CN103508836A - 6, 6-disubstituted-6-H-benzo[cd]pyrene derivative, and preparation method and applications thereof - Google Patents
6, 6-disubstituted-6-H-benzo[cd]pyrene derivative, and preparation method and applications thereof Download PDFInfo
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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 C6-C30 aromatic hydrocarbon or polycyclic aromatic hydrocarbon; 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 C6-C30 aromatic hydrocarbon or polycyclic aromatic hydrocarbon; 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.
Description
Technical field
The present invention relates to a kind of organic compound, relate in particular to a kind of for 6 of organic electroluminescence device, two replacement-6-H-benzo [cd] pyrene derivatives of 6-and the application in organic electroluminescence device thereof.
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 can be so that can 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 greatly 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.
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.
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.
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.
Summary of the invention
The object of the present invention is to provide a kind of 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, and this derivative is applied to organic electro luminescent layer as the material of main part of fluorescence or red phosphorescent, and then obtain the organic electroluminescence device that a kind of driving voltage is low, luminous efficiency is high.
The technical 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 structural formula as the formula (1):
Wherein:
Work as R
5, R
6while being H simultaneously, R
7, R
8respectively independently selected from C
6-C
30aromatic hydrocarbons or condensed-nuclei aromatics, 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
6-C
30aromatic hydrocarbons or condensed-nuclei aromatics, 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 polycyclic aromatic hydrocarbons; 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.
Further, described compound has the structure shown in formula (2) or formula (3):
Described R
5, R
6, R
7, R
8independent of each other is phenyl, substituted-phenyl, naphthyl, phenanthryl, anthryl, pyrenyl or fluorenyl.
Preferably, R
5with R
6identical, R
7with R
8identical.
Further, described compound is selected from following structural formula:
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 the intermediate shown in formula (4) or formula (5) and obtain;
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.
Further, described intermediate is the structure shown in formula (A), formula (B), formula (C) or formula (D):
The invention provides a kind of method of preparing described intermediate A, comprise 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);
The invention provides a kind of method of preparing described intermediate B, 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);
The present invention also provides a kind of method of preparing described intermediate C, comprises the steps:
(1), by dimethyl anthrone and carbon tetrabromide, under triphenylphosphine exists, there is Corey-Fuchs bis-
Bromine olefination, obtains 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, can prepare the intermediate shown in formula (C).
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;
(5) by compound shown in formula D-V through Br
2-PPh
3reagent effect, obtains the intermediate shown in formula (D);
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.
Described 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-are as the fluorescence material of main part in organic electroluminescence device or red phosphorescent material of main part.
Compared with prior art, tool of the present invention has the following advantages:
(1) research and design based on contriver oneself synthetic, tested the organic materials 6 of a class for OLED device, two replacement-6-H benzo [cd] pyrene derivatives of 6-, and proposed with 2, 10-and 3, disubstituted this class 6 of 9-, the type material of two replacement-6-H benzo [cd] pyrene derivatives of 6-, because molecule has the parent nucleus of large conjugated structure, on parent nucleus, be connected with various aromatic groups, further improved the electron delocalization of compound, these compounds have good carrier transport ability, by regulating different substituted radicals can further regulate original just good high heat and chemical stability.We find that these materials can be used as fluorescence or the red phosphorescent material of main part with high electronic transmission performance in efficient OLED device;
(2) compound of the present invention can be used as fluorescence or the red phosphorescent material of main part with high electronic transmission performance in efficient OLED device.
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 TM8 in the embodiment of the present invention 12 nuclear magnetic spectrogram (
1h);
Fig. 7 be compound TM10 in the embodiment of the present invention 14 nuclear magnetic spectrogram (
1h);
Fig. 8 be compound TM15 in the embodiment of the present invention 19 nuclear magnetic spectrogram (
1h);
Fig. 9 be compound TM19 in the embodiment of the present invention 23 nuclear magnetic spectrogram (
1h);
Figure 10 be compound TM22 in the embodiment of the present invention 26 nuclear magnetic spectrogram (
1h);
Figure 11 be compound TM28 in the embodiment of the present invention 32 nuclear magnetic spectrogram (
1h);
Figure 12 be compound TM29 in the embodiment of the present invention 33 nuclear magnetic spectrogram (
1h);
Figure 13 be compound TM33 in the embodiment of the present invention 37 nuclear magnetic spectrogram (
1h);
Figure 14 be compound TM40 in the embodiment of the present invention 44 nuclear magnetic spectrogram (
1h);
Figure 15 be compound TM42 in the embodiment of the present invention 46 nuclear magnetic spectrogram (
1h);
Figure 16 be compound TM45 in the embodiment of the present invention 49 nuclear magnetic spectrogram (
1h);
Figure 17 be compound TM46 in the embodiment of the present invention 50 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), during synthetic compound of the present invention, linked reaction boric acid used is 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:
Synthetic route is as follows:
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 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 the addition of C H
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 0.1 gPtCl
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
1.35gA-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.
