CN103508940B - 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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CN103508940B
CN103508940B CN201310250838.1A CN201310250838A CN103508940B CN 103508940 B CN103508940 B CN 103508940B CN 201310250838 A CN201310250838 A CN 201310250838A CN 103508940 B CN103508940 B CN 103508940B
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boronic acids
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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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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

Disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- of one kind, intermediate and preparation method And application
Technical field
The present invention relates to a kind of organic compound, more particularly to a kind of compound for organic electroluminescence device and its Preparation method and application of the compound in organic electroluminescence device；The invention further relates to the intermediate of the compound and should The preparation method of intermediate.
Background technology
Electro optical phenomenon most early in 20th century the '30s be found, initial luminescent material is ZnS powder, is thus sent out LED technology is put on display, has been widely applied to now on energy-conserving light source.And organic electroluminescent phenomenon is Pope in 1963 et al. Find earliest, they have found that the single layer crystal of anthracene under the driving of more than 100V voltages, can send faint blue light.Until Organic fluorescent dye is made bi-layer devices by doctor Deng Qingyun of Kodak in 1987 et al. in vacuum evaporation mode, is being driven Under voltage of the voltage less than 10V, external quantum efficiency has reached 1% so that electroluminescent organic material and device are provided with practicality Possibility, promoted the research of OLED material and device significantly from this.
Relative to phosphor, electroluminescent organic material has advantages below：1. organic material good processability, The method that evaporation or spin coating can be passed through, the film forming on any substrate；2. the diversity of organic molecular structure allows to lead to The method for crossing Molecular Design and modification, adjusts heat endurance, engineering properties, the luminous and electric conductivity of organic material, makes Material is significantly improved space.
The principle of luminosity of organic electroluminescent diode is similar with inorganic light-emitting diode.When element is spread out by direct current During raw forward bias voltage drop, outward in addition voltage energy will drive electronics（Electron）With hole（Hole）Respectively by negative electrode and anode Injection element, when both meet in luminescent layer, combine, that is, forms the compound exciton of so-called electron-hole, and exciton is by luminous The form of relaxation returns to ground state, so as to reach luminous purpose.
What the generation of organic electroluminescent was leaned on is the carrier transmitted in organic semiconducting materials（Electronics and hole）'s Restructuring, it is well known that the electric conductivity of organic material is very poor, from unlike inorganic semiconductor, does not continue in organic semiconductor Energy band, describing, i.e., under the driving of an electric field, electronics is being excited or is being injected into the conventional jump theory of the transmission of carrier In the lumo energy of molecule, the purpose of electric charge transmission is reached via the lumo energy for jumping to another molecule.In order to be able to make Organic electroluminescence device reaches breakthrough in application aspect, it is necessary to overcome organic material electric charge to inject and transmittability difference it is tired It is difficult.The adjustment that scientists pass through device architecture, for example, increase the number of device organic material layer, and makes different organic layers Play the part of different roles, the functional material for example having helps electronics to inject from anode from negative electrode and hole, and some materials are helped The transmission of electric charge, the material for playing the role of then plays stop electronics and hole transport, certainly most important in organic electroluminescent The luminescent material of shades of colour also to reach the purpose matched with adjacent functional material, excellent in efficiency life-span length it is organic Electroluminescent device is typically the result of the optimization collocation of device architecture and various organic materials, and this is just designed for chemists The functionalization material for developing various structures provides great opportunities and challenges.
Common functionalization organic material has：Hole-injecting material, hole mobile material, hole barrier materials, electronics note Enter material, electron transport material, electron-blocking materials and light emitting host material and light-emitting guest（Dyestuff）Deng.
Hole-injecting material（HIM）Its HOMO energy level is required between anode and hole transmission layer, is conducive to increasing boundary Hole injection between face, common hole-injecting material has CuPc, TNATA and PEDT：PSS etc..
Hole mobile material（HTM）, it is desirable to high heat endurance（High Tg）, with anode or hole-injecting material There is less potential barrier, higher cavity transmission ability can vacuum evaporation formation pin-hole free films.It is many that conventional HTM is fragrance Aminated compounds, mainly derivative of tri-arylamine group, such as：NPB（Tg=98℃,μh=1×10-3cm2V-1s-1）,TPD（Tg=60℃, μh=1×10-3cm2V-1s-1）, TCTA（Tg=151℃,μh=1.5×10-4cm2V-1s-1, for blue phosphorescent OLED）, DTASi（Tg =106℃,μh=1×10-3cm2V-1s-1, for blue phosphorescent OLED）Deng.
Electron transport material（Electron transport Material, ETM）It is required that ETM has reversible and sufficiently high Electrochemical reduction current potential, suitable HOMO and LUMO can rank value electronics is preferably injected, and be preferably provided with sky Cave blocking capability；Higher electron transport ability, the film forming having had and heat endurance.ETM is typically electron deficient knot The aromatic of the conjugate planes of structure.Common electron transport material has AlQ3（μe=5×10-6cm2V-1s-1）、Bphen（μe= 4×10-4cm2V-1s-1）, BCP (LUMO=3.0eV, μe=1.1×10-3cm2V-1s-1)、PBD（μe=1.9×10-5cm2V-1s-1） Deng.
Luminescent layer material of main part（host）Need to have following characteristics：Reversible electrochemical redox current potential is and adjacent Hole and the electron transfer layer HOMO that matches and LUMO can rank, the good and hole that matches and electron transport ability, it is good High heat endurance well and film forming, and suitable singlet or triplet state energy gap are for controlling exciton in luminescent layer, Energy transfer also good between corresponding fluorescent dye or phosphorescent coloring.
The luminescent material of luminescent layer needs to have had the special feature that：With high fluorescence or phosphorescence quantum efficiency；Dyestuff Absorption spectrum is overlap with what the emission spectrum of main body had had, i.e., main body is adapted to dyestuff energy, can be effectively from main body to dyestuff Energy transmission；The emission peak of red, green, blue color is as narrow as possible, with the excitation for obtaining；Good stability, can be deposited with etc..
The content of the invention
It is an object of the invention to provide a kind of electron transfer layer that can be used for organic electroluminescence device and luminescent layer Organic material, is that the scheme that this present invention takes is：
Disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- of one kind, with such as formula（1）Shown structure：
Wherein：
Work as R5、R6When being H simultaneously, R7、R8Separately it is selected from C5-C30Nitrogen heterocyclic ring, substituted azetidine or thick contain Azepine PAH, and
R1、R2Separately selected from C1-C30Straight or branched alkyl, C6-C30Substituted or unsubstituted benzene Ring, or condensed-nuclei aromatics；Or R1、R2Connect to form cyclic compound by other groups；
Or,
Work as R7、R8When being H simultaneously, R5、R6Separately it is selected from C5-C30Nitrogen heterocyclic ring, substituted azetidine or thick contain Azepine PAH, and
R1、R2Separately selected from C1-C30Straight or branched alkyl, C6-C30Substituted or unsubstituted benzene Ring, or condensed-nuclei aromatics；Or R1、R2Connect to form cyclic compound by other groups.
The R1、R2It is independently of one another methyl, ethyl, n-propyl, isopropyl, the tert-butyl group ,-(CH2)n- and n >=3, phenyl, Substituted-phenyl, naphthyl, substituted naphthyl, phenanthryl, anthryl, 9- replace anthryl, pyrenyl, fluorenyl or replace fluorenyl.
The R1、R2It is directly connected to form cyclic compound, or passes through-CH2CH2CH2CH2- or 2,2 '-xenyl is connected into Cyclic compound.
The derivative has formula（2）Or formula（3）Shown structure：
Further R5、R6、R7、R8It is independent of each other for pyridine radicals, substituted pyridinyl, pyridinylphenyl, imidazoles, replacement Imidazoles, thiazole, substituted thiazole, oxazoles, substituted oxazole, quinolyl or isoquinolyl.
More excellent, R5With R6It is identical, R7With R8It is identical.
