CN103333697A - 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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- 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 28
- -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 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 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 29
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 24
- 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
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 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
- 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
- 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 7
- 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
- HOKWHGYUNYFNTP-UHFFFAOYSA-N 2,2-difluoroethoxybenzene Chemical compound FC(F)COC1=CC=CC=C1 HOKWHGYUNYFNTP-UHFFFAOYSA-N 0.000 claims description 6
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group 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
- 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
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- AVOGLGBKOFOSBN-UHFFFAOYSA-N 1-ethoxy-2,3-difluorobenzene Chemical compound CCOC1=CC=CC(F)=C1F AVOGLGBKOFOSBN-UHFFFAOYSA-N 0.000 claims description 2
- QQRRIMVVXZGZIF-UHFFFAOYSA-N 4-ethyl-2,3-difluorophenol Chemical compound CCC1=CC=C(O)C(F)=C1F QQRRIMVVXZGZIF-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000004990 Smectic liquid crystal Substances 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 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
- 239000007788 liquid Substances 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
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 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
- 230000000007 visual effect Effects 0.000 description 3
- 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
- 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 class 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
- 0 CCc(ccc(*c(cc1)ccc1C#Cc(c(F)c(c(O*)c1F)F)c1F)c1F)c1F Chemical compound CCc(ccc(*c(cc1)ccc1C#Cc(c(F)c(c(O*)c1F)F)c1F)c1F)c1F 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
- 230000015572 biosynthetic process Effects 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
- 238000003810 ethyl acetate extraction Methods 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
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 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
- 238000003786 synthesis reaction Methods 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
- 238000005406 washing Methods 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 a nalkane group ranging from C1 to C8; 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
A class that the present invention relates to use in the liquid crystal flat-panel demonstration contains nematic negative liquid crystal, synthetic method and the application of 2,3,5,6-tetrafluoro diphenyl acetylene class.They can also be used for the photonics system owing to have high degree of birefringence, bigger polarity and low-viscosity.
Background of invention
The development that shows along with liquid crystal flat-panel in order to improve liquid-crystal display (LCDs) display speed and to widen the visual angle of device, has been developed the indicating meter of various different characteristics display formats.Undoubtedly, the negative liquid crystal material with negative dielectric anisotropy is the very important member of liquid crystal display material family.In the active matrix liquid crystal display of practicability (AM-LCD), the difference Δ ε of the axial specific inductivity of molecular axis direction and perpendicular molecules is the liquid crystal of negative, is used widely in VA-TFT LCD pattern (Thin Film Transistor-LCD of molecule arranged vertical).The display image quality that this pattern can produce is outstanding, and not only response speed is fast, and wide visual angle is arranged.Wide visual angle is the outstanding advantage of VA-TFT LCD pattern.
The present invention has synthesized four fluoro liquid crystals compounds, has obtained the nematic liquid crystal of high clearing point and wide temperature range.The liquid crystal molecule of high clearing point can at high temperature not make component failure when being used for device; Introduced 2,3,5,6-tetrafluoro in the molecule for the structure of tolane, the liquid crystalline cpd that obtains not only has high degree of birefringence, and has low viscosity, also is suitable for optical system as adaptive optics modulator mixed crystal material.In fact, the negative liquid crystal material can be used as a component, plane internal switch (IPS) and electrically conerolled birefringence (ECB) pattern of molecule vertical orientated (VA) material, is applicable to the technique of display of large-area flat-plate active matrix.High birefringence negative liquid crystal material also is the important component of double frequency nematic mixture, can be applied in the photonics field.
Summary of the invention
Purpose of the present invention provides a kind of negative liquid crystal compound that contains 2,3,5,6-tetrafluoro diphenyl acetylene class.
Purpose of the present invention also provides a kind of synthetic method of above-mentioned negativity liquefaction compound.
Another object of the present invention provides a kind of above-mentioned negativity liquid application of compound.
2,3,5, the 6-tetrafluoro that contains of the present invention has following molecular formula for the negative liquid crystal of diphenyl acetylene class:
Wherein, the positive alkyl of the alkyl of R=C1-C8, especially C2-C5.
Of the present invention 2,3,5, the synthetic reaction formula of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class is as follows:
Wherein, the positive alkyl of R=C1-C8, the positive alkyl of preferred C2-C5.
