CN104449762B - Fluorinated liquid crystal containing difluoro-methoxy bridged bond and combinations thereof thing - Google Patents

Fluorinated liquid crystal containing difluoro-methoxy bridged bond and combinations thereof thing Download PDF

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CN104449762B
CN104449762B CN201410621417.XA CN201410621417A CN104449762B CN 104449762 B CN104449762 B CN 104449762B CN 201410621417 A CN201410621417 A CN 201410621417A CN 104449762 B CN104449762 B CN 104449762B
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liquid crystal
difluoro
bridged bond
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闻建勋
李继响
王建新
杜宏军
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Fujian Yonghong high tech Material Co., Ltd
Fujian Yongjing Technology Co Ltd
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Shanghai Tianwen Chemical Co Ltd
FUJIAN SHAOWU YONGJING CHEMICAL Co Ltd
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Abstract

The present invention is a kind of containing difluoro-methoxy (CF2O) fluorinated liquid crystal of bridged bond and combinations thereof thing, their preparation method and application.The present invention utilizes the method that difluorodibromomethane makees raw material, not only simple synthetic method, raw material is easy to get, technique is simple, and the fluorinated liquid crystal polarity obtained is greatly, fat-soluble good, when being avoided that low temperature, component separates out, and with the constituent of other liquid-crystal compounds composition, may be used for TFT type liquid crystal display.

Description

Fluorinated liquid crystal containing difluoro-methoxy bridged bond and combinations thereof thing
Technical field
The present invention is that one contains difluoro-methoxy (CF in the molecular structure2O) fluorinated liquid crystal of bridged bond and group thereof Compound, they can be used for TFT type liquid crystal display with the constituent of other Formation of liquid crystals.
Technical background
Flat panel Liquid Crystal shows it is the master of display screen on present portability computer, navigation air line and television set Stream.These are applied and must are fulfilled for high request in terms of response time and image contrast.Physical property at liquid crystal material Energy aspect, it is contemplated that the proof voltage of IC, it is desirable to low driving voltage, i.e. requires the liquid crystal that threshold voltage will be low And liquid-crystal composition.General way is the liquid-crystal compounds using dielectric constant anisotropy Δ ε bigger, can To reduce threshold voltage vt h.For the polarity liquid crystal that this active development dielectric constant anisotropy numerical value is big. Fluorine atom alternatively base being imported liquid crystal molecule, can increase Δ ε, the number of fluorine atom is largely effective.But, Fluorine atom number in molecule is proportional with viscosity.Number of fluorine atoms purpose in liquid crystal molecule increases, and makes liquid Crystalline phase temperature range step-down.While the rising of suppression viscosity, the decline of suppression liquid crystal phase temperature, depend merely on control The change of Δ ε is extremely difficult.
In order to reach this purpose, Germany MERCK company researcher with within 1989, first reported CF2O The synthesis (DE-A4006921,1989) of bridged bond, to the nineties in 20th century, this compounds obtains system and grinds Study carefully (EP0844229A1). research finds some CF2O compound not only low-viscosity, and have good liposoluble Property.Nineteen ninety-five MERCK applies for a patent (DE19531165A1), also applies for after the CHISSO company of Japan Patent (96 11995).
Between 2 phenyl ring of liquid crystal molecule, import bridged bond CF2The compound of O, has been reported that nearly ten years. If bridged bond CF2The contribution of the polarization of O is consistent with the polarity of molecular long axis, it is possible to compared Big Δ ε.Even if 2 fluorine atoms are maintained among molecule, experiment finds that viscosity can be greatly reduced.
Summary of the invention
The object of the invention provides one containing difluoro-methoxy (CF2O) fluorinated liquid crystal of bridged bond and combinations thereof thing, Their preparation method and application.They can be used for TFT type liquid crystal display with the constituent of other Formation of liquid crystals Device.
This work develops containing CF2The fluorochemical of O, feature is to be utilized respectively different end-rings. Especially 3-fluoro-4-trifluoromethylbenzene group, 1,3-dioxa-5-alkyl-2-cyclohexyl-, the side of their polarity To consistent with molecular long axis, contribute to the increase of Δ ε.And due to the CF on phenyl ring3-importing, not only increase Big polarity, and it is remarkably contributing to fat-soluble improvement, it is to avoid during low temperature, component separates out.
At synthesis CF2In the technique of O structure, utilizing the method that difluorodibromomethane makees raw material, technique is simple. When the preparation of liquid-crystal composition, the dicyclo that successfully make use of the high temperature in the patent of the present inventor highly polar is own Base Fourth Ring fluorinated liquid crystal (CN 2012100088035.6).
The present invention containing CF2The fluorinated liquid crystal compound of O bridged bond, its structure is as follows:
Wherein, n=1,2,3,4,5 or 6.
