 10 ℃, after adding, continue reaction 30min.Reaction mixture is poured in frozen water, be extracted with ethyl acetate product, separatory is dry, drains solvent and obtains thick product, and this thick product, by adjusting alkali-acidization to purify, then obtains white solid C-V25g with ethyl alcohol recrystallization, yield 83%;
(5) intermediate 2, and 10-bis-is bromo-6, the preparation of 6-dimethyl-6-H benzo [cd] pyrene (C)
Be equipped with in the 250mL there-necked flask of mechanical stirrer, add triphenylphosphine and dry acetonitrile, under ice-water bath, slowly drip bromine, and control temperature of reaction lower than 40 ℃.Add that to change ice bath after bromine be oil bath, then drip 50mL containing 30g C-V(0.1mol) acetonitrile solution, after adding, reaction system is reacted to 30min at 60-70 ℃, then change water distilling apparatus, steam except acetonitrile.By electric heating bag reacting by heating system, arrive approximately 300 ℃ again, and keep this temperature to stopping discharging HBr.Cooling system, adds sherwood oil, makes product become thin precipitation, filters petroleum ether.Filtrate is through NaOH solution washing, and dry, column chromatography for separation 21g obtains white solid C, yield 50%.Mass spectrometric detection data and the ultimate analysis data of gained Compound C refer to table 1, the nuclear-magnetism detection spectrogram of Compound C ( 1h) refer to accompanying drawing 3.
Embodiment 4
Intermediate shown in the present embodiment preparation formula D:
Figure BDA00003388802900191
Synthetic route is:
Figure BDA00003388802900201
Preparation method is:
(1) D-I's is synthetic
In this step and embodiment 2, the procedure of step (1) is basically identical, obtains the compound shown in formula D-I;
(2) preparation of D-II
This step is basically identical with the step (1) in embodiment 3, and difference is, uses D-I, and add-on is 24.8g(80mmol), obtaining white solid D-II is 20g, yield 50%;
(23) preparation of D-III
This step is basically identical with the step (2) in embodiment 3, and difference is, uses D-II, and add-on is 4g(10mmol), the white solid D-III obtaining is 1.95g, yield 50%;
(4) preparation of D-IV
This step is basically identical with the step (3) in embodiment 3, and difference is, uses D-III, and add-on is 39g(0.1mol), obtaining white solid D-IV is 35g, yield 97%;
(5) preparation of D-V
This step is basically identical with the step (4) in embodiment 3, and difference is, uses D-IV, and add-on is 40g (0.1mol), and the white solid D-V obtaining is 26g, yield 80%;
(6) preparation of intermediate D
This step is basically identical with the step (5) in embodiment 3, and difference is, uses D-V, and add-on is 32.6g(0.1mol), the white solid D obtaining is 27g, yield 60%.Mass spectrometric detection data and the ultimate analysis data of gained Compound D refer to table 1, the nuclear-magnetism detection spectrogram of Compound D ( 1h) refer to accompanying drawing 4.
Embodiment 5-embodiment 56 is for to utilize intermediate A, B, C or D to prepare the embodiment of target compound of the present invention:
Embodiment 5
The present embodiment is prepared compound TM1, and its structure is shown below:
Figure BDA00003388802900211
Synthetic route is:
Figure BDA00003388802900212
Preparation method:
Under nitrogen protection, by 3 shown in 4.3g formula A, 9-bis-bromo-6; 6-dimethyl-6-H benzo [cd] pyrene (10mmol); 3.08g2-pyridine boric acid (25mmol) and 30mL toluene join in three mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mgPd (PPh 3) 4(0.2mmol, 2%eq.), stirs, and is warming up to backflow, by TLC, monitor reaction to complete, stopped reaction, filtered while hot, then rinse with methylene dichloride 50mL, remove solvent under reduced pressure, the thick product obtaining obtains 2.7g white solid TM1, productive rate 65% with sherwood oil/methylene dichloride system column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM1 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM1 ( 1h) refer to accompanying drawing 5.
Embodiment 6
The present embodiment is prepared compound TM2, and its structure is shown below:
Figure BDA00003388802900213
Synthetic route is:
Figure BDA00003388802900214
Preparation method is:
Under nitrogen protection, by 4.3g intermediate 2,10-bis-bromo-6; 6-dimethyl-6-H benzo [cd] pyrene (C) (10mmol); 3.08g2-pyridine boric acid (25mmol) and 30mL toluene join in tri-mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mgPd (PPh 3) 4(0.2mmol, 2%eq.), stir, be warming up to backflow, reaction is monitored by TLC, after reacting completely, stopped reaction, filtered while hot, with methylene dichloride 50mL, rinse again, remove solvent under reduced pressure, the thick product obtaining obtains 3.0g white solid TM2, productive rate 70% with sherwood oil/methylene dichloride system column chromatography.Mass spectrometric detection data and the ultimate analysis data of gained compound TM2 refer to table 1.
