CN103570620B - The luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], intermediate and preparation method and application - Google Patents

The luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], intermediate and preparation method and application Download PDF

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CN103570620B
CN103570620B CN201210364372.3A CN201210364372A CN103570620B CN 103570620 B CN103570620 B CN 103570620B CN 201210364372 A CN201210364372 A CN 201210364372A CN 103570620 B CN103570620 B CN 103570620B
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imino group
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CN103570620A (en
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邱勇
王占奇
段炼
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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Abstract

The invention discloses the luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], have the structural formula as shown in formula I, wherein, Ar1, Ar2, Ar3 is separately selected from C6-C50Aromatic radical, replacement C6-C50Aromatic radical or C1-C20Alkyl. This compound can be used as the fluorescent light-emitting layer of organic electroluminescence device and the material of main part of phosphorescence luminescent layer, it is possible to makes the brightness of organic electroluminescence device and luminous efficiency improve, and reduces its driving voltage, extends the life-span of organic electroluminescence device.

Description

The luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], intermediate and preparation method and application
Technical field
The present invention relates to a kind of organic compound, particularly for the compound of organic electroluminescence device luminescent layer material of main part; Intermediate that the invention still further relates to this compound and preparation method thereof and the application in organic electroluminescence device thereof.
Background technology
Organic electroluminescent (hereinafter referred to as OLED) and corresponding research began to as far back as the sixties in 20th century. First P.Pope in 1963 et al. is found that the electro optical phenomenon of Organic Crystals anthracene, but due to the restriction of technical conditions, its driving voltage, up to 400V, fails to cause and pays close attention to widely. C.W.Tang of Kodak in 1987 et al. uses evaporating Al q3Being made for a kind of amorphous membranous type organic electroluminescence device, within driving voltage is fallen below 20V, OLED just causes common people to pay close attention to (Appl.Phys.Lett.198751 (12): 913-915). This kind of organic electroluminescence device is owing to having brightness height, visual angle width, photoelectric response speed is fast, and voltage is low, and power consumption is little, rich color, contrast is high, and structure is frivolous, simple technological process and other advantages, can be widely used for planar light-emitting element such as flat faced display and area source, therefore obtain and be extensively studied, develop and use.
Dyestuff is generally not capable of the luminescent layer separately as OLED, it is necessary to be entrained in suitable material of main part, forms Subjective and Objective luminescent layer. Such as the anthracene derivative material of main part disclosed in the patents such as US5935721, US20050245752, EP1553154, it is the fluorescent host material of inclined electron type, and in existing general organic electroluminescence device structure, the carrier mobility of hole mobile material is far longer than the carrier mobility of electron transport material, cause in the back cavitation preparing into organic electroluminescence device/electric transmission uneven, thus affecting the luminous efficiency of organic electroluminescence device, and the fluorescent host material of electron type strengthens this effect partially.Thus exploitation tool cavity type or ambipolar material of main part are advantageously in solving the unbalanced problem of carrier transport, thus obtaining high efficiency, long-life luminescent properties. In phosphorescent emitter system, in order to realize the transmission of effective energy, usually require that the triplet ET of material of main part is higher than the triplet ET of dye molecule. For red or green phosphorescent dye, material of main part CBP(structural formula conventional at present is as shown in Figure 1) show original. But for blue phosphorescent dyes, the triplet energy state of itself is higher, the material of main part finding matched more high triplet energy is just comparatively difficult. For blue phosphorescent dyes FIrpic conventional at present, its triplet is 2.65eV, and the triplet of Common main body CBP is 2.56eV, thus the energy transfer process between CBP to FIrpic is endothermic process. Research finds, for the phosphorescence guest-host system of endothermic energy transmission, in organic electroluminescence device preparation process, water oxygen contamination as introduced trace will result in organic electroluminescence device efficiency and is substantially reduced; And, when temperature reduces, endothermic energy transmittance process is subjected to restrain. Simultaneously as a large amount of triplet excitons are present in main body and energy can not pass to phosphorescent coloring in time, this is also one of reason of causing blue phosphorescent organic electroluminescent device short-lived. Therefore, one of material of main part main path becoming solution blue phosphorescent organic electroluminescent device life-span and efficiency finding high triplet energy.
From 2003, people are by reducing molecular conjugation degree, design has synthesized mCP, UGH, CDBP, SimCP etc. and has had the material of main part of high triplet energy (2.7-3.2eV), for CBP material of main part, substantially increases the efficiency of blue phosphorescent organic electroluminescent device. It addition, research finds the glass transition temperature Tg not high enough (such as mCP) of material of main part, or there is no T at allg(such as CBP), is easy to crystallization under filminess, can largely effect on stability and the life-span of corresponding organic electroluminescence device. In the work of early stage, we study and report the TBCPF series blue phosphorescent material of main part TBCPF based on carbazole/fluorenyl, there is high triplet energy level and the high stability of 2.84ev, particularly also achieve the high efficiency blue phosphorescent device of the little molecular monolayer of wet-layer preparation (Tetrahedron, 63 (2007): 10161-10168). Aforementioned body material is the material of main part of the inclined hole transport ability containing carbazole host group mostly.
In recent years, in order to balance electronics in OLED organic electroluminescence device and hole, electrophilic phosphorus oxygen base and benzimidazole group are introduced in the MOLECULE DESIGN of phosphorescent light body material, obtain some and there is electronics or the material of main part of bipolar transmission ability, improve the blue phosphorescent even efficiency of navy blue phosphorescent organic electroluminescent device to some extent. Such as, phosphorescent light body material PPO2, there is the high triplet energy level of 3.0ev, use FCNIr to make phosphorescent dopants, obtain the external quantum efficiency (AdvancedFunctionalMaterials2009,19:3644-3649) up to 18.4%; BM2CB makes main body, Ir (ppy)3Make adulterant, obtain the organic electroluminescence device (J.Phys.Chem.C2010,114,51935198) of luminous efficiency 73.4lm/W, external quantum efficiency 18.7%. With preparing the other materials of OLED organic electroluminescence device and the change of organic electroluminescence device structure (such as hybrid agent material, double; two hole transmission layers, hole blocking layer etc.), having broken through 25% based on the luminous external quantum efficiency of the blue phosphorescent organic electroluminescent device that FIrpic is dyestuff is the highest, the problem that efficiency declines with the increase of electric current density have also been obtained a degree of improvement.But it is noted that, overwhelming majority material of main part still realizes blue phosphorescent organic electroluminescent device using FIrpic as dyestuff, and the luminous efficiency height difference of the FIrpic blue phosphorescent organic electroluminescent device of collocation different subjects material is very big. And blue phosphorescent main body requires to have high triplet, thus the conjugated degree of this kind of material and molecular weight requirement all can not be too big, and the material meeting so requirement often can not meet material and have high Tg(glass transition temperature) is thus obtaining high efficiency and the long-life blue phosphorescent organic electroluminescent device of high stability.
The material structure formula related in background technology is as follows:
Summary of the invention
The technical problem to be solved is in that existing luminescent layer material of main part can not cause organic electroluminescence device inefficiency with blue phosphorescent dyes adaptation, the problem that life-span is short, thus provide a kind of new luxuriant and rich with fragrance compounds of 1, the 12-imino group benzo [c] being used as blue emitting phosphor luminescent layer material of main part.
Another object of the present invention is to provide a kind of intermediate for preparing the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c].
Another object of the present invention is to provide a kind of method of intermediate for preparing the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c].
It is a further object of the present invention to provide a kind of method for preparing the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c].
Another object of the present invention is to provide that a kind of luminous efficiency is high, driving voltage is low, the organic electroluminescence device of long service life.
For achieving the above object, the technical scheme that the present invention takes is as follows:
The luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], has the structural formula as shown in formula I:
Wherein, Ar1, Ar2, Ar3, separately selected from C6-C50 aromatic radical, replaces C6-C50 aromatic radical or C1-C20 alkyl.
Preferably, described replacement C6-C50 aromatic radical is that C6-C50 aromatic radical is replaced by the alkyl of C1-C12; Described C1-C20 alkyl is the alkyl of the straight chained alkyl of C1-C20, branched alkyl or cycloalkyl substituted.
It is further preferred that described Ar1, Ar2, Ar3 are separately selected from C6-C24 aromatic radical, replace C6-C24 aromatic radical or C1-C8 alkyl.
Most preferably, described Ar1, Ar2, Ar3 is separately selected from formula (1) to substituent group shown in formula (212):
The luxuriant and rich with fragrance compounds of 1,12-described imino group benzo [c] is selected from following structural formula:
A kind of intermediate for preparing the luxuriant and rich with fragrance compounds of 1,12-described imino group benzo [c], has the structural formula as shown in formula (M5):
One prepares the method for the luxuriant and rich with fragrance compounds of described 1,12-imino group benzo [c], comprises the steps:
Intermediate shown in described formula (M5) generates the N-intermediate replaced through N-alkylation or N-arylation, generates 4,9 double; two bromination products through bromo-reaction, is then passed through suzuki coupling reaction or SN2 substitution reaction, it is thus achieved that target product.
One prepares the method for intermediate shown in described formula (M5), comprises the steps:
Shown in formula (M2), compound reacts compound shown in production (M3) by Witting-horner; Shown in formula (M3), compound reacts compound shown in production (M4) by intramolecular coupling; Compound shown in compound production under reducing atmosphere (M5) shown in formula (M4).
Preferably, one prepares the method for intermediate shown in described formula (M5), comprises the steps:
(1) synthesis of the bromo-2-of 1-shown in formula (M3) [2-(the bromo-3-nitro-phenyl of 2-)-vinyl]-8-nitro-naphthalene
Compound and NSC 6513 shown in formula (M2) are under nitrogen protection, lower the temperature after back flow reaction 2-6 hour under oil bath, and add solvent, sodium hydride, the bromo-3-nitrobenzaldehyde of 2-, it is to slowly warm up to 38-42 DEG C react 1.5-2.5 hour, it is warming up to 50-60 DEG C again to react 1.5-2.5 hour, it is then refluxed for reaction 5-7 hour, cooling, it is slowly added to the sodium hydride of dehydrated alcohol decomposing excessive, afterwards reactant liquor it is poured in water and stirs 1.5-2.5 hour, dichloromethane extraction product, washing dichloromethane extract, dry extraction liquid also adopts silica gel column chromatography to separate, ethyl acetate: petroleum ether volume ratio=1:(1.8-2.2) eluting, obtain yellow solid M3,
(2) synthesis that 1,12-dinitro base benzo [c] shown in formula (M4) is luxuriant and rich with fragrance
Under argon shield, by dimethylbenzene, compound shown in formula (M3), copper powder back flow reaction 40-60 hour; cooling, washs filtering residue dry mother solution after filtration; employing silica gel column chromatography separates, ethyl acetate: petroleum ether volume ratio=1:(1.5-3) eluting, obtain yellow solid M4
(3) synthesis that 1,12-imino group benzo [c] shown in formula (M5) is luxuriant and rich with fragrance
Adding ethanol, compound shown in water, formula (M4), after sodium hydroxide, it is warming up to backflow, adds zinc powder, and continue backflow 1.5-2.5 hour, cooling, uses washed with dichloromethane filtrate after filtration, separatory after mother solution merging, water layer dichloromethane extraction, merges organic layer, and washing organic layer is to neutral, after drying, dichloromethane layer is evaporated, and adopts silica gel column chromatography to separate, ethyl acetate: petroleum ether volume ratio=1:(5-8) eluting, obtain faint yellow solid M5.