Disubstituted -6-H- benzos [cd] pyrene derivatives of 6 described, 6-, selected from following structural formula：
Present invention also offers a kind of centre for preparing described disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- Body, the intermediate has formula（4）Or formula（5）Shown structure：
Wherein, R1、R2Separately selected from C1-C30Straight or branched alkyl, C6-C30Replacement or unsubstituted Phenyl ring, or condensed-nuclei aromatics；Or R1、R2Connect to form cyclic compound by other groups.
The intermediate is formula（A）, formula（B）, formula（C）Or formula（D）Shown structure：
Present invention also offers a kind of method for preparing described intermediate A, comprises the steps：
（1）Be there is into nitration reaction in 10, the 10- dimethyl anthrone shown in formula A-I and nitric acid, obtain shown in formula A- II double takes For nitro compound；
（2）By compound shown in formula A-II and carbon tetrabromide, in the presence of triphenylphosphine, there is Corey-Fuchs dibromos Olefination, obtains 1, the 1- dibromoalkene compounds shown in formula A-III；
（3）Under nitrogen protection, by compound shown in formula A-III and trimethylsilyl acetylene in PdCl2(PPh3)2Deposit with CuI Under, there is Sonogashira reactions, carry out being catalyzed double alkine compounds that de- trimethyl silicon substrate obtains shown in formula A-IV then；
（4）Under nitrogen protection, compound shown in formula A-IV is dissolved in dry toluene, adds PtCl2Generation cyclization Reaction, obtains the compound shown in formula A-V；
（5）Compound shown in formula A-V is dissolved in the mixed solvent of ethanol and THF, in the presence of Pd/C, is catalyzed Nitro is reduced into amido by hydrogenation, diazotising-bromination reaction is carried out then and obtains formula（A）Shown intermediate；
Present invention also offers a kind of method for preparing the intermediate B, comprises the steps：
（1）Under conditions of potassium tert-butoxide is as alkali, there are double alkyl cyclizations and obtain in anthrone with the iodobutane of Isosorbide-5-Nitrae-two Compound shown in formula B-I；
（2）Be there is into nitration reaction in the presence of the concentrated sulfuric acid in the disubstituted anthracyclinone derivatives shown in formula B-I and nitric acid, obtained Disubstituted nitro compound shown in formula B-II；
（3）By compound shown in formula B-II and carbon tetrabromide, in the presence of triphenylphosphine, there is Corey-Fuchs dibromos Olefination, obtains 1, the 1- dibromoalkene compounds shown in formula B-III；
（4）Under nitrogen protection, by compound shown in formula B-III and trimethylsilyl acetylene in PdCl2(PPh3)2And CuI In the presence of, there is Sonogashira reactions, carry out being catalyzed double ethynylations conjunction that de- trimethyl silicon substrate obtains shown in formula B-IV then Thing；
（5）Under nitrogen protection, compound shown in formula B-IV is dissolved in dry toluene, adds PtCl2Generation cyclization Reaction, obtains the compound shown in formula B-V；
（6）Compound shown in formula B-V is dissolved in the mixed solvent of ethanol and THF, in the presence of Pd/C, is catalyzed Nitro is reduced into amido by hydrogenation, diazotising-bromination reaction is carried out then and obtains formula（B）Shown intermediate；
Present invention also offers a kind of method for preparing described intermediate C, comprises the steps：
（1）By dimethyl anthrone and carbon tetrabromide shown in formula C-I, in the presence of triphenylphosphine, there is Corey-Fuchs Dibromo olefination, obtains 1, the 1- dibromoalkene compounds shown in formula C-II；
（2）By Pd (PPh3)4The cross-coupling reaction of the C-II and Reformasky reagent of catalysis, obtains shown in C-III Dibasic acid esters based compound；
（3）By the basic hydrolysis of compound Jing shown in formula C-III, chloride, the compound shown in formula C-IV is obtained；
（4）By the compound shown in formula C-IV through AlCl3The ring closure reaction of catalysis is obtained the bis-phenol chemical combination shown in formula C-V Thing；
（5）By the Br of compound Jing shown in formula C-V2-PPh3Reagent is acted on, and obtains formula（C）Shown intermediate；
Present invention also offers a kind of method for preparing described intermediate D, comprises the steps：
（1）Under conditions of potassium tert-butoxide is as alkali, there are double alkyl cyclizations and obtain in anthrone with the iodobutane of Isosorbide-5-Nitrae-two Compound shown in formula D-I；
（2）By compound and carbon tetrabromide shown in D-I, in the presence of triphenylphosphine, there is Corey-Fuchs dibromo alkene Glycosylation reaction, obtains 1, the 1- dibromoalkene compounds shown in formula D-II；
（3）By Pd (PPh3)4The cross-coupling reaction of the D-II and Reformasky reagent of catalysis, obtains shown in D-III Dibasic acid esters based compound；
（4）By the basic hydrolysis of compound Jing shown in formula D-III, chloride, the compound shown in formula D-IV is obtained；
（5）By the compound shown in formula D-IV through AlCl3The ring closure reaction of catalysis is obtained the bis-phenol chemical combination shown in formula D-V Thing；
（6）By the Br of compound Jing shown in formula D-V2-PPh3Reagent is acted on, and obtains formula（D）Shown intermediate；
Present invention also offers the method that one kind prepares disubstituted -6-H- benzos [cd] pyrene derivatives of 6, the 6-, that is, exist Under nitrogen protection, described intermediate is obtained through coupling reaction.
Present invention also offers a kind of luminescent layer material of main part of organic electroluminescence device, described material of main part is institute Disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- stated.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, several luminescence unit layers and cathode layer；
Described luminescence unit layer includes hole transmission layer, organic luminous layer and electron transfer layer, the luminescent layer Material of main part is disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- described in one or more.
The luminescent layer includes red phosphorescent luminescent layer, and described red phosphorescent luminescent layer material of main part is one or more Disubstituted -6-H- benzos [cd] pyrene derivatives of 6 described, 6-.
Present invention also offers a kind of described disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- are sent out for organic electroluminescence Application in optical device.
Compared with prior art, compound of the invention has the advantage that：
（1）In the present invention, we have proposed with the disubstituted -6-H benzos of disubstituted this kind of 6, the 6- of 2,10- and 3,9- The new material of [cd] pyrene derivatives, nitrogen heterocyclic ring such as pyridine radicals, thiazolyl, oxazolyls, imidazoles with electron deficient in molecule The group such as base or quinolyl, isoquinolyl, these compounds have good electron transport ability, by adjusting different taking Natively high well heat and chemical stability can be further adjusted for group.
（2）This kind of new material in the present invention can be used as electron transport material in efficient OLED, can also make For fluorescence or red phosphorescent material of main part.