Embodiment 7
The present embodiment is prepared compound TM3, and its structure is shown below:
Figure BDA00003388802900221
Synthetic route is:
Figure BDA00003388802900222
Preparation method is:
Under nitrogen protection, intermediate B (10mmol), 3.08g2-pyridine boric acid (25mmol) and 30mL toluene join in tri-mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mg Pd (PPh 3) 4(0.2mmol, 2%eq.), stir, be warming up to backflow, reaction is monitored by TLC, after reacting completely, stopped reaction, filtered while hot, with methylene dichloride 50mL, rinse again, remove solvent under reduced pressure, the thick product obtaining obtains 3.4g white solid TM3, productive rate 76% with sherwood oil/methylene dichloride system column chromatography.Mass spectrometric detection data and the ultimate analysis data of gained compound TM3 refer to table 1.
Embodiment 8
The present embodiment is prepared compound TM4, and its structure is shown below:
Figure BDA00003388802900223
Synthetic route is:
Preparation method is:
Under nitrogen protection, by 4.5g intermediate D (10mmol), 3.08g2-pyridine boric acid (25mmol) and 30mL toluene join in tri-mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mg Pd (PPh 3) 4(0.2mmol, 2%eq.), stirs, and is warming up to backflow, by TLC, monitor reaction to reacting completely, stopped reaction, filtered while hot, then rinse with methylene dichloride 50mL, remove solvent under reduced pressure, the thick product obtaining obtains 3.2g white solid TM4, productive rate 71% with sherwood oil/methylene dichloride system column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM4 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM4 ( 1h) refer to accompanying drawing 6.
Embodiment 9
The present embodiment is prepared compound TM5, and its structure is shown below:
Figure BDA00003388802900231
The 3-pyridine boric acid that 2-pyridine boric acid in embodiment 5 is changed to equivalent, other raw material and step are all same as embodiment 5, and the white solid TM5 obtaining is 2.7g, productive rate 63%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM5 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM5 ( 1h) refer to accompanying drawing 7.
Embodiment 10
The present embodiment is prepared compound TM6, and its structure is shown below:
Figure BDA00003388802900232
The 3-pyridine boric acid that 2-pyridine boric acid in embodiment 6 is changed to equivalent, other raw material and step are all same as embodiment 6, obtain 3.0g white solid TM6, productive rate 72%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM6 refer to table 1.
Embodiment 11
The present embodiment is prepared compound TM7, and its structure is shown below:
Figure BDA00003388802900233
The 3-pyridine boric acid that 2-pyridine boric acid in embodiment 7 is changed to equivalent, other raw material and step are all same as embodiment 7, obtain 3.1g white solid TM7, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM7 refer to table 1.
Embodiment 12
The present embodiment is prepared compound TM8, and its structure is shown below:
Figure BDA00003388802900241
The 3-pyridine boric acid that 2-pyridine boric acid in embodiment 8 is changed to equivalent, other raw material and step are all same as embodiment 8, obtain 2.96g white solid TM8, productive rate 66%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM8 refer to table 1.
Embodiment 13
The present embodiment is prepared compound TM9, and its structure is shown below:
Figure BDA00003388802900242
The 4-pyridine boric acid that 2-pyridine boric acid in embodiment 5 is changed to equivalent, other raw material and step are all same as embodiment 5, obtain 2.96g white solid TM9, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM9 refer to table 1.
Embodiment 14
The present embodiment is prepared compound TM10, and its structure is shown below:
Figure BDA00003388802900243
The 4-pyridine boric acid that 2-pyridine boric acid in embodiment 6 is changed to equivalent, other raw material and step are all same as embodiment 6, obtain 2.7g white solid TM10, productive rate 64%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM10 refer to table 1.
Embodiment 15
The present embodiment is prepared compound TM11, and its structure is shown below:
The 4-pyridine boric acid that 2-pyridine boric acid in embodiment 7 is changed to equivalent, other raw material and step are all same as embodiment 7, obtain 3.18g white solid TM11, productive rate 71%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM11 refer to table 1.
Embodiment 16
The present embodiment is prepared compound TM12, and its structure is shown below:
Figure BDA00003388802900251
The 4-pyridine boric acid that 2-pyridine boric acid in embodiment 8 is changed to equivalent, other raw material and step are all same as embodiment 8, obtain 3.14g white solid TM12, and productive rate is 70%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM12 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM12 ( 1h) refer to accompanying drawing 8.
Embodiment 17
The present embodiment is prepared compound TM13, and its structure is shown below:
5-phenyl-2-pyridine the boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.0g white solid TM13, and productive rate is 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM13 refer to table 1.
Embodiment 18 the present embodiment are prepared compound TM14, and its structure is shown below:
Figure BDA00003388802900253
5-phenyl-2-pyridine the boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 4.77g white solid TM14, productive rate 83%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM14 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM14 ( 1h) refer to accompanying drawing 9.
Embodiment 19 the present embodiment are prepared compound TM15, and its structure is shown below:
Figure BDA00003388802900254
5-phenyl-2-pyridine the boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 4.9g white solid TM15, productive rate 83%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM15 refer to table 1.
Embodiment 20 the present embodiment are prepared compound TM16, and its structure is shown below:
5-phenyl-2-pyridine the boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.2g white solid TM16, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM16 refer to table 1.
Embodiment 21 the present embodiment are prepared compound TM17, and its structure is shown below:
6-phenyl-3-pyridine the boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.5g white solid TM17, productive rate 78%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM17 refer to table 1.