The synthetic method of 1-bromo-2-bromomethyl-8-nitronaphthalene shown in described formula (M2) comprises the steps:
The bromo-2-methyl naphthalene of 1-prepares compound shown in formula (M1) by nitration reaction, and compound shown in formula (M1) is by compound shown in bromo-reaction production (M2).
Preferably, shown in formula (M2), the synthetic method of compound comprises the steps
(4) synthesis of 1-bromo-2-methyl-8-nitronaphthalene shown in formula (M1)
By bromo-for 1-2-methyl naphthalene, concentrated sulphuric acid, 1, after the mixing of 2-dichloroethanes, and control temperature at-10 DEG C to 0 DEG C, under stirring, it is slowly added dropwise nitric acid, and keeps stirring 1.5-2.5 hour under 0～5 DEG C of temperature conditions, be then slowly poured in frozen water, separatory, organic layers with water is washed, and washes after sodium carbonate liquor washing, then magnesium sulfate is adopted to dry, silica gel column chromatography is adopted to separate after concentration, ethyl acetate: petroleum ether volume ratio=1:(1.5-3) eluting, obtain light yellow product M1;
(5) synthesis of 1-bromo-2-bromomethyl-8-nitronaphthalene shown in formula (M2)
By the methyl-8-nitronaphthalene of the bromo-2-of 1-shown in formula (M1); carbon tetrachloride; N-bromo-succinimide and a small amount of benzoyl peroxide Hybrid Heating reflux 4-6 hour; cooling; filtering reacting liquid; silica gel column chromatography is adopted to separate after mother liquor concentrations is dry, ethyl acetate: petroleum ether volume ratio=1:(3-10) eluting, obtain yellow solid M2.
The luminescent layer of a kind of organic electroluminescence device, including material of main part and dyestuff: described material of main part adopts the luxuriant and rich with fragrance compounds of 1,12-described imino group benzo [c] to prepare.
Described luminescent layer includes blue light-emitting layer, and wherein dyestuff is blue dyes, it is preferable that blue phosphorescent dyes or blue luminescence dyestuff.
Described luminescent layer includes green light emitting layer, and wherein dyestuff is green colouring material, it is preferable that green phosphorescent dye.
Described luminescent layer includes red light emitting layer, and wherein dyestuff is orchil, it is preferable that red phosphorescent dye.
The weight part ratio of described material of main part and described dyestuff is 100:(2-10).
A kind of organic electroluminescence device, including substrate, and sequentially forms anode layer on the substrate, several luminescence unit layer and cathode layers;
Described luminescence unit layer includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described hole injection layer is formed on described anode layer, described hole transmission layer is formed on described hole injection layer, described cathode layer is formed on described electron transfer layer, is luminescent layer between described hole transmission layer and described electron transfer layer;
Described luminescent layer is arbitrary described luminescent layer.
Compared with prior art, the advantage of the luxuriant and rich with fragrance compounds of 1, the 12-imino group benzo [c] of the present invention is:
1, when compound shown in formula I prepared by the present invention is used as blue phosphorescent luminescent layer material of main part, owing to its triplet ET is higher than the triplet ET of dye molecule, can better realize effective energy transmission, and blue phosphorescent dyes with the use of time can improve efficiency and the life-span of organic electroluminescence device preferably.
2, in addition, compound shown in formula I prepared by the present invention serves not only as the material of main part of blue phosphorescent luminescent layer, when it is used as the material of main part of blue luminescence layer, the performance of organic electroluminescence device can also be greatly improved, make it have high brightness, high efficiency, low driving voltage, longer service life. Embodiment 31 is known, compound shown in the formula I of the present invention is used to be used as the material of main part of blue luminescence layer, brightness and the luminous efficiency of organic electroluminescence device can be improved, and reduce driving voltage, thus the service life of organic electroluminescence device can be extended.
3, further, compound shown in formula I prepared by the present invention is with making red phosphorescent luminescent layer and the material of main part of green phosphorescent luminescent layer, embodiment 33 and embodiment 34 it is known that, compared with traditional material of main part, when the compound of the use present invention is as material of main part, the brightness of equally possible raising organic electroluminescence device and luminous efficiency, and effectively reduce driving voltage, extend organic electroluminescence device service life.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of the compound (P1) of the embodiment of the present invention 4.
Fig. 2 is the mass spectrum of the compound (P4) of the embodiment of the present invention 5.
Fig. 3 is the mass spectrum of the compound (P5) of the embodiment of the present invention 6.
Fig. 4 is the mass spectrum of the compound (P14) of the embodiment of the present invention 7.
Fig. 5 is the mass spectrum of the compound (P2) of the embodiment of the present invention 8.
Fig. 6 is the mass spectrum of the compound (P6) of the embodiment of the present invention 9.
Fig. 7 is the mass spectrum of the compound (P16) of the embodiment of the present invention 10.
Fig. 8 is the mass spectrum of the compound (P28) of the embodiment of the present invention 11.
Fig. 9 is the mass spectrum of the compound (P7) of the embodiment of the present invention 12.
Figure 10 is the mass spectrum of the compound (P12) of the embodiment of the present invention 13.
Figure 11 is the mass spectrum of the compound (P22) of the embodiment of the present invention 14.
Figure 12 is the mass spectrum of the compound (P45) of the embodiment of the present invention 15.
Figure 13 is the mass spectrum of the compound (P52) of the embodiment of the present invention 16.
Figure 14 is the mass spectrum of the compound (P55) of the embodiment of the present invention 17.
Figure 15 is the mass spectrum of the compound (P61) of the embodiment of the present invention 18.
Figure 16 is the mass spectrum of the compound (P99) of the embodiment of the present invention 19.
Figure 17 is the mass spectrum of the compound (P100) of the embodiment of the present invention 20.
Figure 18 is the mass spectrum of the compound (P8) of the embodiment of the present invention 21.
Figure 19 is the mass spectrum of the compound (P60) of the embodiment of the present invention 22.
Figure 20 is the mass spectrum of the compound (P9) of the embodiment of the present invention 23.
Figure 21 is the mass spectrum of the compound (P15) of the embodiment of the present invention 24.
Figure 22 is the mass spectrum of the compound (P19) of the embodiment of the present invention 25.
Figure 23 is the mass spectrum of the compound (P20) of the embodiment of the present invention 26.
Figure 24 is the mass spectrum of the compound (P32) of the embodiment of the present invention 27.
Figure 25 is the mass spectrum of the compound (P75) of the embodiment of the present invention 28.
Figure 26 is the mass spectrum of the compound (P76) of the embodiment of the present invention 29.
Figure 27 is the mass spectrum of the compound (P77) of the embodiment of the present invention 30.
Figure 28 be the compound (P1) of the embodiment of the present invention 4 nuclear magnetic spectrogram (1H).
Figure 29 be the compound (P4) of the embodiment of the present invention 5 nuclear magnetic spectrogram (1H).
Figure 30 be the compound (P12) of the embodiment of the present invention 13 nuclear magnetic spectrogram (1H).
Figure 31 be the compound (P39) of the embodiment of the present invention 55 nuclear magnetic spectrogram (1H).
Figure 32 be the compound (P77) of the embodiment of the present invention 30 nuclear magnetic spectrogram (1H).
Figure 33 be the compound (P107) of the embodiment of the present invention 113 nuclear magnetic spectrogram (1H).
Detailed description of the invention
Following by specific embodiment, the invention will be further described.
Embodiment 1 to embodiment 3 is the preparation embodiment of intermediate M5 of the present invention:
Embodiment 1
The present embodiment prepares intermediate shown in formula (M5):
Synthetic route is as follows:
Preparation method is:
(1) synthesis of M1
In 500 milliliters of there-necked flasks, add the bromo-2-methyl naphthalene of 22.1g1-, 50 milliliters of concentrated sulphuric acids, 100 milliliter 1, 2-dichloroethanes, cryosel bath controls temperature lower than 0 DEG C, under stirring, it is slowly added dropwise the nitric acid of 9.3g68%, finish, 0～5 DEG C is kept to stir 2 hours, slowly it is poured in 300 milliliters of frozen water, separatory, organic layers with water is washed, 5% sodium carbonate washing, washing, magnesium sulfate dries, silica gel column chromatography is adopted to separate after concentration is dry, ethyl acetate: petroleum ether volume ratio=1:2 eluting, obtain light yellow product M114.2g, MS(m/e): 267, melting range 102～103.5 DEG C, yield 53.4%.
(2) synthesis of M2
In 500 milliliters of there-necked flasks, add 14gM1,300 milliliters of carbon tetrachloride, 9.4gN-bromo-succinimide and a small amount of benzoyl peroxide, reflux 5 hours, cooling, filtering reacting liquid, adopt silica gel column chromatography to separate after mother liquor concentrations is dry, ethyl acetate: petroleum ether volume ratio=1:5 eluting, obtain yellow solid M212.4g, MS(m/e): 345, yield 68%.
(3) synthesis of M3
In 500 milliliters of there-necked flasks, add 12gM2, 20g NSC 6513, under nitrogen protection, back flow reaction 4 hours under oil bath, slow cooling, add 300 milliliters of oxolanes, 3.8g sodium hydride, the bromo-3-nitrobenzaldehyde of 8.05g2-, it is to slowly warm up to 40 DEG C react 2 hours, it is warming up to 55 DEG C again to react 2 hours, it is then refluxed for reaction 6 hours, cooling, it is slowly added to the sodium hydride of 30 milliliters of dehydrated alcohol decomposing excessives, after stirring 30 minutes, reactant liquor is poured in 500 milliliters of water, stir 2 hours, dichloromethane extraction product, washing dichloromethane extract is to neutral, dried over sodium sulfate, organic layer is concentrated into dry, employing silica gel column chromatography separates, ethyl acetate: petroleum ether volume ratio=1:2 eluting, obtain yellow solid M39.7g, MS(m/e): 478, melting range 211～214 DEG C, yield 58%.
(4) synthesis of M4
250 milliliters of there-necked flasks, under argon shield, add 150 milliliters of dimethylbenzene; 8.0gM3,1g copper powder, back flow reaction 48 hours; cooling, uses washed with dichloromethane filtrate after filtration, separatory after mother solution merging; water layer dichloromethane extraction, magnesium sulfate dries, and adopts silica gel column chromatography to separate; ethyl acetate: petroleum ether volume ratio=1:2 eluting; obtain yellow solid M44.16g, MS(m/e): 318, yield 78.1%.