Description of the drawings
Fig. 1 is the nuclear magnetic spectrogram of compound A in the embodiment of the present invention 1（1H）；
Fig. 2 is the nuclear magnetic spectrogram of compound B in the embodiment of the present invention 2（1H）；
Fig. 3 is the nuclear magnetic spectrogram of compound C in the embodiment of the present invention 3（1H）；
Fig. 4 is the nuclear magnetic spectrogram of compound D in the embodiment of the present invention 4（1H）；
Fig. 5 is the nuclear magnetic spectrogram of compound TM1 in the embodiment of the present invention 5（1H）；
Fig. 6 is the nuclear magnetic spectrogram of compound TM4 in the embodiment of the present invention 8（1H）；
Fig. 7 is the nuclear magnetic spectrogram of compound TM5 in the embodiment of the present invention 9（1H）；
Fig. 8 is the nuclear magnetic spectrogram of compound TM12 in the embodiment of the present invention 16（1H）；
Fig. 9 is the nuclear magnetic spectrogram of compound TM14 in the embodiment of the present invention 18（1H）；
Figure 10 is the nuclear magnetic spectrogram of compound TM19 in the embodiment of the present invention 23（1H）；
Figure 11 is the nuclear magnetic spectrogram of compound TM24 in the embodiment of the present invention 28（1H）；
Figure 12 is the nuclear magnetic spectrogram of compound TM27 in the embodiment of the present invention 31（1H）；
Figure 13 is the nuclear magnetic spectrogram of compound TM30 in the embodiment of the present invention 34（1H）；
Figure 14 is the nuclear magnetic spectrogram of compound TM33 in the embodiment of the present invention 37（1H）；
Figure 15 is the nuclear magnetic spectrogram of compound TM38 in the embodiment of the present invention 42（1H）；
Figure 16 is the nuclear magnetic spectrogram of compound TM42 in the embodiment of the present invention 46（1H）；
Figure 17 is the nuclear magnetic spectrogram of compound TM43 in the embodiment of the present invention 47（1H）；
Figure 18 is the nuclear magnetic spectrogram of compound TM45 in the embodiment of the present invention 49（1H）；
Figure 19 is the nuclear magnetic spectrogram of compound TM48 in the embodiment of the present invention 52（1H）；
Figure 20 is the nuclear magnetic spectrogram of compound TM49 in the embodiment of the present invention 53（1H）；
Figure 21 is the nuclear magnetic spectrogram of compound TM52 in the embodiment of the present invention 56（1H）；
Figure 22 is the nuclear magnetic spectrogram of compound TM53 in the embodiment of the present invention 57（1H）；
Figure 23 is the nuclear magnetic spectrogram of compound TM54 in the embodiment of the present invention 58（1H）.
Specific embodiment
Nitric acid used, sulfuric acid, carbon tetrabromide in the present invention, triphenylphosphine, trimethylsilyl acetylene, cuprous iodide, two（Triphen Base phosphine）Palladium chloride, tetrabutyl ammonium fluoride, platinous chloride, 10% palladium/carbon, natrium nitrosum, cuprous bromide, 48% hydrobromic acid, zinc Powder, bromoacetate, four（Triphenyl phosphorus）Palladium, lithium hydroxide, thionyl chloride, alchlor, bromine, the iodobutanes of 1,4- bis-, anthracene The chemical products such as ketone, tert-butyl group potassium alcoholate, carbazole are bought from domestic chemical products market, and 9,9- dimethyl anthrones press literature method Synthesis（J.Am.Chem.Soc.1975,97,6790）, the boric acid used in final step coupling reaction can by purchase, or According to literature method (D.J.Hall, Boronic Acids:Preparation and Applications in Organic Synthesis and Medicine, Wiley-Vch, 2005) prepare.
Embodiment 1-4 is the preparation embodiment of intermediate of the present invention：
Embodiment 1
The present embodiment formula（A）Shown intermediate 3, bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes of 9- bis-：
Synthetic route is as follows：
Preparation method is：
（1）The synthesis of A-II
150mL fuming nitric aicds are added in 500mL there-necked flasks, with ice-water bath about 5 DEG C are cooled to, be dividedly in some parts under stirring 22.2g10,10- dimethyl anthrone A-I (0.1mol), control charging rate causes reacting liquid temperature to be not higher than 10 DEG C, reactant After adding, reacting liquid temperature is kept in 5 DEG C of about 30min.Reactant is poured in 400mL frozen water, is stirred vigorously, then suction filtration. Filter cake Jing is washed, and is dried, and with ethanol-petroleum ether mixed solvent recrystallization, obtains 25g faint yellow solids A- II, yield 80%；
（2）The synthesis of A-III
Corey-Fuchs dibromo olefinations：In the voltage-resistant reactor of the drying of 500mL, 25gA-II is added （80mmol）, 53g carbon tetrabromides（160mmol）, reaction system Jing after three evacuation-nitrogen circulations, add 250mL dry benzenes, Mixture stirs 5min, adds 83.7g triphenylphosphines（320mmol）.Reactant mixture is stirred vigorously reaction 48h at 150 DEG C, Room temperature is cooled to etc. system, enough CH are added2Cl2Dissolving reactant mixture.Crude by column chromatography is separated（Pure petroleum ether）Obtain 22.5g faint yellow solid A-III, yield 60%；
（3）The synthesis of A-IV
Under nitrogen protection, in the pressure reaction bulb of 250mL, 100mL is added to contain 5.7mL trimethylsilyl acetylene （40mmol）Triethylamine solution, add 4.7g dibromo compound A-III（10mmol）, 0.7g PdCl2(PPh3)2 （1mmol）With 0.38g CuI（2mmol）, reactant mixture is heated to into 100 DEG C, and 20h is reacted at this temperature.System is cold But to after room temperature, 100mL CH are added2Cl2, then priority saturated ammonium chloride solution and water washes twice respectively, is dried.Crude product 3.77g Light brown solids, yield 75% are obtained by pillar layer separation；
Above-mentioned Light brown solid is dissolved in into 30mL CH2Cl2, 15mL is slowly added dropwise and contains the hydration of 10g tetrabutyl ammonium fluorides three The CH of thing2Cl2Solution, is stirred at room temperature reaction about 1h after adding, TLC detection reactions are completed.Reaction solution is passed through into a silica gel Short column is filtered, and is drained solvent and is obtained 2.7g white solids A- IV, yield close 100%；
（4）The synthesis of A-V
Under nitrogen protection, 2.7g（7.5mmol）Compound A-IV is dissolved in the toluene of 50mL dryings, adds 0.1gPtCl2 (0.38m mol, 5%eq.）.Back flow reaction 6h, reactant liquor is decolourized without precipitation with short silicagel column, obtains 1.35g orange solids chemical combination Thing A-V, yield 50%；
（5）Intermediate 3 shown in formula A, the synthesis of bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes of 9- bis-
1.35g A-V are dissolved in into the 1 of 10mL ethanol and THF:In 1 mixed solvent, 1g10%Pd/C is added, by evacuating-putting Hydrogen is changed so that system is into hydrogen atmosphere, and it is ortho-hydrogen pressure to keep system by hydrogen balloon, mixture is stirred at room temperature reaction 10h, raw material disappears, and is filtered to remove palladium-carbon catalyst, and filtrate obtains 1.3g faint yellow solids, yield 95% after draining；
By 2.98g（10mmol）Above-mentioned faint yellow solid is dissolved in 15mL48% hydrobromic acids, with ice-water bath that reaction system is cold But to less than 5 DEG C, 10mL NaNO containing 2.1g are slowly added dropwise2（30mmol）The aqueous solution, during dropwise addition keep system temperature not Higher than 10 DEG C, continue to stir 0.5h at 5 DEG C after dripping off.It is subsequently adding 5g CuBr-48%HBr（10mL）Solution, the system adds Heat is to 80 DEG C and stirs 3h at this temperature, using CH2Cl2The generated product of extraction, and point liquid drying, pillar layer separation is obtained 3.2g white solid A, yield 75%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound A refer to table 1, the nuclear-magnetism detection spectrogram of compound A （1H）Refer to accompanying drawing 1.
Embodiment 2
Bromo- 6,6- cyclobutyl -6-H benzos [cd] pyrenes of intermediate 3,9- bis- shown in the present embodiment formula B：
Synthetic route is as follows：
Preparation method：
（1）The synthesis of B-I
19.4g anthrones are added in 250mL there-necked flasks（0.1mol）, 150mL be dried THF, add under agitation 34.1g1, the iodobutanes of 4- bis-（0.11mol）With 26.8g potassium tert-butoxides（0.24mol）, reaction system is stirred at room temperature 3h, then Back flow reaction 3h.Add saturated ammonium chloride solution that reaction is quenched, extracted using ethyl acetate, point liquid is dried, column chromatography point From obtaining 13.6g white solid B-I, yield 55%；
（2）The synthesis of B-II
Step in this step and embodiment 1（1）Basically identical, difference is to use B-I as initiation material（Plus Enter amount for 24.6g (0.1mol)）, the faint yellow solid B-II for obtaining be 26.4g, yield 78%；
（3）The synthesis of B-III
Step in this step and embodiment 1（2）Basically identical, difference is to use B-II to be initiation material（Plus Enter amount for 27g（80mmol））, faint yellow solid B-III is obtained for 31.9g（Yield 65%）；
（4）The synthesis of B-IV
Step in this step and embodiment 1（3）Basically identical, difference is, dibromo compound B-III additions For 4.8g（10mmol）, the white solid B- IV for finally obtaining is 2.4g, and two step total recoverys are about 67%；
（5）The synthesis of B-V
Step in this step and embodiment 1（4）Basically identical, difference is that compound B-IV additions are 2.4g（6.7mmol）, the orange solids compound B-V for obtaining be 1.2g, yield 50%；
（6）Intermediate（B）Synthesis
Step in this step and embodiment 1（5）Basically identical, difference is that the addition of B-V is 1.2g, is obtained The faint yellow solid for arriving be 1.15g, yield 94%；The faint yellow solid is in synthetic intermediate（B）During addition be 3.24g（10mmol）The white solid B for obtaining be 3.5g, yield 78%.The Mass Spectrometer Method data and element point of gained compound B Analysis data refer to table 1, the nuclear-magnetism detection spectrogram of compound B（1H）Refer to accompanying drawing 2.
