CN104418714B - Benzophenanthrene discotic mesogenic dimer and synthetic method thereof - Google Patents

Benzophenanthrene discotic mesogenic dimer and synthetic method thereof Download PDF

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CN104418714B
CN104418714B CN201310397248.1A CN201310397248A CN104418714B CN 104418714 B CN104418714 B CN 104418714B CN 201310397248 A CN201310397248 A CN 201310397248A CN 104418714 B CN104418714 B CN 104418714B
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dichloromethane
benzophenanthrene
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蒲嘉陵
王艺飞
张春秀
吴昊
张铭霞
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Beijing Institute of Graphic Communication
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Abstract

The present invention relates to a kind of Benzophenanthrene discotic mesogenic dimer and synthetic method thereof, this dimeric structural formula is as follows:Wherein, n=4,5,6,7,8,9,10,11,12 orWherein, the chemical substance that the m=4 present invention obtains contains benzophenanthrene disk-like mesogens, and has dimeric structure, has outstanding dissolubility, can be dissolved in the Conventional solvents such as dichloromethane.Meanwhile, film property is better than Benzophenanthrene liquid crystal monomer, can construct large-area homogeneous orientation.In the application of the charge transport materials as photoelectric devices such as OTFT, Organic Light Emitting Diode, organic solar batteries, there is potential using value.Present invention safety simple to operate simultaneously, raw material economics is easy to get, product cost economical rationality, has important potential commercial value.

Description

Benzophenanthrene discotic mesogenic dimer and synthetic method thereof
Technical field
The present invention relates to a kind of Benzophenanthrene discotic mesogenic dimer and synthetic method thereof, particular by a kind of Benzophenanthrene monomer with single functional groups of synthesis as the Material synthesis dimeric preparation method of Benzophenanthrene discotic mesogenic.The invention belongs to liquid crystal material and charge transport materials field.
Background technology
Austrian botanist Lai Nicier (F.Reinitzer) in 1888 first observed when studying cholesteryl benzoate has arrived liquid crystal phenomenon, 1989 Germany scientist Lay graceful (OttoLehmann) by the material called after " liquid crystal " of this intermediateness being between liquid and crystal.Research shows, liquid crystal state is the thermodynamically stable phase of the one between crystalline state and liquid, and it had both had the mobility of liquid, maintains again the order of crystalline state.
1954, French physician moral so receive (deGennes) foretold the existence of liquid crystalline phase in disklike molecule.1977, India scientist Chandrasehkar was found that the liquid crystalline phase of disklike molecule first in the research to equal six phenyl esters, and " discotic mesogenic " has been done discussed the most clearly.Discotic liquid-crystalline molecules generally includes two elements: the circumjacent flexible aliphatic side chains of the aromatic series centronucleus with plane or hither plane of rigidity and outside, and around the stone of center, can to pass through the forms such as ether, thioether, ester, benzoate, alkynyl coupled for flexible aliphatic chain.The structure of this uniqueness, makes disklike molecule can form columnar phase by molecular self-assembling when liquid crystalline phase, and has the one-dimensional carrier transmission performance of brilliance because the π-electronics of disklike molecule self is stacking.
Benzophenanthrene was synthesized by Mannich et al. reported first in 1907, and 1978 is be suggested first as discotic mesogenic material.Within 1994, D.Haarer has delivered one section of article about discotic mesogenic photoconductive property on Nature, the reported first photoconductive property of six alkylthio group benzophenanthrenes (HTT6), and this section of article has also lighted the enthusiasm to discotic mesogenic photoconductive property research simultaneously.Thereafter, owing to it is with low cost, it is simple to purify, have abundant structure change and more phase, it is prone between electrode spontaneous ordered arrangement, and having good thermal stability and outstanding charge transport properties and huge application potential, benzophenanthrene is always up the hot fields of liquid crystal semiconducter research.
Currently, it is thus achieved that more there is the benzophenanthrene discotic mesogenic material of excellent in performance and the preparation method of its simple and effective, have become as this field development in the urgent need to.
Summary of the invention
It is an object of the invention to provide a kind of Benzophenanthrene dimer with butoxy side chain and flexible bridge chain link and synthetic method thereof, this material can serve as the charge transport materials of the photoelectric devices such as organic field-effect tube, Organic Light Emitting Diode, solaode.
