CN103012083A - Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof - Google Patents
Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof Download PDFInfo
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- CN103012083A CN103012083A CN2012105858132A CN201210585813A CN103012083A CN 103012083 A CN103012083 A CN 103012083A CN 2012105858132 A CN2012105858132 A CN 2012105858132A CN 201210585813 A CN201210585813 A CN 201210585813A CN 103012083 A CN103012083 A CN 103012083A
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Abstract
The invention relates to a tetracyclic fluorinated negative liquid crystal compound, and a synthesis method and application thereof. The compound has a molecular formula shown in the specification. The synthesis method is simple; and the compound can be used as a high-temperature component of a mixed liquid crystal and can be further used for preparing a negative liquid crystal having wide working temperature range, thermal stability and high birefringence degree.
Description
Technical field
The present invention relates to two fluorine-containing tolane liquid crystalline cpds of dicyclohexyl, have high birefringence rate, low-viscosity and clearing point up to 300 ℃ can be used for the good high birefringence rate mixture liquid crystal of processability.Be used for developing visible light, infrared light and laser self-adoptive optical modulator, many new application are arranged aspect photonics.
Background of invention
Now, the liquid crystal flat-panel technique of display is widely used among the social life.Particularly entered since 21 century, because the TFT mode LCD is popularized in mobile phone, computer and TV tech, it has become the main flow of flat pannel display.In addition, liquid crystal device as developed aspect the modulator techniques of ADAPTIVE OPTICS SYSTEMS, became the new Application Areas of a kind of liquid crystal device that develops rapidly (Wen, C.H. at visible light, near infrared and laser wavelength in recent years; W, S.T.Appl.Phys.Lett.2005,86,231104).
The TFT liquid-crystal display mainly uses the fluorinated liquid crystal material, is because the introducing of fluorine, so that the stability of liquid crystalline cpd (voltage retention) uprises, and the viscosity step-down, double refractive inde is low, and is quite suitable for one-level minimum (requiring △ n=0.1).The nematic liquid crystal that has dielectric anisotropy and be negative value (Δ ε＜0) is an important composition colony of liquid crystal material, it can be used for vertically aligned (VA), in in-plane switching (IPS) and electrically controlled birefringence mode (ECB) liquid crystal mode, make the giant-screen Active Matrix Display.In addition, the negative liquid crystal of high birefringence rate (△ n〉0.25) also can be used as double frequency to the main component of row mixture, obtains important application in the photonics field.So far research is learnt, have the liquid crystal that utilizes high birefringence rate only, the liquid crystal compound that just may use thin as far as possible liquid crystal cell and respond fast, might be able to reach high-speed response (2.5 microns of cel-gap, the time of response＜3ms), thus satisfy the requirement of the wide band-adaptive optical system of visible light, near infrared light and laser modulator.Many physicalies of fluorine-containing tolane liquid crystal can satisfy above requirement.High birefringence rate for example, low-viscosity, nematic phase (working temperature zone) is wide etc.Single nematic phase only appears in the fluorine-containing diphenyl acetylene class negative liquid crystal compound that 2 dicyclohexyls of the present invention replace, and clearing point temperature is very high simultaneously, can reach about 300 ℃.Can be used as the high-temperature component of mixed liquid crystal, prepare the negative liquid crystal of very wide thermally-stabilised, the high birefringence rate of good working temperature.
Summary of the invention
The object of the invention provides the fluorine-containing negative liquid crystal compound in a kind of Fourth Ring, preparation method and use.
The fluorine-containing negative liquid crystal compound in Fourth Ring of the present invention has following molecular formula:
Fourth Ring of the present invention fluorine-containing negative liquid crystal compou nd synthesis reaction formula is as follows:
Wherein: n=2,3
With 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2,3-two fluoro-4-phenetole acetylene, dichloro two (triphenyl phosphorus) palladium, cuprous iodide and triethylamine flow down reaction 1 ~ 5h next time in nitrogen protection;
Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2, the mol ratio of 3-two fluoro-4-phenetole acetylene and triethylamine is 1 ~ 1,2:0.8 ~ 1.0:1 ~ 100; Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene mmole, dichloro two (triphenyl phosphorus) palladium milligram weight and cuprous iodide milligram weight ratio are 1:45 ~ 60:50 ~ 100.