(5) synthesis of M5
500 milliliters of there-necked flasks, add 100 milliliters of ethanol, 100 milliliters of water, 4.0gM4, 15 grams of sodium hydroxide, it is warming up to backflow, it is dividedly in some parts 8g zinc powder, finish then backflow 2 hours, cooling, washed with dichloromethane filtrate is used after filtration, separatory after mother solution merging, water layer dichloromethane extraction, merge organic layer, washing organic layer is to neutral, after drying, it is evaporated, employing silica gel column chromatography separates, ethyl acetate: petroleum ether volume ratio=1:6 eluting, obtain faint yellow solid M52.67g, MS(m/e): 241, yield 88%(M4 molecular weight 318, put into 4g and roll over 0.01258Mol, M5 molecular weight 241, output 2.67g rolls over 0.0111Mol, 0.0111/0.01258=88%).
Embodiment 2
The present embodiment prepares intermediate shown in formula (M5), and basic step is with embodiment 1, wherein:
Being 1.5 hours for mixing time in step (1), ethyl acetate: petroleum ether volume ratio=1:1.6 eluting, controlling temperature is-10 DEG C to 0 DEG C.
Step (2) is 6 hours for return time, ethyl acetate: petroleum ether volume ratio=1:4;
In step (3), under oil bath, back flow reaction was lowered the temperature after 2 hours, and add solvent, sodium hydride, the bromo-3-nitrobenzaldehyde of 2-, it is to slowly warm up to 42 DEG C react 1.5 hours, it is warming up to 50 DEG C again to react 2.5 hours, is then refluxed for reaction 7 hours, cooling, it is slowly added to the sodium hydride stirring of dehydrated alcohol decomposing excessive, afterwards reactant liquor inclined in water and stir 2.5 hours, dichloromethane extraction, washing, dry, employing silica gel column chromatography separates, and ethyl acetate: petroleum ether volume ratio=1:2.2 eluting obtains yellow solid M3;
Step (4) is 40 hours for return time, ethyl acetate: petroleum ether volume ratio=1:2.7;
Step (5) is 1.5 hours for return time, ethyl acetate: petroleum ether volume ratio=1:5.6.
M5 yield 86%.
Embodiment 3
The present embodiment prepares intermediate shown in formula (M5), and basic step is with embodiment 1, wherein:
Step (1) is 2.5 hours for mixing time, ethyl acetate: petroleum ether volume ratio=1:2.8 eluting;
Step (2) is 4 hours for return time, ethyl acetate: petroleum ether volume ratio=1:6;
In step (3), under oil bath, back flow reaction was lowered the temperature after 6 hours, and add solvent, sodium hydride, the bromo-3-nitrobenzaldehyde of 2-, it is to slowly warm up to 38 DEG C react 2.5 hours, it is warming up to 60 DEG C again to react 1.5 hours, is then refluxed for reaction 5 hours, cooling, it is slowly added to the sodium hydride stirring of dehydrated alcohol decomposing excessive, afterwards reactant liquor inclined in water and stir 1.5 hours, dichloromethane extraction, washing, dry, employing silica gel column chromatography separates, and ethyl acetate: petroleum ether volume ratio=1:2 eluting obtains yellow solid M3;
Step (4) is 60 hours for return time, ethyl acetate: petroleum ether volume ratio=1:1.6;
Step (5) is 1.5 hours for return time, ethyl acetate: petroleum ether volume ratio=1:7.2.
M5 yield 85%.
Embodiment 4 to embodiment 30 is the embodiment of the preparation target compound of the present invention utilizing intermediate M5:
Embodiment 4
4,9, N-triphenyl-1 shown in compound prepared by the present embodiment such as formula (P1), 12-imino group benzo [c] is luxuriant and rich with fragrance:
Synthetic route is as follows:
4,9, N-triphenyl-1 shown in formula (P1), the preparation method that 12-imino group benzo [c] is luxuriant and rich with fragrance:
(1) synthesis of M6
500 milliliters of there-necked flasks, under nitrogen protection, add 60 milliliters of DMPU(1; 3-DMPU), 2.5gM5,2.5g iodobenzene; 2.7g potassium carbonate, 0.1g Hydro-Giene (Water Science)., 0.05g18-crown-6; oil bath is heated to reflux 2 hours, cooling, is poured into by reactant liquor in 200 milliliters of water; dichloromethane extraction, magnesium sulfate dries, with ethanol and toluene Mixed Solvent crystallization after concentration is dry; obtain slightly yellow solid M62.57g, MS(m/e): 317, yield 78%.
(2) synthesis of M7
In 250 milliliters of there-necked flasks, add 20 milliliters of DMF(dimethylformamides), 1.2gM6, control the solution of 10 milliliters of DMF of temperature 30～35 DEG C dropping 1.5gN-bromo-succinimide, finish control 30～35 DEG C to react 6 hours, reactant liquor is poured in 100 milliliters of water, precipitates out yellow solid, filter, ethanol and chloroform mixed solvent recrystallization, obtain bright yellow solid M71.53g, MS(m/e): 475, yield 85%.
(3) synthesis of target compound P1
250 milliliters of there-necked flasks, under nitrogen protection, add 30 milliliters of toluene; 30 milliliters of ethanol, 20 milliliters of water, 1.0gM7; 0.62g phenylboric acid, 2.0g potassium carbonate, 0.03g tetra-triphenylphosphine palladium; heating reflux reaction 8 hours, cooling, separatory; organic layer is washed, and magnesium sulfate is dried, adopts silica gel column chromatography to separate; obtain yellow solid P10.84g, MS(m/e): 469, yield 85%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P1 is tested, spectrogram is shown in shown in accompanying drawing 1; Compound P1 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 28.
Embodiment 5
4,9-bis-(2-naphthyl)-N-phenyl-1 shown in compound prepared by the present embodiment such as formula (P4), 12-imino group benzo [c] is luxuriant and rich with fragrance:
Synthetic route is as follows:
Synthetic method, with the synthesis of P1, simply changes phenylboric acid into 1-naphthalene boronic acids, obtains product 1.25g, MS(m/e): 569, yield 82%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P4 is tested, spectrogram is shown in shown in accompanying drawing 2; Compound P4 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 29.
Embodiment 6
4,9-bis-(2-naphthyl)-N-phenyl-1 shown in compound prepared by the present embodiment such as formula (P5), 12-imino group benzo [c] is luxuriant and rich with fragrance:
Synthetic route is as follows:
Synthetic method, with the synthesis of P4, simply changes 1-naphthalene boronic acids into 2-naphthalene boronic acids, obtains product 1.42g, MS(m/e): 569, yield 93%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P5 is tested, spectrogram is shown in shown in accompanying drawing 3.
Embodiment 7
4,9-bis-(3,4-3,5-dimethylphenyl)-N-phenyl-1 shown in compound prepared by the present embodiment such as formula (P14), 12-imino group benzo [c] is luxuriant and rich with fragrance:
Synthetic route is as follows:
The same P1 of synthetic method, simply changes phenylboric acid into 3,4-dimethylphenyl boronic acids, obtains product 11g, MS(m/e): 525, yield 96.8%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P14 is tested, spectrogram is shown in shown in accompanying drawing 4.
Embodiment 8
4, N-diphenyl-9-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P2))-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4, N-diphenyl-9-(4-aminomethyl phenyl shown in formula (P2)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M6 is with embodiment 1:
(1) synthesis of M8
In 250 milliliters of there-necked flasks, add 40 milliliters of DMF, 1.2gM6, control temperature 30～35 DEG C and drip 20 milliliters of solution being dissolved with the DMF of 0.67gNBS, finish control 30～35 DEG C to react 6 hours, reactant liquor is poured in 100 milliliters of water, precipitate out yellow solid, filter, dried employing silica gel column chromatography of crossing separates, and ethyl acetate: petroleum ether volume ratio=1:10 eluting obtains bright yellow solid M71.08g, MS(m/e): 395, yield 72%.
(2) synthesis of M9
250 milliliters of there-necked flasks, under nitrogen protection, add 30 milliliters of toluene; 30 milliliters of ethanol, 20 milliliters of water, 1.0gM8; 0.41g4-methylphenylboronic acid, 1.0g potassium carbonate, 0.015g tetra-triphenylphosphine palladium; heating reflux reaction 8 hours, cooling, separatory; organic layer is washed, and magnesium sulfate is dried, adopts silica gel column chromatography to separate; obtain yellow solid M90.98g, MS(m/e): 407, yield 95%.
(3) synthesis of M10
In 250 milliliters of there-necked flasks, add 20 milliliters of DMF, 0.90gM9, control the solution of 10 milliliters of DMF of temperature 30～35 DEG C dropping 0.43gNBS, finish control 30～35 DEG C to react 6 hours, reactant liquor is poured in 50 milliliters of water, precipitate out yellow solid, filter, dried employing silica gel column chromatography of crossing separates, and ethyl acetate: petroleum ether volume ratio=1:10 eluting obtains bright yellow solid M101.02g, MS(m/e): 487, yield 95%.
(4) synthesis of compound P2
250 milliliters of there-necked flasks, under nitrogen protection, add 30 milliliters of toluene; 30 milliliters of ethanol, 20 milliliters of water, 0.98gM10; 0.29g phenylboric acid, 1.0g potassium carbonate, 0.01g tetra-triphenylphosphine palladium; heating reflux reaction 8 hours, cooling, separatory; organic layer is washed, and magnesium sulfate is dried, adopts silica gel column chromatography to separate; obtain yellow solid P20.94g, MS(m/e): 483, yield 97%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P2 is tested, spectrogram is shown in shown in accompanying drawing 5.
Embodiment 9
4,9-bis-(1-naphthyl)-N-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P6))-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4,9-bis-(1-naphthyl)-N-(4-aminomethyl phenyl shown in formula (P6)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M5 is with embodiment 1:
(1) synthesis of M11
Synthetic method, with the synthesis of M6, simply changes iodobenzene into 4-methyl iodobenzene, obtains product 12.2g, MS(m/e): 331, yield 82%.
(2) synthesis of M12
Synthetic method is with the synthesis of M7, and simply raw material M6 changes M11 into, obtains product 12g, MS(m/s): 489, yield 92%.
(3) synthesis of compound P6
Synthetic method, with the synthesis of P1, simply changes M7 into M12, phenylboric acid changes into 1-naphthalene boronic acids, obtains product 6.5g, MS(m/s): 583, yield 89%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P6 is tested, spectrogram is shown in shown in accompanying drawing 6.
Embodiment 10
4,9-bis-(4-phenyl)-N-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P16))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(4-phenyl)-N-(4-aminomethyl phenyl shown in compound P16) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M12 is with embodiment 9:
The same P6 of synthetic method, simply changes 1-naphthalene boronic acids into 4-biphenylboronic acid, obtains product 3g, MS(m/e): 635, yield 88%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P16 is tested, spectrogram is shown in shown in accompanying drawing 7.
Embodiment 11
4,9-bis-(2-phenyl)-N-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P28))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(2-phenyl)-N-(4-aminomethyl phenyl shown in formula (P28)) the luxuriant and rich with fragrance synthetic method of-1,12-imino group benzo [c]:
The same P16 of synthetic method, simply changes 4-biphenylboronic acid into 2-phenyl phenylboric acid, obtains product 3g, MS(m/e): 635, yield 53%.Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P28 is tested, spectrogram is shown in shown in accompanying drawing 8.