For achieving the above object, the present invention takes techniques below scheme:
A kind of Benzophenanthrene discotic mesogenic dimer, for the triphenylene containing butoxy side chain and flexible bridge chain link, this dimeric structural formula of benzophenanthrene discotic mesogenic is as follows:
Wherein, n=, 4,5,6,7,8,9,10,11,12, i.e. n=4-12；
Or
Wherein, m=4
The above-mentioned dimeric synthetic method of Benzophenanthrene discotic mesogenic, comprises the steps:
(1) compound 1(1,2-Dibutoxy Benzene) synthesis
Under mechanical stirring, catechol adds Anhydrous potassium carbonate, is then sequentially added into dehydrated alcohol and acetone under nitrogen protection, after stirring, add bromination of n-butane, be warming up to 60 DEG C of condensing refluxes；Thin plate chromatograph monitoring reaction process, to reacting completely, sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, obtains colourless transparent liquid (compound 1)；
(2) compound 2(2,3,6,7,10,11-six butoxy benzophenanthrene) synthesis
Under agitation, the colourless transparent liquid (compound 1) that step (1) obtains adds the dichloromethane dewatered, then under nitrogen protection, stirring, add anhydrous ferric trichloride, under room temperature, continue reaction；Reactant liquor is all poured in ice methanol, sucking filtration, repeatedly rinse with ethanol, obtain filter cake；Under agitation, under nitrogen protection, above-mentioned filter cake is sequentially added into bromination of n-butane, Anhydrous potassium carbonate and acetone, is warming up to 60 DEG C of backflows；After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid (compound 2)；
(3) compound 3(2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrenes) synthesis
Under agitation, adding the dichloromethane dewatered in catechol, then under nitrogen protection, under cryosel bath, stirring condition, inject Boron tribromide with syringe by constant voltage dropper, add rear 20-40min and remove cryosel bath, room temperature continues to react；Decompression distillation, obtains white needle-like crystals B-bromo catechol, and the dichloromethane solution being made into 0.5M is standby；
The light yellow solid (compound 2) that step (2) obtains adds the dichloromethane dewatered; then under nitrogen protection; under room temperature, stirring condition, injected the dichloromethane solution of B-bromo catechol with syringe by constant voltage dropper, be warming up to 40 DEG C of condensing refluxes；After reaction, question response liquid is cooled to room temperature, is poured into by reactant liquor in frozen water, after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration is taken filtrate, rotation is evaporated off solvent, adopts column chromatography to purify, and ethyl alcohol recrystallization obtains white solid (compound 3)；
(4) compound 4(flexible chain bridge joint benzophenanthrene ethers dimer) synthesis.
Under the protection of nitrogen, in dehydrated alcohol and acetone, it is sequentially added into white solid (compound 3) and K that step (3) obtains2CO3, stirring, it is heated to reflux, add dibromoalkane hydrocarbon, backflow, cooling, filter, washing filter cake, filtrate filter cake is used that dichloromethane extraction, and rotation is evaporated off solvent, by gained material chromatography over CC, normal hexane and ethanol (normal hexane: ethanol volume ratio 2:1～3:1) recrystallization, obtain white solid (compound 4).
The process of above-mentioned reaction is:
Or, the synthetic method of above-mentioned Benzophenanthrene liquid crystal-line dimeric, comprise the steps:
(1) compound 1(1,2-Dibutoxy Benzene) synthesis
Under mechanical stirring, catechol adds Anhydrous potassium carbonate, is then sequentially added into dehydrated alcohol and acetone under nitrogen protection, after stirring, add bromination of n-butane, be warming up to 60 DEG C of condensing refluxes；Thin plate chromatograph monitoring reaction process, to reacting completely, sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, obtains colourless transparent liquid (compound 1)；
(2) compound 2(2,3,6,7,10,11-six butoxy benzophenanthrene) synthesis
Under agitation, the colourless transparent liquid (compound 1) that step (1) obtains adds the dichloromethane dewatered, then under nitrogen protection, stirring, add anhydrous ferric trichloride, under room temperature, continue reaction；Reactant liquor is all poured in ice methanol, sucking filtration, repeatedly rinse with ethanol, obtain filter cake；Under agitation, under nitrogen protection, above-mentioned filter cake is sequentially added into bromination of n-butane, Anhydrous potassium carbonate and acetone, is warming up to 60 DEG C of backflows；After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid (compound 2)；
(3) compound 3(2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrenes) synthesis
Under agitation, adding the dichloromethane dewatered in catechol, then under nitrogen protection, under cryosel bath, stirring condition, inject Boron tribromide with syringe by constant voltage dropper, add rear 20-40min and remove cryosel bath, room temperature continues to react；Decompression distillation, obtains white needle-like crystals B-bromo catechol, and the dichloromethane solution being made into 0.5M is standby；
The light yellow solid (compound 2) that step (2) obtains adds the dichloromethane dewatered; then under nitrogen protection; under room temperature, stirring condition, injected the dichloromethane solution of B-bromo catechol with syringe by constant voltage dropper, be warming up to 40 DEG C of condensing refluxes；After reaction, question response liquid is cooled to room temperature, is poured into by reactant liquor in frozen water, after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration is taken filtrate, rotation is evaporated off solvent, adopts column chromatography to purify, and ethyl alcohol recrystallization obtains white solid (compound 3)；
(4) compound 5(flexible chain bridge joint benzophenanthrene esters dimer) synthesis
Under agitation, adding white solid (compound 3), adipic acid that step (3) obtains, DCC, DMAP in dichloromethane, rubber stopper seal is reacted, after having reacted, by gained mixture sucking filtration, and with the NaOH/NaHCO of 5wt%3Extracting after solution and deionized water wash, anhydrous sodium sulfate is dried overnight, sucking filtration, removes solvent, and chromatographic column purifies, and ethyl alcohol recrystallization obtains white powder (compound 5).