Described reaction product is through filtration, washing, drying, and concentrated, column chromatography or recrystallization purifying are processed.
The fluorine-containing negative liquid crystal compound in Fourth Ring of the present invention is simple synthetic method not only, and can be as the high-temperature component of mixed liquid crystal, the negative liquid crystal of thermally-stabilised, the high birefringence rate that the preparation work temperature is very wide.
Embodiment
The present invention can be further understood by following embodiment, but content of the present invention can not be limited.Anyly the simple replacement done of invention or improvement etc. are all belonged within the technical scheme that the present invention protects those skilled in that art
Embodiment:
Trans with 1-[, trans-4 '-n-propyl (1,1 '-dicyclohexyl)-4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene acetylene) benzene (B) synthesize example:
[1 '-hydroxyl-4 '-(trans-4 " n-propyl cyclohexyl) cyclohexyl] benzene is synthetic
Under nitrogen protection; the magnesium of 2.37g (0.099mol) and the tetrahydrofuran (THF) of 100ml drying are added in the there-necked flask of 250ml; the bromobenzene of 14.85g (0.094mol) is splashed into from dropping funnel; heat up behind the 5min; drip off behind the 30min; continue to stir 1h, obtain brownish black liquid, stand-by.
Being dissolved in the tetrahydrofuran (THF) of 50ml and adding in the there-necked flask of 250ml by 4 '-n-propyl bicyclohexanone 20.6g (.085mol), the grignard reagent that makes is splashed into from the normal pressure dropping funnel of 250ml, the control temperature is below 40 ℃, and 40min drips off.And continuation reaction 3h.The meteorological tracking reacts completely.Drip the hydrochloric acid of 20ml10%, separatory with the hexane extraction water of 20ml, merges organic phase, uses successively saturated sodium bicarbonate aqueous solution, and each the 20ml washing of salt solution and water obtains the organic phase drying, is spin-dried for, and gets solid 26g.y：97.1%。
[4 '-(trans-4 " n-propyl cyclohexyl) tetrahydrobenzene-1 '-yl] benzene synthetic
Take by weighing 24.5g (0.078mol) [1 '-hydroxyl-4 '-(trans-4 " n-propyl cyclohexyl) cyclohexyl] tosic acid one water complex of benzene and 1.6g adds in the there-necked flask of 250ml; add the toluene of 80ml; stirring and refluxing, and use fraction water device water-dividing.React completely, add 30ml water and stirring, separatory is used the toluene aqueous layer extracted, merges organic phase.Organic phase is used saturated sodium bicarbonate aqueous solution successively, and salt solution and water washing get the organic phase drying, are spin-dried for, and use the sherwood oil recrystallization, obtain product 18g.y：78%。
Synthesizing of cis-trans configurations mixture 4-n-propyl-{ (dicyclohexyl)-4-yl } benzene
Take by weighing 18g (0.061mol) [4 '-(trans-4 " n-propyl cyclohexyl) tetrahydrobenzene-1 '-yl] benzene is dissolved in the toluene of 150ml; add reactor; add the Pd/C of catalytic amount; be pressed into the hydrogen of an amount of pressure; and spend the night at 40 ℃ of lower stirring reactions, react completely, suction filtration is removed solid residue; toluene is removed in underpressure distillation, obtains cis-trans configurations mixture product 17.7g.y：97%。
Synthesizing of 4-n-propyl-{ (trans, trans-dicyclohexyl)-4-yl } benzene
In the there-necked flask of 250ml, cis-trans configurations mixture 4-n-propyl-{ (dicyclohexyl)-4-yl } benzene 17.67g is dissolved in the 120ml dimethyl formamide (DMF), add again potassium tert.-butoxide under nitrogen protection, refluxed 5 hours.Use chromatogram tracking, treat cis-isomeride be converted into trans after, be chilled to room temperature, add entry 150ml and toluene 150ml the extraction 2 times.Hydrochloric acid with 10%, saturated sodium bicarbonate aqueous solution washing.Use dried over mgso after the washing.The underpressure distillation desolventizing obtains solid residue.With ethyl alcohol recrystallization 2 times, obtain white solid product 16.7g, yield 94%.
