CN103333697B - Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application - Google Patents
Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application Download PDFInfo
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- CN103333697B CN103333697B CN201310298390.0A CN201310298390A CN103333697B CN 103333697 B CN103333697 B CN 103333697B CN 201310298390 A CN201310298390 A CN 201310298390A CN 103333697 B CN103333697 B CN 103333697B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- UQHXWNURZZHGAA-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3-(2-phenylethynyl)benzene Chemical compound FC1=CC(F)=C(F)C(C#CC=2C=CC=CC=2)=C1F UQHXWNURZZHGAA-UHFFFAOYSA-N 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- -1 2,3,5,6-tetrachlorofluorophenylene group Chemical group 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 25
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- GHICCUXQJBDNRN-UHFFFAOYSA-N 4-iodobenzoic acid Chemical compound OC(=O)C1=CC=C(I)C=C1 GHICCUXQJBDNRN-UHFFFAOYSA-N 0.000 claims description 13
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- BEIGGOLWLJIYBF-UHFFFAOYSA-N 1-ethyl-2-fluoro-4-(2-fluoroethoxy)benzene Chemical compound C(C)C1=C(C=C(C=C1)OCCF)F BEIGGOLWLJIYBF-UHFFFAOYSA-N 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Substances Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920001774 Perfluoroether Polymers 0.000 claims description 8
- GFSFKWHVGTYIOS-UHFFFAOYSA-N 2-(2,3,4,5,6-pentafluorophenyl)ethynyl-tris(trifluoromethyl)silane Chemical group FC([Si](C(F)(F)F)(C(F)(F)F)C#CC1=C(C(=C(C(=C1F)F)F)F)F)(F)F GFSFKWHVGTYIOS-UHFFFAOYSA-N 0.000 claims description 7
- HHOXWPCTCQMHNN-UHFFFAOYSA-N C1(=CC=CC=C1)I.[F] Chemical class C1(=CC=CC=C1)I.[F] HHOXWPCTCQMHNN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 5
- AVOGLGBKOFOSBN-UHFFFAOYSA-N 1-ethoxy-2,3-difluorobenzene Chemical compound CCOC1=CC=CC(F)=C1F AVOGLGBKOFOSBN-UHFFFAOYSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- QQRRIMVVXZGZIF-UHFFFAOYSA-N 4-ethyl-2,3-difluorophenol Chemical compound CCC1=CC=C(O)C(F)=C1F QQRRIMVVXZGZIF-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims 3
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000004990 Smectic liquid crystal Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical class FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HOKWHGYUNYFNTP-UHFFFAOYSA-N 2,2-difluoroethoxybenzene Chemical compound FC(F)COC1=CC=CC=C1 HOKWHGYUNYFNTP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QRNCWFPELHRDJI-UHFFFAOYSA-N 4-[2-(2,3,5,6-tetrafluoro-4-pentoxyphenyl)ethynyl]benzoic acid Chemical compound C(CCCC)OC1=C(C(=C(C(=C1F)F)C#CC1=CC=C(C(=O)O)C=C1)F)F QRNCWFPELHRDJI-UHFFFAOYSA-N 0.000 description 1
- GZKSDNKYYKJZPV-UHFFFAOYSA-N 4-ethyl-2-fluorophenol Chemical compound CCC1=CC=C(O)C(F)=C1 GZKSDNKYYKJZPV-UHFFFAOYSA-N 0.000 description 1
- XBXLFMTZQYDXSJ-UHFFFAOYSA-N C(CCC)OC1=C(C(=C(C(=C1F)F)C#CC1=CC=C(C=C1)C(=O)O)F)F Chemical compound C(CCC)OC1=C(C(=C(C(=C1F)F)C#CC1=CC=C(C=C1)C(=O)O)F)F XBXLFMTZQYDXSJ-UHFFFAOYSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a nematic negative liquid crystal which contains 2,3,5,6-tetrafluorotolane and has the following structural formula, a synthetic method and an application, wherein R represents C1-C8 n-alkane. A 2,3,5,6-tetrachlorofluorophenylene group is guided into a negative liquid crystal molecule; and triple bonds are used for bridged bond connection, and a negative liquid crystal containing the 2,3,5,6-tetrachlorofluorophenylene is obtained. The nonpolar tetrachlorofluorophenylene group is guided into, so that the response speed is increased, the specific resistance is increased, and the chemical stability is improved. The series of the liquid crystals are all univariant nematic-phase liquid crystals, and no smectic phase exists; and the method can be applied to preparation of a negative liquid crystal compound material.