Embodiment 12
4,9-bis-(1-naphthyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P7))-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4,9-bis-(1-naphthyl)-N-(3,4-3,5-dimethylphenyl shown in formula (P7)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M5 is with embodiment 1:
(1) synthesis of M13
Synthetic method, with the synthesis of M11, simply changes 4-methyl iodobenzene into 3,4-dimethyl iodobenzenes, obtains product 20g, MS(m/e): 345, yield 75%.
(2) synthesis of M14
The same M12 of synthetic method, simply changes M11 into M13, obtains product 24.1g, MS(m/e): 503, yield 91%.
(3) synthesis of compound P7
The same P6 of synthetic method, simply changes M12 into M14, obtains product 18.5g, MS(m/e): 597, yield 91.1%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P7 is tested, spectrogram is shown in shown in accompanying drawing 9.
Embodiment 13
4,9, N-tri-(3,4-3,5-dimethylphenyl)-1,12-shown in compound prepared by the present embodiment such as formula (P12) imino group benzo [c] is luxuriant and rich with fragrance:
Synthetic route is as follows:
The same P7 of synthetic method, simply changes 1-naphthalene boronic acids into 3,4-dimethylphenyl boronic acids, obtains product 18g, MS(m/e): 553, yield 93%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P12 is tested, spectrogram is shown in shown in accompanying drawing 10; Compound P12 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 30.
Embodiment 14
4,9-bis-(3-phenyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P22))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(3-phenyl)-N-(3,4-3,5-dimethylphenyl shown in formula (P22)) the luxuriant and rich with fragrance synthetic method of-1,12-imino group benzo [c]:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 3-phenyl phenylboric acid, obtains product 3.5g, MS(m/e): 649, yield 86%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P22 is tested, spectrogram is shown in shown in accompanying drawing 11.
Embodiment 15
4,9-bis-(9-phenanthryl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P45))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(9-phenanthryl)-N-(3,4-3,5-dimethylphenyl shown in formula (P45)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 9-phenanthrene boric acid, obtains product 6.2g, MS(m/e): 697, yield 80%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P45 is tested, spectrogram is shown in shown in accompanying drawing 12.
Embodiment 16
4,9-bis-(N-carbazyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P52))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(N-carbazyl)-N-(3,4-3,5-dimethylphenyl shown in formula (P52)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
1000 milliliters of there-necked flasks, add 300 milliliters of dimethylbenzene, 25.2gM14 under nitrogen protection; 25.1g carbazole, 14.4g sodium tert-butoxide, double; two (the two subunit acetone) palladium of 0.5g; the toluene solution of the tri-butyl phosphine of 2.6g10%, is heated to reflux 24 hours, is down to room temperature; add water separatory, and organic layer is washed to neutrality, adopts silica gel column chromatography to separate after concentration is dry; ethyl acetate: petroleum ether volume ratio=1:5 eluting; obtain yellow green product 21.6g, MS(m/e): 675, yield 32%.Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P52 is tested, spectrogram is shown in shown in accompanying drawing 13.
Embodiment 17
4,9-bis-(3-(N-phenyl) carbazyl shown in compound prepared by the present embodiment such as formula (P55))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(3-(N-phenyl) carbazyl shown in formula (P55))-N-(3,4-3,5-dimethylphenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 9-phenyl carbazole-3--boric acid, obtains product 1.9g, MS(m/e): 827, yield 69%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P55 is tested, spectrogram is shown in shown in accompanying drawing 14.
Embodiment 18
4,9-bis-(4-(2-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P61))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(4-(2-naphthyl) phenyl shown in formula (P61))-N-(3,4-3,5-dimethylphenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 4-(2-naphthyl) phenylboric acid, obtains product 5.0g, MS(m/e): 749, yield 70%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P61 is tested, spectrogram is shown in shown in accompanying drawing 18.
Embodiment 19
4,9-bis-(2-pyridine radicals)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P99))-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(2-pyridine radicals)-N-(3,4-3,5-dimethylphenyl shown in formula (P99))-1,12-imino group benzo
The preparation method that [c] is luxuriant and rich with fragrance:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into pyridine-2--boric acid, obtains product 6.1g, MS(m/e): 499, yield 60%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P99 is tested, spectrogram is shown in shown in accompanying drawing 16.
Embodiment 20
4,9-bis-(5-phenyl) pyridine-2-base shown in compound prepared by the present embodiment such as formula (P100))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(5-phenylpyridine-2-base)-N-(3,4-3,5-dimethylphenyl shown in formula (P100)) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
The same P12 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 5-phenylpyridine-2--boric acid, obtains product 3.5g, MS(m/e): 651, yield 66%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P100 is tested, spectrogram is shown in compound P100 mass spectrum shown in accompanying drawing 17.
Embodiment 21
4-(2-naphthyl shown in compound prepared by the present embodiment such as formula (P8))-9-(4-aminomethyl phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4-(2-naphthyl shown in formula (P8))-9-(4-aminomethyl phenyl)-N-(3,4-3,5-dimethylphenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M13 is with embodiment 6:
(1) synthesis of M15
The same M8 of synthetic method, simply changes M6 into M13, obtains product 6.2g, MS(m/e): 423, yield 82.6%.
(2) synthesis of M16
The same M9 of synthetic method, simply changes M8 into M15, obtains product 5.0g, MS(m/e): 435, yield 96%
(3) synthesis of M17
The same M10 of synthetic method, simply changes M9 into M16, obtains product 5.3g, MS(m/s): 513, yield 92%.
(4) synthesis of compound P8
The same P2 of synthetic method, simply changes M10 into M17, and phenylboric acid changes 2-naphthalene boronic acids into, obtains product 4.6g, MS(m/e): 561, yield 95%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P8 is tested, spectrogram is shown in shown in accompanying drawing 18.
Embodiment 22
4-(N-carbazyl shown in compound prepared by the present embodiment such as formula (P60)) 9-(4-aminomethyl phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
4-(N-carbazyl shown in formula (P60)) 9-(4-aminomethyl phenyl)-N-(3,4-3,5-dimethylphenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c]:
The same P52 of synthetic method, simply changes M14 into M17, obtains product 2.6g, MS(m/e): 600, yield 69%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P60 is tested, spectrogram is shown in shown in accompanying drawing 19.
Embodiment 23
4-(1-naphthyl shown in compound prepared by the present embodiment such as formula (P9))-9-(3,4-3,5-dimethylphenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4-(1-naphthyl shown in formula (P9))-9-(3,4-3,5-dimethylphenyl)-N-(4-aminomethyl phenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M5 is with embodiment 1:
(1) synthesis of M18
The same M13 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 4-methyl iodobenzene, obtains product 22.1g, MS(m/e): 331, yield 87%.
(2) synthesis of M19
The same M15 of synthetic method, simply changes M13 into M18, obtains product 15g, MS(m/e): 409, yield 76.1%.
(3) synthesis of M20
The same M16 of synthetic method, simply changing M15 into M19,4-methylphenylboronic acid changes 3,4-dimethylphenyl boronic acids into, obtains product 14g, MS(m/e): 435, yield 97%.
(4) synthesis of M21
The same M17 of synthetic method, simply changes M16 into M20, obtains product 13.5g, MS(m/e): 513, yield 91%.
(5) synthesis of compound P9
The same P8 of synthetic method, simply changes M17 into M21, changes 2-naphthalene boronic acids into 1-naphthalene boronic acids, obtain product 10.2g, MS(m/e): 561, yield 89%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P9 is tested, spectrogram is shown in shown in accompanying drawing 20.
Embodiment 24
4,9-bis-(4-phenyl)-N-((4-(4-methyl shown in compound prepared by the present embodiment such as formula (P15)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4,9-bis-(4-phenyl)-N-((4-(4-methyl shown in formula (P15)) phenyl) phenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M5 is with embodiment 1;
(1) synthesis of M22
The same M18 of synthetic method, simply changes 4-methyl iodobenzene into 4-((4-methyl) phenyl) iodobenzene, obtain product 9.5g, MS(m/e): 407, yield 66%.
(2) synthesis of M23
The same M12 of synthetic method, simply changes M11 into M22, obtains product 11g, MS(m/e): 565, yield 96%.
(3) synthesis of compound P15
The same P14 of synthetic method, simply changes M7 into M23, and 3,4-dimethylphenyl boronic acids change 4-biphenylboronic acid into, obtain product 10g, MS(m/e): 711, yield 85%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P15 is tested, spectrogram is shown in shown in accompanying drawing 21.
Embodiment 25
4,9-diphenyl-N-((4-(4-methyl shown in compound prepared by the present embodiment such as formula (P19)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-diphenyl-N-((4-(4-methyl shown in compound P19) phenyl) phenyl) the luxuriant and rich with fragrance synthesis of-1,12-imino group benzo [c]:
The same P15 of synthetic method, simply changes 4-biphenylboronic acid into phenylboric acid, obtains product 2.5g, MS(m/e): 559, yield 89.3%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P19 is tested, spectrogram is shown in shown in accompanying drawing 22.
Embodiment 26
4,9-diphenyl-N-(5,4'-dimethyl-1 shown in compound prepared by the present embodiment such as formula (P20), 1'-biphenyl-2-base)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4,9-diphenyl-N-(5,4'-dimethyl-1 shown in formula (P20), 1'-biphenyl-2-base)-1,12-imino group benzo [c] is luxuriant and rich with fragrance: preparation method: wherein the preparation method of M5 with the step (1) of embodiment 1 to step (5)
(1) synthesis of M24
The same M22 of synthetic method, simply by 4-((4-methyl) phenyl) iodobenzene changes 2-((4-methyl) phenyl)-4-methyl iodobenzene into, obtains product 18g, MS(m/e): 421, yield 55.3%.
(2) synthesis of M25
The same M23 of synthetic method, simply changes M22 into M24, obtains product 16.5g, MS(m/e): 579, yield 89.2%.
(3) synthesis of compound P20
The same P19 of synthetic method, simply changes M23 into M25, obtains product 5.8g, MS(m/e): 573, yield 90.1%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P20 is tested, spectrogram is shown in shown in accompanying drawing 23.
Embodiment 27
4,9-diphenyl-N-(4-(3,6-Dimethylcarbazole-9-base shown in compound prepared by the present embodiment such as formula (P32)) phenyl)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4,9-diphenyl-N-(4-(3,6-Dimethylcarbazole-9-base shown in formula (P32)) phenyl) the luxuriant and rich with fragrance preparation method of-1,12-imino group benzo [c], wherein the preparation method of M5 with the step (1) of embodiment 1 to step (5)
(1) synthesis of M26
The same M24 of synthetic method, simply changes 2-(4-aminomethyl phenyl)-4-methyl iodobenzene into 3,6-dimethyl-9-(4-iodophenyls) carbazole, obtain product 11g, MS(m/e): 510, yield 38.6%.
(2) synthesis of M27
The same M25 of synthetic method, simply changes M24 into M26, obtains product 10.5g, MS(m/e): 668, yield 85%.
(3) synthesis of compound P32
The same P20 of synthetic method, simply changes M25 into M27, obtains product 3.2g, MS(m/e): 662, yield 84.1%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P32 is tested, spectrogram is shown in shown in accompanying drawing 24.