Embodiment 22 the present embodiment are prepared compound TM18, and its structure is shown below:
Figure BDA00003388802900263
6-phenyl-3-pyridine the boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.96g white solid TM18, productive rate 69%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM18 refer to table 1.
Embodiment 23 the present embodiment are prepared compound TM19, and its structure is shown below:
6-phenyl-3-pyridine the boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 4.9g white solid TM19, productive rate 81%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM19 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM19 ( 1h) refer to accompanying drawing 10.
Embodiment 24 the present embodiment are prepared compound TM20, and its structure is shown below:
Figure BDA00003388802900271
6-phenyl-3 pyridine the boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.3g white solid TM20, productive rate 72%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM20 refer to table 1.
Embodiment 25 the present embodiment are prepared compound TM21, and its structure is shown below:
Figure BDA00003388802900272
2-pyridine boric acid in embodiment 5 is replaced with to the 4-(2-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 5, obtain 3.8g white solid TM21, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM21 refer to table 1.
Embodiment 26 the present embodiment are prepared compound TM22, and its structure is shown below:
Figure BDA00003388802900273
2-pyridine boric acid in embodiment 6 is replaced with to the 4-(2-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 6, obtain 3.7g white solid TM22, productive rate 64%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM22 refer to table 1.
Embodiment 27 the present embodiment are prepared compound TM23, and its structure is shown below:
Figure BDA00003388802900274
2-pyridine boric acid in embodiment 7 is replaced with to the 4-(2-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 7, obtain 3.7g white solid TM23, productive rate 62%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM23 refer to table 1.
Embodiment 28 the present embodiment are prepared compound TM24, and its structure is shown below:
2-pyridine boric acid in embodiment 8 is replaced with to the 4-(2-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 8, obtain 3.4g white solid TM24, productive rate 59%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM24 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM24 ( 1h) refer to accompanying drawing 11.
Embodiment 29 the present embodiment are prepared compound TM25, and its structure is shown below:
Figure BDA00003388802900282
2-pyridine boric acid in embodiment 5 is replaced with to the 4-(3-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 5, obtain 3.54g white solid TM25, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM25 refer to table 1.
Embodiment 30 the present embodiment are prepared compound TM26, and its structure is shown below:
Figure BDA00003388802900283
2-pyridine boric acid in embodiment 6 is replaced with to the 4-(3-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 6, obtain 3.85g white solid TM26, productive rate 64%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM26 refer to table 1.
Embodiment 31 the present embodiment are prepared compound TM27, and its structure is shown below:
Figure BDA00003388802900284
2-pyridine boric acid in embodiment 7 is replaced with to the 4-(3-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 7, obtain 3.6g white solid TM27, productive rate 62%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM27 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM27 ( 1h) refer to accompanying drawing 12.
Embodiment 32 the present embodiment are prepared compound TM28, and its structure is shown below:
Figure BDA00003388802900291
2-pyridine boric acid in embodiment 8 is replaced with to the 4-(3-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 8, obtain 3.6g white solid TM28, productive rate 59%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM28 refer to table 1.
Embodiment 33 the present embodiment are prepared compound TM29, and its structure is shown below:
Figure BDA00003388802900292
2-pyridine boric acid in embodiment 5 is replaced with to the 4-(4-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 5, obtain 3.4g white solid TM29, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM29 refer to table 1.
Embodiment 34 the present embodiment are prepared compound TM30, and its structure is shown below:
Figure BDA00003388802900293
2-pyridine boric acid in embodiment 6 is replaced with to the 4-(4-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 6, obtain 3.2g white solid TM30, productive rate 55%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM30 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM30 ( 1h) refer to accompanying drawing 13.
Embodiment 35 the present embodiment are prepared compound TM31, and its structure is shown below:
Figure BDA00003388802900294
2-pyridine boric acid in embodiment 7 is replaced with to the 4-(4-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 7, obtain 3.1g white solid TM31, productive rate 52%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM31 refer to table 1.
Embodiment 36 the present embodiment are prepared compound TM32, and its structure is shown below:
Figure BDA00003388802900301
2-pyridine boric acid in embodiment 8 is replaced with to the 4-(4-pyridyl of equivalent) phenylo boric acid, other raw material and step are all same as embodiment 8, obtain 3g white solid TM32, productive rate 50%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM32 refer to table 1.
Embodiment 37 the present embodiment are prepared compound TM33, and its structure is shown below:
Figure BDA00003388802900302
The 2-quinoline boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 2.7g white solid TM33, productive rate 57%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM33 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM33 ( 1h) refer to accompanying drawing 14.
Embodiment 38 the present embodiment are prepared compound TM34, and its structure is shown below:
Figure BDA00003388802900303
The 2-quinoline boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 2.6g white solid TM34, productive rate 50%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM34 refer to table 1.
Embodiment 39 the present embodiment are prepared compound TM35, and its structure is shown below:
Figure BDA00003388802900304
The 2-quinoline boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.7g white solid TM35, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM35 refer to table 1.
Embodiment 40 the present embodiment are prepared compound TM36, and its structure is shown below:
Figure BDA00003388802900311
The 2-quinoline boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.66g white solid TM36, productive rate 66%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM36 refer to table 1.