Description
Technical field
The class that the present invention relates to use in liquid crystal flat-panel display contains the nematic negative liquid crystal of 2,3,5,6-tetrafluoro diphenyl acetylene class, synthetic method and application.They, owing to having high degree of birefringence, larger polarity and low-viscosity, can also be used for photonics systems.
Background of invention
Along with the development of liquid crystal flat-panel display, in order to improve liquid-crystal display (LCDs) display speed and widen the visual angle of device, develop the indicating meter of various different characteristics display format.Certainly, the negative liquid crystal material with negative dielectric anisotropy is the very important member of liquid crystal display material family.In practical active matrix liquid crystal display (AM-LCD), the difference Δ ε of molecular axis direction and the axial specific inductivity of perpendicular molecules is the liquid crystal of negative, is used widely in VA-TFT LCD pattern (Thin Film Transistor-LCD that molecule is arranged vertically).The display image quality that this pattern can produce is outstanding, not only fast response time, and has wide viewing angle.Wide viewing angle is the outstanding advantage of VA-TFT LCD pattern.
The present invention has synthesized four fluoro liquid crystals compounds, obtains the nematic liquid crystal of high clearing point and wide temperature range.The liquid crystal molecule of high clearing point at high temperature can not make component failure when being used for device; Introduce the structure of 2,3,5,6-tetra-fluoro tolane in molecule, the liquid crystalline cpd obtained not only has high degree of birefringence, and has low viscosity, is also suitable for optical system as adaptive optics modulator mixed crystal material.In fact, negative liquid crystal material can be used as a component of molecule vertical orientated (VA) material, plane internal switch (IPS) and electrically conerolled birefringence (ECB) pattern, is applicable to the technique of display of large-area flat-plate active matrix.High birefringence negative liquid crystal material is also the important component of double frequency nematic mixture, can be applied at photonics.
Summary of the invention
Object of the present invention provides a kind of negative liquid crystal compound containing 2,3,5,6-tetrafluoro diphenyl acetylene class.
Object of the present invention also provides a kind of synthetic method of above-mentioned negativity compound.
Another object of the present invention is to provide a kind of application of above-mentioned negativity compound.
The negative liquid crystal containing 2,3,5,6-tetra-fluoro diphenyl acetylene class of the present invention has following molecular formula:
Wherein, the alkyl of R=C1-C8, the especially alkyl of C2-C5.
The negative liquid crystal compou nd synthesis reaction formula of 2,3,5,6-tetrafluoro diphenyl acetylene classes of the present invention is as follows:
Wherein, the alkyl of R=C1-C8, the alkyl of preferred C2-C5.
Concrete synthesis step is as follows
1) synthesis of compound 4-ethyl-2,3-difluoroethoxy benzene A
In organic solvent, the reaction of 2,3-difluoroethoxy benzene, BuLi hexane solution and iodoethane obtains compound 4-ethyl-2,3-difluoroethoxy benzene A for 1-5 hour.The mol ratio of described 2,3-difluoroethoxy benzene, BuLi and iodoethane is 1:1.5 ~ 2:3 ~ 3.5.
In the reaction, control temperature of reaction and be about-80 DEG C, temperature of reaction is unsuitable too low or too high, is naturally warming up to room temperature after completion of the reaction, obtains high compound 4-ethyl-2, the 3-difluoroethoxy benzene A of purity through aftertreatment.Recommend to react under nitrogen protection.
2) synthesis of compound 4-ethyl-2,3-difluorophenol B
4-ethyl-2,3-difluoroethoxy benzene, 47% HBr solution and acetic acid reflux 20 ~ 35 hours.The mol ratio of described 4-ethyl-2,3-difluoroethoxy benzene, HBr and acetic acid is 1:1.3 ~ 1.5:10 ~ 12.