Embodiment 3
Intermediate 2 shown in the present embodiment formula C, bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes of 10- bis-：
Synthetic route is：
Preparation method：
（1）The synthesis of C-II
Step in this step and embodiment 1（2）Basically identical, difference is, the addition of dimethyl anthrone C-I For 22.2g（80mmol）, white solid C- II is obtained for 24.5g, yield 65%；
（2）The preparation of C-III
N2Under protection, in 250mL there-necked flasks, the DMF for adding 2.6g zinc powders (0.04mol), a small amount of iodine, and 100mL to be dried, Stir to red disappearance, add 5g bromoacetates（30mmol）, be heated to 60 DEG C, stir 3h, by the solution of generation filter to In the 250mL there-necked flasks of another drying.The C-II for adding 3.78g to obtain（10mmol）With 0.55g Pd (PPh3)4(0.5mmol, 5%eq.), 120 DEG C, and stirring reaction 15h at this temperature are heated to.Add saturated ammonium chloride solution that reaction is quenched, using second Acetoacetic ester is extracted, and point liquid is dried, and pillar layer separation obtains 2g white solid C-III, yield 55%；
（3）The preparation of C-IV
By 36.4g C-III（0.1mol）In being dissolved in 100mL THF, 100mL LiOH containing 12g are added（0.5mol）Water Solution, is stirred at room temperature to system and becomes homogeneous settled solution.Reduced pressure concentration reactant liquor volume to 50mL or so, cooling. It is 1 to adjust pH with watery hydrochloric acid under ice bath, separates out a large amount of white solids, is filtered, washing, dry 32g white solids, yield 97%；
The above-mentioned white solids of 32g are dissolved in into 100mL dichloromethane, 40mL SOCl are added2, it is heated to reflux 3h.It is removed under reduced pressure Solvent and unreacted thionyl chloride, obtain weak yellow liquid C-IV；
（4）The preparation of C-V
37.3g C-IV (0.1mol) are dissolved in into 200mL CCl4In, reaction system is cooled to into 0 DEG C, then it is slowly added into The powdery AlCl of 40g newly distillations3(0.3mol), controlling reaction temperature is not higher than 10 DEG C, after adding, and continues to react 30min.Will be anti- Answer mixture to pour in frozen water, be extracted with ethyl acetate product, point liquid is dried, and drains solvent and obtains crude product, the crude product is led to Alkali tune-acidization purification is crossed, then white solid C-V25g, yield 83% is obtained with ethyl alcohol recrystallization；
（5）Intermediate 2, bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes of 10- bis-（C）Preparation
In 250mL there-necked flasks equipped with mechanical agitator, triphenylphosphine and the acetonitrile being dried are added, under ice-water bath slowly Bromine is added dropwise, and controlling reaction temperature is less than 40 DEG C.It is oil bath to add and change after bromine ice bath, and 50mL C-V containing 30g are then added dropwise （0.1mol）Acetonitrile solution, reaction system is reacted into 30min at 60-70 DEG C after adding, then change distilling apparatus, be evaporated off Acetonitrile.Again with electric heating bag heating response system to about 300 DEG C, and this temperature is kept to stopping release HBr.Cooling system, adds Petroleum ether, makes product into thin precipitation, filters, petroleum ether.Filtrate Jing NaOH solutions are washed, and are dried, column chromatography for separation 21g Obtain white solid C, yield 50%.The Mass Spectrometer Method data and Elemental analysis data of gained compound C refer to table 1, compound C Nuclear-magnetism detection spectrogram（1H）Refer to accompanying drawing 3.
Embodiment 4
Intermediate shown in the present embodiment formula D：
Synthetic route is：
Preparation method is：
（1）The synthesis of D-I
This step and step in embodiment 2（1）Procedure it is basically identical, obtain the compound shown in formula D-I；
（2）The preparation of D-II
Step in this step and embodiment 3（1）Basically identical, difference is, using D-I, addition is 24.8g （80mmol）, white solid D-II is obtained for 20g, yield 50%；
（23）The preparation of D-III
Step in this step and embodiment 3（2）Basically identical, difference is, using D-II, addition is 4g （10mmol）, the white solid D-III for obtaining be 1.95g, yield 50%；
（4）The preparation of D-IV
Step in this step and embodiment 3（3）Basically identical, difference is, using D-III, addition is 39g （0.1mol）, white solid D-IV is obtained for 35g, yield 97%；
（5）The preparation of D-V
Step in this step and embodiment 3（4）Basically identical, difference is, using D-IV, addition is 40g (0.1mol) the white solid D- V for, obtaining be 26g, yield 80%；
（6）The preparation of intermediate D
Step in this step and embodiment 3（5）Basically identical, difference is, using D-V, addition is 32.6g （0.1mol）, the white solid D for obtaining be 27g, yield 60%.The Mass Spectrometer Method data and Elemental 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 the embodiment that target compound of the present invention is prepared using intermediate A, B, C or D：
Embodiment 5
The present embodiment prepare compound TM1, its structure is shown below：
Synthetic route is：
Preparation method：
Under nitrogen protection, by bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes (10mmol) of 3,9- bis- shown in 4.3g formulas A, 3.08g2- pyridine boronic acids (25mmol) and 30mL toluene are added in three mouthfuls of reaction bulbs of 250mL, are subsequently adding 20mL ethanol, 30mL saturations Na2CO3Solution and 232mgPd (PPh3)4(0.2mmol, 2%eq.), stirring, and backflow is warming up to, supervised by TLC Reaction is surveyed to complete, stops reaction, filtered while hot, then rinsed with dichloromethane 50mL, remove solvent under reduced pressure, the crude product for obtaining 2.7g white solid TM1, yield 65% are obtained with petroleum ether/dichloromethane system column chromatography.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM1 refer to table 1, the nuclear-magnetism detection of compound TM1 Spectrogram（1H）Refer to accompanying drawing 5.
Embodiment 6
The present embodiment prepare compound TM2, its structure is shown below：
Synthetic route is：
Preparation method is：
Under nitrogen protection, by 4.3g intermediates 2, bromo- 6,6- dimethyl -6-H benzos [cd] pyrenes of 10- bis-（C）(10mmol), 3.08g2- pyridine boronic acids (25mmol) and 30mL toluene are added in tri- mouthfuls of reaction bulbs of 250mL, are subsequently adding 20mL ethanol, 30mL saturations Na2CO3Solution and 232mgPd (PPh3)4(0.2mmol, 2%eq.), stirring is warming up to backflow, and reaction passes through TLC Monitoring, after reaction completely, stops reaction, filters while hot, then is rinsed with dichloromethane 50mL, removes solvent under reduced pressure, and what is obtained is thick Product obtains 3.0g white solid TM2, yield 70% with petroleum ether/dichloromethane system column chromatography.The mass spectrum of gained compound TM2 Detection data and Elemental analysis data refer to table 1.