The process of above-mentioned reaction is:
It is an advantage of the current invention that:
The chemical substance that the present invention obtains contains benzophenanthrene disk-like mesogens, and has dimeric structure, has outstanding dissolubility, can be dissolved in the Conventional solvents such as dichloromethane.Meanwhile, film property is better than Benzophenanthrene liquid crystal monomer, can construct large-area homogeneous orientation.Compound 4(n=4,5,6,7,8,9,10,11,12 that the present invention obtains) and compound 5 be respectively provided with liquid crystal property, the liquid crystal having broadness is interval, and its liquid crystal property can at room temperature stable existence.Therefore, in the application of the charge transport materials as photoelectric devices such as OTFT, Organic Light Emitting Diode, organic solar batteries, there is potential using value.
Present invention safety simple to operate, raw material economics is easy to get, product cost economical rationality, has important potential commercial value.
Accompanying drawing explanation
Fig. 1 is 2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrene1HNMR spectrogram.
Fig. 2 is 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane1HNMR spectrogram.
Fig. 3 is polarizing microscope (POM) texture pattern of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane.
Fig. 4 is 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane1HNMR spectrogram.
Fig. 5 is polarizing microscope (POM) texture pattern of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane.
Detailed description of the invention
The reaction mechanism of the liquid crystal monomer of the present invention:
The present invention proposes the synthetic method of described liquid crystal monomer according to reaction mechanism, step specific as follows:
(1) compound 1(1,2-Dibutoxy Benzene) synthesis
Equipped with mechanical agitator, spherical condensation tube there-necked flask in be sequentially added into catechol, Anhydrous potassium carbonate, be sequentially added into dehydrated alcohol, acetone under nitrogen protection as solvent, stir 60min, be slowly added to bromination of n-butane, be warming up to 60 DEG C of condensing refluxes.Thin plate chromatograph monitoring reaction process, to reacting completely, sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, obtains colourless transparent liquid 1.
(2) compound 2(2,3,6,7,10,11-six butoxy benzophenanthrene) synthesis
Equipped with, in the there-necked flask of magnetic stirring apparatus, being sequentially added into compound 1, dry dichloromethane, evacuation, repeatedly logical nitrogen three times, after stirring 30min, it is slowly added to anhydrous ferric trichloride, under room temperature, continues reaction 2h.Above-mentioned reactant liquor is all poured slowly in ice methanol, sucking filtration, repeatedly rinses with ethanol, takes filter cake.Equipped with mechanical agitator, reflux condensing tube there-necked flask in, evacuation, repeatedly logical nitrogen three times, be sequentially added into above-mentioned filter cake, bromination of n-butane, Anhydrous potassium carbonate, acetone under nitrogen protection, be warming up to 60 DEG C of backflows.After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid 2 after being completely dried.
(3) compound 3(2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrenes) synthesis
Equipped with magnetic stirring apparatus, constant voltage dropper there-necked flask in be sequentially added into catechol, dry methylene chloride, evacuation, repeatedly logical nitrogen three times.Under cryosel bath, stirring condition, in constant voltage dropper, inject Boron tribromide with syringe, be slowly added dropwise to reaction bulb.Finishing rear 20-40min and remove cryosel bath, room temperature continues reaction 3h.Decompression distillation, obtains white needle-like crystals B-bromo catechol.The dichloromethane solution being made into 0.5M is standby.
Equipped with reflux condensing tube, constant voltage dropper there-necked flask in be sequentially added into compound 2, dry methylene chloride, evacuation, repeatedly logical nitrogen three times, under room temperature, stirring condition, with syringe to the dichloromethane solution injecting B-bromo catechol in constant voltage dropper, it is slowly added in reaction bulb, is warming up to 40 DEG C of condensing refluxes.After reaction 24h, question response liquid is cooled to room temperature, is poured slowly in frozen water by reactant liquor, and after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, adopts column chromatography to purify.Ethyl alcohol recrystallization obtains white solid 3.
(4) compound 4(flexible chain bridge joint benzophenanthrene ethers dimer) synthesis.
Under the protection of nitrogen, successively by compound 3, K2CO3It is equipped with in the there-necked flask of dehydrated alcohol and acetone, magnetic agitation, it is heated to reflux 1h, adds dibromoalkane hydrocarbon, reflux 72h, and cooling is filtered, and washes filter cake, and filtrate filter cake is used that dichloromethane extraction, and rotation is evaporated off solvent, by gained material chromatography over CC.Normal hexane and ethyl alcohol recrystallization, obtain white solid 4.