3) synthesis of compound 4-Iodobenzoic acid (the fluoro-4-oxyethyl group of 2,3-bis-) phenyl ester C
In room temperature and organic solvent, 4-Iodobenzoic acid, 2,3-bis-fluoro-4-thanatols, dicyclohexylcarbodiimide and DMAP reaction 15 ~ 30 hours.The mol ratio of described 4-Iodobenzoic acid, 2,3-bis-fluoro-4-thanatols, N, N-dicyclohexylcarbodiimide and DMAP is 1:0.93 ~ 0.1:1.5 ~ 1.7:0.9 ~ 0.1.
4) synthesis of compound five fluorine iodobenzene D
In organic solvent, five bromofluorobenzenes, iodine and magnesium are about 0 DEG C reaction 4.5 hours in temperature.
When reacting, five bromofluorobenzenes and reactive magnesium before this, this reaction is violent, and dripping five bromofluorobenzenes must be slow, fully react; Still complete by magnesium unreacted after reaction terminates, should attention be added during process.Five described bromofluorobenzenes, the mol ratio of iodine and magnesium is 1:1.12 ~ 1.5:1.12 ~ 1.React under nitrogen protection.
5) synthesis of compound perfluorophenyl trimethylsilyl acetylene E
Pd (PPh
3)
2cl
2, CuI, triethylamine, five fluorine iodobenzenes and trimethylsilyl acetylene react 30 hours at 50 DEG C.Described Pd (PPh
3)
2cl
2, CuI, triethylamine, five fluorine iodobenzenes and trimethylsilyl acetylene mol ratio be 0.004 ~ 0.006:0.015 ~ 0.02:27 ~ 30:0.85 ~ 1.0:1.Recommend to react under nitrogen protection.
6) compound aligns the synthesis of perfluoroalkoxy phenylacetylene F
Under normal temperature, add perfluorophenyl trimethylsilyl acetylene E in organic solvent, salt of wormwood and positive C1-C8 alcohol.Wherein positive C1-C8 alcohol preferably positive C2-C5 alcohol.Described perfluorophenyl trimethylsilyl acetylene E, the mol ratio of salt of wormwood and positive C1-C8 alcohol is 1:2 ~ 2.5:2 ~ 3.
7) synthesis of compound 4-[(4-positive C1-C8 alkoxyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester G
Pd(PPh
3)
2cl
2, CuI, 4-Iodobenzoic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester C, align the preferential positive C2-C5 perfluoroalkoxy phenylacetylene F of C1-C8 perfluoroalkoxy phenylacetylene F() and triethylamine react 1 ~ 5h at a reflux temperature.Described 4-Iodobenzoic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester C, aligns the preferential positive C2-C5 perfluoroalkoxy phenylacetylene F of C1-C8 perfluoroalkoxy phenylacetylene F(), Pd(PPh
3)
2cl
2, CuI, and the mol ratio of triethylamine is 1:0.9 ~ 1.0:0.17 ~ 0.2:0.66 ~ 0.8:75 ~ 80.
The method purifying such as the product of above-mentioned steps can adopt filtration, organic solvent extraction is separated, dry, concentrated, column chromatography or recrystallization.
The negative liquid crystal compound containing 2,3,5,6-tetrafluoro diphenyl acetylene class of the present invention, is conducive to improving response speed, resistivity and chemical stability owing to importing nonpolar tetrafluoro phenylene.This series liquid crystal is all monotropic nematic liquid crystal, there is not smectic phase, may be used for preparing negative liquid crystal compound-material.