Concrete synthesis step is as follows
1) compound 4-ethyl-2,3-difluoroethoxy benzene A's is synthetic
In organic solvent, 2,3-difluoroethoxy benzene, BuLi hexane solution and iodoethane reaction obtained compound 4-ethyl-2,3-difluoroethoxy benzene A in 1-5 hour.Described 2, the mol ratio of 3-difluoroethoxy benzene, BuLi and iodoethane is 1:1.5～2:3～3.5.
In this reaction, the control temperature of reaction is about-80 ℃, and temperature of reaction should not be crossed low or too high, is warming up to room temperature naturally after reaction finishes, and gets the high compound 4-ethyl-2 of purity, 3-difluoroethoxy benzene A through aftertreatment.Be recommended under the nitrogen protection and react.
2) compound 4-ethyl-2,3-difluorophenol B's is synthetic
4-ethyl-2,3-difluoroethoxy benzene, 47% HBr solution and acetic acid reflux 20～35 hours.Described 4-ethyl-2, the mol ratio of 3-difluoroethoxy benzene, HBr and acetic acid is 1:1.3～1.5:10～12.
3) compound 4-Iodobenzoic acid (2,3-, two fluoro-4-oxyethyl groups) phenyl ester C's is synthetic
In room temperature and organic solvent, 4-Iodobenzoic acid, 2,3-two fluoro-4-thanatols, dicyclohexylcarbodiimide and 4-Dimethylamino pyridine reacted 15～30 hours.Described 4-Iodobenzoic acid, 2,3-two fluoro-4-thanatols, N, the mol ratio of N-dicyclohexylcarbodiimide and 4-Dimethylamino pyridine is 1:0.93～0.1:1.5～1.7:0.9～0.1.
4) compound five fluorine iodobenzene D's is synthetic
In organic solvent, five bromofluorobenzenes, iodine and magnesium are to react 4.5 hours about 0 ℃ in temperature.
In when reaction, five bromofluorobenzenes and reactive magnesium before this, this reaction is violent, and dripping five bromofluorobenzenes must be slow, fully react; Reaction is still complete by the magnesium unreacted after finishing, and should add attention during processing.Described five bromofluorobenzenes, the mol ratio of iodine and magnesium are 1:1.12～1.5:1.12～1.Under nitrogen protection, react.
5) compound perfluorophenyl trimethylsilyl acetylene E's is synthetic
Pd (PPh
3)
2Cl
2, CuI, triethylamine, five fluorine iodobenzenes and trimethylsilyl acetylene be 50 ℃ of reactions 30 hours down.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.Be recommended under the nitrogen protection and react.
6) compound aligns the synthetic of alkoxyl group perfluor phenylacetylene F
Under the normal temperature, in organic solvent, add perfluorophenyl trimethylsilyl acetylene E, salt of wormwood and positive C1-C8 alcohol.The preferred positive C2-C5 alcohol of positive C1-C8 alcohol wherein.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) the ethynyl positive C1-C8 alkoxyl group-2,3,5 of compound 4-[(4-, 6-tetrafluoro phenyl)] phenylformic acid (2,3-, two fluoro-4-ethyls) phenyl ester G synthetic
Pd(PPh
3)
2Cl
2, CuI, 4-Iodobenzoic acid (2,3-, two fluoro-4-ethyls) phenyl ester C aligns the preferential positive C2-C5 alkoxyl group perfluor phenylacetylene F of C1-C8 alkoxyl group perfluor phenylacetylene F() and triethylamine under reflux temperature, react 1～5h.Described 4-Iodobenzoic acid (2,3-, two fluoro-4-ethyls) phenyl ester C aligns the preferential positive C2-C5 alkoxyl group perfluor phenylacetylene F of C1-C8 alkoxyl group perfluor phenylacetylene F(), Pd(PPh
3)
2Cl
2, the mol ratio of CuI and triethylamine is 1:0.9～1.0:0.17～0.2:0.66～0.8:75～80.
The product of above-mentioned steps can adopt filtration, organic solvent extraction separate, dry, concentrate, method purifying such as column chromatography or recrystallization.
The negative liquid crystal compound that contains 2,3,5,6-tetrafluoro diphenyl acetylene class of the present invention is conducive to improve response speed, resistivity and chemical stability owing to import nonpolar tetrafluoro phenylene.This series liquid crystal all is monotropic nematic liquid crystal, does not have smectic phase, can be for the preparation of the negative liquid crystal compound-material.