Synthesizing of 4-n-propyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene
In the there-necked flask of 100ml, the 4-propyl group of adding 5g (16.8mmol)-{ (trans, trans-dicyclohexyl)-4-yl } benzene, the iodine of 3.05g (12mmol), Periodic acid two water complexs of 3.3g (14.5mmol).Add again 1 of the Glacial acetic acid of 8ml and 10ml, 2-ethylene dichloride, under agitation oil bath reflux 5h.Wait react completely after, be cooled to room temperature, add 10% aqueous solution of sodium bisulfite 100ml, stir, eliminate residual iodine.With the toluene extraction, obtain organic phase, with twice of salt washing.With the organic phase dried over mgso.Removal of solvent under reduced pressure obtains solid residue.Use ethanol: ethyl acetate (10:1) mixing solutions recrystallization gets product 5g.Yield y:70%.
Synthesizing of 2,3-, two fluoro-4-oxyethyl group iodobenzenes
With 2 of 10g (0.063mol); 3; the tetrahydrofuran (THF) of-difluoroethoxy benzene and 70ml drying adds in the there-necked flask of 250ml under nitrogen protection; mechanical stirring; be cooled to below-78 ℃, drip the n-Butyl Lithium of 40ml (2M), 20min drips off; the control temperature is reacted 1.5h between-70--80 ℃; automatic heating drips the solution that 20g (0.079mol) iodine is dissolved in 50mlTHF to-60 ℃ the time, and 40min drips off, and the control temperature is reacted 2h between-60--70 ℃; stop; automatic heating adds saturated aqueous ammonium chloride solution 200ml, layering to normal temperature; twice of ethyl acetate extraction of inorganic phase; merge organic phase, and wash three times with aqueous solution of sodium bisulfite, wash twice; get the organic phase anhydrous magnesium sulfate drying; water pump underpressure distillation desolventizing, 84-88 ℃/2mmHg of cut is collected in the oil pump underpressure distillation; get thick product 9.5g, get white solid product 7.1g with the sherwood oil recrystallization again.Y:39%.1,1-dimethyl-3-(2,3-, two fluoro-4-phenetoles)-2-propine-1-alcohol synthetic
With 2 of 4g (0.014mol); the 3-difluoro is to the oxyethyl group iodobenzene; 1.5g (0.018mol) 1; 1 dimethyl-2-propine-1-alcohol; dichloro two (triphenyl phosphorus) palladium of 100mg; the cuprous iodide of 120mg and the triethylamine of 80ml add in the there-necked flask of 100ml under nitrogen protection; magnetic agitation, temperature are controlled at about 40 ℃ reacts 3h, and TLC follows the tracks of and reacts completely; cooling; suction filtration, solid is washed with ethyl acetate, gets mother liquor pressure reducing and steaming solvent; use ethyl acetate: the eluent of normal hexane=5:1 is crossed pillar, gets yellow liquid product 3.2g.y:95%.
Synthesizing of 2,3-, two fluoro-4-phenetole acetylene
With 1 of 3.29g (13.7mmol), 1-dimethyl-3-(2,3-two fluoro-4-phenetoles)-2-propine-1-alcohol, 0.9g potassium hydroxide (16.1mmol) and the toluene of 80ml add in the single port flask of 100ml, magnetic agitation, the lower reaction 3h that refluxes, TLC follows the tracks of and reacts completely, cooling, suction filtration, solid is washed with toluene, gets mother liquor pressure reducing and steaming solvent, use sherwood oil: the eluent of ethyl acetate=10:1 is crossed post, get yellow liquid, crystallisation by cooling is used the sherwood oil recrystallization, get white solid product 1.14g, y:46%.
1-[is trans, trans-4 '-n-propyl or ethyl (1,1 '-dicyclohexyl)-4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene ethynyl) benzene synthetic
With the 4-propyl group of 440mg (1.11mmol) or ethyl-{ (trans; trans-dicyclohexyl)-the 4-yl } iodobenzene; 2 of 182mg (0.83mmol); 3-two fluoro-4-phenetole acetylene; dichloro two (triphenyl phosphorus) palladium of 45mg; the cuprous iodide of 100mg and the triethylamine of 60ml add in the there-necked flask of 100ml under nitrogen protection; magnetic agitation; reaction 4h under refluxing, TLC follows the tracks of and reacts completely, cooling; suction filtration; solid is washed with ethyl acetate, gets mother liquor and washes with water three times, gets the organic phase anhydrous sodium sulfate drying; the pressure reducing and steaming solvent; use sherwood oil: the eluent of toluene=8:1 is crossed post, gets white solid crude product ethanol/toluene recrystallization, gets white solid product.