The present invention containing CF2The fluorinated liquid crystal compound of O bridged bond can be prepared by following method respectively:
1, containing CF2The compound two fluoro-[(5-alkyl-1,3-dioxa-cyclohexyl)-2,6-difluorophenyl] of O bridged bond- The synthesis of (3,4,5-trifluoro-benzene epoxide) methane (B-b)
First, diethyl malonate generates the substituted diethyl malonate of alkyl, the most hydrogenated aluminum with nalka bromide Lithium is reduced into substituted propylene glycol, then with 3, the reaction of 5-difluorobenzaldehyde obtains B7 after n-BuLi pulls out hydrogen Difluorodibromomethane reacts to obtain B8 and 3,4,5-trifluoromethyl phenols react target compound two fluoro-[(5-alkyl-1, 3-dioxa-cyclohexyl)-2,6-difluorophenyl]-(3,4,5-trifluoro-benzene epoxide) methane, described alkyl refers to Methyl, ethyl, propyl group, butyl, amyl group or hexyl, preferably alkyl refer to methyl, ethyl, propyl group, fourth Base or amyl group.Concrete synthetic route is as follows:
Wherein, n=1,2,3,4,5 or 6.
The synthesis of compound B-b, in organic polar solvent and under reflux temperature, 2-(4-difluorobromomethyl-3,5- Difluorophenyl) alkyl-1 of-5-(C1-C6), 3-dioxanes, 3,4,5 trifluoromethyl phenols, tetrabutyl ammonium bromide and carbon Acid nak response 1-3 hour；Alkyl-the 1,3-of described 2-(4-difluorobromomethyl-3,5-difluorophenyl)-5-(C1-C6) Dioxanes, 3,4,5 trifluoromethyl phenols, the mol ratio of tetrabutyl ammonium bromide and potassium carbonate is 1:1-3:0.05-1:0.5-3； Described polar organic is DMF DMF, methyl tertiary butyl ether(MTBE) etc..
2, containing CF2The compound two fluoro-[4-n-pro-pyl-2,6-difluorophenyl] of O bridged bond-(3,5,3', 4', 5'-five fluorine connection Phenoxy group) synthesis of methane
First 3,5-difluoro bromobenzene is made grignard reagent and is reacted generation C3 with positive propionic aldehyde, and C3 is after dehydration hydrogenation Obtaining 3,5-difluoro n-proplbenzene C5, C5 react with difluorodibromomethane after n-BuLi pulls out hydrogen and obtain compound C6, C6 and 3, the reaction of 5-difluorophenol pulled out on hydrogen after iodine with 3 by n-BuLi again, and 4,5-trifluoro-benzene boric acid pass through Suzuki coupling reaction: under dehydrated alcohol and reflux temperature, compound C8 bis-fluoro-[4-n-pro-pyl-2,6-difluoro Phenyl]-(3,5-bis-fluoro-4-iodobenzene epoxide) methane, compound C93,4,5-trifluoro-benzene boric acid, catalytic amount Pd(PPh3)4React 1-5 hour with potassium carbonate；Described compound C8,3,4,5-trifluoro-benzene boric acid, Pd (PPh3)4 It is 1:1-3:0.05-0.5:0.5-2 with the mol ratio of potassium carbonate；
3, containing CF2Compound two fluoro-[4-n-pro-pyl-1,3-difluorophenyl]-[(the 2,3,4,5,6-phenyl-pentafluoride of O bridged bond Base) acetenyl]-3,5-difluorobenzene epoxide] synthesis of methane
Fluoro-[4-n-pro-pyl-1,3-difluorophenyl]-[(2,3,4,5,6-pentafluorophenyl group) acetylene of compound two Base]-3,5-difluorobenzene epoxide] synthetic route and the fluoro-[4-n-pro-pyl-2,6-difluorobenzene of target compound two of methane Base]-(3,5,3', 4', 5'-five fluorine biphenylyloxy) methane is similar to.Its final step compound C8 Yu C10 leads to Cross Sonogashira reaction and generate the fluoro-[4-n-pro-pyl-1,3-difluorobenzene of target product two Base]-[(2,3,4,5,6-pentafluorophenyl group) acetenyl]-3,5-difluorobenzene epoxide] methane: deposit at solvent triethylamine Under lower and reflux temperature, compound C8 bis-fluoro-[4-n-pro-pyl-2,6-difluorophenyl]-(3,5-bis-fluoro-4-iodobenzenes Epoxide) methane, compound C10 phenyl-pentafluoride acetylene, the Pd (PPh of catalytic amount3)2Cl2With CuI, 1-5 is little in reaction Time；Described compound C8 bis-fluoro-[4-n-pro-pyl-2,6-difluorophenyl]-(3,5-bis-fluoro-4-iodobenzene epoxide) first Alkane, phenyl-pentafluoride acetylene, Pd (PPh3)2Cl2It is 1:1-3:0.05-0.5:0.05-0.5 with CuI mol ratio.