(5) compound 5(flexible chain bridge joint benzophenanthrene esters dimer) synthesis
Adding dichloromethane in equipped with the single port bottle of magnetic stirring apparatus, be sequentially added into compound 3, adipic acid, DCC, DMAP, rubber stopper seal reaction 36h, by gained mixture sucking filtration, and with the NaOH/NaHCO of mass fraction 5%3Extracting after solution and deionized water wash, anhydrous sodium sulfate is dried overnight, sucking filtration, removes solvent, and chromatographic column purifies, and ethyl alcohol recrystallization obtains white powder 5.
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1,1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane synthesis
Reaction mechanism:
(1) synthesis of 1,2-Dibutoxy Benzene
Equipped with mechanical agitator, spherical condensation tube 1000ml there-necked flask in be sequentially added into catechol 88g; Anhydrous potassium carbonate 442g, is sequentially added into dehydrated alcohol 200ml, acetone 200ml under nitrogen protection, stirs 60min; add bromination of n-butane 410.79g, be warming up to 60 DEG C of condensing refluxes.Thin plate chromatograph monitoring reaction process, reacts completely after about 36h, and sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, takes the fraction of about 132 DEG C, obtains colourless transparent liquid 160g, productivity 90%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 6.99-6.87(m, 4H, aromatic), 4.10-3.99 (t, 4H ,-OCH2-), 1.86-1.77 (m, 4H ,-O-CH2CH2),1.58-1.48(m,28H,-CH2-),1.07-0.97(t,30H,CH3)。
(2) synthesis of 2,3,6,7,10,11-six butoxy benzophenanthrene
Equipped with, in the 250ml there-necked flask of magnetic stirring apparatus, being sequentially added into adjacent benzene diamyl ether 15g, dry dichloromethane 100ml, evacuation, repeatedly logical nitrogen three times, after stirring 30min, be slowly added to anhydrous ferric trichloride 33g, continue reaction 2h under room temperature.Above-mentioned reactant liquor is all poured slowly in 700ml ice methanol, sucking filtration, repeatedly rinses with ethanol, takes filter cake.Equipped with mechanical agitator, reflux condensing tube 250ml there-necked flask in, evacuation, repeatedly logical nitrogen three times, be sequentially added into above-mentioned filter cake, bromo pentane 18.5g, Anhydrous potassium carbonate 370g, acetone 150ml under nitrogen protection, be warming up to 60 DEG C of backflows.After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid 10g after being completely dried, and productivity is 67.5%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum, 1H-NMR (CDCl3, δ=ppm) and concrete data are: 7.846(6H, s, aromatic), 4.26-4.22(12H, t ,-O-CH2), 1.98-1.89(12H, m ,-CH2-), 1.67-1.62(12H, m ,-CH2-), 1.07-1.02(18H, t, CH3).
(3) 2-hydroxyl-3, the synthesis of 6,7,10,11-five butoxy benzophenanthrenes
The preparation of catalysts B-bromo catechol: equipped with magnetic stirring apparatus, constant voltage dropper 100ml there-necked flask in be sequentially added into catechol 11g (1.0equiv.), dry methylene chloride 70ml, evacuation, repeatedly logical nitrogen three times.Under cryosel bath, stirring condition, in constant voltage dropper, inject Boron tribromide 10.6ml (1.1equiv.) with syringe, be slowly added dropwise in reaction bulb.Finishing latter 10 minutes and remove cryosel bath, room temperature continues reaction 3 hours.Fraction at decompression distillation collection about 120 DEG C, obtains white needles 13.64g.The dichloromethane solution being made into 0.5mol/L is standby.
Equipped with reflux condensing tube, constant voltage dropper 250ml there-necked flask in be sequentially added into 2,3,6,7,10,11-six amoxy benzophenanthrene 13g (1.0equiv.), dry methylene chloride 200ml, evacuation, repeatedly logical nitrogen three times, under room temperature, stirring condition, with syringe to the dichloromethane solution 47.3ml (1.4equiv.) injecting B-bromo catechol in constant voltage dropper, it is slowly added in reaction bulb, is warming up to 40 DEG C of condensing refluxes.After reacting 24 hours, question response liquid is cooled to room temperature, is poured slowly in frozen water by reactant liquor, after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, employing column chromatography purifies, and eluent is ethyl acetate and petroleum ether, gradient elution.Rotation obtains faint yellow solid after solvent is evaporated off, and vacuum drying oven obtains white solid 4.8g with ethyl alcohol recrystallization after drying, and productivity is 40%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 7.97-7.78 (m, 6H, aromatic), 5.91 (s, 1H, OH), 4.33-4.20 (t, 10H ,-CH2-),1.95-1.89(m,10H,-O-CH2CH2),1.67-1.56(m,10H,-CH2-), 1.09-0.96(t, 15H, CH3)。
(4) synthesis of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane
Under the protection of nitrogen, successively by 2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrenes (0.5g, 826.7umol), 1,6-dibromo-hexane (0.08g, 330.68umol), K2CO3(1g, 7.24mmol), it is sequentially added into equipped with in the 100ml there-necked flask of 25ml dehydrated alcohol and 25ml acetone, magnetic agitation, 70 DEG C are heated to reflux 36h, filtering, dichloromethane rinse filter cake, rotation is evaporated off solvent, by gained material chromatography over CC, normal hexane: ethanol/3:1 recrystallization, obtains white solid 0.21g, productivity 49%.