Embodiment 28
4,9-bis-(1-naphthyl)-N-(4-(3,6-Dimethylcarbazole-9-base shown in compound prepared by the present embodiment such as formula (P75)) phenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(1-naphthyl)-N-(4-(3,6-Dimethylcarbazole-9-base shown in formula (P75)) phenyl) the luxuriant and rich with fragrance synthetic method of-1,12-imino group benzo [c]:
The same P32 of synthetic method, simply changes phenylboric acid into 1-naphthalene boronic acids, obtains product 3.1g, MS(m/e): 762, yield 89%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P75 is tested, spectrogram is shown in shown in accompanying drawing 25.
Embodiment 29
4,9-bis-(4-phenyl)-N-(4-(3,6-Dimethylcarbazole-9-base shown in compound prepared by the present embodiment such as formula (P76)) phenyl)-1,12-imino group benzo [c] phenanthrene:
4,9-bis-(4-phenyl)-N-(4-(3,6-Dimethylcarbazole-9-base shown in formula (P76)) phenyl) the luxuriant and rich with fragrance synthetic method of-1,12-imino group benzo [c]:
The same P75 of synthetic method, simply changes 1-naphthalene boronic acids into 4-phenyl phenylboric acid, obtains product 5.2g, MS(m/e): 814, yield 81.2%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P76 is tested, spectrogram is shown in shown in accompanying drawing 26.
Embodiment 30
4-((4-(4-methyl shown in compound prepared by the present embodiment such as formula (P77)) phenyl) phenyl)-9-(4-(carbazole-9-base) phenyl) N-(4-(3,6-Dimethylcarbazole-9-base) phenyl)-1,12-imino group benzo [c] phenanthrene:
Synthetic route is as follows:
4-((4-(4-methyl shown in formula (P77)) phenyl) phenyl)-9-(4-(carbazole-9-base) phenyl) N-(4-(3,6-Dimethylcarbazole-9-base) phenyl)-1, the preparation method that 12-imino group benzo [c] is luxuriant and rich with fragrance, wherein the preparation method of M26 is with embodiment 17:
(1) synthesis of M28
The same M19 of synthetic method, simply changes M18 into M26, obtains product 28g, MS(m/e): 588, yield 60.2%
(2) synthesis of M29
The same M20 of synthetic method, simply changes M19 into M28, and 3,4-dimethylphenyl boronic acids change 4-((4-methyl into) phenyl) phenylboric acid, obtain product 12g, MS(m/e): 676, yield 94%.
(3) synthesis of M30
The same M21 of synthetic method, simply changes M20 into M29, obtains product 10.5g, MS(m/e): 754, yield 93%.
(4) synthesis of compound P77
The same P9 of synthetic method, simply changes M21 into M30, changes 1-naphthalene boronic acids into 4-(9-carbazyl) phenylboric acid, obtain product 6.5g, MS(m/e): 917, yield 76%. Using Matrix-assisted laser desorption ionization (being called for short MALDI-TOF-MS) that compound P77 is tested, spectrogram is shown in shown in accompanying drawing 27; Compound P77 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 32.
The following is the Application Example of the compounds of this invention:
The typical structure of OLED organic electroluminescence device is:
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 organic electroluminescence device, for instance: glass or plastics. Anode material can adopt transparent high conductivity material, for instance indium stannum oxygen (ITO), indium zinc oxygen (IZO), tin ash (SnO2), zinc oxide (ZnO) etc.Selecting glass substrate in the organic electroluminescence device of the present invention makes, ITO makes anode material.
Hole transmission layer can adopt N, N '-two (3-tolyl)-N, N '-diphenyl-[1,1-xenyl]-4,4 '-diamidogen (TPD) or N, N '-diphenyl-N, N '-two (1-naphthyl)-(1,1 '-xenyl)-4,4 ' the tri-arylamine group material such as-diamidogen (NPB). Wherein NPB is conventional hole mobile material, and hole mobile material selected in the organic electroluminescence device of the present invention makes selects NPB.
Organic electroluminescence device structure can also be able to be multi-luminescent layer structure for single-shot photosphere.
Electron transfer layer adopts Alq3 or TAZ or TPBi or takes from the collocation of any two kinds of these three material.
In the organic electroluminescence device of the present invention makes, selected cathode material is LiF/Al.
Under the different materials concrete structure used in the present invention is shown in:
Embodiment 31:
The compound of the present invention is as the material of main part in blue-fluorescence OLED organic electroluminescence device:
Preparing 18 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(40nm)/Blue-light emitting host material (30nm): DPAVBi [5%]/Alq3(20nm)/LiF(0.5nm)/Al(150nm).
One of them is contrast organic electroluminescence device, and Blue-light emitting host material selects ADN, and other 17 organic electroluminescence devices select the material of the present invention.
Organic electroluminescence device preparation process is as follows: will be coated with glass plate supersound process in commercial detergent of transparent conductive layer; rinse in deionized water; at acetone: ultrasonic oil removing in alcohol mixed solvent; it is baked under clean environment and completely removes moisture content; by ultraviolet light and ozone clean, and with mental retardation cation bundle bombarded surface;
The above-mentioned glass substrate with anode being placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Vacuum evaporation Blue-light emitting host material on hole transmission layer: DPAVBi [5%] is as the luminescent layer of organic electroluminescence device, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm; Wherein " DPAVBi [5%] " refers to the doping ratio of blue light dyestuff, and namely Blue-light emitting host material is 100:5 with the weight part ratio of DPAVBi.
On luminescent layer, vacuum evaporation Alq3 is as the electron transfer layer of organic electroluminescence device, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The Al of LiF, the Al150nm of vacuum evaporation 0.5nm is as negative electrode on the electron transport layer.
Organic electroluminescence device performance is shown in following table:
By upper table it will be seen that adopt the organic electroluminescence device of the compounds of this invention to obtain good effect relative to the organic electroluminescence device adopting the ADN commonly used in the industry, it is thus achieved that higher current efficiency and relatively low driving voltage.
Embodiment 32:
The compound of the present invention is as the material of main part in blue phosphorescent OLED organic electroluminescence device:
Preparing 17 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(40nm)/Blue-light emitting host material (30nm): FIrpic [5%]/TAZ(20nm)/LiF(0.5nm)/Al(150nm).
One of them is contrast organic electroluminescence device, and Blue-light emitting host material selects mCP, and other 16 organic electroluminescence devices select the material of the present invention.
Organic electroluminescence device preparation process is as follows: will be coated with glass plate supersound process in commercial detergent of transparent conductive layer; rinse in deionized water; at acetone: ultrasonic oil removing in alcohol mixed solvent; it is baked under clean environment and completely removes moisture content; by ultraviolet light and ozone clean, and with mental retardation cation bundle bombarded surface;
The above-mentioned glass substrate with anode being placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Vacuum evaporation Blue-light emitting host material on hole transmission layer: FIrpic [5%] is as the luminescent layer of organic electroluminescence device, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm; Wherein " FIrpic [5%] " refers to the doping ratio of blue light dyestuff, and namely Blue-light emitting host material is 100:5 with the weight part ratio of FIrpic.
On luminescent layer, vacuum evaporation TAZ is as the electron transfer layer of organic electroluminescence device, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
The Al of LiF, the Al150nm of vacuum evaporation 0.5nm is as negative electrode on the electron transport layer.
Organic electroluminescence device performance is shown in following table:
By upper table it will be seen that adopt chemical combination of the present invention as the organic electroluminescence device of phosphorescence host relative to adopting the mCP organic electroluminescence device as main body to obtain good effect, it is thus achieved that higher current efficiency and relatively low driving voltage.
Embodiment 33:
The compound of the present invention is as the material of main part in red phosphorescent OLED organic electroluminescence device:
Preparing 6 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(20nm)/HONGGUANG material of main part (30nm): Ir(piq) 3 [5%]/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm).
One of them is contrast organic electroluminescence device, and HONGGUANG material of main part selects CBP, and other 5 organic electroluminescence devices select the material of the present invention.
Organic electroluminescence device preparation process is as follows: will be coated with glass plate supersound process in commercial detergent of transparent conductive layer; rinse in deionized water; at acetone: ultrasonic oil removing in alcohol mixed solvent; it is baked under clean environment and completely removes moisture content; by ultraviolet light and ozone clean, and with mental retardation cation bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, vacuum evaporation hole transmission layer NPB on above-mentioned anode tunic, evaporation rate is 0.1nm/s, and evaporation thickness is 20nm;
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as the luminescent layer of organic electroluminescence device, evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
Vacuum evaporation electron transfer layer TPBI and Alq3 successively on luminescent layer, its evaporation rate is 0.1nm/s, is deposited with thickness respectively 10nm and 15nm;
The Al of LiF, the 150nm of vacuum evaporation 0.5nm is as negative electrode on the electron transport layer.
Organic electroluminescence device performance is shown in following table:
By upper table it will be seen that adopt chemical combination of the present invention as the organic electroluminescence device of phosphorescence host relative to adopting the CBP organic electroluminescence device as main body to obtain good effect, it is thus achieved that higher current efficiency and relatively low driving voltage.
Embodiment 34:
The compound of the present invention is as the material of main part in green phosphorescent OLED organic electroluminescence device:
Preparing 6 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(20nm)/green glow material of main part (30nm): Ir(ppy) 3 [7%]/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm).
One of them is contrast organic electroluminescence device, and green glow material of main part selects CBP, and other 5 organic electroluminescence devices select the material of the present invention.
Organic electroluminescence device preparation process is as follows: will be coated with glass plate supersound process in commercial detergent of transparent conductive layer; rinse in deionized water; at acetone: ultrasonic oil removing in alcohol mixed solvent; it is baked under clean environment and completely removes moisture content; by ultraviolet light and ozone clean, and with mental retardation cation bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, vacuum evaporation hole transmission layer NPB on above-mentioned anode tunic, evaporation rate is 0.1nm/s, and evaporation thickness is 20nm;
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as the luminescent layer of organic electroluminescence device, evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
Vacuum evaporation electron transfer layer TPBI and Alq3 successively on luminescent layer, its evaporation rate is 0.1nm/s, is deposited with thickness respectively 10nm and 15nm;
The Al of LiF, the 150nm of vacuum evaporation 0.5nm is as electron injecting layer and negative electrode on the electron transport layer.
Organic electroluminescence device performance is shown in following table:
By upper table it will be seen that adopt chemical combination of the present invention as the organic electroluminescence device of phosphorescence host relative to adopting the CBP organic electroluminescence device as main body to obtain good effect, it is thus achieved that higher current efficiency and relatively low driving voltage.
Embodiment 35
4,9-diphenyl-N-(4-aminomethyl phenyls shown in shown in compound prepared by the present embodiment such as formula (P3))-1,12-imino group benzo [c] phenanthrene:
The same P1 of synthetic method, simply changes iodobenzene into 4-methyl iodobenzene, obtains product 2.5g, MS(m/e): 483.
Embodiment 36
4-(2-naphthyl shown in compound prepared by the present embodiment such as formula (P10))-9, N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene:
The same P8 of synthetic method, simply changes 4-methylphenylboronic acid into 3,4-dimethylphenyl boronic acids, obtains product 5.2g, MS(m/e): 575.