Concrete synthetic route is as follows:
4, containing CF2New compound two fluoro-[4-n-alkyl-phenyl-2,6-difluorophenyl]-(the fluoro-4-of 3-tri-of O bridged bond Toluene fluoride epoxide) synthesis (D-d) of methane
Concrete synthetic route is as follows:
Wherein, n=1,2,3,4,5 or 6.
Suzuki coupling reaction obtains compound D3, and D3 reacts with difluorodibromomethane after pulling out hydrogen by n-BuLi Compound D4 difluoro one bromo-(4-alkyl phenyl-2,6-difluorophenyl)-methane.Bromo-(the 4-of D4 difluoro one Alkyl phenyl-2,6-difluorophenyl)-methane with D83-fluoro-4-trifloro methyl phenol at potassium carbonate, DMF bar Fluoro-[4-n-alkyl-phenyl-2,6-difluorophenyl]-(the 3-fluoro-4-benzotrifluoride of target compound two is generated under part Epoxide) methane: time in organic polar solvent with 90-100 DEG C, bromo-(the 4-alkyl of compound D4 difluoro one Phenyl-2,6-difluorophenyl)-methane and compound D83-fluoro-4-trifloro methyl phenol, Anhydrous potassium carbonate and four Butylammonium bromide is reacted 1-4 hour；Described compound D4 and compound D8, tetrabutyl ammonium bromide and nothing Aqueous carbonate potassium mol ratio is 1:1-3:0.05-1:0.5-3；Described alkyl refers to methyl, ethyl, propyl group, fourth Base, amyl group or hexyl, preferably alkyl refer to methyl, ethyl, propyl group, butyl or amyl group；Described has Machine polarity is DMF DMF, methyl tertiary butyl ether(MTBE) etc..
The liquid-crystal compounds of the present invention not only simple synthetic method, raw material is easy to get, and technique is simple, and increases pole Property, fat-soluble good, it is to avoid during low temperature, component separates out, and compound can be grouped with other liquid-crystal compounds, May be used for TFT type liquid crystal display.
Detailed description of the invention
By following embodiment it will be further appreciated that the present invention, but present disclosure can not be limited.Any Simply replacement or improvement etc. that invention is done by those skilled in that art belong to the technology that the present invention is protected Within scheme.
Experimental apparatus: Bruker 400 (400MHz) type nuclear magnetic resonance analyser is surveyed, G2577A type mass spectrograph, Nicolet Magna-I 550 type infrared spectrometer.XPV-203E type polarizing microscope, Dimand DSC type differential scanning amount Hot instrument.
Embodiment 1 two fluoro-[(5-alkyl-1,3-dioxanes base)-2,6-difluorophenyl]-(3,4,5-trifluoros Phenoxy group) synthesis (B-b n=5) of methane
1) synthesis of 2-amyl malonic acid diethylester
In a 500mL there-necked flask being dried, add sodium sheet 11.5g, dehydrated alcohol 250mL, load onto back Stream condensing tube and Dropping funnel, after waiting sodium reaction completely, drip diethyl malonate 80.0g, drip After n-amyl bromide 83.0g adds, reflux half an hour, add acetic acid and neutralize, be filtered to remove sodium bromide solid, filtrate Removing solvent, add dilute hydrochloric acid, extract with methyl tertiary butyl ether(MTBE), anhydrous magnesium sulfate is dried, removal of solvent under reduced pressure, Gains decompression distillation (82-84 DEG C/1mmHg) obtain colourless liquid 70.0g.Productivity: 61%.
2) 2-amyl group-propyl-1,3-glycol C5H11CH(CH2OH)2Synthesis
In a 500mL there-necked flask being dried, load onto reflux condensing tube and Dropping funnel, add under nitrogen protection Enter LiAlH415.0g, THF 250mL, the most slowly dropping 2-amyl malonic acid diethylester 40.0g, drips Finish, reflux one hour, cooling, slowly dropping 15mL water, more slowly dropping 10%NaOH aqueous solution, directly All becoming white to solid, filter, filtrate is dried with anhydrous magnesium sulfate, removal of solvent under reduced pressure, and gains subtract Pressure distills to obtain colourless liquid 15.0g, productivity: 59%.
3) synthesis of 3,5-difluorobenzaldehyde
In a 500mL there-necked flask being dried, add magnesium chips 10.0g, THF 300mL, the most slowly drip 3,5-difluoro bromobenzene 77.2g, make grignard reagent, are cooled to less than 0 DEG C, slowly dropping DMF 32mL, so Relief its be naturally warmed to room temperature, react 4 hours, add water, methyl tertiary butyl ether(MTBE) extract, anhydrous magnesium sulfate is dried, Removal of solvent under reduced pressure, white liquid 41.0g, productivity: 72% are distilled to obtain in gains decompression.