The product finally given, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 7.84(m, 12H, aromatic), 4.29-4.22 (t, 24H ,-OCH2-), 2.03-1.91 (m, 24H ,-O-C-CH2), 1.73-1.63 (m, 24H ,-CH2-), 1.07-1.00 (t, 30H, CH3)。
As it is shown in figure 1, prepare obtained for 2-hydroxyl-3 for the present embodiment, 6,7,10,11-five butoxy benzophenanthrenes1HNMR spectrogram；
Fig. 2 is that the present embodiment prepares obtained 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane1HNMR spectrogram.
Fig. 3 is polarizing microscope (POM) texture pattern of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) hexane prepared by the present embodiment, shows that this compound has column plastic crystal phase (Col in figurep) typical case's texture.
Embodiment 2,1,11-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) undecanoic synthesis
Reaction mechanism:
(1) synthesis of 1,2-Dibutoxy Benzene
Equipped with mechanical agitator, spherical condensation tube 1000ml there-necked flask in be sequentially added into catechol 88g; Anhydrous potassium carbonate 442g, is sequentially added into dehydrated alcohol 200ml, acetone 200ml under nitrogen protection, stirs 60min; add bromination of n-butane 410.79g, be warming up to 60 DEG C of condensing refluxes.Thin plate chromatograph monitoring reaction process, reacts completely after about 36h, and sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, takes the fraction of about 132 DEG C, obtains colourless transparent liquid 160g, productivity 90%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 6.99-6.87(m, 4H, aromatic), 4.10-3.99 (t, 4H ,-OCH2-), 1.86-1.77 (m, 4H ,-O-CH2CH2), 1.58-1.48 (m, 28H ,-CH2-), 1.07-0.97 (t, 30H, CH3)。
(2) synthesis of 2,3,6,7,10,11-six butoxy benzophenanthrene
Equipped with, in the 250ml there-necked flask of magnetic stirring apparatus, being sequentially added into adjacent benzene diamyl ether 15g, dry dichloromethane 100ml, evacuation, repeatedly logical nitrogen three times, after stirring 30min, be slowly added to anhydrous ferric trichloride 33g, continue reaction 2h under room temperature.Above-mentioned reactant liquor is all poured slowly in 700ml ice methanol, sucking filtration, repeatedly rinses with ethanol, takes filter cake.Equipped with mechanical agitator, reflux condensing tube 250ml there-necked flask in, evacuation, repeatedly logical nitrogen three times, be sequentially added into above-mentioned filter cake, bromo pentane 18.5g, Anhydrous potassium carbonate 370g, acetone 150ml under nitrogen protection, be warming up to 60 DEG C of backflows.After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid 10g after being completely dried, and productivity is 67.5%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum, 1H-NMR (CDCl3, δ=ppm) and concrete data are: 7.846(6H, s, aromatic), 4.26-4.22(12H, t ,-O-CH2), 1.98-1.89(12H, m ,-CH2-), 1.67-1.62(12H, m ,-CH2-), 1.07-1.02(18H, t, CH3).
(3) 2-hydroxyl-3, the synthesis of 6,7,10,11-five butoxy benzophenanthrenes
The preparation of catalysts B-bromo catechol: equipped with magnetic stirring apparatus, constant voltage dropper 100ml there-necked flask in be sequentially added into catechol 11g (1.0equiv.), dry methylene chloride 70ml, evacuation, repeatedly logical nitrogen three times.Under cryosel bath, stirring condition, in constant voltage dropper, inject Boron tribromide 10.6ml (1.1equiv.) with syringe, be slowly added dropwise in reaction bulb.Finishing latter 10 minutes and remove cryosel bath, room temperature continues reaction 3 hours.Fraction at decompression distillation collection about 120 DEG C, obtains white needles 13.64g.The dichloromethane solution being made into 0.5mol/L is standby.
Equipped with reflux condensing tube, constant voltage dropper 250ml there-necked flask in be sequentially added into 2,3,6,7,10,11-six amoxy benzophenanthrene 13g (1.0equiv.), dry methylene chloride 200ml, evacuation, repeatedly logical nitrogen three times, under room temperature, stirring condition, with syringe to the dichloromethane solution 47.3ml (1.4equiv.) injecting B-bromo catechol in constant voltage dropper, it is slowly added in reaction bulb, is warming up to 40 DEG C of condensing refluxes.After reacting 24 hours, question response liquid is cooled to room temperature, is poured slowly in frozen water by reactant liquor, after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, employing column chromatography purifies, and eluent is ethyl acetate and petroleum ether, gradient elution.Rotation obtains faint yellow solid after solvent is evaporated off, and vacuum drying oven obtains white solid 4.8g with ethyl alcohol recrystallization after drying, and productivity is 40%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 7.97-7.78 (m, 6H, aromatic), 5.91 (s, 1H, OH), 4.33-4.20 (t, 10H ,-CH2-), 1.95-1.89 (m, 10H ,-O-CH2CH2), 1.67-1.56 (m, 10H ,-CH2-), 1.09-0.96(t, 15H, CH3)。
(4) 1,11-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-oxygen base) undecanoic synthesis
Under the protection of nitrogen, successively by 2-hydroxyl-3,6,7,10,11-five butoxy benzophenanthrenes (0.5g, 826.7umol), 1,11-bis-bromo-n-11 (0.1g, 318.36umol), K2CO3(1g, 7.24mmol), it is sequentially added into equipped with in the 100ml there-necked flask of 25ml dehydrated alcohol and 25ml acetone, magnetic agitation, 70 DEG C are heated to reflux 36h, filtering, dichloromethane rinse filter cake, rotation is evaporated off solvent, by gained material chromatography over CC, normal hexane: ethanol/3:1 recrystallization, obtains white solid 0.23g, productivity 47%.