Embodiment 7
The present embodiment prepare compound TM3, its structure is shown below：
Synthetic route is：
Preparation method is：
Under nitrogen protection, intermediate B (10mmol), 3.08g2- pyridine boronic acids (25mmol) and 30mL toluene are added to In tri- mouthfuls of reaction bulbs of 250mL, 20mL ethanol, 30mL saturations Na are subsequently adding2CO3Solution and 232mg Pd (PPh3)4 (0.2mmol, 2%eq.), stirring is warming up to backflow, reacts and is monitored by TLC, after reaction completely, stops reaction, filters while hot, Rinsed with dichloromethane 50mL again, remove solvent under reduced pressure, the crude product for obtaining is obtained with petroleum ether/dichloromethane system column chromatography 3.4g white solid TM3, yield 76%.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM3 refer to table 1.
Embodiment 8
The present embodiment prepare compound TM4, its structure is shown below：
Synthetic route is：
Preparation method is：
Under nitrogen protection, 4.5g intermediate D (10mmol), 3.08g2- pyridine boronic acids (25mmol) and 30mL toluene are added Enter in tri- mouthfuls of reaction bulbs of 250mL, be subsequently adding 20mL ethanol, 30mL saturations Na2CO3Solution and 232mg Pd (PPh3)4 (0.2mmol, 2%eq.), stirring, is warming up to backflow, by TLC monitorings reaction to reacting complete, stops reaction, filters while hot, Rinsed with dichloromethane 50mL again, remove solvent under reduced pressure, the crude product for obtaining is obtained with petroleum ether/dichloromethane system column chromatography 3.2g white solid TM4, yield 71%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM4 refer to table 1, the nuclear-magnetism detection of compound TM4 Spectrogram（1H）Refer to accompanying drawing 6.
Embodiment 9
The present embodiment prepare compound TM5, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are changed to into the 3- pyridine boronic acids of equivalent, other raw materials and step are same as reality Apply example 5, the white solid TM5 for obtaining be 2.7g, yield 63%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM5 refer to table 1, the nuclear-magnetism detection of compound TM5 Spectrogram（1H）Refer to accompanying drawing 7.
Embodiment 10
The present embodiment prepare compound TM6, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are changed to into the 3- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 6 is applied, 3.0g white solid TM6, yield 72% is obtained.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM6 are detailed It is shown in Table 1.
Embodiment 11
The present embodiment prepare compound TM7, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are changed to into the 3- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 7 is applied, 3.1g white solid TM7, yield 70% is obtained.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM7 are detailed It is shown in Table 1.
Embodiment 12
The present embodiment prepare compound TM8, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are changed to into the 3- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 8 is applied, 2.96g white solid TM8, yield 66% is obtained.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM8 Refer to table 1.
Embodiment 13
The present embodiment prepare compound TM9, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are changed to into the 4- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 5 is applied, 2.96g white solid TM9, yield 70% is obtained.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM9 Refer to table 1.
Embodiment 14
The present embodiment prepare compound TM10, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are changed to into the 4- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 6 is applied, 2.7g white solid TM10, yield 64% is obtained.The Mass Spectrometer Method data and Elemental analysis data of gained compound TM10 Refer to table 1.
Embodiment 15
The present embodiment prepare compound TM11, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are changed to into the 4- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 7 is applied, 3.18g white solid TM11, yield 71% is obtained.The Mass Spectrometer Method data and elementary analysis number of gained compound TM11 According to referring to table 1.
Embodiment 16
The present embodiment prepare compound TM12, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are changed to into the 4- pyridine boronic acids of equivalent, other raw materials and step are same as reality Example 8 is applied, 3.14g white solid TM12 are obtained, yield is 70%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM12 refer to table 1, the nuclear-magnetism inspection of compound TM12 Survey spectrogram（1H）Refer to accompanying drawing 8.
Embodiment 17
The present embodiment prepare compound TM13, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 5- phenyl -2- pyridine boronic acids of equivalent, other raw materials and step Embodiment 5 is same as, 4.0g white solid TM13 are obtained, yield is 70%.The Mass Spectrometer Method data of gained compound TM13 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM14 of embodiment 18, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 5- phenyl -2- pyridine boronic acids of equivalent, other raw materials and step Embodiment 6 is same as, 4.77g white solid TM14, yield 83% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM14 refer to table 1, the nuclear-magnetism inspection of compound TM14 Survey spectrogram（1H）Refer to accompanying drawing 9.
The present embodiment prepare compound TM15 of embodiment 19, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 5- phenyl -2- pyridine boronic acids of equivalent, other raw materials and step Embodiment 7 is same as, 4.9g white solid TM15, yield 83% is obtained.The Mass Spectrometer Method data and element of gained compound TM15 Analyze data refers to table 1.
The present embodiment prepare compound TM16 of embodiment 20, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 5- phenyl -2- pyridine boronic acids of equivalent, other raw materials and step Embodiment 8 is same as, 4.2g white solid TM16, yield 70% is obtained.The Mass Spectrometer Method data and element of gained compound TM16 Analyze data refers to table 1.
The present embodiment prepare compound TM17 of embodiment 21, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 6- phenyl -3- pyridine boronic acids of equivalent, other raw materials and step Embodiment 5 is same as, 4.5g white solid TM17, yield 78% is obtained.The Mass Spectrometer Method data and element of gained compound TM17 Analyze data refers to table 1.
The present embodiment prepare compound TM18 of embodiment 22, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 6- phenyl -3- pyridine boronic acids of equivalent, other raw materials and step Embodiment 6 is same as, 3.96g white solid TM18, yield 69% is obtained.The Mass Spectrometer Method data of gained compound TM18 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM19 of embodiment 23, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 6- phenyl -3- pyridine boronic acids of equivalent, other raw materials and step Embodiment 7 is same as, 4.9g white solid TM19, yield 81% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM19 refer to table 1, the nuclear-magnetism inspection of compound TM19 Survey spectrogram（1H）Refer to accompanying drawing 10.
The present embodiment prepare compound TM20 of embodiment 24, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the pyridine boronic acid of 6- phenyl -3 of equivalent, other raw materials and step Embodiment 8 is same as, 4.3g white solid TM20, yield 72% is obtained.The Mass Spectrometer Method data and element of gained compound TM20 Analyze data refers to table 1.
The present embodiment prepare compound TM21 of embodiment 25, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 4- of equivalent（2- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 5 is same as, obtains 3.8g white solid TM21, yield 65%.The Mass Spectrometer Method data of gained compound TM21 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM22 of embodiment 26, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 4- of equivalent（2- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 6 is same as, obtains 3.7g white solid TM22, yield 64%.The Mass Spectrometer Method data of gained compound TM22 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM23 of embodiment 27, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 4- of equivalent（2- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 7 is same as, obtains 3.7g white solid TM23, yield 62%.The Mass Spectrometer Method data of gained compound TM23 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM24 of embodiment 28, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 4- of equivalent（2- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 8 is same as, obtains 3.4g white solid TM24, yield 59%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM24 refer to table 1, the nuclear-magnetism inspection of compound TM24 Survey spectrogram（1H）Refer to accompanying drawing 11.
The present embodiment prepare compound TM25 of embodiment 29, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 4- of equivalent（3- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 5 is same as, obtains 3.54g white solid TM25, yield 65%.Gained compound TM25 Mass Spectrometer Method data and Elemental analysis data refers to table 1.
The present embodiment prepare compound TM26 of embodiment 30, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 4- of equivalent（3- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 6 is same as, obtains 3.85g white solid TM26, yield 64%.Gained compound TM26 Mass Spectrometer Method data and Elemental analysis data refers to table 1.
The present embodiment prepare compound TM27 of embodiment 31, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 4- of equivalent（3- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 7 is same as, obtains 3.6g white solid TM27, yield 62%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM27 refer to table 1, the nuclear-magnetism inspection of compound TM27 Survey spectrogram（1H）Refer to accompanying drawing 12.