4) synthesis of 2-(3,5-difluorophenyl)-5-amyl group-1,3-dioxanes
Addition 3,5-difluorobenzaldehyde 4.0g, p-methyl benzenesulfonic acid 0.5g, toluene 150 in a 500mL single port bottle ML, 2-amyl group-propyl-1,3-glycol 4.6g, it is then refluxed for a point water, when no longer there being water out (about 3 hours), Stop heating, cooling, add K2CO32.5g, stirs 10 minutes, and washing, anhydrous magnesium sulfate is dried, and subtracts Pressure removes solvent, and column chromatography for separation (petroleum ether: dichloromethane=9:1), obtaining petroleum coal ether recrystallization must produce Thing 4.6g, productivity: 61%.
MS (m/z, %): 270.1 (M+,100.00),141.0(61.29)；
1H NMR(400MHz,CDCl3):δ0.81-1.54(m,11H),2.25(m,1H),4.02(m,2H),4.04-4.30 (m,2H),5.34(s,1H),6.97-7.04(m,3H)。
The synthetic method of homologue is the same, changes raw material,
2-(3,5-difluorobenzene) base-5-propyl group-1,3-dioxanes
MS (m/z, %): 242.1 (M+,100.00),141.0(61.29)。
5) synthesis of 2-(4-difluorobromomethyl-3,5-difluorophenyl)-5-amyl group-1,3-dioxanes
In 100mL there-necked flask, load onto Dropping funnel and cryogenic thermometer, under nitrogen protection, add 2-(3,5- Difluorophenyl)-5-amyl group-1,3-dioxanes 2.2g, dry tetrahydrofuran 40mL, acetone-liquid nitrogen is cooled to-70 DEG C, After dropping n-BuLi 4mL, control temperature about-70 DEG C and react 2 hours, then drip CF2Br22.0g, drips Complete control temperature about-70 DEG C 2 hours stopped reaction of reaction, are naturally warmed to room temperature, add 20mL water, methyl Tertbutyl ether extracts, and anhydrous magnesium sulfate is dried, and removal of solvent under reduced pressure petroleum ether crosses post, and petroleum ether recrystallization must produce Thing 2.0g, productivity: 65%.
MS (m/z, %): 397.0 (M+,5.54),319.1(100.00)；
1H NMR(400MHz,CDCl3):δ0.83-1.55(m,11H),2.35(m,1H),4.12(m,2H),4.14-4.40 (m,2H),5.14(s,1H),6.97-7.05(m,2H).
Change raw material 2-(3,5-difluorobenzene) base-5-propyl group-1,3-dioxanes, use identical synthetic method to obtain same It is thing,
2-(4-difluorobromomethyl-3,5-difluorophenyl)-5-propyl group-1,3-dioxanes
MS (m/z, %): 369.0 (M+,5.67),291.1(100.00)；
1H NMR(400MHz,CDCl3):δ0.83-1.55(m,7H),2.35(m,1H),4.12(m,2H),4.14-4.40 (m,2H),5.14(s,1H),6.97-7.05(m,2H).
6) target compound two fluoro-[(5-alkyl-1,3-dioxanes base)-2,6-difluorophenyl]-(3,4,5-trifluoro-benzenes Epoxide) synthesis of methane (n=5)
100mL there-necked flask adds 2-(4-difluorobromomethyl-3,5-difluorophenyl)-5-amyl group-1,3-dioxanes 2.0g, 3,4,5 trifluoromethyl phenol 0.8g, tetrabutyl ammonium bromide 1.0g, potassium carbonate 2.5g, DMF 50mL, add Upper reflux condensing tube, reacts 3 hours between 90-100 DEG C, cooling, adds 40mL water stirring solid and dissolves, Methyl tertiary butyl ether(MTBE) extracts, and organic facies is washed, and anhydrous magnesium sulfate is dried, removal of solvent under reduced pressure, and petroleum ether crosses post, Recrystallizing methanol 2 times, obtains white crystal 0.5g, productivity 29%.
Phase transition temperature (DEG C) Cr 41.67 I 10.32 Recr.Recr becomes crystal when representing cooling procedure.
MS (m/z, %): 466.1 (M+,4.39),319.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.89 (t, J=6.4Hz 3H), 1.29-1.31 (m, 6H), 1.55 (s, 2H), 2.08-2.11(m,1H)4.12(m,2H),3.49-4.25(m,4H),5.36(m,1H),6.93-6.96(m,2H), 7.12-7.15(m,2H).