The product finally given, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 7.84(m, 12H, aromatic), 4.26-4.22 (t, 24H ,-OCH2-), 1.96-1.89 (m, 24H ,-O-C-CH2), 1.67-1.56 (m, 34H ,-CH2-), 1.07-1.02 (t, 30H, CH3)。
Embodiment 3,1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane synthesis
Reaction mechanism:
(1) synthesis of 1,2-Dibutoxy Benzene
Equipped with mechanical agitator, spherical condensation tube 1000ml there-necked flask in be sequentially added into catechol 88g; Anhydrous potassium carbonate 442g, is sequentially added into dehydrated alcohol 200ml, acetone 200ml under nitrogen protection, stirs 60min; add bromination of n-butane 410.79g, be warming up to 60 DEG C of condensing refluxes.Thin plate chromatograph monitoring reaction process, reacts completely after about 36h, and sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, takes the fraction of about 132 DEG C, obtains colourless transparent liquid 160g, productivity 90%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 6.99-6.87(m, 4H, aromatic), 4.10-3.99 (t, 4H ,-OCH2-), 1.86-1.77 (m, 4H ,-O-CH2CH2), 1.58-1.48 (m, 28H ,-CH2-), 1.07-0.97 (t, 30H, CH3)。
(2) synthesis of 2,3,6,7,10,11-six butoxy benzophenanthrene
Equipped with, in the 250ml there-necked flask of magnetic stirring apparatus, being sequentially added into adjacent benzene diamyl ether 15g, dry dichloromethane 100ml, evacuation, repeatedly logical nitrogen three times, after stirring 30min, be slowly added to anhydrous ferric trichloride 33g, continue reaction 2h under room temperature.Above-mentioned reactant liquor is all poured slowly in 700ml ice methanol, sucking filtration, repeatedly rinses with ethanol, takes filter cake.Equipped with mechanical agitator, reflux condensing tube 250ml there-necked flask in, evacuation, repeatedly logical nitrogen three times, be sequentially added into above-mentioned filter cake, bromo pentane 18.5g, Anhydrous potassium carbonate 370g, acetone 150ml under nitrogen protection, be warming up to 60 DEG C of backflows.After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid 10g after being completely dried, and productivity is 67.5%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum, 1H-NMR (CDCl3, δ=ppm) and concrete data are: 7.846(6H, s, aromatic), 4.26-4.22(12H, t ,-O-CH2), 1.98-1.89(12H, m ,-CH2-), 1.67-1.62(12H, m ,-CH2-), 1.07-1.02(18H, t, CH3).
(3) 2-hydroxyl-3, the synthesis of 6,7,10,11-five butoxy benzophenanthrenes
The preparation of catalysts B-bromo catechol: equipped with magnetic stirring apparatus, constant voltage dropper 100ml there-necked flask in be sequentially added into catechol 11g (1.0equiv.), dry methylene chloride 70ml, evacuation, repeatedly logical nitrogen three times.Under cryosel bath, stirring condition, in constant voltage dropper, inject Boron tribromide 10.6ml (1.1equiv.) with syringe, be slowly added dropwise in reaction bulb.Finishing latter 10 minutes and remove cryosel bath, room temperature continues reaction 3 hours.Fraction at decompression distillation collection about 120 DEG C, obtains white needles 13.64g.The dichloromethane solution being made into 0.5mol/L is standby.
Equipped with reflux condensing tube, constant voltage dropper 250ml there-necked flask in be sequentially added into 2,3,6,7,10,11-six amoxy benzophenanthrene 13g (1.0equiv.), dry methylene chloride 200ml, evacuation, repeatedly logical nitrogen three times, under room temperature, stirring condition, with syringe to the dichloromethane solution 7.3ml (1.4equiv.) injecting B-bromo catechol in constant voltage dropper, it is slowly added in reaction bulb, is warming up to 40 DEG C of condensing refluxes.After reacting 24 hours, question response liquid is cooled to room temperature, is poured slowly in frozen water by reactant liquor, after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, employing column chromatography purifies, and eluent is ethyl acetate and petroleum ether, gradient elution.Rotation obtains faint yellow solid after solvent is evaporated off, and vacuum drying oven obtains white solid 4.8g with ethyl alcohol recrystallization after drying, and productivity is 40%.