The present embodiment prepare compound TM28 of embodiment 32, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 4- of equivalent（3- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 8 is same as, obtains 3.6g white solid TM28, yield 59%.The Mass Spectrometer Method data of gained compound TM28 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM29 of embodiment 33, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 4- of equivalent（4- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 5 is same as, obtains 3.4g white solid TM29, yield 65%.The Mass Spectrometer Method data of gained compound TM29 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM30 of embodiment 34, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 4- of equivalent（4- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 6 is same as, obtains 3.2g white solid TM30, yield 55%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM30 refer to table 1, the nuclear-magnetism inspection of compound TM30 Survey spectrogram（1H）Refer to accompanying drawing 13.
The present embodiment prepare compound TM31 of embodiment 35, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 4- of equivalent（4- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 7 is same as, obtains 3.1g white solid TM31, yield 52%.The Mass Spectrometer Method data of gained compound TM31 and unit Plain analyze data refers to table 1.
The present embodiment prepare compound TM32 of embodiment 36, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 4- of equivalent（4- pyridine radicals）Phenyl boric acid, other raw materials and step Suddenly embodiment 8 is same as, obtains 3g white solid TM32, yield 50%.The Mass Spectrometer Method data and element of gained compound TM32 Analyze data refers to table 1.
The present embodiment prepare compound TM33 of embodiment 37, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 2- quinoline boronic acids of equivalent, other raw materials and step are same as Embodiment 5, obtains 2.7g white solid TM33, yield 57%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM33 refer to table 1, the nuclear-magnetism inspection of compound TM33 Survey spectrogram（1H）Refer to accompanying drawing 14.
The present embodiment prepare compound TM34 of embodiment 38, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 2- quinoline boronic acids of equivalent, other raw materials and step are same as Embodiment 6, obtains 2.6g white solid TM34, yield 50%.The Mass Spectrometer Method data and elementary analysis number of gained compound TM34 According to referring to table 1.
The present embodiment prepare compound TM35 of embodiment 39, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 2- quinoline boronic acids of equivalent, other raw materials and step are same as Embodiment 7, obtains 3.7g white solid TM35, yield 65%.The Mass Spectrometer Method data and elementary analysis number of gained compound TM35 According to referring to table 1.
The present embodiment prepare compound TM36 of embodiment 40, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 2- quinoline boronic acids of equivalent, other raw materials and step are same as Embodiment 8, obtains 3.66g white solid TM36, yield 66%.The Mass Spectrometer Method data of gained compound TM36 and elementary analysis Data refer to table 1.
The present embodiment prepare compound TM37 of embodiment 41, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 1- isoquinolin boric acid of equivalent, other raw materials and step are same In embodiment 5,3.5g white solid TM37, yield 65% are obtained.The Mass Spectrometer Method data of gained compound TM37 and elementary analysis Data refer to table 1.
The present embodiment prepare compound TM38 of embodiment 42, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 1- isoquinolin boric acid of equivalent, other raw materials and step are same In embodiment 6,3.2g white solid TM38, yield 58% are obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM38 refer to table 1, the nuclear-magnetism inspection of compound TM38 Survey spectrogram（1H）Refer to accompanying drawing 15.
The present embodiment prepare compound TM39 of embodiment 43, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 1- isoquinolin boric acid of equivalent, other raw materials and step are same In embodiment 7,3.26g white solid TM39, yield 60% are obtained.The Mass Spectrometer Method data and element point of gained compound TM39 Analysis data refer to table 1.
The present embodiment prepare compound TM40 of embodiment 44, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 1- isoquinolin boric acid of equivalent, other raw materials and step are same In embodiment 8,3.73g white solid TM40, yield 68% are obtained.The Mass Spectrometer Method data and element point of gained compound TM40 Analysis data refer to table 1.
The present embodiment prepare compound TM41 of embodiment 45, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into 4- (2- phenyl -1-1H- benzimidazoles) phenyl boric acid of equivalent, Other raw materials and step are same as embodiment 5, obtain 5.4g white solid TM41, yield 67%.The mass spectrum of gained compound TM41 Detection data and Elemental analysis data refer to table 1.
The present embodiment prepare compound TM42 of embodiment 46, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into 4- (2- phenyl -1-1H- benzimidazoles) phenyl boric acid of equivalent, Other raw materials and step are same as embodiment 6, obtain 4.75g white solid TM42, yield 59%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM42 refer to table 1, the nuclear-magnetism inspection of compound TM42 Survey spectrogram（1H）Refer to accompanying drawing 16.
The present embodiment prepare compound TM43 of embodiment 47, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into 4- (2- phenyl -1-1H- benzimidazoles) phenyl boric acid of equivalent, Other raw materials and step are same as embodiment 7, obtain 4.57g white solid TM43, yield 55%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM43 refer to table 1, the nuclear-magnetism inspection of compound TM43 Survey spectrogram（1H）Refer to accompanying drawing 17.
The present embodiment prepare compound TM44 of embodiment 48, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into 4- (2- phenyl -1-1H- benzimidazoles) phenyl boric acid of equivalent, Other raw materials and step are same as embodiment 8, obtain 5.65g white solid TM44, yield 68%.The matter of gained compound TM43 Spectrum detection data and Elemental analysis data refer to table 1.
The present embodiment prepare compound TM45 of embodiment 49, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the 2-[4-morpholinodithio boric acid of equivalent, other raw materials and step are equal Embodiment 5 is same as, 3.16g white solid TM45, yield 59% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM45 refer to table 1, the nuclear-magnetism inspection of compound TM45 Survey spectrogram（1H）Refer to accompanying drawing 18.
The present embodiment prepare compound TM46 of embodiment 50, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the 2-[4-morpholinodithio boric acid of equivalent, other raw materials and step are equal Embodiment 6 is same as, 3.85g white solid TM46, yield 72% is obtained.The Mass Spectrometer Method data and element of gained compound TM46 Analyze data refers to table 1.
The present embodiment prepare compound TM47 of embodiment 51, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the 2-[4-morpholinodithio boric acid of equivalent, other raw materials and step are equal Embodiment 7 is same as, 3.42g white solid TM47, yield 61% is obtained.The Mass Spectrometer Method data and element of gained compound TM47 Analyze data refers to table 1.
The present embodiment prepare compound TM48 of embodiment 52, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the 2-[4-morpholinodithio boric acid of equivalent, other raw materials and step are equal Embodiment 8 is same as, 4.2g white solid TM48, yield 75% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM48 refer to table 1, the nuclear-magnetism inspection of compound TM48 Survey spectrogram（1H）Refer to accompanying drawing 19.
The present embodiment prepare compound TM49 of embodiment 53, its structure is shown below：
2- pyridine boronic acids in embodiment 5 are replaced with into the diphenyl-oxazole boric acid of equivalent, other raw materials and step are equal Embodiment 5 is same as, 4.46g white solid TM49, yield 63% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM49 refer to table 1, the nuclear-magnetism inspection of compound TM49 Survey spectrogram（1H）Refer to accompanying drawing 20.
The present embodiment prepare compound TM50 of embodiment 54, its structure is shown below：
2- pyridine boronic acids in embodiment 6 are replaced with into the diphenyl-oxazole boric acid of equivalent, other raw materials and step are equal Embodiment 6 is same as, 5.24g white solid TM50, yield 74% is obtained.The Mass Spectrometer Method data and element of gained compound TM50 Analyze data refers to table 1.
The present embodiment prepare compound TM51 of embodiment 55, its structure is shown below：
2- pyridine boronic acids in embodiment 7 are replaced with into the diphenyl-oxazole boric acid of equivalent, other raw materials and step are equal Embodiment 7 is same as, 5g white solid TM51, yield 68% is obtained.The Mass Spectrometer Method data of gained compound TM51 and elementary analysis Data refer to table 1.
The present embodiment prepare compound TM52 of embodiment 56, its structure is shown below：
2- pyridine boronic acids in embodiment 8 are replaced with into the diphenyl-oxazole boric acid of equivalent, other raw materials and step are equal Embodiment 8 is same as, 5.51g white solid TM52, yield 75% is obtained.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM52 refer to table 1, the nuclear-magnetism inspection of compound TM52 Survey spectrogram（1H）Refer to accompanying drawing 21.
