CN103012083B - Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof - Google Patents
Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof Download PDFInfo
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- CN103012083B CN103012083B CN201210585813.2A CN201210585813A CN103012083B CN 103012083 B CN103012083 B CN 103012083B CN 201210585813 A CN201210585813 A CN 201210585813A CN 103012083 B CN103012083 B CN 103012083B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title abstract 3
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical class C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 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
- 239000012452 mother liquor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GJCVKXZWLSUSGU-SBHPSCBMSA-N C1(=CC=CC=C1)C1(CCC(CC1)[C@@H]1CC[C@H](CC1)CCC)O Chemical compound C1(=CC=CC=C1)C1(CCC(CC1)[C@@H]1CC[C@H](CC1)CCC)O GJCVKXZWLSUSGU-SBHPSCBMSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 n-propyl cyclohexyl Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- FRKVGIKPQJABFV-UHFFFAOYSA-N 2-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1C(=O)CCCC1 FRKVGIKPQJABFV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a tetracyclic fluorinated negative liquid crystal compound, and a synthesis method and application thereof. The compound has a molecular formula shown in the specification. The synthesis method is simple; and the compound can be used as a high-temperature component of a mixed liquid crystal and can be further used for preparing a negative liquid crystal having wide working temperature range, thermal stability and high birefringence degree.
Description
Technical field
The present invention relates to two fluorine-containing tolane liquid crystalline cpds of dicyclohexyl, have high birefringence rate, low-viscosity and the clearing point up to 300 DEG C, can be used for the good high birefringence rate mixture liquid crystal of processability.Be used for developing visible ray, infrared light and laser self-adoptive optical modulator, aspect photonics, have many new application.
Background of invention
Now, liquid crystal flat-panel technique of display has been widely used among social life.Since particularly entering 21 century, because TFT mode LCD is popularized in mobile phone, computer and TV tech, it has become the main flow of flat pannel display.In addition, liquid crystal device, at visible ray, near infrared and laser wavelength as developed aspect the modulator techniques of ADAPTIVE OPTICS SYSTEMS, became the new Application Areas of a kind of liquid crystal device developing rapidly (Wen, C.H. in recent years; W, S.T.Appl.Phys.Lett.2005,86,231104).
TFT liquid-crystal display mainly uses fluorinated liquid crystal material, is because the introducing of fluorine uprises the stability (voltage retention) of liquid crystalline cpd, viscosity step-down, and double refractive inde is low, quite suitable for one-level minimum (requiring △ n=0.1).The nematic liquid crystal that has dielectric anisotropy and be negative value (Δ ε <0) is an important composition colony of liquid crystal material, it can be for vertically aligned (VA), in in-plane switching (IPS) and electrically controlled birefringence mode (ECB) liquid crystal mode, manufacture giant-screen Active Matrix Display.In addition, the negative liquid crystal of high birefringence rate (△ n>0.25) also can be used as the main component of double frequency to row mixture, obtains important application in photonics field.Research is so far learnt, have the liquid crystal that utilizes high birefringence rate only, the liquid crystal compound that just may apply thin as far as possible liquid crystal cell and respond fast, likely can reach high-speed response (2.5 microns of cel-gap, time of response <3ms), thus meet the requirement of the wide band-adaptive optical system of visible ray, near infrared light and laser modulator.Many physicalies of fluorine-containing tolane liquid crystal can meet above requirement.For example high birefringence rate, low-viscosity, nematic phase (working temperature region) is wide etc.Only there is single nematic phase in the fluorine-containing diphenyl acetylene class negative liquid crystal compound that 2 dicyclohexyls of the present invention replace, clearing point temperature is very high simultaneously, can reach 300 DEG C of left and right.Can be used as the high-temperature component of mixed liquid crystal, prepare the negative liquid crystal of very wide thermally-stabilised, the high birefringence rate of good working temperature.
Summary of the invention
The object of the invention is to provide the fluorine-containing negative liquid crystal compound in a kind of Fourth Ring, preparation method and use.
The fluorine-containing negative liquid crystal compound in Fourth Ring of the present invention has following molecular formula:
Fourth Ring of the present invention fluorine-containing negative liquid crystal compou nd synthesis reaction formula is as follows:
Wherein: n=2,3
By 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2, the fluoro-4-phenetole of 3-bis-acetylene, dichloro two (triphenyl phosphorus) palladium, cuprous iodide and triethylamine flow down reaction 1 ~ 5h next time in nitrogen protection;
Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2, the mol ratio of 3-bis-fluoro-4-phenetole acetylene and triethylamine is 1 ~ 1,2:0.8 ~ 1.0:1 ~ 100; Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene mmole, dichloro two (triphenyl phosphorus) palladium milligram weight and cuprous iodide milligram weight ratio are 1:45 ~ 60:50 ~ 100.