Intermediate 3 shown in the present embodiment preparation formula B, 9-bis-is bromo-6,6-cyclobutyl-6-H benzo [cd] pyrene:
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 C 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.
Intermediate 2 shown in the present embodiment preparation formula C, 10-bis-is bromo-6,6-dimethyl-6-H benzo [cd] pyrene:
Synthetic route is:
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.Add 3.78g C-II(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 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.Again by electric heating bag reacting by heating system to 300 ℃, 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.
Intermediate shown in the present embodiment preparation formula D:
Synthetic route is:
Preparation method is:
(1) preparation of D-I
In this step and embodiment 2, 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%;
(3) 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 48 is for to utilize intermediate A, B, C or D to prepare the embodiment of target compound of the present invention:
The present embodiment is prepared target compound TM1, and its structure is shown below:
Synthetic route is:
Preparation method is:
Under nitrogen protection, by the intermediate 3 shown in 4.3g formula A, 9-bis-bromo-6; 6-dimethyl-6-H benzo [cd] pyrene (10mmol); 3.0g phenylo 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.), stir, and be warming up to back flow reaction, 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.
The present embodiment is prepared target compound TM2, and its structure is as shown below:
Synthetic route is:
Preparation method is:
Under nitrogen protection, by the intermediate 2 shown in 4.3g formula C, 10-bis-bromo-6; 6-dimethyl-6-H benzo [cd] pyrene (10mmol); 3.0g phenylo 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 back flow reaction, 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 2.7g white solid TM2, productive rate 65% 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.
The present embodiment is prepared target compound TM3, and its structure is as shown below:
Synthetic route is:
Preparation method is:
Under nitrogen protection, by the intermediate B (10mmol) shown in 4.5g formula B, 3.0g phenylo 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 back flow reaction, 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 2.7g white solid TM3, productive rate 65% 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.
The present embodiment is prepared target compound TM4, and its structure is as shown below:
Synthetic route is:
Preparation method is:
Under nitrogen protection, by 4.5g intermediate D (10mmol), 3.0g phenylo 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 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 TM4, productive rate 65% 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 present embodiment is prepared target compound TM5, and its structure is as shown below:
The 4-biphenyl boric acid that phenylo 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 3.95g, productive rate 69%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM5 refer to table 1.
The present embodiment is prepared target compound TM6, and its structure is as shown below:
The 4-biphenyl boric acid that phenylo boric acid in embodiment 6 is changed to equivalent, other raw material and step are all same as embodiment 6, obtain 3.72g white solid TM6, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM6 refer to table 1.
The present embodiment is prepared target compound TM7, and its structure is shown below:
The 4-biphenyl boric acid that phenylo boric acid in embodiment 7 is changed to equivalent, other raw material and step are all same as embodiment 7, obtain 4.2g white solid TM7, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM7 refer to table 1.
The present embodiment is prepared target compound TM8, and its structure is shown below:
The 4-biphenyl boric acid that phenylo boric acid in embodiment 8 is changed to equivalent, other raw material and step are all same as embodiment 8, obtain 4.67g white solid TM8, productive rate 78%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM8 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM8 (
1h) refer to accompanying drawing 6.
The present embodiment is prepared target compound TM9, and its structure is shown below:
The 3-biphenyl boric acid that phenylo boric acid in embodiment 5 is changed to equivalent, other raw material and step are all same as embodiment 5, obtain 4.0g white solid TM9, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM9 refer to table 1.
The present embodiment is prepared target compound TM10, and its structure is shown below:
The 3-biphenyl boric acid that phenylo boric acid in embodiment 6 is changed to equivalent, other raw material and step are all same as embodiment 6, obtain 3.66g white solid TM10, productive rate 64%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM10 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM10 (
1h) refer to accompanying drawing 7.