The present embodiment prepare compound TM53 of embodiment 57, its structure is shown below：
Preparation method is：
（1）The synthesis of E-II
26.4gE-I is added in 500mL there-necked flasks（According to the method that J.Org.Chem.1992,57,2917-2921 is provided Prepare）With 250mL dichloromethane, the activated manganese dioxide of fresh preparation, TLC monitoring reactions is added constantly to add work after dissolving Property manganese dioxide until reaction it is complete, be filtered to remove manganese dioxide, filtrate concentration, the crude product Jing ethyl alcohol recrystallization for obtaining is obtained 22g white solid E-II, yield is 79%；
（2）The synthesis of E-III
150mL fuming nitric aicds are added in 500mL there-necked flasks, with ice-water bath about 5 DEG C are cooled to, be dividedly in some parts under stirring 27.8g10- ethyls -10- normal-butyls base anthrone I (0.1mol), control charging rate causes reacting liquid temperature to be not higher than 10 DEG C, instead After answering thing to add, reacting liquid temperature is kept in 5 DEG C of about 30min.Reactant is poured in 400mL frozen water, is stirred vigorously, then taken out Filter.Filter cake Jing is washed, and is dried, and with ethanol-petroleum ether mixed solvent recrystallization, obtains 27.6g faint yellow solid E-III, yield 75%；
（3）The synthesis of E-IV
Corey-Fuchs dibromo olefinations：In the voltage-resistant reactor of the drying of 500mL, 2.95g E-III are added （80mmol）, 53g carbon tetrabromides（160mmol）, reaction system Jing after three evacuation-nitrogen circulations, add 250mL dry benzenes, Mixture stirs 5min, adds 83.7g triphenylphosphines（320mmol）.Reactant mixture is stirred vigorously reaction 48h at 150 DEG C, Room temperature is cooled to etc. system, enough CH are added2Cl2Dissolving reactant mixture.Crude by column chromatography is separated（Pure petroleum ether）Obtain 27.2g faint yellow solid E-IV, yield 65%；
（4）The synthesis of E-V
Under nitrogen protection, in the pressure reaction bulb of 250mL, 100mL is added to contain 5.7mL trimethylsilyl acetylene （40mmol）Triethylamine solution, add 5.2g dibromo compound E-IV（10mmol）, 0.7g PdCl2(PPh3)2（1mmol） With 0.38g CuI（2mmol）, reactant mixture is heated to into 100 DEG C, and 20h is reacted at this temperature.System is cooled to room temperature Afterwards, 100mL CH are added2Cl2, then priority saturated ammonium chloride solution and water washes twice respectively, is dried.Crude product passes through post color Compose isolated 3.9g Light brown solids, yield 70%；
Above-mentioned Light brown solid is dissolved in into 30mL CH2Cl2, 15mL is slowly added dropwise and contains the hydration of 10g tetrabutyl ammonium fluorides three The CH of thing2Cl2Solution, is stirred at room temperature reaction about 1h after adding, TLC detection reactions are completed.Reaction solution is passed through into a silica gel Short column is filtered, and is drained solvent and is obtained 2.9g white solid E-V, yield close 100%；
（5）The synthesis of E-VI
Under nitrogen protection, 3.1g（7.5mmol）Compound E-V is dissolved in the toluene of 50mL dryings, adds 0.1gPtCl2 (0.38m mol, 5%eq.）.Back flow reaction 6h, reactant liquor is decolourized without precipitation with short silicagel column, obtains 1.71g orange solids chemical combination Thing E-VI, yield 55%；
（6）The synthesis of bromo- 6- ethyls -6- normal-butyls -6-H benzos [cd] pyrene of intermediate 3,9- shown in formula E bis-
1.71g E-VI are dissolved in into the 1 of 10mL ethanol and THF:In 1 mixed solvent, add 1g10%Pd/C, by evacuate- Replacing hydrogen causes system into hydrogen atmosphere, and it is ortho-hydrogen pressure to keep system by hydrogen balloon, and mixture is stirred at room temperature instead Answer 10h, raw material to disappear, be filtered to remove palladium-carbon catalyst, filtrate obtains 1.65g faint yellow solids, yield 98% after draining；
By 3.5g（10mmol）Above-mentioned faint yellow solid is dissolved in 15mL48% hydrobromic acids, with ice-water bath that reaction system is cold But to less than 5 DEG C, 10mL NaNO containing 2.1g are slowly added dropwise2（30mmol）The aqueous solution, during dropwise addition keep system temperature not Higher than 10 DEG C, continue to stir 0.5h at 5 DEG C after dripping off.It is subsequently adding 5g CuBr-48%HBr（10mL）Solution, the system adds Heat is to 80 DEG C and stirs 3h at this temperature, using CH2Cl2The generated product of extraction, and point liquid drying, pillar layer separation is obtained 3.3g white solid E, yield 69%；
(7) synthesis of TM53
Under nitrogen protection, 4.82g E (10mmol), 3.06g1- pyridine boronic acids (25mmol) and 30mL toluene are added to In three mouthfuls of reaction bulbs of 250mL, 20mL ethanol, 30mL saturations Na are subsequently adding2CO3Solution and 232mg Pd (PPh3)4 (0.2mmol, 2%eq.), stirring, and backflow is warming up to, and by TLC monitorings reaction to complete, stop reaction, filter while hot, then Rinsed with dichloromethane 50mL, remove solvent under reduced pressure, the crude product for obtaining is obtained with petroleum ether/dichloromethane system column chromatography 3.3g white solid TM53, yield 70%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM53 refer to table 1, the nuclear-magnetism inspection of compound TM53 Survey spectrogram（1H）Refer to accompanying drawing 22.
The present embodiment prepare compound TM54 of embodiment 58, its structure and synthesis step are shown below：
Preparation method is：
（1）The synthesis of F-II
Under nitrogen protection, 32.6gF-I is added in 500mL there-necked flasks（0.1mol）（According to Angew.Chem., Int.Ed., it is prepared by 48 (22), the method that 4009-4012 is provided）The THF being dried with 150mL, is bathed reactant with dry ice-propanone System is cooled to -78 DEG C, is sufficiently stirred for lower instillation 50mL2.4M n-BuLi (120mmol), continues to stir at this temperature after adding 1h, is then slowly added dropwise the 9-Fluorenone for being dissolved in 50mL THF（18g, 0.1mol）, it is completely rear to keep low temperature 0.5h, then slowly heat up To room temperature, and it is stirred at room temperature overnight.Reaction is quenched with saturated ammonium chloride solution, ethyl acetate is extracted three times, is merged organic Phase, is dried, and drains the crude product of solvent, Jing column chromatography for separation to white solid F-II26.7g, yield 81%；
（2）The synthesis of F-III
33gF-II is added in 500mL there-necked flasks（0.1mol）With 250mL dichloromethane, fresh preparation is added after dissolving Activated manganese dioxide, TLC monitoring reactions constantly add activated manganese dioxide until reaction is complete, are filtered to remove manganese dioxide, filter Liquid is concentrated, and the crude product Jing ethyl alcohol recrystallization for obtaining obtains 29.2g white solid F-III, and yield is 85%；
（3）The synthesis of F-IV
Corey-Fuchs dibromo olefinations：In the voltage-resistant reactor of the drying of 500mL, 27.5g F-III are added （80mmol）, 53g carbon tetrabromides（160mmol）, reaction system Jing after three evacuation-nitrogen circulations, add 250mL dry benzenes, Mixture stirs 5min, adds 83.7g triphenylphosphines（320mmol）.Reactant mixture is stirred vigorously reaction 48h at 150 DEG C, Room temperature is cooled to etc. system, appropriate CH is added2Cl2Dissolving reactant mixture.Crude by column chromatography is separated（Pure petroleum ether）Obtain 25.2g faint yellow solid F-IV, yield 63%；
（4）The synthesis of F-V
N2Under protection, in 250mL there-necked flasks, the DMF for adding 2.6g zinc powders (0.04mol), a small amount of iodine, and 100mL to be dried, Stir to red disappearance, add 5g bromoacetates（30mmol）, be heated to 60 DEG C, stir 3h, by the solution of generation filter to In the 250mL there-necked flasks of another drying.Add 5g F-IV（10mmol）With 0.55g Pd (PPh3)4(0.5mmol, 5%eq.), plus Heat is to 120 DEG C, and stirring reaction 15h at this temperature.Add saturated ammonium chloride solution that reaction is quenched, extracted using ethyl acetate Take, point liquid is dried, pillar layer separation obtains 3.2g white solid F-V, yield 62%；
（5）The synthesis of F-VI
By 51g F-V（0.1mol）In being dissolved in 100mL THF, 100mL LiOH containing 12g are added（0.5mol）The aqueous solution, It is stirred at room temperature to system and becomes homogeneous settled solution.Reduced pressure concentration reactant liquor volume to 50mL or so, cooling.Under ice bath It is 1 to adjust pH with watery hydrochloric acid, separates out a large amount of white solids, is filtered, washing, dry 44g white solids, yield 95%；
The above-mentioned white solids of 44g are dissolved in into 100mL dichloromethane, 40mL SOCl are added2, it is heated to reflux 3h.It is removed under reduced pressure Solvent and unreacted thionyl chloride, obtain weak yellow liquid F-VI；
（6）The preparation of F-VII
49.5g F-VI (0.1mol) are dissolved in into 200mL CCl4In, reaction system is cooled to into 0 DEG C, then it is slowly added into The powdery AlCl of 40g newly distillations3(0.3mol), controlling reaction temperature is not higher than 10 DEG C, after adding, and continues to react 30min.Will be anti- Answer mixture to pour in frozen water, be extracted with ethyl acetate product, point liquid is dried, and drains solvent and obtains crude product, the crude product is led to Alkali tune-acidization purification is crossed, then white solid F-VII33.8g, yield 80% is obtained with ethyl alcohol recrystallization.