Embodiment
The present invention can be understood further by following embodiment, but content of the present invention can not be limited.Anyly all to belong within the technical scheme that the present invention protects inventing the simple replacement done or improvement etc. those skilled in that art
Embodiment 1: synthesize example with 4-[(4-oxyethyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester:
The preparation of 4-ethyl-2,3-difluorophenol
Under nitrogen protection; 2 are added in the four-hole boiling flask of 250ml; the tetrahydrofuran THF of 3-difluoroethoxy benzene 11.9g (0.075mol) and 120ml; now cool to about-80 DEG C; drip BuLi hexane solution 56.5ml(0.14mol); about 30 minutes; stirring 2.5 hours is continued at this temperature; then in solution, iodoethane 37.5g(0.24mol is dripped) and the mixing solutions of 30mlTHF; within 20 minutes, dropwise, continue reaction 1.5 hours at such a temperature, stopped reaction; naturally be warming up to room temperature, spend the night.In this solution, pour the water of 250ml into, be extracted with ethyl acetate, merge organic phase, with anhydrous sodium sulfate drying, water pump pressure reducing and steaming solvent, then oil pump underpressure distillation, collect 65-70 DEG C/4mmHg and obtain colourless product 9.49g(productive rate 68%).
4-ethyl-2,3-difluoroethoxy benzene 9,49g(0.05mol is added in the there-necked flask of 100ml), the HBr solution 30ml of 47%, acetic acid 32ml, reflux, now, temperature is about 110 DEG C, and GC follows the tracks of reaction, after 30 hours, reacts complete, is cooled to room temperature.With the extraction of appropriate toluene, with anhydrous magnesium sulfate drying, water pump pressure reducing and steaming solvent, then oil pump underpressure distillation, collect 48-52 DEG C/2mmHg and obtain colourless product 6.6g(productive rate 84%).
MS(m/z,%):158(M+,10.82),143(100)。
The synthesis of 4-Iodobenzoic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester
Under nitrogen protection; by 2 of 3.16g (20.0mmol); the fluoro-4-ethylphenol of 3-bis-; the 4-Iodobenzoic acid of 5.0g (20.2mmol), the N of 2.3g (12mmol), the DMAP of N-dicyclohexylcarbodiimide and 180mg (1.48mmol) adds in the there-necked flask of 250ml; the tetrahydrofuran (THF) adding 100ml dissolves; normal temperature lower magnetic force stirs, and TCL follows the tracks of reaction, reacts completely after 30 hours.
This reaction solution of suction filtration, and use washed with dichloromethane solid, obtain the acetic acid that mother liquor uses 5% respectively, salt solution and water respectively wash three times, merge organic phase, with anhydrous sodium sulfate drying, water pump pressure reducing and steaming solvent, the solid sherwood oil obtained: the eluent of methylene dichloride=1:1 crosses post, the crude product obtained uses sherwood oil again: the proportioning recrystallization of methylene dichloride=20:1, obtains white solid product 5.0g(productive rate 65%).
1H NMR(400MHz,CDCl3)δ8.22–8.01(m,2H),7.93–7.72(m,2H),7.23–6.54(m,2H),1.78(dq,J=8.6,6.6Hz,2H),1.27(t,J=7.6Hz,3H).
MS(m/z,%):388(M+,0.34),231(100)。
The synthesis of five fluorine iodobenzenes
Under nitrogen protection; by 3.6g(0.15mol) tetrahydrofuran (THF) (THF) of magnesium and 100ml adds in the there-necked flask of 250ml; slow dropping 32.2g(0.13mol) mixed solution of five bromofluorobenzenes and 50mlTHF; solution changes color after several minutes; and react violent and a large amount of heat release, cryosel bath controls, at about 0 DEG C, to drip off after half an hour; continue stirring reaction 1h, solution colour becomes black.By 34.3g(0.135mol) iodine is dissolved in 70mlTHF, drops in reaction solution, is incubated at about 0 DEG C, within one hour, drip off, and continues reaction one hour, and gas phase is followed the tracks of, and reacts complete.
The solution that 28ml concentrated hydrochloric acid and 50ml water are made into is added in reaction solution, stir, dissolution of solid, a large amount of heat release, then uses the aqueous solution of Sulfothiorine (10%) to wash ten times, methyl tertiary butyl ether extracts, merge organic phase, with anhydrous sodium sulfate drying, underpressure distillation, collect the product of 52-56 DEG C/14mmHg, obtain pink colour product liquid 23.7g(productive rate 62%).
