CN106244169B - The application of the super fluorine liquid-crystal compounds of three rings - Google Patents
The application of the super fluorine liquid-crystal compounds of three rings Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 31
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 7
- 239000011737 fluorine Substances 0.000 title abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- XTLJKHBPNDOAGE-UHFFFAOYSA-N 3-fluoro-4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C(F)=C1 XTLJKHBPNDOAGE-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QWQBQRYFWNIDOC-UHFFFAOYSA-N (3,5-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC(F)=CC(F)=C1 QWQBQRYFWNIDOC-UHFFFAOYSA-N 0.000 description 3
- JHLKSIOJYMGSMB-UHFFFAOYSA-N 1-bromo-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(Br)=C1 JHLKSIOJYMGSMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 3-fluoro-4-trifluoromethylphenyl group Chemical group 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Composition the present invention relates to a kind of super fluorine liquid-crystal compounds of three ring is used for the purposes of TFT type liquid crystal displays, and the super fluorine liquid-crystal compounds of three ring has following structural formula：Wherein, A is represented：1,4- benzene Brace or 1,1- hexamethylenes Brace；X1,X2,X3,X4Independent H or F atom are represented respectively；Y1Represent F, CF3Or OCF3；P represents 1 or 2；R1Represent CnH2n+1, the integer of n=1~10.
Description
Technical Field
The invention contains difluoromethoxy (CF) in the molecular structure2O) bridge bond, and their combination with other liquid crystal can be used in TFT type liquid crystal display.
Technical Field
The flat panel liquid crystal display is the mainstream of display screens on portable computers, navigation and aviation systems and televisions at present. These applications have to meet high requirements in terms of response time and image contrast. In terms of physical properties of liquid crystal materials, low driving voltage, that is, low threshold voltage, is required in consideration of withstand voltage of IC, and liquid crystal compositions are required. In general, a liquid crystal compound having a large dielectric anisotropy Δ is used, and the threshold voltage Vth can be reduced. For this reason, a polar liquid crystal having a large value of dielectric anisotropy is actively developed.
When fluorine atoms are introduced as substituents into liquid crystal molecules, Δ can be increased, and the number of fluorine atoms is effective. However, the number of fluorine atoms in a molecule is proportional to the viscosity. The number of fluorine atoms in the liquid crystal molecules increases, and the liquid crystal phase temperature range becomes lower. It is very difficult to control the change of Δ by suppressing the increase of viscosity and the decrease of liquid crystal phase temperature.
To achieve this, CF was first reported in 1989 by MERCK in Germany2Synthesis of O-bridges (DE-A4006921,1989), until the 90 s of the 20 th century, these compounds were systematically studied (EP0844229A1)2The O compound has not only low viscosity but also good lipid solubility. MERCK was applied in 1995 (DE19531165A1), and CHISSO in Japan was also applied later (9611995).
Introduction of bridge CF between 2 benzene rings of liquid crystal molecule2The compounds of O have been reported for almost more than ten years. If the bridge bond is CF2The polarization contribution of O is consistent with the polarity of the long axis of the molecule, and a relatively large Δ can be obtained. Even if 2 fluorine atoms remain in the molecule, experiments have found that the viscosity can be greatly reduced.
Disclosure of Invention
The object of the present invention is to provide a compound containing difluoromethoxy (CF)2Compositions of tricyclic superfluoride liquid crystal compounds with a bridge of O), a process for their preparation and their use. Their compositions with other liquid crystal compounds are useful for TFT type liquid crystal displays.
The present invention develops a compound having difluoromethoxy (CF)2O) bridge bond, characterized in that different terminal rings are respectively utilized. In particular, 3-fluoro-4-trifluoromethylphenyl group, 4 ' -n-alkyl-2 ', 3,5,6 ' -tetrafluorobiphenyl group, whose polarity is oriented in accordance with the molecular long axis, contributes to an increase in Δ. And due to CF on the benzene ring3The introduction of (A) not only increases the polarity but also greatly contributes to the improvement of the lipid solubility and avoids the separation of components at low temperatures.
In the synthesis of CF2In the process of the O structure, the method using the difluorodibromomethane as the raw material has simple process. The high-temperature highly polar triphenylcyclic fluorine-containing liquid crystal of the present invention is successfully used in the production of a liquid crystal composition.
The compound of the present invention contains difluoromethoxy (CF)2A tricyclic superfluoride liquid crystal compound having a bridge of O) having the formula:
wherein,
a represents: the 1, 4-benzene breast or 1, 1-cyclohexane;
X1,X2,X3,X4each represents independentlyH or F atom of (1);
Y1represents F, CF3Or OCF3；
P represents 1 or 2;
R1represents CnH2n+1And n is an integer of 1 to 10.
The tricyclic superfluorine liquid crystal compounds containing difluoromethoxy bridge bond of the present invention are preferably n ═ an integer of 2 to 5, especially difluoro- (4 ' -n-propyl-2 ' 3,5,6 ' -tetrafluorobiphenyl) - (3-fluoro-4-trifluoromethylphenoxy) methane.