Embodiment
The present invention can be further understood by following embodiment, but content of the present invention can not be limited.Anyly the simple replacement done of invention or improvement etc. are all belonged within the technical scheme that the present invention protects those skilled in that art
Embodiment 1: with 4-[(4-oxyethyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (2,3-, two fluoro-4-ethyls) phenyl ester synthesize example:
4-ethyl-2, the preparation of 3-difluorophenol
Under nitrogen protection; in the four-hole boiling flask of 250ml, add 2; the tetrahydrofuran THF of 3-difluoroethoxy benzene 11.9g (0.075mol) and 120ml; cool to about-80 ℃ this moment; drip BuLi hexane solution 56.5ml(0.14mol); about 30 minutes; continue under this temperature to stir about 2.5 hours; drip iodoethane 37.5g(0.24mol then in the solution) and the mixing solutions of 30mlTHF; dropwised in 20 minutes, and under this temperature, continued reaction 1.5 hours, stopped reaction; naturally be warming up to room temperature, spend the night.Pour the water of 250ml in this solution into, use ethyl acetate extraction, merge organic phase, use anhydrous sodium sulfate drying, water pump pressure reducing and steaming solvent, oil pump underpressure distillation again, 65-70 ℃/4mmHg of collection gets colourless product 9.49g(productive rate 68%).
In the there-necked flask of 100ml, add 4-ethyl-2,3-difluoroethoxy benzene 9,49g(0.05mol), and 47% HBr solution 30ml, acetic acid 32ml, reflux, temperature is about 110 ℃ in this moment, and GC follows the tracks of reaction, and after 30 hours, reaction finishes, and is cooled to room temperature.With an amount of toluene extraction, use anhydrous magnesium sulfate drying, water pump pressure reducing and steaming solvent, oil pump underpressure distillation is again collected 48-52 ℃/2mmHg and is got colourless product 6.6g(productive rate 84%).
MS(m/z,%):158(M+,10.82),143(100)。
Synthesizing of 4-Iodobenzoic acid (2,3-, two fluoro-4-ethyls) phenyl ester
Under the nitrogen protection; with 2 of 3.16g (20.0mmol); 3-two fluoro-4-ethylphenols; 5.0g 4-Iodobenzoic acid (20.2mmol), the N of 2.3g (12mmol), the 4-Dimethylamino pyridine of N-dicyclohexylcarbodiimide and 180mg (1.48mmol) add in the there-necked flask of 250ml; the tetrahydrofuran (THF) dissolving that adds 100ml; the normal temperature lower magnetic force stirs, and TCL follows the tracks of reaction, and afterreaction was complete in 30 hours.
This reaction solution of suction filtration, and use the washed with dichloromethane solid, obtain mother liquor and use 5% acetic acid respectively, salt solution and water are respectively given a baby a bath on the third day after its birth time, merge organic phase, use anhydrous sodium sulfate drying, water pump pressure reducing and steaming solvent, the solid sherwood oil that obtains: the eluent of methylene dichloride=1:1 is crossed post, and the crude product that obtains is used the proportioning recrystallization of sherwood oil: methylene dichloride=20:1 again, gets 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)。
Synthesizing of five fluorine iodobenzenes
Under nitrogen protection; with 3.6g(0.15mol) tetrahydrofuran (THF) (THF) of magnesium and 100ml adds in the there-necked flask of 250ml; the slow 32.2g(0.13mol that drips) mixed solution of five bromofluorobenzenes and 50mlTHF; solution changes color behind the several minutes; and the violent and a large amount of heat releases of reaction, cryosel is bathed control about 0 ℃, drips off after half an hour; continue stirring reaction 1h, solution colour becomes black.With 34.3g(0.135mol) iodine is dissolved in 70mlTHF, drops in the reaction solution, and insulation dripped off about 0 ℃ in one hour, continued reaction one hour, and gas phase is followed the tracks of, and reaction finishes.