Embodiment 41 the present embodiment are prepared compound TM37, and its structure is shown below:
Figure BDA00003388802900312
The 1-isoquinoline 99.9 boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 3.5g white solid TM37, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM37 refer to table 1.
Embodiment 42 the present embodiment are prepared compound TM38, and its structure is shown below:
Figure BDA00003388802900313
The 1-isoquinoline 99.9 boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.2g white solid TM38, productive rate 58%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM38 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM38 ( 1h) refer to accompanying drawing 15.
Embodiment 43 the present embodiment are prepared compound TM39, and its structure is shown below:
Figure BDA00003388802900314
The 1-isoquinoline 99.9 boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.26g white solid TM39, productive rate 60%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM39 refer to table 1.
Embodiment 44 the present embodiment are prepared compound TM40, and its structure is shown below:
Figure BDA00003388802900321
The 1-isoquinoline 99.9 boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.73g white solid TM40, productive rate 68%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM40 refer to table 1.
Embodiment 45 the present embodiment are prepared compound TM41, and its structure is shown below:
Figure BDA00003388802900322
4-(2-phenyl-1-1H-benzoglyoxaline) phenylo boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 5.4g white solid TM41, productive rate 67%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM41 refer to table 1.
Embodiment 46 the present embodiment are prepared compound TM42, and its structure is shown below:
Figure BDA00003388802900323
4-(2-phenyl-1-1H-benzoglyoxaline) phenylo boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 4.75g white solid TM42, productive rate 59%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM42 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM42 ( 1h) refer to accompanying drawing 16.
Embodiment 47 the present embodiment are prepared compound TM43, and its structure is shown below:
Figure BDA00003388802900324
4-(2-phenyl-1-1H-benzoglyoxaline) phenylo boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 4.57g white solid TM43, productive rate 55%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM43 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM43 ( 1h) refer to accompanying drawing 17.
Embodiment 48 the present embodiment are prepared compound TM44, and its structure is shown below:
Figure BDA00003388802900331
4-(2-phenyl-1-1H-benzoglyoxaline) phenylo boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 5.65g white solid TM44, productive rate 68%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM43 refer to table 1.
Embodiment 49 the present embodiment are prepared compound TM45, and its structure is shown below:
The 2-[4-morpholinodithio boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 3.16g white solid TM45, productive rate 59%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM45 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM45 ( 1h) refer to accompanying drawing 18.
Embodiment 50 the present embodiment are prepared compound TM46, and its structure is shown below:
Figure BDA00003388802900333
The 2-[4-morpholinodithio boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.85g white solid TM46, productive rate 72%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM46 refer to table 1.
Embodiment 51 the present embodiment are prepared compound TM47, and its structure is shown below:
Figure BDA00003388802900334
The 2-[4-morpholinodithio boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.42g white solid TM47, productive rate 61%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM47 refer to table 1.
Embodiment 52 the present embodiment are prepared compound TM48, and its structure is shown below:
Figure BDA00003388802900341
The 2-[4-morpholinodithio boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.2g white solid TM48, productive rate 75%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM48 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM48 ( 1h) refer to accompanying drawing 19.
Embodiment 53 the present embodiment are prepared compound TM49, and its structure is shown below:
The diphenyl-oxazole boric acid that 2-pyridine boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.46g white solid TM49, productive rate 63%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM49 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM49 ( 1h) refer to accompanying drawing 20.
Embodiment 54 the present embodiment are prepared compound TM50, and its structure is shown below:
Figure BDA00003388802900343
The diphenyl-oxazole boric acid that 2-pyridine boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 5.24g white solid TM50, productive rate 74%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM50 refer to table 1.
Embodiment 55 the present embodiment are prepared compound TM51, and its structure is shown below:
Figure BDA00003388802900344
The diphenyl-oxazole boric acid that 2-pyridine boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 5g white solid TM51, productive rate 68%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM51 refer to table 1.
Embodiment 56 the present embodiment are prepared compound TM52, and its structure is shown below:
Figure BDA00003388802900351
The diphenyl-oxazole boric acid that 2-pyridine boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 5.51g white solid TM52, productive rate 75%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM52 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM52 ( 1h) refer to accompanying drawing 21.