Target compound two fluoro-[(5-alkyl-1,3-dioxanes base)-2,6-difluorophenyl]-(3,4,5-trifluoro-benzenes Epoxide) methane (n=3), same procedure,
MS (m/z, %): 438.1 (M+,0.98),291.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.88 (t, J=6.4Hz 3H), 1.29-1.33 (m, 2H), 1.54 (s, 2H), 2.09-2.12(m,1H),4.13(m,2H),3.48-4.24(m,4H),5.37(m,1H),6.92-6.967(m,2H), 7.11-7.16(m,2H)。
Phase transition temperature (DEG C) Cr 40.21 I 17.39 Recr.
Embodiment 2 two fluoro-[4-n-pro-pyl-2,6-difluorophenyl]-(3,5,3', 4', 5'-five fluorine biphenylyloxy) first The synthesis (C-c) of methane series row
1) synthesis of C3
Oxolane 2.5g magnesium and 20mL being dried adds in the there-necked flask of 250mL under nitrogen protection, Magnetic agitation, then 19.3g3,5-difluoro bromobenzene is dissolved in the oxolane that 70mL is dried and adds 100mL Constant pressure addition funnel in, instill a small amount of (10mL) and make magnesium chips activate, heat up after 5 minutes and reflux, continue droplet Add remaining mixed liquor, within 40 minutes, drip off, continue normal-temperature reaction 1.5 hours, drip propionic aldehyde 5.8g and 60mL The mixed liquor of ether, drips off for 10 minutes, is heated to reflux 2 hours, cooling, is slowly added into 250mL saturated Ammonium chloride solution (too fast meeting bumping), first has precipitation and generates, continue dropping resolution of precipitate.Use methyl-tert fourth Base ether extracts mixed liquor twice, obtains organic facies and is washed with water twice, is dried, is spin-dried for, and crosses post (stone: second=20:1), Obtain weak yellow liquid 13.4g.Productivity: 78%.
MS (m/z, %): 172.1 (M+,12.41),143.0(100.00)；
1H NMR(400MHz,CDCl3): δ 0.82 (t, J=7.2Hz 3H), 1.60-1.68 (m, 2H), 2.23 (s, 1H), 4.48 (t, J=6.4Hz 1H), 6.58-6.79 (m, 3H).
2) synthesis of C5
By in the normal hexane of 130mL and the there-necked flask of 28.4g phosphorus pentoxide addition 250mL, machinery stirs Mix, be slowly added into 13.4g 1-(3,5-difluorophenyl)-propyl group-1-alcohol, be heated between 50 DEG C-60 DEG C reacting, 2.5 After hour, some plate reaction is complete, and sucking filtration obtains mother solution.Mother solution is added in reactor, adds the Pd/C of catalytic amount, Under the Hydrogen Vapor Pressure of 3MPa, stirring at normal temperature is overnight.Gas phase is followed the tracks of, and reaction is complete, and sucking filtration obtains mother solution and is spin-dried for, The fraction 6.0g of 20mmHg/58 DEG C-60 DEG C, productivity 50% are collected in decompression distillation.
3) synthesis of C6
The oxolane that 4.0g 3,5-difluoro propyl benzene and 70mL are dried is added 100mL's under nitrogen protection In there-necked flask, be cooled to less than-78 DEG C dropping 12mL n-BuLis, control temperature below-70 DEG C, Within 20 minutes, drip off, continue low-temp reaction 2 hours, drip CF2Br28mL, dropping control temperature-70 DEG C with Under, within 5 minutes, dripping off, continue reaction 2 hours, gas phase is followed the tracks of, and reaction completely, stops, automatically ramping up to room temperature, Add water 30mL, by methyl tert-butyl ether extraction organic facies twice, be dried, be spin-dried for, cross post with petroleum ether, Obtain product 6.3g, productivity: 86%.
4) synthesis of C7
By 4.5g 2-(bromo-difluoromethyl)-1,3-two fluoro-5-propylbenzene, 2.3g 3,5-difluorophenol, four fourths of 1.1g The DMF of base ammonium bromide, the potassium carbonate of 4.5g and 80mL adds in the there-necked flask of 100mL, magnetic agitation, Being heated to about 100 DEG C to react 3 hours, put plate, reaction completely, cools down, and adds the stirring of 60mL water and makes solid Body dissolves, and by methyl tert-butyl ether extraction organic facies three times, merges organic facies, is washed with water once, obtains organic It is dried mutually, is spin-dried for, cross post with petroleum ether, obtain colourless liquid 3.0g, productivity: 57%.
MS (m/z, %): 334.1 (M+,2.42),205.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.95 (t, J=7.2Hz 3H), 1.62-1.68 (m, 2H), 2.59 (t, J=7.6Hz 2H),6.68-6.85(m,5H).