Embodiment 37
4-phenyl-9 shown in compound prepared by the present embodiment such as formula (P11), N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] is luxuriant and rich with fragrance:
The same P10 of synthetic method, simply changes 2-naphthalene boronic acids into phenylboric acid, obtains product 6.8g, MS(m/e): 525.
Embodiment 38
4-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P13))-9, N-diphenyl-1,12-imino group benzo [c] is luxuriant and rich with fragrance:
The same P2 of synthetic method, simply changes 4-methylphenylboronic acid into 3,4-dimethylphenyl boronic acids, obtains product 10.1g, MS(m/e): 497.
Embodiment 39
4-(4-phenyl shown in compound prepared by the present embodiment such as formula (P18))-9, N-bis-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene:
The same P11 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 4-methyl iodobenzene, and by 3 ,-dimethylphenyl boronic acid changes 4-methylphenylboronic acid into, phenylboric acid changes into biphenyl-4-boric acid and obtains product 3.6g, MS(m/e): 573.
Embodiment 40
4,9-bis-(3-phenyl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P21)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene:
The same P20 of synthetic method, simply changes 2-(4-aminomethyl phenyl)-4-methyl iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, phenylboric acid changes into 3-phenyl phenylboric acid, obtains product 4.2g, MS(m/e): 725.
Embodiment 41
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P23))-9-(4-aminomethyl phenyl)-N-(4-methyl-3-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, changes 3,4-dimethylphenyl boronic acids into 4-methylphenylboronic acid, 1-naphthalene boronic acids changes into 3-phenyl phenylboric acid, obtains product 2.6g, MS(m/e): 663.
Embodiment 42
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P24))-9, N-bis-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P23 of synthetic method, simply changes 3-(4-aminomethyl phenyl)-4-methyl iodobenzene into 4-methyl iodobenzene, obtains product 2.2g, MS(m/e): 573.
Embodiment 43
4,9-diphenyl-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P25)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P1 of synthetic method, simply changes iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, obtains product 5.2g, MS(m/e): 573.
Embodiment 44
4,9-diphenyl-N-(4-methyl-2-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P26)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P25 of synthetic method, simply changes 3-(4-aminomethyl phenyl)-4-methyl iodobenzene into 2-(4-aminomethyl phenyl)-4-methyl iodobenzene, and 2 obtain product 6.1, MS(m/e): 573.
Embodiment 45
4,9-bis-(2-phenyl)-N-(4-methyl-2-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P27)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P26 of synthetic method, simply changes phenylboric acid into 2-phenyl phenylboric acid, obtains product 5.1g, MS(m/e): 725.
Embodiment 46
4-(2-phenyl shown in compound prepared by the present embodiment such as formula (P29))-9-(3,4-3,5-dimethylphenyl)-N-(4-methyl-2-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 2-(4-aminomethyl phenyl)-4-methyl iodobenzene, 1-naphthalene boronic acids changes into 2-phenyl phenylboric acid, obtains product 6.1g, MS(m/e): 677.
Embodiment 47
4-(2-phenyl shown in compound prepared by the present embodiment such as formula (P30))-9-(3,4-3,5-dimethylphenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 1-naphthalene boronic acids into 2-phenyl phenylboric acid, obtains product 10.1g, MS(m/e): 587.
Embodiment 48
4,9-diphenyl-N-(4-methyl-2-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P31)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-methyl iodobenzene into 2-(4-aminomethyl phenyl)-4-methyl iodobenzene, obtains product 3.9g, MS(m/e): 573.
Embodiment 49
4,9-bis-(4-phenyl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P33)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-methyl iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, phenylboric acid changes into biphenyl-4-boric acid, obtains product 3.9g, MS(m/e): 725.
Embodiment 50
4-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P34)) phenyl) phenyl)-9-(3-phenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 4-(4-aminomethyl phenyl) phenylboric acid, 1-naphthalene boronic acids is changed into 3-phenyl phenylboric acid, obtains product 3.8g, MS(m/e): 649.
Embodiment 51
4-(4-phenyl shown in compound prepared by the present embodiment such as formula (P35))-9-(3,4-3,5-dimethylphenyl) N-(4-methyl-3-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, 1-naphthalene boronic acids changes into 4-phenyl phenylboric acid, obtains product 2.8g, MS(m/e): 677.
Embodiment 52
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P36))-9, N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P10 of synthetic method, simply changes 2-naphthalene boronic acids into 3-phenyl phenylboric acid, obtains product 8.9g, MS(m/e): 601.
Embodiment 53
4,9-bis-(4-cyclohexyl phenyl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P37)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P25 of synthetic method, simply changes phenylboric acid into 4-cyclohexyl benzene boric acid, obtains product 5.0g, MS(m/e): 737.
Embodiment 54
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P38))-9-(4-((4-methyl) phenyl) phenyl)-N-(4-methyl-3-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3-(4-aminomethyl phenyl)-4-methyl iodobenzene, by 3,4-dimethylphenyl boronic acid changes 4-(4-aminomethyl phenyl into) phenylboric acid, 1-naphthalene boronic acids is changed into 3-phenyl phenylboric acid, obtains product 6.1g, MS(m/e): 739.
Embodiment 55
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P39))-9-(4-((4-methyl) phenyl) phenyl)-N-(4-methyl-2-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P38 of synthetic method, simply changes 3-(4-aminomethyl phenyl)-4-methyl iodobenzene into 2-(4-aminomethyl phenyl)-4-methyl iodobenzene, obtains product 5.1g, MS(m/e): 739. Compound P39 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 31
Embodiment 56
4-(2-phenyl shown in compound prepared by the present embodiment such as formula (P40))-9-(4-((4-methyl) phenyl) phenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 3,4-dimethylphenyl boronic acids into 3-(4-aminomethyl phenyl) phenylboric acid, 1-naphthalene boronic acids is changed into 2-phenyl phenylboric acid, obtains product 1.9g, MS(m/e): 649.
Embodiment 57
4-(3-phenyl shown in compound prepared by the present embodiment such as formula (P41))-9-(3,4-3,5-dimethylphenyl)-N-(4-methyl-2-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P39 of synthetic method, simply by 3-(4-aminomethyl phenyl) phenylboric acid changes 3,4-dimethylphenyl boronic acids into, obtains product 2.5g, MS(m/e): 677.
Embodiment 58
4-(2-phenyl shown in compound prepared by the present embodiment such as formula (P42))-9-(3,4-3,5-dimethylphenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 1-naphthalene boronic acids into 2-phenyl phenylboric acid, obtains product 5.8g, MS(m/e): 587.
Embodiment 59
4,9-bis-(3,4-3,5-dimethylphenyl)-N-(4-methyl-2-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P43)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P20 of synthetic method, simply changes phenylboric acid into 3,4-dimethylphenyl boronic acids, obtains product 6.6g, MS(m/e): 629.
Embodiment 60
4-(3-((3 shown in compound prepared by the present embodiment such as formula (P44), 4,5-trimethyls) phenyl) phenyl)-9-(4-((3,4,5-trimethyl) phenyl) phenyl)-N-(4-methyl-3-(4-(4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P39 of synthetic method, simply by 4-(4-aminomethyl phenyl) phenylboric acid changes 4-(3 into, 4,5-trimethylphenyls) phenylboric acid, change 3-phenylboric acid into 3-(3,4,5-trimethylphenyls) phenylboric acid, obtain product 1.6g, MS(m/e): 809.
Embodiment 61
4,9-bis-(9-phenanthryl)-N-(3,4,5-trimethylphenyls shown in compound prepared by the present embodiment such as formula (P46))-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-methyl iodobenzene into 3,4,5-trimethyl iodobenzenes, phenylboric acid changes into 9-phenanthrene boric acid, obtains product 6.2g, MS(m/e): 711.
Embodiment 62
4,9-bis-(9-phenanthryl)-N-(2,3,4,5-trimethylphenyls shown in compound prepared by the present embodiment such as formula (P47))-1,12-imino group benzo [c] phenanthrene.
The same P46 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 2,3,4,5-tetramethyl iodobenzenes, obtains product 1.9g, MS(m/e): 725.
Implement 63
4,9-bis-(9-phenanthryl)-N-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P48))-1,12-imino group benzo [c] phenanthrene.
The same P46 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 4-methyl iodobenzene, obtains product 6.2g, MS(m/e): 683.
Embodiment 64
4-(9-phenanthryl shown in compound prepared by the present embodiment such as formula (P49))-9-(3,4-3,5-dimethylphenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 1-naphthalene boronic acids into 9-phenanthrene boric acid, obtains product 11.2g, MS(m/e): 611.
Embodiment 65
4-(9-phenanthryl shown in compound prepared by the present embodiment such as formula (P50))-9, N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P10 of synthetic method, simply changes 2-naphthalene boronic acids into 9-phenanthrene boric acid, obtains product 8.1g, MS(m/e): 625.
Embodiment 66
4-(9-phenanthryl shown in compound prepared by the present embodiment such as formula (P51))-9-(4-aminomethyl phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3,4-dimethyl iodobenzenes, changes 3,4-dimethylphenyl boronic acids into 4-methylphenylboronic acid, 1-naphthalene boronic acids changes into 9-phenanthrene boric acid, obtains product 5.8g, MS(m/e): 611.
Embodiment 67
4,9-bis-((4-(N-carbazyl) phenyl)-N-(3,4,5-trimethylphenyls shown in compound prepared by the present embodiment such as formula (P53))-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-methyl iodobenzene into 3,4,5-trimethyl iodobenzenes, phenylboric acid changes into 4-(N-carbazyl) phenylboric acid, obtain product 7.1g, MS(m/e): 841.
Embodiment 68
4,9-bis-(N-carbazyl)-N-(4-cyclohexyl phenyl shown in compound prepared by the present embodiment such as formula (P54))-1,12-imino group benzo [c] phenanthrene.
The same P52 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 4-cyclohexyl iodobenzene, obtains product 11.8g, MS(m/e): 729.
Embodiment 69
4,9-bis-((N-methyl carbazole)-3-base)-N-(3,4,5-trimethylphenyls shown in compound prepared by the present embodiment such as formula (P56))-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-methyl iodobenzene into 3,4,5-trimethyl iodobenzenes, phenylboric acid changes into N-methyl carbazole-3-boric acid, obtains product 2.9g, MS(m/e): 717.
Embodiment 70
9-(4-(N-carbazyl shown in compound prepared by the present embodiment such as formula (P57)) phenyl)-4, N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene
The same P10 of synthetic method, simply changes 2-naphthalene boronic acids into 4-(N-carbazyl) phenylboric acid, obtain product 6.5g, MS(m/e): 690.
Embodiment 71
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P58))-N-(2,3,4,5-tetramethylphenyls)-1,12-imino group benzo [c] phenanthrene.
The same P53 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 2,3,4,5-tetramethyl iodobenzenes, obtains product 2.5g, MS(m/e): 855.
Embodiment 72
4,9-bis-(3,6-Dimethylcarbazole-N-base)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P59))-1,12-imino group benzo [c] phenanthrene.
The same P52 of synthetic method, simply changes carbazole into 3,6-Dimethylcarbazoles, obtains product 8.0g, MS(m/e): 731.
Embodiment 73
4,9-bis-(4-(2-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P62))-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-(2-naphthyl into by phenylboric acid) phenylboric acid, obtain product 4.9g, MS(m/e): 735.