Embodiment 57 the present embodiment are prepared compound TM53, and its structure is shown below:
Figure BDA00003388802900352
Preparation method is:
(1) E-II's is synthetic
In 500mL there-necked flask, add 26.4gE-I(according to J.Org.Chem.1992,57, prepared by the method that 2917-2921 provides) and 250mL methylene dichloride, the activated manganese dioxide that adds fresh preparation after dissolving, TLC monitors reaction, constantly adds activated manganese dioxide until react completely, remove by filter Manganse Dioxide, filtrate is concentrated, and the thick product obtaining obtains 22g white solid E-II through ethyl alcohol recrystallization, and yield is 79%;
(2) E-III's is synthetic
In 500mL there-necked flask, add 150mL nitrosonitric acid, with ice-water bath, be cooled to approximately 5 ℃, under stirring, add 27.8g10-ethyl-10-normal-butyl base anthrone I (0.1mol) in batches, controlling feed rate makes reacting liquid temperature not higher than 10 ℃, after reactant adds, keep reacting liquid temperature at 5 ℃ of about 30min.Reactant is poured in 400mL frozen water into vigorous stirring, then suction filtration.Filter cake is through washing, dry, with ethanol-sherwood oil mixed solvent recrystallization, obtains 27.6g faint yellow solid E-III, yield 75%;
(3) E-IV's is synthetic
In the dry voltage-resistant reactor of Corey-Fuchs dibromo olefination: 500mL, add 2.95g E-III(80mmol), 53g carbon tetrabromide (160mmol), reaction system is after three find time-nitrogen circulation, add 250mL dry benzene, mixture stirs 5min, adds 83.7g triphenylphosphine (320mmol).Reaction mixture is vigorous stirring reaction 48h at 150 ℃, etc. system, cools to room temperature, adds enough CH 2cl 2solubilizing reaction mixture.Crude product obtains 27.2g faint yellow solid E-IV, yield 65% through column chromatography for separation (pure sherwood oil);
(4) E-V's is synthetic
Under nitrogen protection, in the withstand voltage reaction flask of 250mL, the triethylamine solution that adds 100mL to contain 5.7mL trimethylsilyl acetylene (40mmol), then add 5.2g dibromo compound E-IV(10mmol), 0.7g PdCl 2(PPh 3) 2(1mmol) with 0.38g CuI(2mmol), reaction mixture is heated to 100 ℃, and reacts 20h at this temperature.After system cool to room temperature, add 100mL CH 2cl 2, more successively by saturated ammonium chloride solution and water difference washed twice, dry.Thick product obtains 3.9g light brown solid, yield 70% by column chromatography separation;
Above-mentioned light brown solid is dissolved in to 30mL CH 2cl 2, slowly drip the CH that 15mL contains 10g 4-butyl ammonium fluoride trihydrate 2cl 2solution, the about 1h of stirring reaction at room temperature after adding, TLC detection reaction completes.Reaction soln is filtered by a silica gel short column, drain solvent and obtain 2.9g white solid E-V, yield approaches 100%;
(5) E-VI's is synthetic
Under nitrogen protection, 3.1g(7.5mmol) compd E-V is dissolved in the toluene that 50mL is dry, adds 0.1gPtCl 2(0.38m mol, 5%eq.).Back flow reaction 6h, reaction solution, without precipitation, with short silicagel column decolouring, obtains 1.71g orange solids compd E-VI, productive rate 55%;
(6) intermediate 3 shown in formula E, 9-bis-bromo-6-ethyl-6-normal-butyl-6-H benzo [cd] pyrene synthetic
1.71g E-VI is dissolved in the 1:1 mixed solvent of 10mL ethanol and THF, add 1g10%Pd/C, by find time-replacing hydrogen, make system become hydrogen atmosphere, and be positive hydrogen pressure by hydrogen balloon holder, mixture is stirring reaction 10h at room temperature, and raw material disappears, and removes by filter palladium-carbon catalyst, filtrate obtains 1.65g faint yellow solid, yield 98% after draining;
By 3.5g(10mmol) above-mentioned faint yellow solid is dissolved in 15mL48% Hydrogen bromide, with ice-water bath, reaction system is cooled to below 5 ℃, slowly drips 10mL containing 2.1g NaNO 2(30mmol) the aqueous solution, keeps system temperature not higher than 10 ℃ in dropping process, drip off rear continuation and stir 0.5h at 5 ℃.Then add 5g CuBr-48%HBr(10mL) solution, this system is heated to 80 ℃ and stir 3h at this temperature, adopts CH 2cl 2the product that extraction generates, and separatory is dry, separated 3.3g white solid E, the yield 69% of obtaining of column chromatography;
(7) TM53's is synthetic
Under nitrogen protection, by 4.82g E (10mmol), 3.06g1-pyridine boric acid (25mmol) and 30mL toluene join in three mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mg Pd (PPh 3) 4(0.2mmol, 2%eq.), stirs, and is warming up to backflow, by TLC, monitor reaction to complete, stopped reaction, filtered while hot, then rinse with methylene dichloride 50mL, remove solvent under reduced pressure, the thick product obtaining obtains 3.3g white solid TM53, productive rate 70% with sherwood oil/methylene dichloride system column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM53 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM53 ( 1h) refer to accompanying drawing 22.