The compound of the present invention contains difluoromethoxy (CF)2The tricyclic super-fluorine liquid crystal compound of the bridge bond of O) can be prepared by the following method:
a represents: the 1, 4-benzene breast or 1, 1-cyclohexane;
X1,X2,X3,X4each represents independently a H or F atom;
Y1represents F, CF3Or OCF3；
P represents 1 or 2;
n represents an integer of 1 to 10.
The method comprises the following steps of reacting an A6 compound, an A7 compound, namely 3-fluoro-4-trifluoromethylphenol, tetra-n-butylammonium bromide, and a monovalent metal carbonate or monovalent metal bicarbonate in a polar organic solvent at a reflux temperature of 80 ℃ for 1-4 hours to obtain an A-A compound, wherein the molar ratio of the A6 compound to the A7 compound, namely 3-fluoro-4-trifluoromethylphenol, tetra-n-butylammonium bromide, to the monovalent metal carbonate or monovalent metal bicarbonate is 1: 1-1.2: 0.9-1.0.
with the method of the invention, it is recommended to carry out under nitrogen protection.
The polar organic solvent is N, N-dimethylformamide, methyl tert-butyl ether, dimethyl sulfoxide and the like.
The product of the invention is suggested to be extracted by organic solvent, washed by aqueous solution, dried and purified by column chromatography.
The process of the present invention can be further described as an example of the synthesis of difluoro- (4 ' -n-alkyl-3, 5,2 ', 6 ' -tetrafluorobiphenyl) - (3-fluoro-4-trifluoromethylphenoxy) methane as follows:
firstly, 3, 5-difluorobromobenzene and n-alkyl bromide are used for generating 3, 5-difluoro n-alkylbenzene, then iodine is added for generating 3, 5-difluoro-4-iodo n-alkylbenzene, the product is reacted with 3, 5-difluorophenylboronic acid to obtain A6, after n-butyl lithium is removed from the product, difluorodibromomethane is reacted to obtain A7, and the product is reacted with 3-fluoro-4-trifluoromethylphenol to obtain the target compound difluoro- (4 ' -n-alkyl-2 ', 3,5,6 ' -tetrafluorobiphenyl) - (3-fluoro-4-trifluoromethylphenoxy) ] methane, wherein the alkyl refers to ethyl, propyl, butyl, pentyl or hexyl, preferably the alkyl refers to ethyl, propyl, butyl or pentyl. The specific synthetic route is as follows:
wherein, a is magnesium and tetrahydrofuran, 50 ℃; b, 3, 5-difluorobromobenzene and tetrahydrofuran, 50 ℃; iodine, tetrahydrofuran, n-butyllithium, -70 ℃; d 3, 5-difluorophenylboronic acid, Pd (PPh)3)4Heating and refluxing potassium carbonate and absolute ethyl alcohol; e, difluorodibromomethane, tetrahydrofuran, n-butyllithium, and the temperature of-70 ℃; f, 3-fluoro-4-trifluoromethylphenol, tetrabutylammonium bromide, potassium carbonate and N, N-dimethylformamide at 80 ℃.
The invention not only has simple process by using the difluorodibromomethane as the raw material, but also has good fat solubility and can avoid the separation of components at low temperature.
Detailed Description
The present invention will be further understood from the following examples, which are not intended to limit the scope of the present invention. Any simple replacement or improvement made by the invention by the person skilled in the art is within the technical scheme protected by the invention.
An experimental instrument: bruker 400(400MHz) model NMR spectrometer, G2577A model mass spectrometer, NicoletMagna-I550 model infrared spectrometer. XPV-203E type polarizing microscope, Dimand DSC type differential scanning calorimeter.
Example 1 Synthesis of the compound difluoro- (4 '-n-alkyl-2' 3,5,6 '-tetrafluorobiphenyl) - (3-fluoro-4-trifluoromethylphenoxy) methane (A-A' n ═ 3)
1) Synthesis of compound (a 3', n ═ 3):
adding Mg (24.2 g; 1.02mol) into a dry 500ml four-neck flask under the protection of nitrogen, then adding 80ml dry tetrahydrofuran THF, adding 1-3 drops of 1, 2-dibromoethane for activation, dissolving bromo-n-propane (104g,0.84mol) into 300ml dry THF after activation, slowly dropping into the system, reacting at 50-60 ℃ for 1 hour, then adding (0.8 g; 0.0007mol) tetrakis (triphenylphosphine) palladium and 3, 5-difluorobromobenzene (80g,0.421mol) slowly dropping, reacting the mixture at 50-60 ℃ for 1 hour, TLC tracing reaction till completion, adding water for quenching, extracting the reaction solution with ethyl acetate, drying with anhydrous magnesium sulfate, removing the solvent in vacuum, distilling at normal pressure (140-150 ℃) to obtain 47g colorless transparent liquid with purity of 89.4%, the yield is 71.5 percent
2) Synthesis of compound (a 4', n ═ 3):
in a dry 2L four-necked flaskUnder nitrogen protection, (45g,0.29mol) compound a 3' (n ═ 3)) was dissolved in 500ml of dry THF and cooled to-70 ℃ and slowly added dropwise to the above solution (220 ml; 0.351mol) of n-butyllithium (1.6mol/L), and the mixed solution was stirred at the above temperature for further 2 hours, and iodine (91 g; 0.355mol) in 300ml of dry THF, slowly dropwise added to the system, the reaction mixture was warmed to-60 ℃ and the reaction was continued at this temperature for 1 hour, quenched with sodium thiosulfate solution. The reaction solution was saturated with Na2S2O3Washing the solution twice, extracting with ethyl acetate, drying the organic phase with anhydrous magnesium sulfate, filtering, spin-drying to obtain a crude product, distilling the crude product under reduced pressure, (80-82 ℃/2mmHg), and then performing column chromatography separation with petroleum ether to obtain a colorless transparent liquid 69g, the purity: 97.8%, yield: 85 percent.