（7）The preparation of F
In 250mL there-necked flasks equipped with mechanical agitator, triphenylphosphine and the acetonitrile being dried are added, under ice-water bath slowly Bromine is added dropwise, and controlling reaction temperature is less than 40 DEG C.It is oil bath to add and change after bromine ice bath, and 50mL F- containing 42.2g are then added dropwise VII（0.1mol）Acetonitrile solution, reaction system is reacted into 30min at 60-70 DEG C after adding, then change distilling apparatus, Acetonitrile is evaporated off.Again with electric heating bag heating response system to about 300 DEG C, and this temperature is kept to stopping release HBr.Cooling system, Petroleum ether is added, makes product into thin precipitation, filtered, petroleum ether.Filtrate Jing NaOH solutions are washed, and are dried, column chromatography point White solid F, yield 50% are obtained from 27g；
(8) synthesis of TM54
Under nitrogen protection, by 5.48g F (10mmol), 4.95g2- phenyl 5- pyridine boronic acids (25mmol) and 30mL toluene In being added to three mouthfuls of reaction bulbs of 250mL, 20mL ethanol, 30mL saturations Na are subsequently adding2CO3Solution and 232mg Pd (PPh3)4 (0.2mmol, 2%eq.), stirring, and backflow is warming up to, and by TLC monitorings reaction to complete, stop reaction, filter while hot, then Rinsed with dichloromethane 50mL, remove solvent under reduced pressure, the crude product for obtaining is obtained with petroleum ether/dichloromethane system column chromatography 5.56g white solid TM54, yield 80%.
The Mass Spectrometer Method data and Elemental analysis data of gained compound TM54 refer to table 1, the nuclear-magnetism inspection of compound TM54 Survey spectrogram（1H）Refer to accompanying drawing 23.
The mass spectrum and Elemental analysis data of the aforesaid compound TM1-TM54 of the present invention refers to table 1 below：
The mass spectrum and Elemental analysis data of the compound TM1-TM54 of table 1
Embodiment 59 is the Application Example of each compound of the invention
Compare the transmission performance of these electron transport materials for convenience, the present invention devises a simple electroluminescent cell Part, TBPe is adulterated as luminescent layer using EM1（EM1 is material of main part, and TBPe is luminescent material）, using high electronic transmission performance Material Bphen as a comparison.
The structure of organic electroluminescence device is in the embodiment of the present invention：
Substrate/anode/hole transmission layer（HTL）/ organic luminous layer（EL）/ electron transfer layer (ETL)/negative electrode.
Substrate can use the substrate in conventional organic luminescence device, for example：Glass or plastics.In the Organic Electricity of the present invention Electroluminescence device selects glass substrate, ITO to make anode material in making.
Hole transmission layer can adopt various tri-arylamine group materials.The institute in the organic electroluminescence device of the present invention makes From hole mobile material be NPB.
Negative electrode can be using metal and its mixture structure, such as Mg：Ag、Ca：Ag etc., or electron injecting layer/gold Category Rotating fields, such as LiF/Al, Li2The common cathode structure such as O/Al.It is selected in the organic electroluminescence device of the present invention makes Cathode material is LiF/Al.
Embodiment 60
, used as the electron transport material in organic electroluminescence device, EML is used as luminescent layer for compound in the present embodiment Material, is prepared for altogether multiple organic electroluminescence devices, and its structure is：ITO/NPB（40nm）/ EML (30nm)/ETL materials （30nm）/LiF（0.5nm）/Al（150nm）；
A contrast organic electroluminescence device in substrate, electron transport material selects Bphen, remaining organic electroluminescent Material of the device from the present invention.
Organic electroluminescence device preparation process is as follows in the present embodiment：
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, rinse in deionized water, In acetone：Ultrasonic oil removing, is baked under clean environment and completely removes moisture content in alcohol mixed solvent, clear with ultraviolet light and ozone Wash, and with low energy cation beam bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10 is evacuated to-5～9 × 10-3Pa, above-mentioned Used as hole transmission layer, evaporation rate is 0.1nm/s to anode tunic vacuum evaporation NPB, and evaporation thickness is 40nm；
The method vacuum evaporation material of main part EM1 steamed altogether using double source on hole transmission layer and doped luminescent material The speed ratio of TBPe, EM1 and TBPe is 100:5, EM1 evaporation rates are 0.1nm/s, and TBPe evaporation rates are 0.005nm/s, are steamed Plating total film thickness is 30nm；
Electricity of the compound or Bphen of one layer of present invention of vacuum evaporation as organic electroluminescence device on luminescent layer Sub- transport layer, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm；
In electron transfer layer（ETL）, used as electron injecting layer, the Al of 150nm is used as the moon for the LiF of upper vacuum evaporation 0.5nm Pole.
Organic electroluminescence device performance see the table below：
Can be seen by upper table, the organic material of the present invention can serve as electron transfer layer in organic electroluminescence device Materials'use.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (5)

1. one kind 6, disubstituted -6-H- benzos [cd] pyrene derivatives of 6-, it is characterised in that
The derivative is selected from following structural formula：
2. the luminescent layer material of main part of a kind of organic electroluminescence device, it is characterised in that described material of main part will for right Seek disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- described in 1.
3. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, several Light unit layer and cathode layer；
Described luminescence unit layer includes hole transmission layer, organic luminous layer and electron transfer layer, it is characterised in that：
The material of main part of the luminescent layer is disubstituted -6-H- benzos [cd] pyrenes of 6,6- described in one or more claim 1 Derivative.
4. organic electroluminescence device according to claim 3, it is characterised in that：
The luminescent layer includes red phosphorescent luminescent layer, and described red phosphorescent luminescent layer material of main part is one or more right Require disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- described in 1.
5. disubstituted -6-H- benzos [cd] pyrene derivatives of 6,6- described in a kind of claim 1 are used for organic electroluminescence device In application.
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