Embodiment 58 the present embodiment are prepared compound TM54, and its structure and synthesis step are shown below:
Figure BDA00003388802900371
Preparation method is:
(1) F-II's is synthetic
Under nitrogen protection; in 500mL there-necked flask, add 32.6gF-I(0.1mol) (according to Angew.Chem.; Int.Ed.; 48 (22); prepared by the method that 4009-4012 provides) and the dry THF of 150mL; with dry ice-propanone, bathe and reaction system is cooled to-78 ℃; under fully stirring, splash into 50mL2.4M n-BuLi (120mmol); add rear continuation and stir 1h at this temperature; then slowly drip the 9-Fluorenone (18g, 0.1mol) that is dissolved in 50mL THF, the completely rear low temperature 0.5h that keeps; slowly be warmed up to again room temperature, and at room temperature stir and spend the night.With saturated ammonium chloride solution cancellation reaction, ethyl acetate extraction three times, merges organic phase, dry, drains the thick product of solvent, through column chromatography for separation to white solid F-II26.7g, yield 81%;
(2) F-III's is synthetic
In 500mL there-necked flask, add 33gF-II(0.1mol) and 250mL methylene dichloride, the activated manganese dioxide that adds fresh preparation after dissolving, TLC monitors reaction, constantly add activated manganese dioxide until react completely, remove by filter Manganse Dioxide, filtrate is concentrated, and the thick product obtaining obtains 29.2g white solid F-III through ethyl alcohol recrystallization, and yield is 85%;
(3) F-IV's is synthetic
In the dry voltage-resistant reactor of Corey-Fuchs dibromo olefination: 500mL, add 27.5g F-III(80mmol), 53g carbon tetrabromide (160mmol), reaction system is after three find time-nitrogen circulation, add 250mL dry benzene, mixture stirs 5min, adds 83.7g triphenylphosphine (320mmol).Reaction mixture is vigorous stirring reaction 48h at 150 ℃, etc. system, cools to room temperature, adds the addition of C H 2cl 2solubilizing reaction mixture.Crude product obtains 25.2g faint yellow solid F-IV, yield 63% through column chromatography for separation (pure sherwood oil);
(4) F-V's is synthetic
N 2under protection, in 250mL there-necked flask, add 2.6g zinc powder (0.04mol), a small amount of iodine; with the dry DMF of 100mL, be stirred to red disappearance, add 5g ethyl bromoacetate (30mmol); be heated to 60 ℃, stir 3h, by the solution filter generating to another dry 250mL there-necked flask.Add 5g F-IV(10mmol) and 0.55g Pd (PPh 3) 4(0.5mmol, 5%eq.), is heated to 120 ℃, and at this temperature stirring reaction 15h.Add saturated ammonium chloride solution cancellation reaction, profit is extracted with ethyl acetate, and separatory is dry, separated 3.2g white solid F-V, the yield 62% of obtaining of column chromatography;
(5) F-VI's is synthetic
By 51g F-V(0.1mol) be dissolved in 100mL THF, add 100mL to contain 12g LiOH(0.5mol) the aqueous solution, the system that is at room temperature stirred to becomes homogeneous phase settled solution.Concentrating under reduced pressure reaction solution volume is to 50mL left and right, cooling.Under ice bath, with dilute hydrochloric acid, regulating pH is 1, separates out a large amount of white solids, filters, and washing, is dried to obtain 44g white solid, yield 95%;
The above-mentioned white solid of 44g is dissolved in to 100mL methylene dichloride, adds 40mL SOCl 2, reflux 3h.Removal of solvent under reduced pressure and unreacted sulfur oxychloride, obtain weak yellow liquid F-VI;
(6) preparation of F-VII
49.5g F-VI (0.1mol) is dissolved in to 200mL CCl 4in, reaction system is cooled to 0 ℃, then slowly add the powdery AlCl of the new distillation of 40g 3(0.3mol), control temperature of reaction not higher than 10 ℃, after adding, continue reaction 30min.Reaction mixture is poured in frozen water, be extracted with ethyl acetate product, separatory is dry, drains solvent and obtains thick product, and this thick product, by adjusting alkali-acidization to purify, then obtains white solid F-VII33.8g with ethyl alcohol recrystallization, yield 80%.
(7) preparation of F
Be equipped with in the 250mL there-necked flask of mechanical stirrer, add triphenylphosphine and dry acetonitrile, under ice-water bath, slowly drip bromine, and control temperature of reaction lower than 40 ℃.Add that to change ice bath after bromine be oil bath, then drip 50mL containing 42.2g F-VII(0.1mol) acetonitrile solution, after adding, reaction system is reacted to 30min at 60-70 ℃, then change water distilling apparatus, steam except acetonitrile.By electric heating bag reacting by heating system, arrive approximately 300 ℃ again, and keep this temperature to stopping discharging HBr.Cooling system, adds sherwood oil, makes product become thin precipitation, filters petroleum ether.Filtrate is through NaOH solution washing, and dry, column chromatography for separation 27g obtains white solid F, yield 50%;
(8) TM54's is synthetic
Under nitrogen protection, by 5.48g F (10mmol), 4.95g2-phenyl 5-pyridine boric acid (25mmol) and 30mL toluene join in three mouthfuls of reaction flasks of 250mL, then add 20mL ethanol, the saturated Na of 30mL 2cO 3solution and 232mg Pd (PPh 3) 4(0.2mmol, 2%eq.), stirs, and is warming up to backflow, by TLC, monitor reaction to complete, stopped reaction, filtered while hot, then rinse with methylene dichloride 50mL, remove solvent under reduced pressure, the thick product obtaining obtains 5.56g white solid TM54, productive rate 80% with sherwood oil/methylene dichloride system column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM54 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM54 ( 1h) refer to accompanying drawing 23.
Mass spectrum and the ultimate analysis data of the aforesaid compound TM1-TM54 of the present invention refer to following table 1:
The mass spectrum of table 1 compound TM1-TM54 and ultimate analysis data
Figure BDA00003388802900391
Figure BDA00003388802900401
Figure BDA00003388802900411
Figure BDA00003388802900421
Embodiment 59 is the Application Example of each compound of the present invention
For the convenient relatively transmission performance of these electron transport materials, the present invention has designed a simple electroluminescent device, use EM1 doping TBPe as luminescent layer (EM1 is material of main part, and TBPe is luminescent material), use the material B phen of high electronic transmission performance as a comparison.