19F NMR(300MHz,CDCl
3):δ41.2(d,J=18.8Hz,2F),74.4(t,J=18.8Hz,1F),81.5(m,2F)
The synthesis of perfluorophenyl trimethylsilyl acetylene
Under nitrogen protection; 0.45gPd (PPh3) 2Cl2 and 0.6g cuprous iodide is joined in the there-necked flask of 500ml; pour the triethylamine of 250ml drying into; after 5 minutes; add 17.64g(60mmol) five fluorine iodobenzene and 8.00g(80mmol) trimethylsilyl acetylene; magnetic agitation; temperature controls between 25-40 DEG C; after 40h, TCL follows the tracks of and reacts completely, and adds the methyl tertiary butyl ether of 200ml, suction filtration in reaction solution; methyl tertiary butyl ether washs; wash with water repeatedly, obtain sorrel liquid, use anhydrous Na
2sO
4drying, except desolventizing, underpressure distillation, collects 62 DEG C/3mmHg cut, obtains colorless liquid product 12.7g(productive rate 80%).
1H NMR(300MHz,CDCl
3):δ0.13(s,1H)
19F NMR(300MHz,CDCl
3):δ59.63(m,2F),76.33(t,1F),85.90(m,2F)
To the synthesis of ethoxyperfluoro phenylacetylene
Normal temperature lower magnetic force stirs, by 2.45g (17.8mmol) salt of wormwood, Pentyl alcohol 3.5g(39.8mmol), perfluorophenyl trimethylsilyl acetylene 2.45(10.0mmol) and the dimethyl formyl of 40ml join in the there-necked flask of 50ml by (DMF), react under normal temperature, TCL follows the tracks of reaction, react completely after 72h, add the water of 40ml, with methyl tertiary butyl ether extraction, with anhydrous sodium sulfate drying, pressure reducing and steaming solvent, cross post with sherwood oil, obtain weak yellow liquid 1.98g(productive rate 76%).
1H NMR(300MHz,CDCl
3):δ1.40(t,J=6Hz,3H),3.40(s,1H),4.20(q,J=6Hz,2H)
19F NMR(300MHz,CDCl
3):δ60.83(d,J=18.8Hz,2F),80.67(d,J=18.8Hz,2F).
The synthesis of 4-[(4-oxyethyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester
Under nitrogen protection magnetic agitation, in the there-necked flask of 100ml, add the Pd(PPh of 0.1g successively
3)
2cl
2, 0,15gCuI, 430mg(1.1mmol) 4-Iodobenzoic acid (2, the fluoro-4-oxyethyl group of 3-bis-) phenyl ester, 262mg(1.2mmol) the triethylamine to ethoxyperfluoro phenylacetylene and 75ml, reflux, TCL follows the tracks of reaction, react completely after 4.5 hours, cooling, suction filtration washs with methyl tertiary butyl ether simultaneously, then wash with water, use anhydrous Na
2sO
4drying, pressure reducing and steaming solvent, with sherwood oil: the eluent of ethyl acetate=40:1 crosses post, obtains white solid crude product sherwood oil recrystallization, obtains product as white needles 0.47g(productive rate 85%).
1H NMR(400MHz,CDCl3)δ8.39–8.04(m,2H),7.89–7.60(m,2H),7.02–6.94(m,2H),4.38(qt,J=7.1,1.1Hz,2H),2.72(qd,J=7.5,1.3Hz,2H),1.45(t,J=7.0Hz,3H),1.26(t,J=7.6Hz,3H).
IR(KBr,
max,cm
-1):3451,2961,2933,2867,1738,1606,1514,1494,1440,1394,1272,1244,1119,1072,1018,982,858,762
MS(m/z,%):478(M+,2.72),321.1(100)。
Polarized light microscope observing: Cr102 DEG C N171.3 DEG C I167.8 DEG C N 61.2 DEG C of Cr
DSC detects data: Cr60.48 DEG C N165.40 DEG C I166.14 DEG C N101.42 DEG C Cr.