Embodiment 74
4,9-bis-(4-(2-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P63))-N-(3,4,5-trimethylphenyls)-1,12-imino group benzo [c] phenanthrene.
The same P62 of synthetic method, simply changes 4-methyl iodobenzene into 3,4,5-trimethyl iodobenzenes, obtains product 3.8g, MS(m/e): 763.
Embodiment 75
4,9-bis-(4-(2-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P64))-N-(2,3,4,5-tetramethylphenyls)-1,12-imino group benzo [c] phenanthrene.
The same P62 of synthetic method, simply changes 4-methyl iodobenzene into 2,3,4,5-tetramethyl iodobenzenes, obtains product 3.8g, MS(m/e): 777.
Embodiment 76
4,9-bis-(3-(1-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P65))-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 3-(1-naphthyl into by phenylboric acid) phenylboric acid, obtain product 5.5g, MS(m/e): 735.
Embodiment 77
4,9-bis-(3-(1-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P66))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P65 of synthetic method, simply changes 4-methyl iodobenzene into 3,4-dimethyl iodobenzenes, obtains product 5.6g, MS(m/e): 749.
Embodiment 78
4,9-bis-(3-(1-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P67))-N-(2,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P65 of synthetic method, simply changes 4-methyl iodobenzene into 2,4-dimethyl iodobenzenes, obtains product 6.6g, MS(m/e): 749.
Embodiment 79
4,9-bis-(3-(1-naphthyl) phenyl shown in compound prepared by the present embodiment such as formula (P68))-N-(3,4,6-trimethylphenyls)-1,12-imino group benzo [c] phenanthrene.
The same P65 of synthetic method, simply changes 4-methyl iodobenzene into 3,4,6-trimethyl iodobenzenes, obtains product 5.0g, MS(m/e): 763.
Embodiment 80
4-(1-naphthyl shown in compound prepared by the present embodiment such as formula (P69))-9-(4-(3,6-Dimethylcarbazole-N-base) phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3,4-dimethyl iodobenzenes, 3,4-dimethylphenyl boronic acids changes into 4-(3,6-Dimethylcarbazole-N-base) phenylboric acid, obtain product 8.8g, MS(m/e): 740.
Embodiment 81
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P70))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P53 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 3,4 dimethyl iodobenzenes, obtains product 4.8g, MS(m/e): 827.
Embodiment 82
4-(2-naphthyl shown in compound prepared by the present embodiment such as formula (P71))-9-(4-(N-carbazyl) phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 3,4-dimethyl iodobenzenes, 3,4-dimethylphenyl boronic acids changes into 4-(3,6-Dimethylcarbazole-N-base) phenylboric acid, change 1-naphthalene boronic acids into 2-naphthalene boronic acids, obtain product 6.2g, MS(m/e): 740.
Embodiment 83
4-(N-carbazyl shown in compound prepared by the present embodiment such as formula (P72))-9, N-bis-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P60 of synthetic method, simply changes 4-methylphenylboronic acid into 3,4-dimethylphenyl boronic acids, obtains product 5.2g, MS(m/e) 614.
Embodiment 84
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P73))-N-(3-ethyl-4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P53 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 3-ethyl-4-methyl iodobenzene, obtains product 5.6g, MS(m/e): 841.
Embodiment 85
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P74))-N-(4-cyclohexyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P53 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 4 cyclohexyl iodobenzenes, obtains product 11.0g, MS(m/e): 881.
Embodiment 86
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P78))-N-(4-((4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P53 of synthetic method, simply changes 3,4,5-trimethyl iodobenzenes into 4 (4-aminomethyl phenyl) iodobenzene, obtains product 6.5g, MS(m/e): 889.
Embodiment 87
4,9-bis-(N-carbazyl)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P79)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P52 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 4 (4-aminomethyl phenyl) iodobenzene, obtains product 5.1g, MS(m/e): 737.
Embodiment 88
4-(N-carbazyl shown in compound prepared by the present embodiment such as formula (P80))-9-(3,4-3,5-dimethylphenyl)-N-(4-((4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P60 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 4 (4-aminomethyl phenyl) iodobenzene, changes 4-methylphenylboronic acid into 3,4-dimethylphenyl boronic acids, obtain product 2.6g, MS(m/e): 676.
Embodiment 89
4,9-bis-(2-naphthyl)-N-(4-(3,6-Dimethylcarbazole-N-base shown in compound prepared by the present embodiment such as formula (P81)) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-(3,6-Dimethylcarbazole-N-base into by 4-methyl iodobenzene) iodobenzene, phenylboric acid is changed into 2-naphthalene boronic acids, obtains product, MS(m/e): 762.
Embodiment 90
4,9-bis-(3-phenyl)-N-(4-(3,6-Dimethylcarbazole-N-base shown in compound prepared by the present embodiment such as formula (P82)) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P81 of synthetic method, simply changes 2-naphthalene boronic acids into 3-phenyl phenylboric acid, obtains product 2.0g, MS(m/e): 814.
Embodiment 91
4-(4-methyl-3-((4-methyl shown in compound prepared by the present embodiment such as formula (P83)) phenyl) phenyl) 9-(4-(N-carbazyl) phenyl)-N-(4-(3,6-Dimethylcarbazole-N-base-) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-(3,6-Dimethylcarbazole-N-base into by 4-methyl iodobenzene) iodobenzene, 3,4-dimethylphenyl boronic acids are changed into 4-methyl-3-(4-aminomethyl phenyl) phenylboric acid, change 1-naphthalene boronic acids into 4-(N-carbazyl) phenylboric acid, obtain product 2.9g, MS(m/e): 931.
Embodiment 92
4,9-bis-(4-(N-carbazyl) phenyl shown in compound prepared by the present embodiment such as formula (P84))-N-(4-methyl-3-((4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
3,4,5-trimethyl iodobenzenes are simply changed into 4-methyl-3-(4-aminomethyl phenyl by the same P53 of synthetic method) iodobenzene, obtain product 5.0g, MS(m/e): 903.
Embodiment 93
4,9-bis-(N-carbazyl)-N-(4-methyl-3-((4-methyl shown in compound prepared by the present embodiment such as formula (P85)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
3,4-dimethyl iodobenzenes are simply changed into 4-methyl-3-(4-aminomethyl phenyl by the same P52 of synthetic method) iodobenzene, obtain product 1.9g, MS(m/e): 751.
Embodiment 94
4-(N-carbazyl shown in compound prepared by the present embodiment such as formula (P86))-9-(3,4-3,5-dimethylphenyl)-N-(4-methyl-3-((4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
3,4-dimethyl iodobenzenes are simply changed into 4-methyl-3-(4-aminomethyl phenyl by the same P60 of synthetic method) iodobenzene, change 4-methylphenylboronic acid into 3,4-dimethylphenyl boronic acids, obtain product 2.9g, MS(m/e): 690.
Embodiment 95
4,9-bis--(9-phenanthryl)-N-(2,5-dimethyl-4-(3,6-Dimethylcarbazole-N-base-shown in compound prepared by the present embodiment such as formula (P87)) phenyl)-1,12-imino group benzo [c] phenanthrene.
3,4-dimethyl iodobenzenes are simply changed into 2,5-dimethyl-4-(3,6-Dimethylcarbazole-N-bases by the same P45 of synthetic method) iodobenzene, obtain product 1.9g, MS(m/e): 890.
Embodiment 96
4,9-bis--(9-phenanthryl)-N-(4-(3,6-Dimethylcarbazole-N-base-shown in compound prepared by the present embodiment such as formula (P88)) phenyl)-1,12-imino group benzo [c] phenanthrene.
3,4-dimethyl iodobenzenes are simply changed into 4-(3,6-Dimethylcarbazole-N-base by the same P45 of synthetic method) iodobenzene, obtain product 7.0g, MS(m/e): 862.
Embodiment 97
4,9-bis-(1-naphthyl)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P89)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P19 of synthetic method, simply changes phenylboric acid into 1-naphthalene boronic acids, obtains product 8.1g, MS(m/e): 659.
Embodiment 98
4,9-bis-(2-naphthyl)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P90)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P89 of synthetic method, simply changes 1-naphthalene boronic acids into 2-naphthalene boronic acids, obtains product 10.2g, MS(m/e): 659.
Embodiment 99
4,9-bis-(1-naphthyl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P91)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P89 of synthetic method, simply by 4-(4-aminomethyl phenyl) iodobenzene changes 4-methyl-3-(4-aminomethyl phenyl into) iodobenzene, obtain product 6.2g, MS(m/e): 673.
Embodiment 100
4,9-bis-(2-naphthyl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P92)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P91 of synthetic method, simply changes 1-naphthalene boronic acids into 2-naphthalene boronic acids, obtains product 11.9g, MS(m/e): 673.
Embodiment 101
4,9-bis-(9-phenanthryl)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P93)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P19 of synthetic method, simply changes phenylboric acid into 9-phenanthrene boric acid, obtains product 6.3g, MS(m/e): 759.
Embodiment 102
4,9-bis-(9-phenanthryl)-N-(4-methyl-3-(4-(4-methyl shown in compound prepared by the present embodiment such as formula (P94)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P91 of synthetic method, simply changes 1-naphthalene boronic acids into 9-phenanthrene boric acid, obtains product 5.2g, MS(m/e): 773.
Embodiment 103
4,9-bis-(3-phenyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P95))-1,12-imino group benzo [c] phenanthrene.
The same P66 of synthetic method, simply by 3-(1-naphthyl) phenylboric acid changes 3-phenyl phenylboric acid into, obtains product 7.1g, MS(m/e): 649.
Embodiment 104
4,9-bis-(4-cyclohexyl phenyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P96))-1,12-imino group benzo [c] phenanthrene.
The same P95 of synthetic method, simply changes 3-phenyl phenylboric acid into 3-cyclohexyl benzene boric acid, obtains product 5.8g, MS(m/e): 661.
Embodiment 105
4,9-bis-(4-phenyl)-N-(3,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P97))-1,12-imino group benzo [c] phenanthrene.
The same P96 of synthetic method, simply changes 3-cyclohexyl benzene boric acid into 4-phenyl phenylboric acid, obtains product 3.8g, MS(m/e): 649.
Embodiment 106
4,9-bis-(3-(3,4,5-trimethylphenyl) phenyl shown in compound prepared by the present embodiment such as formula (P98))-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P96 of synthetic method, simply changes 3-cyclohexyl benzene boric acid into 3-(3,4,5-trimethylphenyls) phenylboric acid, obtain product 2.0g, MS(m/e): 733.
Embodiment 107
4,9-bis-(2-pyridine radicals)-N-(2,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P101))-1,12-imino group benzo [c] phenanthrene.
The same P100 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 2,4-dimethyl iodobenzenes, changes 5-phenylpyridine-2-boric acid into pyridine-2-boric acid, obtain product 3.8g, MS(m/e): 499.
Embodiment 108
4,9-bis-(5-phenylpyridine-2-base)-N-(2,4-3,5-dimethylphenyl shown in compound prepared by the present embodiment such as formula (P102))-1,12-imino group benzo [c] phenanthrene.