5) synthesis of C8
Under nitrogen protection by diisopropylamine and the there-necked flask of 30mL oxolane addition 100mL of 0.4g In, it is cooled to less than-5 DEG C, drips n-BuLi, drip off continuation low-temp reaction 1 hour, stop, stand-by. The tetrahydrochysene that 2-[(3,5-difluorobenzene hydroxyl)-difluoromethyl]-1,3-two fluoro-5-propylbenzene and the 30mL of 1.0g are dried Furan adds in 100mL there-necked flask, and nitrogen is protected, and is cooled to less than-78 DEG C, dropping LDA, 10 minutes Dripping off, continue low-temp reaction 2 hours, automatic heating, to-60 DEG C, drips iodine, drips off continuation-60 DEG C anti- Answer 1.5 hours.Stop, automatic heating to room temperature, add the saturated ammonium chloride solution of 50mL, layering, nothing Which floor is washed three times by ethyl acetate, merges organic facies, then washes three times with sodium thiosulfate solution, obtains organic facies It is dried.It is spin-dried for, crosses post with petroleum ether, obtain product 0.98g, productivity 70%.
MS (m/z, %): 460.0 (M+,12.98),205.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.95 (t, J=7.2Hz 3H), 1.62-1.68 (m, 2H), 2.59 (t, J=7.6Hz 2H),6.79-6.90(m,4H).
6) target compound two fluoro-[4-n-pro-pyl-2,6-difluorophenyl]-(3,5,3', 4', 5'-five fluorine biphenylyloxy) first The synthesis of alkane
In the there-necked flask that 100mL is dried, add compound C80.8g, add solvent dehydrated alcohol 60mL, Stirring makes material dissolution, adds compound C9 0.34g, the Pd (PPh of catalytic amount3)4With potassium carbonate.Heat back React 5 hours under the conditions of stream, stopped reaction.Reactant liquor is cooled to room temperature, sucking filtration, obtains mother solution methyl-tert fourth Base ether and water hybrid extraction, obtain organic facies and wash once, be dried, concentrate, and petroleum ether is crossed post and obtained target chemical combination Thing 0.57g, productivity: 71%.
Phase transition temperature (DEG C) Cr 44.0 I-10 Recr；
MS (m/z, %): 464.1 (M+,11.03),205.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.96 (t, J=7.2Hz 3H), 1.64-1.69 (m, 2H), 2.61 (t, J=7.2Hz 2H),6.81-6.84(m,2H),6.97-6.99(m,2H),7.08-7.12(m,2H).
Fluoro-[4-n-pro-pyl-1,3-difluorophenyl]-[(the 2,3,4,5,6-pentafluorophenyl group) of embodiment 3 compound two Acetenyl]-3,5-difluorobenzene epoxide] methane series synthesis
In the there-necked flask that 100mL is dried, add compound C8 0.8g, add solvent triethylamine 60mL, Stirring makes material dissolution, adds compound C10 0.37g, the Pd (PPh of catalytic amount3)2Cl2With CuI.Heat back React 5 hours under the conditions of stream, stopped reaction.Reactant liquor is cooled to room temperature, sucking filtration, obtains mother solution methyl-tert fourth Base ether and water hybrid extraction, obtain organic facies and wash once, be dried, concentrate, and petroleum ether is crossed post and obtained target chemical combination Thing 0.55g, productivity: 60%.
Phase transition temperature (DEG C) Cr 46.4 I 15.5 Recr；
MS (m/z, %): 524.1 (M+,12.58),205.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.95 (t, J=7.2Hz, 3H), 1.61-1.68 (m, 2H), 2.61 (t, J=8.0Hz, 2H),6.80-6.83(m,2H),6.93-6.96(m,2H)。
Fluoro-[4-n-alkyl-phenyl-2,6-difluorophenyl]-(the 3-fluoro-4-benzotrifluoride oxygen of embodiment 4 compound two Base) methane series synthesis (D-d)
1) synthesis of D3 (n=5)
Compound D1 (n=5) 10.0g and chemical combination is added under nitrogen protection in dry 250mL there-necked flask Thing D27.7g, adds dry dehydrated alcohol 150mL and is stirred to dissolve.Add potassium carbonate 5.0g, catalyst Pd(PPh3)41.0g, reacts 5 hours under counterflow condition, stopped reaction.Reactant liquor sucking filtration, filter cake methyl-tert fourth Base ether washs 2 times, adds a small amount of water, and methyl tertiary butyl ether(MTBE) extracts, and merges organic facies, is dried with anhydrous magnesium sulfate. Sucking filtration, Rotary Evaporators removes solvent, and petroleum ether is crossed post and obtained white solid 8.0g, productivity: 70%.