Embodiment 15
The present embodiment is prepared target compound TM11, and its structure is shown below:
The 3-biphenyl boric acid that phenylo boric acid in embodiment 7 is changed to equivalent, other raw material and step are all same as embodiment 7, obtain 4.25g white solid TM11, productive rate 71%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM11 refer to table 1.
The present embodiment is prepared target compound TM12, and its structure is shown below:
The 3-biphenyl boric acid that phenylo boric acid in embodiment 8 is changed to equivalent, other raw material and step are all same as embodiment 8, obtain 4.37g white solid TM12, and productive rate is 73%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM12 refer to table 1.
The present embodiment is prepared target compound TM13, and its structure is shown below:
Phenylo boric acid in embodiment 5 is replaced with to 3 of equivalent, 5-diphenyl benzene boric acid, 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 is prepared target compound TM14, and its structure is shown below:
2-pyridine boric acid in embodiment 6 is replaced with to 3 of equivalent, 5-diphenyl benzene boric acid, other raw material and step are all same as embodiment 6, obtain 5.37g white solid TM14, productive rate 74%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM14 refer to table 1.
The present embodiment is prepared target compound TM15, and its structure is shown below:
Phenylo boric acid in embodiment 7 is replaced with to 3 of equivalent, 5-diphenyl benzene boric acid, other raw material and step are all same as embodiment 7, obtain 5.33g white solid TM15, productive rate 71%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM15 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM15 (
1h) refer to accompanying drawing 8.
Embodiment 20
The present embodiment is prepared target compound TM16, and its structure is shown below:
Phenylo boric acid in embodiment 8 is replaced with to 3 of equivalent, 5-diphenyl benzene boric acid, other raw material and step are all same as embodiment 8, obtain 5.93g white solid TM16, productive rate 79%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM16 refer to table 1.
The present embodiment is prepared target compound TM17, and its structure is shown below:
The 2-naphthalene boronic acids that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.27g white solid TM17, productive rate 82%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM17 refer to table 1.
The present embodiment is prepared target compound TM18, and its structure is shown below:
The 2-naphthalene boronic acids that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.33g white solid TM18, productive rate 64%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM18 refer to table 1.
The present embodiment is prepared target compound TM19, and its structure is shown below:
The 2-naphthalene boronic acids that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.88g white solid TM19, productive rate 71%.
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 9.
Embodiment 24 the present embodiment are prepared target compound TM20, and its structure is shown below:
The 2-naphthalene boronic acids that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.83g white solid TM20, productive rate 70%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM20 refer to table 1.
Embodiment 25
The present embodiment is prepared target compound TM21, and its structure is shown below:
The 1-naphthalene boronic acids that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 2.66g white solid TM21, productive rate 51%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM21 refer to table 1.
The present embodiment is prepared target compound TM22, and its structure is shown below:
The 1-naphthalene boronic acids that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.23g white solid TM22, productive rate 62%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM22 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM22 (
1h) refer to accompanying drawing 10.
Embodiment 27
The present embodiment is prepared target compound TM23, and its structure is shown below:
The 1-naphthalene boronic acids that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.39g 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 is prepared target compound TM24, and its structure is shown below:
The 1-naphthalene boronic acids that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.23g white solid TM24, productive rate 59%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM24 refer to table 1.
Embodiment 29
The present embodiment is prepared target compound TM25, and its structure is shown below:
The luxuriant and rich with fragrance boric acid of 9-that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 3.48g white solid TM25, productive rate 56%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM25 refer to table 1.
The present embodiment is prepared target compound TM26, and its structure is shown below:
The luxuriant and rich with fragrance boric acid of 9-that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.97g 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 is prepared target compound TM27, and its structure is shown below:
The luxuriant and rich with fragrance boric acid of 9-that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 4.01g white solid TM27, productive rate 62%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM27 refer to table 1.
Embodiment 32
The present embodiment is prepared target compound TM28, and its structure is shown below:
The luxuriant and rich with fragrance boric acid of 9-that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.85g white solid TM28, productive rate 59%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM28 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM28 (
1h) refer to accompanying drawing 11.
Embodiment 33
The present embodiment is prepared target compound TM29, and its structure is shown below:
The 9-anthracene boric acid that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 2.79g white solid TM29, productive rate 45%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM29 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM29 (
1h) refer to accompanying drawing 12.
Embodiment 34
The present embodiment is prepared target compound TM30, and its structure is shown below:
The 9-anthracene boric acid that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 2.67g white solid TM30, productive rate 43%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM30 refer to table 1.