The product obtained, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 7.97-7.78 (m, 6H, aromatic), 5.91 (s, 1H, OH), 4.33-4.20 (t, 10H ,-CH2-), 1.95-1.89 (m, 10H ,-O-CH2CH2), 1.67-1.56 (m, 10H ,-CH2-), 1.09-0.96(t, 15H, CH3)。
(4) synthesis of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane
The single port bottle of the 50ml equipped with magnetic stirring apparatus adds 30ml dichloromethane, it is sequentially added into 2,6-dihydroxy-3,7,10, the synthesis 0.5g of 11-tetra-butoxy benzophenanthrene, adipic acid 0.048g, DCC0.189g, DMAP0.0078g, rubber stopper seal is reacted 36 hours, by gained mixture sucking filtration, and with the NaOH/NaHCO of mass fraction 5%3Extracting after solution and deionized water wash, anhydrous sodium sulfate is dried overnight, sucking filtration, removes solvent, and chromatographic column purifies (ethyl acetate/petroleum ether: 1/35) and obtains white powder 0.25g, productivity 43%.
The product finally given, by hydrogen nuclear magnetic resonance analysis of spectrum,1H-NMR(CDCl3, δ=ppm) and concrete data are: 8.09-7.77(m, 12H, aromatic), 4.28-4.17 (t, 24H ,-OCH2-), 2.80(t, 4H ,-OCOCH2-), 2.06 (t, 4H ,-OCOC-CH2-), 1.97-1.84 (m, 20H ,-O-C-CH2), 1.58-1.53 (m, 20H ,-CH2-), 1.08-0.98 (t, 30H, CH3)。
As shown in Figure 4, for the present embodiment prepare obtained 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane proton nmr spectra (1HNMR) figure.
Fig. 5 is polarizing microscope (POM) texture pattern of 1,6-bis-(3,6,7,10,11-five butoxy benzophenanthrene-2-ester group) hexane prepared by the present embodiment, and this compound has typical hexagonal columnar phase (Colh) conical texture.
Benzophenanthrene ethers dimer compound 4(n=4,5,6,7,8,9,10,11,12 of flexible chain that the present invention obtains bridge joint) and the benzophenanthrene esters dimer compound 5(m=4 of flexible chain bridge joint) it being respectively provided with liquid crystal property, its liquid crystal property has been studied by the means such as use thermogravimetric analysis (TG), differential scanning calorimetry (DSC).In n=4,5,6,7,8,9,10,11,12, or during m=4, the heat decomposition temperature of all of compound 4 or compound 5 is above its melt temperature, and namely its compound under whole phase transformation interval is stable existence.The display of polarizing microscope (POM) image compound 4(n=4,5,6,7,8,9,10,11,12) there is column plastic crystal phase (Colp) typical case's texture, compound 5(m=4) there is typical hexagonal columnar phase (Colh) conical texture.The liquid crystal state of all compounds can retain formation glassy liquid crystals, wherein compound 4(n=6,8,9,10,11 under room temperature (25 DEG C)) can retain more than 3 weeks, compound 5(m=4) can retain more than 1 month.Use flight time method (time-of-flight) that the carrier transmission performance of prepared compound is tested, result shows that obtained compound is respectively provided with higher hole transport performance, compound 4(n=8,9,10,11) carrier mobility up to 1.0 × 10-2cm2v-1s-1, higher than most disc liquid-crystal compounds (mobilitys 1.0 × 10-4～10-3cm2v-1s-1), it is outstanding carrier transmission material.
Benzophenanthrene discotic mesogenic dimer compound prepared by the present invention can be widely used in electronic device, can as the carrier transmission material of Organic Light Emitting Diode (OLED), field effect transistor (FET) and solaode etc..Compared with other discotic mesogenic primitive, the benzophenanthrene discotic mesogenic dimer molecule with butoxy side chain has more orderly post inner structure, there is higher carrier mobility, and there is good film property and good dissolubility, be conducive to its application in photoconductive device.