The synthetic method of the similar target compound of embodiment 2 is with embodiment 1:
Wherein, at normal temperatures with perfluorophenyl trimethylsilyl acetylene D in DMF solvent, when salt of wormwood is followed successively by 1:1 ~ 2:1 ~ 5 with the mol ratio of alkyl (C1-C8) alcohol respectively, 72h is reacted.Then continue reaction with embodiment 1, the results obtained are as follows:
4-[(4-positive propoxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester
1H NMR(400MHz,CDCl3)δ8.58–8.02(m,2H),7.83–7.51(m,2H),7.04–6.84(m,2H),4.26(tt,J=6.6,1.1Hz,3H),2.72(qd,J=7.6,1.4Hz,2H),1.83(h,J=7.1Hz,2H),1.26(t,J=7.5Hz,3H),1.06(t,J=7.4Hz,3H).
MS(m/z,%):492.1(M+,2.65),335.1(100).
Polarized light microscope observing: Cr103.5 DEG C N170 DEG C I157.2 DEG C N64.6 DEG C Cr
DSC detects data: Cr65.51 DEG C N153.38 DEG C I153.96 DEG C N100.47 DEG C Cr.
4-[(4-n-butoxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester
1H NMR(400MHz,CDCl3)δ8.33–8.02(m,2H),7.87–7.60(m,2H),7.16–6.74(m,2H),4.30(tt,J=6.5,1.1Hz,2H),2.72(qd,J=7.6,1.4Hz,2H),1.78(dq,J=8.6,6.6Hz,2H),1.55–1.43(m,2H),1.27(t,J=7.6Hz,3H),0.99(t,J=7.4Hz,3H).
MS(m/z,%):506.1(M+,2.29),349.1(100)。
Polarized light microscope observing: Cr104.6 DEG C N158.5 DEG C I154.6 DEG C N66.3 DEG C Cr
DSC detects data: Cr7.51 DEG C N151.68 DEG C I152.52 DEG C N103.28 DEG C Cr.
4-[(4-n-pentyloxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester
1H NMR(400MHz,CDCl3)δ8.33–8.08(m,2H),7.78–7.58(m,2H),7.11–6.86(m,2H),4.29(tt,J=6.7,1.1Hz,2H),2.72(qd,J=7.5,1.3Hz,2H),1.80(dt,J=8.1,6.5Hz,2H),1.48–1.42(m,2H),1.42–1.35(m,2H),1.26(t,J=7.5Hz,3H),0.94(t,J=7.0Hz,3H).
MS(m/z,%):520.1(M+,2.57),363.1(100)。
Polarized light microscope observing: Cr99.6 DEG C N146.8 DEG C I144 DEG C N67.6 DEG C Cr
DSC detects data: Cr70.70 DEG C N137.40 DEG C I138.30 DEG C N89.82 DEG C Cr.
Claims (8)
1. the negative liquid crystal containing 2,3,5,6-tetrafluoro diphenyl acetylene class, has following molecular formula:
Wherein, the alkyl of R=C1-C8.
2. the negative liquid crystal containing 2,3,5,6-tetrafluoro diphenyl acetylene class as claimed in claim 1, is characterized in that the alkyl of described R=C2-C5.