3) Synthesis of compound a 5' (n ═ 3):
a dry 500ml four-necked flask was charged with (40 g; 0.142mol) Compound A4' (n-3), (27 g; 0.174mol)3, 5-difluorophenylboronic acid, Pd (PPh) under nitrogen3)4(0.5g,0.00043mol) and potassium carbonate (29.5 g; 0.213mol), then 300ml of absolute ethyl alcohol is added, the reaction mixture is heated and refluxed for 24 hours, TLC tracing reaction is carried out until the reaction is completed, water is added for quenching, the reaction solution is extracted by ethyl acetate, anhydrous magnesium sulfate is used for drying, spinning is carried out, petroleum ether is used for dissolving, insoluble substances are filtered, spinning is carried out again, and after spinning, column chromatography separation is carried out by using petroleum ether, 36g of colorless transparent liquid with the purity: 96.02%, yield: 94.5 percent
MS(m/z,％):268(M+,42.82),239.0(100.00)；219(21.45)
4) Synthesis of Compound A6' (n ═ 3)
In a dry 1L four-necked flask, under nitrogen protection, (36g,0.135mol) of compound a 5' (n ═ 3) was dissolved in 400ml of dry THF and cooled to-70 ℃, n-butyllithium (1.6mol/L) was slowly added dropwise to the above solution (101ml,0.162mol), the mixed solution was stirred at the above temperature for 2 hours, CF2Br2 (42.6g,0.203mol) was slowly added, the temperature was raised to-60 ℃, the reaction mixture was reacted for 1 hour, and then saturated ammonium chloride solution was added and quenched. Extracting the reaction liquid by using a saturated ammonia chloride solution and ethyl acetate, washing an organic phase twice by using a saturated salt water solution, drying the organic phase by using anhydrous magnesium sulfate, filtering and spin-drying to obtain a crude product, and performing column chromatography separation on the crude product by using petroleum ether to obtain 36g of light yellow oily matter with the purity: 47 percent, the yield is 60 percent,
MS(m/z,％):398.0(M+,1.01),317(100.00)；288(41.72)；219(8.33)
5) synthesis of target Compound A-A' (n ═ 3)
A dry 500ml four-neck flask is added with (32g,0.081mol) A6' (n is 3) with 47% purity, (16.28g,0.09mol) 3-fluoro-4-trifluoromethylphenol, (13.83g,0.10mol) K2CO3, (26.61g,0.097mol) tetra-n-butylammonium bromide (C16H36NBr) under the protection of nitrogen, then 360ml DMF is added, the reaction mixture is stirred for 4 hours under the condition of 80 ℃, TLC tracing reaction is carried out until the reaction is completed, saturated ammonia chloride solution is used for quenching, the reaction liquid is extracted by saturated ammonia chloride solution and ethyl acetate, the organic phase is washed by saturated saline solution twice, the organic phase is dried by anhydrous magnesium sulfate, rotary drying is carried out to obtain a yellow crude product, the crude product is subjected to column chromatography by petroleum ether to obtain colorless transparent liquid, colorless oily transparent liquid is washed by anhydrous ethanol to obtain 9g colorless transparent liquid with purity of 99.7%, the yield is as follows: 22.4 percent
MS(m/z,％):496(M+,1.02),317(100.00)；288(26.66)；219(6.73)
1HNMR(400MHz,CDCl3)::0.958‐0.994(t,J＝6.8Hz,3H),1.649‐1.705(m,2H),2.601‐2.639(m,2H),6.838‐6.861(m,2H),7.136‐7.202(m,4H),7.601‐7.643(m,1H),
Example 2 contains difluoromethoxy (CF)2Tricyclic super-fluorine liquid crystal with O) bridge bond and application of composition thereof
The liquid crystal compositions are prepared by mixing 14 compounds according to the set weight percentage by a conventional mixing method, and the physical parameters of the liquid crystal compositions are respectively clearing point and 95 ℃; Δ n, (0.1010,20 ℃); threshold voltage Vth,1.50 v; Δ,8.5(25 ℃). is suitable for use in TFT liquid crystal display devices.
Claims (1)
1. Use of a composition of tricyclic superfluoride liquid crystal compounds containing difluoromethoxy bridges for TFT type liquid crystal displays, characterized in that the composition comprises the following components in percentage by weight:
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