Claims (2)

1. the dimeric synthetic method of Benzophenanthrene discotic mesogenic, its structural formula is as follows:
Wherein, n=4,5,6,7,8,9,10,11,12
Comprise the steps:
(1) synthesis of 1,2-Dibutoxy Benzene
Under mechanical stirring, catechol adds Anhydrous potassium carbonate, is then sequentially added into dehydrated alcohol and acetone under nitrogen protection, after stirring, add bromination of n-butane, be warming up to 60 DEG C of condensing refluxes；Thin plate chromatograph monitoring reaction process, to reacting completely, sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, obtains colourless transparent liquid；
(2) synthesis of 2,3,6,7,10,11-six butoxy benzophenanthrene
Under agitation, add, in the colourless transparent liquid that step (1) obtains, the dichloromethane dewatered, then under nitrogen protection, stirring, add anhydrous ferric trichloride, under room temperature, continue reaction；Reactant liquor is all poured in ice methanol, sucking filtration, repeatedly rinse with ethanol, obtain filter cake；Under agitation, under nitrogen protection, filter cake is sequentially added into bromination of n-butane, Anhydrous potassium carbonate and acetone, is warming up to 60 DEG C of backflows；After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid；
(3) 2-hydroxyl-3, the synthesis of 6,7,10,11-five butoxy benzophenanthrenes
Under agitation, adding the dichloromethane dewatered in catechol, then under nitrogen protection, under cryosel bath, stirring condition, inject Boron tribromide with syringe by constant voltage dropper, add rear 20-40min and remove cryosel bath, room temperature continues to react；Decompression distillation, obtains white needle-like crystals B-bromo catechol, and the dichloromethane solution being made into 0.5M is standby；
The light yellow solid that step (2) obtains adds the dichloromethane dewatered; then under nitrogen protection; under room temperature, stirring condition, injected the dichloromethane solution of B-bromo catechol with syringe by constant voltage dropper, be warming up to 40 DEG C of condensing refluxes；After reaction, question response liquid is cooled to room temperature, is poured into by reactant liquor in frozen water, and after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, adopts column chromatography to purify, and ethyl alcohol recrystallization obtains white solid；
(4) the dimeric synthesis of benzophenanthrene ethers of flexible chain bridge joint
Under the protection of nitrogen, in dehydrated alcohol and acetone, it is sequentially added into white solid and K that step (3) obtains2CO3, stirring, it is heated to reflux, adds dibromoalkane hydrocarbon, backflow, cooling, filter, wash filter cake, filtrate filter cake is used that dichloromethane extraction, and rotation is evaporated off solvent, by gained material chromatography over CC, normal hexane and ethyl alcohol recrystallization, obtains white solid.
2. the dimeric synthetic method of Benzophenanthrene discotic mesogenic, its structural formula is as follows:
Wherein, m=4,
Comprise the steps:
(1) synthesis of 1,2-Dibutoxy Benzene
Under mechanical stirring, catechol adds Anhydrous potassium carbonate, is then sequentially added into dehydrated alcohol and acetone under nitrogen protection, after stirring, add bromination of n-butane, be warming up to 60 DEG C of condensing refluxes；Thin plate chromatograph monitoring reaction process, to reacting completely, sucking filtration takes filtrate, and solvent is steamed in rotation, by gained liquid pressure-reducing rectification, obtains colourless transparent liquid；
(2) synthesis of 2,3,6,7,10,11-six butoxy benzophenanthrene
Under agitation, add, in the colourless transparent liquid that step (1) obtains, the dichloromethane dewatered, then under nitrogen protection, stirring, add anhydrous ferric trichloride, under room temperature, continue reaction；Reactant liquor is all poured in ice methanol, sucking filtration, repeatedly rinse with ethanol, obtain filter cake；Under agitation, under nitrogen protection, above-mentioned filter cake is sequentially added into bromination of n-butane, Anhydrous potassium carbonate and acetone, is warming up to 60 DEG C of backflows；After reacting completely, question response liquid is cooled to room temperature, and sucking filtration takes filtrate, and light yellow solid is steamed to obtain in rotation, after vacuum drying oven is completely dried, with ethyl alcohol recrystallization, obtains light yellow solid；
(3) 2-hydroxyl-3, the synthesis of 6,7,10,11-five butoxy benzophenanthrenes
Under agitation, adding the dichloromethane dewatered in catechol, then under nitrogen protection, under cryosel bath, stirring condition, inject Boron tribromide with syringe by constant voltage dropper, add rear 20-40min and remove cryosel bath, room temperature continues to react；Decompression distillation, obtains white needle-like crystals B-bromo catechol, and the dichloromethane solution being made into 0.5M is standby；
The light yellow solid that step (2) obtains adds the dichloromethane dewatered; then under nitrogen protection; under room temperature, stirring condition, injected the dichloromethane solution of B-bromo catechol with syringe by constant voltage dropper, be warming up to 40 DEG C of condensing refluxes；After reaction, question response liquid is cooled to room temperature, is poured into by reactant liquor in frozen water, and after repeatedly extracting with dichloromethane, anhydrous sodium sulfate is dried overnight, and mixed solution sucking filtration takes filtrate, and rotation is evaporated off solvent, adopts column chromatography to purify, and ethyl alcohol recrystallization obtains white solid；
(4) the dimeric synthesis of benzophenanthrene esters of flexible chain bridge joint
Under agitation, adding white solid, adipic acid that step (3) obtains, DCC, DMAP in dichloromethane, rubber stopper seal is reacted, after having reacted, by gained mixture sucking filtration, and with the NaOH/NaHCO of 5wt%3Extracting after solution and deionized water wash, anhydrous sodium sulfate is dried overnight, sucking filtration, removes solvent, and chromatographic column purifies, and ethyl alcohol recrystallization obtains white powder.
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