3. the synthetic method of the negative liquid crystal compound of 2,3,5,6-tetrafluoro diphenyl acetylene classes as claimed in claim 1, is characterized in that being obtained by following step:
1) synthesis of compound 4-ethyl-2,3-difluoroethoxy benzene A
In-80 DEG C and organic solvent, the reaction of 2,3-difluoroethoxy benzene, BuLi hexane solution and iodoethane obtains compound 4-ethyl-2,3-difluoroethoxy benzene A for 1-5 hour; The mol ratio of described 2,3-difluoroethoxy benzene, BuLi and iodoethane is 1:1.5 ~ 2:3 ~ 3.5;
2) synthesis of compound 4-ethyl-2,3-difluorophenol B
4-ethyl-2,3-difluoroethoxy benzene, 47% HBr solution and acetic acid reflux 20 ~ 35 hours; The mol ratio of described 4-ethyl-2,3-difluoroethoxy benzene, HBr and acetic acid is 1:1.3 ~ 1.5:10 ~ 12;
3) synthesis of compound 4-Iodobenzoic acid (the fluoro-4-oxyethyl group of 2,3-bis-) phenyl ester C
In room temperature and organic solvent, 4-Iodobenzoic acid, 2,3-bis-fluoro-4-thanatols, dicyclohexylcarbodiimide and DMAP reaction 15 ~ 30 hours; The mol ratio of described 4-Iodobenzoic acid, 2,3-bis-fluoro-4-thanatols, dicyclohexylcarbodiimide and DMAP is 1:0.93 ~ 0.1:1.5 ~ 1.7:0.9 ~ 0.1;
4) synthesis of compound perfluorophenyl trimethylsilyl acetylene E
At room temperature ~ 50 DEG C, Pd (PPh
3)
2cl
2, CuI, triethylamine, five fluorine iodobenzenes and trimethylsilyl acetylene reaction 10 ~ 30 hours; Described Pd (PPh
3)
2cl
2, CuI, triethylamine, five fluorine iodobenzenes and trimethylsilyl acetylene mol ratio be 0.004 ~ 0.006:0.015 ~ 0.02:27 ~ 30:0.85 ~ 1.0:1;
5) compound aligns the synthesis of perfluoroalkoxy phenylacetylene F
At normal temperatures with in organic solvent, perfluorophenyl trimethylsilyl acetylene E, the alkyl alcohol of salt of wormwood and positive C1-C8; Described perfluorophenyl trimethylsilyl acetylene E, the mol ratio of the alkyl alcohol of salt of wormwood and positive C1-C8 is 1:2 ~ 2.5:2 ~ 3;
6) synthesis of compound 4-[(4-positive C1-C8 alkoxyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester G
At a reflux temperature, Pd (PPh
3)
2cl
2, CuI, 4-Iodobenzoic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester C, aligns C1-C8 perfluoroalkoxy phenylacetylene F and triethylamine reacts 1 ~ 5h at a reflux temperature; Described 4-Iodobenzoic acid (the fluoro-4-ethyl of 2,3-bis-) phenyl ester C, aligns C1-C8 perfluoroalkoxy phenylacetylene F, Pd (PPh
3)
2cl
2, CuI, and the mol ratio of triethylamine is 1:0.9 ~ 1.0:0.17 ~ 0.2:0.66 ~ 0.8:75 ~ 80.
4. the synthetic method of the negative liquid crystal compound of 2,3,5,6-tetrafluoro diphenyl acetylene classes as claimed in claim 3, it is characterized in that the product of described every step adopt filter, organic solvent extraction is separated, dry, concentrated, column chromatography or recrystallization method purifying.
5. the synthetic method of the negative liquid crystal compound of 2,3,5,6-tetrafluoro diphenyl acetylene classes as claimed in claim 3, is characterized in that described step 5) described in alcohol be the alkyl alcohol of positive C2-C5.
6. the synthetic method of 2,3,5,6-tetrafluoro diphenyl acetylene class negative liquid crystal compounds as claimed in claim 3, is characterized in that described step 1) or 4) be react under nitrogen protection.
7. the synthetic method of the negative liquid crystal compound of 2,3,5,6-tetrafluoro diphenyl acetylene classes as claimed in claim 3, is characterized in that step 1), 3) or 5) described in organic solvent be dimethyl formamide, tetrahydrofuran (THF), triethylamine or toluene.
8. the negative liquid crystal compound of 2,3,5,6-tetrafluoro diphenyl acetylene classes as claimed in claim 1 is preparing the application in liquid crystal material.
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| TWI507511B (en) * | 2013-11-05 | 2015-11-11 | Ind Tech Res Inst | Liquid crystal compound with negative dielectric anisotropy, liquid crystal display, and optoelectronic device |
| CN104194800B (en) * | 2014-08-11 | 2016-03-09 | 福建省邵武市永晶化工有限公司 | Fluoric bis(diphenyl)acetylene nematic negative liquid crystal, synthetic method and application |
| CN106365950B (en) * | 2016-08-26 | 2018-10-30 | 大连奇凯医药科技有限公司 | A kind of preparation method of five fluorine iodobenzene |
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