Add the solution that 28ml concentrated hydrochloric acid and 50ml water are made in the reaction solution, stir, the solid dissolving, a large amount of heat releases use the aqueous solution of Sulfothiorine (10%) to wash then ten times, the methyl tertiary butyl ether extraction, merge organic phase, use anhydrous sodium sulfate drying, underpressure distillation, collect the product of 52-56 ℃/14mmHg, get 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)
Synthesizing of perfluorophenyl trimethylsilyl acetylene
Under nitrogen protection; 0.45gPd (PPh3) 2Cl2 and 0.6g cuprous iodide are joined in the there-necked flask of 500ml; pour the triethylamine of 250ml drying into; after 5 minutes; adding 17.64g(60mmol) trimethylsilyl acetylene five fluorine iodobenzene and 8.00g(80mmol); magnetic agitation; temperature control is between 25-40 ℃; TCL follows the tracks of and to react completely behind the 40h, adds the methyl tertiary butyl ether of 200ml in the reaction solution, suction filtration; the methyl tertiary butyl ether washing; wash with water repeatedly, get sorrel liquid, use anhydrous Na
2SO
4Drying, desolventizing, 62 ℃/3mmHg cut is collected in underpressure distillation, gets 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 synthesizing of oxyethyl group perfluor phenylacetylene
The normal temperature lower magnetic force stirs, with 2.45g (17.8mmol) salt of wormwood, Pentyl alcohol 3.5g(39.8mmol), 2.45(10.0mmol) perfluorophenyl trimethylsilyl acetylene and the dimethyl formyl of 40ml join in the there-necked flask of 50ml by (DMF), react under the normal temperature, TCL follows the tracks of reaction, and the 72h afterreaction is complete, the water that adds 40ml, with the methyl tertiary butyl ether extraction, use anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, cross post with sherwood oil, get 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).
4-[(4-oxyethyl group-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (2,3-, two fluoro-4-ethyls) phenyl ester synthetic
Under the 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 (2,3-two fluoro-4-oxyethyl groups) phenyl ester, the triethylamine to oxyethyl group perfluor phenylacetylene and 75ml 262mg(1.2mmol), reflux, TCL follows the tracks of reaction, 4.5 hour afterreaction is complete, cooling, and suction filtration washs with methyl tertiary butyl ether simultaneously, wash with water then, use anhydrous Na
2SO
4Drying, the pressure reducing and steaming solvent, use sherwood oil: the eluent of ethyl acetate=40:1 is crossed 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)。
61.2 ℃ of Cr of polarized light microscope observing: Cr102 ℃ N171.3 ℃ I167.8 ℃ N
DSC detects data: Cr60.48 ℃ N165.40 ℃ I166.14 ℃ N101.42 ℃ Cr.
The synthetic method of embodiment 2 similar target compounds is with embodiment 1:
Wherein, at normal temperatures with the DMF solvent in perfluorophenyl trimethylsilyl acetylene D, salt of wormwood is followed successively by 1:1～2:1～5 o'clock reaction 72h with the mol ratio of positive alkyl (C1-C8) alcohol respectively.Continue reaction with embodiment 1 then, the results obtained are as follows:
4-[(4-positive propoxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (2,3-, two fluoro-4-ethyls) 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 ℃ N170 ℃ I157.2 ℃ N64.6 ℃ Cr
DSC detects data: Cr65.51 ℃ N153.38 ℃ I153.96 ℃ N100.47 ℃ Cr.
4-[(4-n-butoxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (2,3-, two fluoro-4-ethyls) 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 ℃ N158.5 ℃ I154.6 ℃ N66.3 ℃ Cr
DSC detects data: Cr7.51 ℃ N151.68 ℃ I152.52 ℃ N103.28 ℃ Cr.
4-[(4-n-pentyloxy-2,3,5,6-tetrafluoro phenyl) ethynyl] phenylformic acid (2,3-, two fluoro-4-ethyls) 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 ℃ N146.8 ℃ I144 ℃ N67.6 ℃ Cr
DSC detects data: Cr70.70 ℃ N137.40 ℃ I138.30 ℃ N89.82 ℃ Cr.
Claims (8)
1. negative liquid crystal that contains 2,3,5,6-tetrafluoro diphenyl acetylene class has following molecular formula:
Wherein, the positive alkyl of R=C1-C8.
2. the negative liquid crystal that contains 2,3,5,6-tetrafluoro diphenyl acetylene class as claimed in claim 1 is characterized in that the positive alkyl of described R=C2-C5.