Embodiment 35
The present embodiment is prepared target compound TM31, and its structure is shown below:
The 9-anthracene boric acid that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 3.36g 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 is prepared target compound TM32, and its structure is shown below:
The 9-anthracene boric acid that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 3.23g 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 is prepared target compound TM33, and its structure is shown below:
10-phenyl-9-anthracene the boric acid that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.4g 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 13.
Embodiment 38
The present embodiment is prepared target compound TM34, and its structure is shown below:
10-phenyl-9-anthracene the boric acid that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.87g 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 is prepared target compound TM35, and its structure is shown below:
10-phenyl-9-anthracene the boric acid that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 5.19g 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 is prepared target compound TM36, and its structure is shown below:
10-phenyl-9-anthracene the boric acid that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.23g white solid TM36, productive rate 53%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM36 refer to table 1.
Embodiment 41
The present embodiment is prepared target compound TM37, and its structure is shown below:
The 2-pyrene boric acid that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 4.35g white solid TM37, productive rate 65%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM37 refer to table 1.
The present embodiment is prepared target compound TM38, and its structure is shown below:
The 2-pyrene boric acid that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 3.88g white solid TM38, productive rate 58%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM38 refer to table 1.
Embodiment 43
The present embodiment is prepared target compound TM39, and its structure is shown below:
The 2-pyrene boric acid that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 4.17g 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 is prepared target compound TM40, and its structure is shown below:
The 2-pyrene boric acid that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.75g white solid TM40, productive rate 68%.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM40 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM40 (
1h) refer to accompanying drawing 14.
Embodiment 45
The present embodiment is prepared target compound TM41, and its structure is shown below:
9, the 9 dimethyl-2-fluorenes boric acid that phenylo boric acid in embodiment 5 is replaced with to equivalent, other raw material and step are all same as embodiment 5, obtain 5.22g white solid TM41, productive rate 80%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM41 refer to table 1.
Embodiment 46
The present embodiment is prepared target compound TM42, and its structure is shown below:
9, the 9 dimethyl-2-fluorenes boric acid that phenylo boric acid in embodiment 6 is replaced with to equivalent, other raw material and step are all same as embodiment 6, obtain 5.42g white solid TM42, productive rate 83%.
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 15.
Embodiment 47
The present embodiment is prepared target compound TM43, and its structure is shown below:
9, the 9 dimethyl-2-fluorenes boric acid that phenylo boric acid in embodiment 7 is replaced with to equivalent, other raw material and step are all same as embodiment 7, obtain 5.09g white solid TM43, productive rate 75%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM43 refer to table 1.
The present embodiment is prepared target compound TM44, and its structure is shown below:
9, the 9 dimethyl-2-fluorenes boric acid that phenylo boric acid in embodiment 8 is replaced with to equivalent, other raw material and step are all same as embodiment 8, obtain 4.61g white solid TM44, productive rate 68%.Mass spectrometric detection data and the ultimate analysis data of gained compound TM44 refer to table 1.
The present embodiment is prepared target compound TM45, and its structure and synthetic route are shown below:
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 the addition of C H
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 0.1g PtCl
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 15mL 48% 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) TM45's is synthetic
Under nitrogen protection, by 4.82g A (10mmol), 3.05g phenylo 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 TM45, productive rate 70% with sherwood oil/methylene dichloride system column chromatography.
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 16.
Embodiment 50
The present embodiment is prepared target compound TM46, and its structure and synthetic route are shown below:
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-VII (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) TM46's is synthetic
Under nitrogen protection, by 5.48g F (10mmol), 4.95g2-naphthalene boronic acids (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 TM46, productive rate 80% with sherwood oil/methylene dichloride system column chromatography.
Mass spectrometric detection data and the ultimate analysis data of gained compound TM46 refer to table 1, the nuclear-magnetism detection spectrogram of compound TM46 (
1h) refer to accompanying drawing 17.
Mass spectrum and the ultimate analysis data of the aforesaid compound TM1-TM44 of the present invention refer to following table 1:
The mass spectrum of table 1 compound TM1-TM54 and ultimate analysis data
Embodiment 51 is the Application Example of the compounds of this invention TM1-TM46
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)/electron injecting layer/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(N-naphthyl-N-phenyl-4,4 '-benzidine).