MS (m/z, %): 260.1 (M+,31.54),203.1(100.00)；
Homologue synthetic method is identical,
D3 (n=3)
MS (m/z, %): 232.1 (M+,31.54),203.1(100.00)。
2) synthesis of D4 (n=5)
Add in dry 100mL there-necked flask under nitrogen protection compound D3 (n=5) 5.0g and be dried Tetrahydrofuran THF 40mL, makes solution temperature be reduced to-70 DEG C with liquid nitrogen-acetone, and dropping is containing n-BuLi 7.7 The 30mL THF mixed liquor of mL (2.5mol/L), control reacting liquid temperature is at about 70 DEG C, after dropping React 2.5 hours under the conditions of 70 DEG C.Dropping difluorodibromomethane 4.4g, control temperature in about 70 DEG C, Drip complete reaction 2 hours.Add a small amount of ammonium chloride saturated solution to stir 5 minutes, be naturally warmed to room temperature, to A small amount of water in reactant liquor, methyl tertiary butyl ether(MTBE) extracts 3 times, merges organic facies, and anhydrous sodium sulfate is dried, and filters, Removal of solvent under reduced pressure, petroleum ether is crossed post and is obtained white solid D4 (n=5) 4.5g, productivity: 61%.
1H NMR(400MHz,CDCl3): δ 0.88 (t, J=7.2Hz, 3H), 1.45-1.64 (m, 6H), 2.55 (t, J=7.6Hz, 2H),6.98-7.03(m,2H),7.15-7.18(m,2H),7.36-7.38(m,2H).
Homologue synthetic method is identical,
D4 (n=3)
1H NMR(400MHz,CDCl3): δ 0.88 (t, J=7.2Hz, 3H), 1.45-1.64 (m, 2H), 2.55 (t, J=7.6Hz, 2H),6.98-7.03(m,2H),7.15-7.18(m,2H),7.36-7.38(m,2H).
3) synthesis of D6
Weigh 75.0gD5 and add in the there-necked flask that 1000mL is dried, by dense for 278mL HCl and 278mL The solution that water is made into instills with stirring, within 15 minutes, drips off, heating in water bath, controls reaction temperature at 60 DEG C of bars React 4 hours under part.Stop heating, make reacting liquid temperature be down to about 0 DEG C with mixture of ice and water, drip 21.0 g NaNO2The solution being made into the water of 50mL, drips off for 25 minutes, and reactant liquor is changed into faint yellow by white, Continue low-temp reaction 1 hour.Claim 92.4gH3PO2It is added dropwise in reactant liquor in 100mL constant pressure addition funnel, Within 25 minutes, dripping, now reacting liquid temperature is 15 DEG C, is further continued for reacting 4 hours, stopped reaction, water pump Sucking filtration, mother solution saline is extracted twice, and obtains organic facies anhydrous magnesium sulfate and is dried, and decompression distillation obtains 50.0g Colourless liquid (66 DEG C-68 DEG C/28mmHg).Petroleum ether is crossed post and is obtained colourless liquid 45.3g, productivity: 64%.
MS (m/z, %): 243.9 (M+, 99.67), 241.9 (100.00)；
1H NMR(400MHz,CDCl3): δ 7.41 (d, J=9.2Hz, 2H), 7.48 (t, J=8.0Hz, 1H).
4) synthesis of 3-fluoro-4-trifluoromethylbenzene boronic acid
At N2The THF being dried by 6.0g compound D6 and 10mL under protection adds three mouthfuls that 100mL is dried In flask, cool to-20 DEG C, drip 35mL i-PrMgCl/THF, within 10 minutes, drip off, insulation reaction 2 hours, Dropping 5.3g triisopropyl borate ester, drips off for 5 minutes, continues low-temp reaction 2 hours, drips 3.6g30% hydrochloric acid, React 1 hour at-10 DEG C, be naturally warmed to room temperature, remove THF under reduced pressure, with ethyl acetate and water mixed dissolution Crude product, layering, aqueous phase is extracted with ethyl acetate three times, merges organic facies, is dried with anhydrous sodium sulfate, subtracts Pressure is evaporated off solvent, obtains the making beating of solid normal hexane, after cooling, stands, sucking filtration, obtains white solid product 3.1g, Productivity: 60%.
MS (m/z, %): 208.0 (M+, 94.32), 144.0 (100.00)；
1H NMR (400MHz, deuterated DMSO): δ 7.74-7.78 (m, 3H), 8.56 (s, 2H),
IR(KBr,νmax,cm-1):3390,3316,1630,1574,1515,1415,1319,1138,1043,904,841,812,684, 608.
5) synthesis of D8
By in fluoro-for 2.1g3-4-fluoroform mL there-necked flask, add glacial acetic acid 3.0g and 80mL THF and be allowed to Dissolve, under magnetic agitation, 24.1g (30%) hydrogen peroxide is slowly instilled from Dropping funnel, temperature controlled water baths Less than 40 DEG C, normal-temperature reaction 24h after temperature stabilization, stopped reaction.The metabisulfite solution adding 15% and methyl Tertbutyl ether hybrid extraction 3 times, merge organic facies, be dried, after concentration cross post (petroleum ether: dichloromethane=1: 1), weak yellow liquid 1.3g is obtained, productivity: 71%.