In the embodiment of the present invention, the structure of organic electroluminescence device is:
Substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can be used the substrate in traditional organic luminescent device, for example: glass or plastics.In organic electroluminescence device of the present invention is made, select glass substrate, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group materials.In organic electroluminescence device of the present invention is made, selected hole mobile material is NPB.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode construction such as O/Al.In organic electroluminescence device of the present invention is made, selected cathode material is LiF/Al.
Embodiment 60
Compound in the present embodiment is as the electron transport material in organic electroluminescence device, EML is as luminescent layer material, prepared altogether a plurality of organic electroluminescence devices, its structure is: ITO/NPB(40nm)/EML (30nm)/ETL material (30nm)/LiF(0.5nm)/Al(150nm);
Figure BDA00003388802900431
A contrast organic electroluminescence device in substrate, electron transport material is selected Bphen, and all the other organic electroluminescence devices are selected material of the present invention.
Figure BDA00003388802900432
In the present embodiment, organic electroluminescence device preparation process is as follows:
Sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer will be coated with; in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent is baked to and removes moisture content completely under clean environment; by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10 -5～9 * 10 -3pa, at above-mentioned anode tunic vacuum evaporation NPB, as hole transmission layer, evaporation speed is 0.1nm/s, evaporation thickness is 40nm;
The method vacuum evaporation material of main part EM1 and the doped luminescent material TBPe that on hole transmission layer, adopt double source to steam altogether, the speed ratio of EM1 and TBPe is 100:5, EM1 evaporation speed is 0.1nm/s, and TBPe evaporation speed is 0.005nm/s, and evaporation total film thickness is 30nm;
On luminescent layer, vacuum evaporation one deck compound of the present invention or Bphen are as the electron transfer layer of organic electroluminescence device, and its evaporation speed is 0.1nm/s, and evaporation total film thickness is 30nm;
On electron transfer layer (ETL), the LiF of vacuum evaporation 0.5nm is as electron injecting layer, and the Al of 150nm is as negative electrode.
Organic electroluminescence device performance sees the following form:
Figure BDA00003388802900433
Figure BDA00003388802900441
By upper table, can be seen, organic materials of the present invention can be used as electron transfer layer materials'use in organic electroluminescence device.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.

Claims (18)

1. one kind 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that having structure as the formula (1):
Figure FDA00003388802800011
Wherein:
Work as R 5, R 6while being H simultaneously, R 7, R 8respectively independently selected from C 5-C 30nitrogen heterocyclic ring, substituted azetidine or thick nitrogen heterocyclic ring aromatic hydrocarbons, and
R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound;
Or,
Work as R 7, R 8while being H simultaneously, R 5, R 6respectively independently selected from C 5-C 30nitrogen heterocyclic ring, substituted azetidine or thick nitrogen heterocyclic ring aromatic hydrocarbons, and
R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound.
2. according to claim 16, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that:
Described R 1, R 2independent of one another is methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl ,-(CH 2) n-and n>=3, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, phenanthryl, anthryl, 9-replacement anthryl, pyrenyl, fluorenyl or replacement fluorenyl.
3. according to claim 16, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that:
Described R 1, R 2directly be connected to form ring compound, or by-CH 2cH 2cH 2cH 2-or 2,2 '-xenyl connects into ring compound.
4. arbitrary described 6 according to claim 1-3, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that, described compound has the structure shown in formula (2) or formula (3):
Figure FDA00003388802800012
Figure FDA00003388802800013
5. arbitrary described 6 according to claim 1-4, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that: R 5, R 6, R 7, R 8independent of each other is pyridyl, substituted pyridinyl, pyridyl phenyl, imidazoles, substituted imidazole, thiazole, substituted thiazole, oxazole, substituted oxazole, quinolyl or isoquinolyl.
6. according to claim 56, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that: R 5with R 6identical, R 7with R 8identical.
7. according to claim 66, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that, described compound is selected from following structural formula:
Figure FDA00003388802800021
Figure FDA00003388802800031
Figure FDA00003388802800041
Figure FDA00003388802800061
Figure FDA00003388802800071
One kind arbitrary described 6 for the preparation of claim 1-7, the intermediate of two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that, described intermediate has the structure shown in formula (4) or formula (5):
Figure FDA00003388802800072
Figure FDA00003388802800073
Wherein, R 1, R 2respectively independently selected from thering is C 1-C 30straight or branched alkyl, C 6-C 30replacement or unsubstituted phenyl ring, or condensed-nuclei aromatics; Or R 1, R 2by other groups, be connected to form ring compound.