Electric transmission layer material is used 4,7-phenylbenzene-1 conventionally, and 10-phenanthroline (BPhen) or Alq3 are used Bphen in element manufacturing of the present invention.
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 element manufacturing of the present invention, selected electron injection material is LiF, and cathode material is Al.
The structural formula of the organic materials that electroluminescent organic material is used is as follows:
Compound in the present embodiment is as the phosphorescent light body material of luminescent layer in organic electroluminescence device, prepared altogether a plurality of organic electroluminescence devices, its structure is: ITO/NPB(50nm)/EML (30nm)/Bphen(15nm)/LiF(0.5nm)/Al(150nm); A contrast organic electroluminescence device in base, phosphorescent light body material is selected CBP, and all the other organic electroluminescence devices are selected material of the present invention.
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 50nm;
The method vacuum evaporation material of main part and the doping agent Ir (piq) that on hole transmission layer, adopt double source to steam altogether
3(main body and doping agent mass ratio are 100:7) as the luminescent layer of device, and material of main part is selected respectively CBP or compound TM4 of the present invention, TM5, TM9, TM13, TM17, TM21, TM27, TM29.The evaporation speed of material of main part is 0.1nm/s, and the evaporation speed of doping agent is 0.007nm/s.Luminescent layer total film thickness is 30nm;
On luminescent layer, vacuum evaporation one Bphen is as the electron transfer layer of organic electroluminescence device, and its evaporation speed is 0.1nm/s, and evaporation total film thickness is 15nm; And then thereon the LiF of vacuum evaporation 0.5nm and the aluminium lamination of 150nm as the negative electrode of organic electroluminescence device.
Organic electroluminescence device in the present embodiment is except changing different luminescent layer material of main parts, and the basic structure of device is consistent with each functional layer material and thickness.
Organic electroluminescence device performance sees the following form:
As seen from the above table, the OLED being manufactured by contrast material of main part CBP, is requiring 5000cd/cm
2brightness under, its corresponding voltage is 7.9V, corresponding efficiency is 6.2cd/A, corresponding CIE chromaticity coordinates is x=0.662, y=0.332.And the OLED that adopts material of main part TM27 of the present invention, TM29, TM37 and TM46 to manufacture is requiring 5000cd/cm
2brightness under, the low energy of its corresponding voltage reaches 6.3V, the most effective 7.4cd/A that reaches compare the advantage that has obvious reduction driving voltage and improve luminous efficiency with contrast material CBP, and therefore purity of color does not suffer damage.
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 (14)
1. one kind 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that having structural formula as the formula (1):
Wherein:
Work as R
5, R
6while being H simultaneously, R
7, R
8respectively independently selected from C
6-C
30aromatic hydrocarbons or condensed-nuclei aromatics, 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
6-C
30aromatic hydrocarbons or condensed-nuclei aromatics, 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):
5. arbitrary described 6 according to claim 1-4, two replacement-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that: described R
5, R
6, R
7, R
8independent of each other is phenyl, substituted-phenyl, naphthyl, phenanthryl, anthryl, pyrenyl or fluorenyl.
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:
One kind to prepare claim 1-7 arbitrary described 6, the method for two replacements-6-H-benzo [cd] pyrene derivatives of 6-, is characterized in that, under nitrogen protection, the intermediate shown in formula (4) or formula (5) is passed through to linked reaction and obtain;
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. according to the preparation 6 described in right 8, the method for 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):
10. a luminescent layer material of main part for organic electroluminescence device, 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-.
11. 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-.
12. organic electroluminescence devices according to claim 11, 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 13. 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.
14. application according to claim 13, described 6, two replacement-6-H-benzo [cd] pyrene derivatives of 6-are as the fluorescence material of main part in organic electroluminescence device or red phosphorescent material of main part.
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| CN104649961B (en) * | 2015-02-04 | 2017-09-19 | 固安鼎材科技有限公司 | Luminescent layer material of main part and organic electroluminescence device |
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| CN104628623A (en) * | 2015-02-04 | 2015-05-20 | 北京鼎材科技有限公司 | 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same |
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| CN104649961B (en) * | 2015-02-04 | 2017-09-19 | 固安鼎材科技有限公司 | Luminescent layer material of main part and organic electroluminescence device |
| CN115490569A (en) * | 2022-02-23 | 2022-12-20 | 陕西莱特迈思光电材料有限公司 | Organic compound, organic electroluminescent device, and electronic device |
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