The same P100 of synthetic method, simply changes 3,4-dimethyl iodobenzenes into 2,4-dimethyl iodobenzenes, obtains product 5.4g, MS(m/e): 651.
Embodiment 109
4,9-bis-(2-pyridine radicals)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P103)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P93 of synthetic method, simply changes 9-phenanthrene boric acid into pyridine-2-boric acid, obtains product 2.6g, MS(m/e): 561.
Embodiment 110
4,9-bis-(5-phenylpyridine-2-base)-N-(4-((4-methyl shown in compound prepared by the present embodiment such as formula (P104)) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P103 of synthetic method, simply changes pyridine-2-boric acid into 5-phenylpyridine-2-boric acid, obtains product 3.1g, MS(m/e): 713.
Embodiment 111
4,9-bis-(4-((2,2-diphenyl) ethylene-1-base shown in compound prepared by the present embodiment such as formula (P105)) phenyl)-N-(4-aminomethyl phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P48 of synthetic method, simply changes 4-(2,2-diphenylethlene-1-base into by 9-phenanthrene boric acid) phenylboric acid, obtain product 5.1g, MS(m/e): 839.
Embodiment 112
4-(4-((2 shown in compound prepared by the present embodiment such as formula (P106), 2-diphenyl) ethylene-1-base) phenyl)-9-(4-((2,2-bis-(4-aminomethyl phenyl)) ethylene-1-base) phenyl)-N-(3,4-3,5-dimethylphenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply change 4-methyl iodobenzene into 3,4-dimethyl iodobenzene, 3,4-dimethylphenyl boronic acids change 4-(2,2-bis-(4-aminomethyl phenyl) ethylene-1-base into) phenylboric acid, change 1-naphthalene boronic acids into 4-(2,2-diphenylethlene-1-base) phenylboric acid, obtain product 2.8g, MS(m/e): 867.
Embodiment 113
4,9-bis-(4-((2,2-diphenyl) ethylene-1-base shown in compound prepared by the present embodiment such as formula (P107)) phenyl)-N-(4-((2,2-bis-(4-aminomethyl phenyl)) ethylene-1-base) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P3 of synthetic method, simply changes 4-(2,2-diphenylethlene-1-base into by 4-methyl iodobenzene) iodobenzene, phenylboric acid is changed into 4-(2,2-diphenylethlene-1-base) phenylboric acid, and obtain product 5.7g, MS(m/e): 1031. Compound P107 nuclear magnetic spectrogram (1H) see shown in accompanying drawing 33
Embodiment 114
4-(4-aminomethyl phenyl shown in compound prepared by the present embodiment such as formula (P17))-9-(4-phenyl)-N-(4-((4-methyl) phenyl) phenyl)-1,12-imino group benzo [c] phenanthrene.
The same P9 of synthetic method, simply changes 4-methyl iodobenzene into 4-(4-aminomethyl phenyl) iodobenzene, change 3,4-dimethylphenyl boronic acids into 4-methylphenylboronic acid, 1-naphthalene boronic acids is changed into 4-phenyl phenylboric acid, obtains product 8.2g, MS(m/e): 649.
Embodiment 115
The compound of the present invention is as the material of main part in blue-fluorescence OLED organic electroluminescence device:
Preparing 80 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(40nm)/Blue-light emitting host material (30nm): DPAVBi [2%]/Alq3(20nm)/LiF(0.5nm)/Al(150nm).
Its preparation method is with embodiment 31, and the weight part ratio that Blue-light emitting host material is the compound of embodiment 35-embodiment 114 preparation, Blue-light emitting host material and described blue light dyestuff DPAVBi is: 100:2.
Embodiment 116
The compound of the present invention is as the material of main part in blue phosphorescent OLED organic electroluminescence device:
Preparing 80 organic electroluminescence devices altogether, organic electroluminescence device structure is:
ITO/NPB(40nm)/Blue-light emitting host material (30nm): FIrpic [5%]/TAZ(20nm)/LiF(0.5nm)/Al(150nm).
Its preparation method is with embodiment 32, and the weight part ratio that Blue-light emitting host material is the compound of embodiment 35-embodiment 114 preparation, Blue-light emitting host material and described blue light dyestuff FIrpic is: 100:10.
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the 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 without also cannot all of embodiment be given exhaustive. And the apparent change thus extended out or variation are still among the protection domain of the invention.

Claims (15)

1. the luxuriant and rich with fragrance compounds of 12-imino group benzo [c], it is characterised in that: there is the structural formula as shown in formula I:
Wherein,
Described Ar1, Ar2, Ar3Separately selected from formula (1) to substituent group shown in formula (212):
2. the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c] according to claim 1, it is characterised in that described compound is selected from following structural formula:
3. the method preparing the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c] described in claim 1 or 2, it is characterised in that comprise the steps:
Shown in formula (M2), compound reacts compound shown in production (M3) by Witting-horner;
Shown in formula (M3), compound reacts compound shown in production (M4) by intramolecular coupling;
Compound shown in compound production under reducing atmosphere (M5) shown in formula (M4);
Intermediate shown in formula (M5) generates the N-intermediate replaced through N-alkylation or N-arylation, generates 4,9 double; two bromination products through bromo-reaction, is then passed through suzuki coupling reaction or SN2 substitution reaction, it is thus achieved that target product.
4. the method preparing the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c] described in claim 1 or 2, it is characterised in that comprise the steps:
(1) synthesis of the bromo-2-of 1-shown in formula (M3) [2-(the bromo-3-nitro-phenyl of 2-)-vinyl]-8-nitro-naphthalene
Compound and NSC 6513 shown in formula (M2) are under nitrogen protection, lower the temperature after back flow reaction 2-6 hour under oil bath, and add solvent, sodium hydride, the bromo-3-nitrobenzaldehyde of 2-, it is to slowly warm up to 38-42 DEG C react 1.5-2.5 hour, it is warming up to 50-60 DEG C again to react 1.5-2.5 hour, it is then refluxed for reaction 5-7 hour, cooling, it is slowly added to the sodium hydride of dehydrated alcohol decomposing excessive, afterwards reactant liquor it is poured in water and stirs 1.5-2.5 hour, dichloromethane extraction product, washing dichloromethane extract, dry extraction liquid also adopts silica gel column chromatography to separate, ethyl acetate: petroleum ether volume ratio=1:(1.8-2.2) eluting, obtain yellow solid M3,
(2) synthesis that 1,12-dinitro benzo [c] shown in formula (M4) is luxuriant and rich with fragrance
Under argon shield, by dimethylbenzene, compound shown in formula (M3), copper powder back flow reaction 40-60 hour, cooling, wash filtering residue after filtration, and dry mother solution, employing silica gel column chromatography separates, ethyl acetate: petroleum ether volume ratio=1:(1.5-3) eluting, obtain yellow solid M4;
(3) synthesis that 1,12-imino group benzo [c] shown in formula (M5) is luxuriant and rich with fragrance
Adding ethanol, compound shown in water, formula (M4), after sodium hydroxide, it is warming up to backflow, adds zinc powder, and continue backflow 1.5-2.5 hour, cooling, uses washed with dichloromethane filtrate after filtration, separatory after mother solution merging, water layer dichloromethane extraction, merges organic layer, and washing organic layer is to neutral, after drying, dichloromethane layer is evaporated, and adopts silica gel column chromatography to separate, ethyl acetate: petroleum ether volume ratio=1:(5-8) eluting, obtain faint yellow solid M5;
(4) intermediate shown in formula (M5) generates the N-intermediate replaced through N-alkylation or N-arylation, generates 4,9 double; two bromination products through bromo-reaction, is then passed through suzuki coupling reaction or SN2 substitution reaction, it is thus achieved that target product.
5. the method according to claim 3 or 4, it is characterised in that:
The synthetic method of 1-bromo-2-bromomethyl-8-nitronaphthalene shown in described formula (M2) comprises the steps:
The bromo-2-methyl naphthalene of 1-prepares compound shown in formula (M1) by nitration reaction, and compound shown in formula (M1) is by compound shown in bromo-reaction production (M2).
6. method according to claim 5, it is characterised in that:
Shown in formula (M2), the synthetic method of compound comprises the steps:
(4) synthesis of 1-bromo-2-methyl-8-nitronaphthalene shown in formula (M1)
By bromo-for 1-2-methyl naphthalene, concentrated sulphuric acid, 1, after the mixing of 2-dichloroethanes, and control temperature at-10 DEG C to 0 DEG C, under stirring, it is slowly added dropwise nitric acid, and keeps stirring 1.5-2.5 hour under 0～5 DEG C of temperature conditions, be then slowly poured in frozen water, separatory, organic layers with water is washed, and washes after sodium carbonate liquor washing, then magnesium sulfate is adopted to dry, silica gel column chromatography is adopted to separate after concentration, ethyl acetate: petroleum ether volume ratio=1:(1.5-3) eluting, obtain light yellow product M1;
(5) synthesis of 1-bromo-2-bromomethyl-8-nitronaphthalene shown in formula (M2)
By the methyl-8-nitronaphthalene of the bromo-2-of 1-shown in formula (M1); carbon tetrachloride; N-bromo-succinimide and a small amount of benzoyl peroxide Hybrid Heating reflux 4-6 hour; cooling; filtering reacting liquid; silica gel column chromatography is adopted to separate after mother liquor concentrations is dry, ethyl acetate: petroleum ether volume ratio=1:(3-10) eluting, obtain yellow solid M2.
7. a luminescent layer for organic electroluminescence device, including material of main part and dyestuff: it is characterized in that, described material of main part adopts the luxuriant and rich with fragrance compounds of 1,12-imino group benzo [c] described in claim 1 or 2 to prepare.
8. the luminescent layer of organic electroluminescence device according to claim 7, it is characterised in that: described luminescent layer includes blue light-emitting layer, and wherein dyestuff is blue dyes.
9. the luminescent layer of organic electroluminescence device according to claim 8, it is characterised in that: described blue dyes is blue phosphorescent dyes or blue luminescence dyestuff.
10. the luminescent layer of organic electroluminescence device according to claim 7, it is characterised in that: described luminescent layer includes green light emitting layer, and wherein dyestuff is green colouring material.
11. the luminescent layer of organic electroluminescence device according to claim 10, it is characterised in that: wherein said green colouring material is green phosphorescent dye.
12. the luminescent layer of organic electroluminescence device according to claim 7, it is characterised in that: described luminescent layer includes red light emitting layer, and wherein dyestuff is orchil.
13. the luminescent layer of organic electroluminescence device according to claim 12, it is characterised in that: described orchil is red phosphorescent dye.
14. the luminescent layer according to the arbitrary described organic electroluminescence device of claim 7-13, it is characterised in that: the weight part ratio of described material of main part and described dyestuff is 100:2-10.
15. an organic electroluminescence device, including substrate, and sequentially form anode layer on the substrate, several luminescence unit layer and cathode layers;
Described luminescence unit layer includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, described hole injection layer is formed on described anode layer, described hole transmission layer is formed on described hole injection layer, described cathode layer is formed on described electron transfer layer, is luminescent layer between described hole transmission layer and described electron transfer layer; It is characterized in that:
Described luminescent layer is the arbitrary described luminescent layer of claim 7-14.
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