MS (m/z, %): 180.0 (M+,100.00),161.0(78.33),130.0(33.37)
1H NMR(400MHz,CDCl3):δ3.74-3.77(m,1H),6.53-6.57(m,3H).
6) target compound two fluoro-[4-n-alkyl-phenyl-2,6-difluorophenyl]-(3-fluoro-4-benzotrifluoride epoxide) first The synthesis of alkane (n=5)
Compound D4 (n=5) 2.0g and compound D81.0g is added in a 100mL there-necked flask being dried, Adding 70mL DMF stirring makes it dissolve, and adds Anhydrous potassium carbonate 1.0g and tetrabutyl ammonium bromide 1.0g.Stirring is also Computer heating control temperature is reacted 4 hours between 90-100 DEG C, and stopped reaction adds water after cooling and makes solid dissolve. Methyl tertiary butyl ether(MTBE) extracts 3 times, merges organic facies, and anhydrous sodium sulfate is dried.Sucking filtration, removal of solvent under reduced pressure, Petroleum ether crosses post, and recrystallizing methanol obtains final white crystal 1.6g, productivity: 64%.
Phase transition temperature (DEG C) Cr 46.2 I 10.4 Recr.
MS (m/z, %): 460.1 (M+,1.98),281.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.97 (t, J=6.8Hz, 3H), 1.66-1.71 (m, 6H), 2.65 (m, 2H), 7.18-7.64(m,9H).
Target compound two fluoro-[4-n-alkyl-phenyl-2,6-difluorophenyl]-(3-fluoro-4-benzotrifluoride epoxide) methane (n=3) phase transition temperature (DEG C) Cr 48.5 I 7.0 Recr.
MS (m/z, %): 488.1 (M+,1.83),309.1(100.00)；
1H NMR(400MHz,CDCl3): δ 0.98 (t, J=6.8Hz, 3H), 1.67-1.73 (m, 2H), 2.66 (m, 2H), 7.19-7.66(m,9H).
The positive polarity liquid-crystal composition of embodiment 5 dielectric constant anisotropy
Use the compositions of 12 effective active liquid-crystal compounds compositions in following table, may be used for TFT type Liquid crystal display.
Result: utilize above 12 compounds, by the part by weight set in literary composition, by conventional mixed method mixing, system Standby liquid-crystal composition. the physical parameter of constituent is respectively as follows: clearing point, 92 DEG C；Δn,(0.1053,20℃)；Threshold value electricity Pressure Vth, 1.48v；Δ ε, 8.13 (25 DEG C). use be applicable to IPS liquid crystal display device.

Claims (4)

1. a preparation method for the fluorinated liquid crystal compound containing difluoro-methoxy bridged bond, is characterized in that by following Method obtains:
Time in organic polar solvent with 90-100 DEG C, difluoro one bromo-(4-alkyl phenyl-2,6-difluorophenyl) -methane, 3-fluoro-4-trifloro methyl phenol, Anhydrous potassium carbonate and tetrabutyl ammonium bromide are reacted 1-4 hour；Described Difluoro one bromo-(4-alkyl phenyl-2,6-difluorophenyl)-methane, 3-fluoro-4-trifloro methyl phenol, anhydrous carbon The mol ratio of acid potassium and tetrabutyl ammonium bromide is 1:1-3:0.05-1:0.5-3；
Described alkyl refers to methyl, ethyl, propyl group, butyl, amyl group or hexyl；Described organic solvent It is DMF, methyl tertiary butyl ether(MTBE)；
The described fluorinated liquid crystal compound containing difluoro-methoxy bridged bond has following structural formula:
Wherein, n=1,2,3,4,5 or 6.
2. the preparation method of the fluorinated liquid crystal compound containing difluoro-methoxy bridged bond as claimed in claim 1, its Feature is that product is washed once through filtration, mother solution methyl tertiary butyl ether(MTBE) and water hybrid extraction, organic facies, Being dried, concentrate, petroleum ether crosses the purification process of post.
3. the preparation method of the fluorinated liquid crystal compound containing difluoro-methoxy bridged bond as claimed in claim 1, its Feature is that product makes solid dissolve through adding water, and extracts 3 times with methyl tertiary butyl ether(MTBE), merges organic facies, Being dried, filter, remove solvent, petroleum ether crosses post or recrystallizing methanol purification process.
4. one kind containing difluoro-methoxy bridged bond fluorinated liquid crystal compound be used for prepare TFT type liquid crystal display In liquid-crystal composition:
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