1H?NMR(400MHz,CDCl3):δ0.81(t,J＝7.2Hz,5H),0.88-1.01(m,3H),1.08-1.09(m,6H),1.18-1.27(m,2H),1.33-1.41(m,5H),1.65-1.85(m,8H),2.34-2.42(m,1H),4.07(q,J＝7.0Hz,2H),6.60-6.64(m,1H),7.08-7.12(m,3H),7.38(d,J＝8.0Hz,2H)。
The mesomorphic phase temperature of A compound (using the warm table polarized light microscope observing):
Cr154.8℃N303.3℃I300.0℃N142.5℃Cr。
1-[is trans, trans-4 '-ethyl (1,1 '-dicyclohexyl)-the 4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene ethynyl) benzene (A)
Obtain 0.25g, productive rate 59%.MS(m/z,%):450.3(M+,100.00),450.3(100.00);
1H?NMR(400MHz,CDCl3):δ0.78-0.82(m,5H),0.89-1.03(m,3H),1.08-1.19(m,6H),1.33-1.42(m,5H),1.66-1.86(m,8H),2.35-2.42(m,1H),4.07(q,J=7.0Hz,2H),6.60-6.64(m,1H),7.08-7.13(m,3H),7.38(d,J＝8.4Hz,2H)。
The mesomorphic phase temperature of B compound (using the warm table polarized light microscope observing):
Cr146.20℃N298.5℃I293.4℃N133.82℃Cr。
Claims (4)
1. fluorine-containing negative liquid crystal compound in Fourth Ring has following molecular formula:
2. fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 1 is characterized in that obtaining by the following method:
With 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2,3-two fluoro-4-phenetole acetylene, dichloro two (triphenyl phosphorus) palladium, cuprous iodide and triethylamine flow down reaction 1 ~ 5h next time in nitrogen protection;
2 of described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 0.83mmol, the mol ratio of 3-two fluoro-4-phenetole acetylene and triethylamine is 1 ~ 1.2:0.8 ~ 1.0:1 ~ 100; Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene mmole, dichloro two (triphenyl phosphorus) palladium milligram weight and cuprous iodide milligram weight ratio are 1:45 ~ 60:50 ~ 100.
3. the synthetic method of the fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 2 is characterized in that product through filtration, washing, drying, and concentrated, column chromatography or recrystallization purifying are processed.
4. the purposes of the fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 1 is characterized in that the high-temperature component as mixed liquid crystal, the negative liquid crystal of thermally-stabilised, the high birefringence rate that the preparation work temperature is very wide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110790650A (en) * | 2019-11-14 | 2020-02-14 | 西安瑞联新材料股份有限公司 | Synthesis method of trans-4 '- (4-alkyl phenyl) (1, 1' -dicyclohexyl) -4-ketone |
| CN111234843A (en) * | 2020-03-02 | 2020-06-05 | 中节能万润股份有限公司 | Preparation method of alkoxy difluoro (trans-4-alkylcyclohexyl) phenylethynyl benzene liquid crystal monomer |
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Cited By (3)
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| CN110790650A (en) * | 2019-11-14 | 2020-02-14 | 西安瑞联新材料股份有限公司 | Synthesis method of trans-4 '- (4-alkyl phenyl) (1, 1' -dicyclohexyl) -4-ketone |
| CN110790650B (en) * | 2019-11-14 | 2023-09-29 | 西安瑞联新材料股份有限公司 | Synthesis method of trans-4 '- (4-alkylphenyl) (1, 1' -dicyclohexyl) -4-ketone |
| CN111234843A (en) * | 2020-03-02 | 2020-06-05 | 中节能万润股份有限公司 | Preparation method of alkoxy difluoro (trans-4-alkylcyclohexyl) phenylethynyl benzene liquid crystal monomer |
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