9. preparation 6 according to claim 8, the intermediate of two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that: described intermediate is the structure shown in formula (A), formula (B), formula (C) or formula (D):
Figure FDA00003388802800074
Figure FDA00003388802800075
Figure FDA00003388802800076
Figure FDA00003388802800077
10. a method of preparing intermediate claimed in claim 9, is characterized in that, comprises the steps:
(1), by 10 shown in formula A-I, 10-dimethyl anthrone and nitric acid generation nitration reaction, obtain the two nitro-compounds that replace shown in formula A-II;
(2) by compound and carbon tetrabromide shown in formula A-II, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula A-III, 1-dibromo olefin(e) compound;
(3) under nitrogen protection, by compound shown in formula A-III and trimethylsilyl acetylene at PdCl 2(PPh 3) 2under existing with CuI, there is Sonogashira reaction, then carry out catalysis and take off the trimethyl silicon based two alkine compounds shown in formula A-IV that obtain;
(4) under nitrogen protection, compound shown in formula A-IV is dissolved in dry toluene, add PtCl 2there is ring closure reaction, obtain the compound shown in formula A-V;
(5) compound shown in formula A-V is dissolved in the mixed solvent of ethanol and THF, under the existence of Pd/C, carries out catalytic hydrogenation nitroreduction is become to amido, then carry out diazotization-bromination reaction and obtain the intermediate shown in formula (A);
Figure FDA00003388802800081
11. 1 kinds of methods of preparing intermediate described in claim 9, comprise the steps:
(1) under the condition as alkali, there are two alkyl cyclizations and obtain the compound shown in formula B-I in anthrone and Isosorbide-5-Nitrae-bis-butyl iodide at potassium tert.-butoxide;
(2) two replacement anthracyclinone derivatives and nitric acid shown in formula B-I are issued to raw nitration reaction in the existence of the vitriol oil, obtain the two nitro-compounds that replace shown in formula B-II;
(3) by compound and carbon tetrabromide shown in formula B-II, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula B-III, 1-dibromo olefin(e) compound;
(4) under nitrogen protection, by compound shown in formula B-III and trimethylsilyl acetylene at PdCl 2(PPh 3) 2under existing with CuI, there is Sonogashira reaction, then carry out catalysis and take off the trimethyl silicon based two alkine compounds shown in formula B-IV that obtain;
(5) under nitrogen protection, compound shown in formula B-IV is dissolved in dry toluene, add PtCl 2there is ring closure reaction, obtain the compound shown in formula B-V;
(6) compound shown in formula B-V is dissolved in the mixed solvent of ethanol and THF, under the existence of Pd/C, carries out catalytic hydrogenation nitroreduction is become to amido, then carry out diazotization-bromination reaction and obtain the intermediate shown in formula (B);
Figure FDA00003388802800091
12. 1 kinds of methods of preparing intermediate claimed in claim 9, is characterized in that, comprise the steps:
(1) by dimethyl anthrone and carbon tetrabromide shown in formula C-I, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula C-II, 1-dibromo olefin(e) compound;
(2) by Pd (PPh 3) 4the cross-coupling reaction of the C-II of catalysis and Reformasky reagent, obtains the di-ester-base compound shown in C-III;
(3) by compound shown in formula C-III through basic hydrolysis, chloride, obtain the compound shown in formula C-IV;
(4) by the compound process AlCl shown in formula C-IV 3the ring closure reaction of catalysis makes the bisphenol cpd shown in formula C-V;
(5) by compound shown in formula C-V through Br 2-PPh 3reagent effect, obtains the intermediate shown in formula (C);
13. 1 kinds of methods of preparing intermediate claimed in claim 9, is characterized in that, comprise the steps:
(1) under the condition as alkali, there are two alkyl cyclizations and obtain the compound shown in formula D-I in anthrone and Isosorbide-5-Nitrae-bis-butyl iodide at potassium tert.-butoxide;
(2) by the compound shown in D-I and carbon tetrabromide, under triphenylphosphine exists, there is Corey-Fuchs dibromo olefination, obtain 1 shown in formula D-II, 1-dibromo olefin(e) compound;
(3) by Pd (PPh 3) 4the cross-coupling reaction of the D-II of catalysis and Reformasky reagent, obtains the di-ester-base compound shown in D-III;
(4) by compound shown in formula D-III through basic hydrolysis, chloride, obtain the compound shown in formula D-IV;
(5) by the compound process AlCl shown in formula D-IV 3the ring closure reaction of catalysis makes the bisphenol cpd shown in formula D-V;
(6) by compound shown in formula D-V through Br 2-PPh 3reagent effect, obtains the intermediate shown in formula (D);
Figure FDA00003388802800101
14. 1 kinds to prepare claim 1-7 arbitrary described 6, and the method for two replacements-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that: under nitrogen protection, the intermediate described in claim 8 or 9 is passed through to linked reaction and obtain.
The luminescent layer material of main part of 15. 1 kinds of organic electroluminescence devices, is characterized in that described material of main part is 6 described in any one in claim 1-7, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
16. 1 kinds of organic electroluminescence devices, comprise substrate, and are formed on successively anode layer, several luminescence unit layer and cathode layers on described substrate;
Described luminescence unit layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The material of main part of described luminescent layer is 6 described in any one in one or more claims 1-7, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
17. organic electroluminescence devices according to claim 16, is characterized in that:
Described luminescent layer comprises red phosphorescent luminescent layer, and described red phosphorescent luminescent layer material of main part is 6 described in any one in one or more claims 1-7, two replacement-6-H-benzo [cd] pyrene derivatives of 6-.
Described in 18. 1 kinds of claim 1-7 are arbitrary 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-are for the application of organic electroluminescence device.
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