One kind as claimed in claim 12,3,5, the synthetic method of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class is characterized in that obtaining by following step:
1) compound 4-ethyl-2,3-difluoroethoxy benzene A's is synthetic
In-80 ℃ and organic solvent, 2,3-difluoroethoxy benzene, BuLi hexane solution and iodoethane reaction obtained compound 4-ethyl-2,3-difluoroethoxy benzene A in 1-5 hour; Described 2, the mol ratio of 3-difluoroethoxy benzene, BuLi and iodoethane is 1:1.5～2:3～3.5;
2) compound 4-ethyl-2,3-difluorophenol B's is synthetic
4-ethyl-2,3-difluoroethoxy benzene, 47% HBr solution and acetic acid reflux 20～35 hours; Described 4-ethyl-2, the mol ratio of 3-difluoroethoxy benzene, HBr and acetic acid is 1:1.3～1.5:10～12;
3) compound 4-Iodobenzoic acid (2,3-, two fluoro-4-oxyethyl groups) phenyl ester C's is synthetic
In room temperature and organic solvent, 4-Iodobenzoic acid, 2,3-two fluoro-4-thanatols, dicyclohexylcarbodiimide and 4-Dimethylamino pyridine reacted 15～30 hours; Described 4-Iodobenzoic acid, 2, the mol ratio of 3-two fluoro-4-thanatols, dicyclohexylcarbodiimide and 4-Dimethylamino pyridine is 1:0.93～0.1:1.5～1.7:0.9～0.1;
4) compound perfluorophenyl trimethylsilyl acetylene E's is synthetic
Under room temperature～50 ℃, 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 synthetic of alkoxyl group perfluor phenylacetylene F
At normal temperatures with organic solvent in, perfluorophenyl trimethylsilyl acetylene E, salt of wormwood and positive C1-C8 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;
6) the ethynyl positive C1-C8 alkoxyl group-2,3,5 of compound 4-[(4-, 6-tetrafluoro phenyl)] phenylformic acid (2,3-, two fluoro-4-ethyls) phenyl ester G synthetic
Under reflux temperature, Pd(PPh
3)
2Cl
2, CuI, 4-Iodobenzoic acid (2,3-, two fluoro-4-ethyls) phenyl ester C aligns the preferential positive C2-C5 alkoxyl group perfluor phenylacetylene F of C1-C8 alkoxyl group perfluor phenylacetylene F() and triethylamine under reflux temperature, react 1～5h.Described 4-Iodobenzoic acid (2,3-, two fluoro-4-ethyls) phenyl ester C aligns the preferential positive C2-C5 alkoxyl group perfluor phenylacetylene F of C1-C8 alkoxyl group perfluor phenylacetylene F(), Pd(PPh
3)
2Cl
2, the mol ratio of CuI and triethylamine is 1:0.9～1.0:0.17～0.2:0.66～0.8:75～80.
4. as claimed in claim 32,3,5, the synthetic method of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class, the product that it is characterized in that described every step adopts and filters, organic solvent extraction separates, dry, concentrate, column chromatography or recrystallization method purifying.
5. as claimed in claim 32,3,5, the synthetic method of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class is characterized in that the alcohol described in the described step 5) is positive C2-C5 alcohol.
6. as claimed in claim 32,3,5, the synthetic method of 6-tetrafluoro diphenyl acetylene class negative liquid crystal compound is characterized in that described step 1) or 4) be under nitrogen protection, to react.
7. as claimed in claim 32,3,5, the synthetic method of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class is characterized in that step 1), 3) or 5) described organic solvent is dimethyl formamide, tetrahydrofuran (THF), triethylamine or toluene.
One kind as claimed in claim 12,3,5, the application of the negative liquid crystal compound of 6-tetrafluoro diphenyl acetylene class in the preparation liquid crystal material.
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| CN106365950A (en) * | 2016-08-26 | 2017-02-01 | 大连奇凯医药科技有限公司 | Preparation method of pentafluoroiodobenzene |
| CN104610975B (en) * | 2013-11-05 | 2017-03-01 | 财团法人工业技术研究院 | Negative dielectric anisotropy liquid crystal compound, liquid crystal display, and electro-optical device |
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| CN110903832B (en) * | 2019-12-20 | 2021-02-12 | 上海瓜呱科技有限公司 | Negative liquid crystal compound, liquid crystal composition containing negative liquid crystal compound and application of negative liquid crystal compound |
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