Described reaction product through filtering, washing, dry, concentrated, column chromatography or recrystallization purifying processing.
Not only simple synthetic method of the fluorine-containing negative liquid crystal compound in Fourth Ring of the present invention, and can be as the high-temperature component of mixed liquid crystal, the negative liquid crystal of very wide thermally-stabilised, the high birefringence rate of preparation work temperature.
Embodiment
The present invention can be further understood by following embodiment, but content of the present invention can not be limited.Any those skilled in that art, invention simple replacement or the improvement etc. done are all belonged to the technical scheme that the present invention protects within
Embodiment:
Trans with 1-[, trans-4 '-n-propyl (1,1 '-dicyclohexyl)-4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene acetylene) benzene (B) synthesize example:
[1 '-hydroxyl-4 '-(trans-4 " n-propyl cyclohexyl) cyclohexyl] benzene is synthetic
Under nitrogen protection; the magnesium of 2.37g (0.099mol) and the dry tetrahydrofuran (THF) of 100ml are added in the there-necked flask of 250ml; the bromobenzene of 14.85g (0.094mol) is splashed into from dropping funnel; after 5min, heat up; after 30min, drip off; continue to stir 1h, obtain brownish black liquid, stand-by.
Being dissolved in the tetrahydrofuran (THF) of 50ml and adding in the there-necked flask of 250ml by 4 '-n-propyl bicyclohexanone 20.6g (.085mol), the grignard reagent making is splashed into from the normal pressure dropping funnel of 250ml, control temperature below 40 DEG C, 40min drips off.And continuation reaction 3h.Meteorological tracking reacts completely.Drip the hydrochloric acid of 20ml10%, separatory, with the hexane extraction water of 20ml, merges organic phase, uses successively saturated sodium bicarbonate aqueous solution, and the each 20ml washing of salt solution and water, obtains organic phase dry, is spin-dried for, and obtains solid 26g.y：97.1%。
[4 '-(trans-4 " n-propyl cyclohexyl) tetrahydrobenzene-1 '-yl] benzene synthetic
Taking [1 '-hydroxyl-4 '-(trans-4 " n-propyl cyclohexyl) cyclohexyl] benzene of 24.5g (0.078mol) and tosic acid one water complex of 1.6g adds in the there-necked flask of 250ml; add the toluene of 80ml; stirring and refluxing, and use fraction water device water-dividing.React completely, add 30ml water and stir, separatory, uses toluene aqueous layer extracted, merges organic phase.Organic phase is used saturated sodium bicarbonate aqueous solution successively, and salt solution and water washing obtain organic phase dry, are spin-dried for, and use sherwood oil recrystallization, obtain product 18g.y：78%。
Synthesizing of cis-trans configurations mixture 4-n-propyl-{ (dicyclohexyl)-4-yl } benzene
[4 '-(trans-4 " n-propyl cyclohexyl) tetrahydrobenzene-1 '-yl] benzene that takes 18g (0.061mol) is dissolved in the toluene of 150ml; add reactor; add the Pd/C of catalytic amount; be pressed into the hydrogen of appropriate pressure; and at 40 DEG C, stirring reaction spends the night, and reacts completely, and suction filtration is removed solid residue; toluene is removed in underpressure distillation, obtains cis-trans configurations mixture product 17.7g.y：97%。
Synthesizing of 4-n-propyl-{ (trans, trans-dicyclohexyl)-4-yl } benzene
In the there-necked flask of 250ml, cis-trans configurations mixture 4-n-propyl-{ (dicyclohexyl)-4-yl } benzene 17.67g is dissolved in 120ml dimethyl formamide (DMF), then adds potassium tert.-butoxide under nitrogen protection, reflux 5 hours.With chromatogram tracking, treat cis-isomeride be converted into trans after, be chilled to room temperature, add water 150ml and toluene 150ml extraction 2 times.Hydrochloric acid with 10%, saturated sodium bicarbonate aqueous solution washing.After washing, use dried over mgso.Underpressure distillation, except desolventizing, obtains solid residue.With ethyl alcohol recrystallization 2 times, obtain white solid product 16.7g, yield 94%.
Synthesizing of 4-n-propyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene
In the there-necked flask of 100ml, add 4-propyl group-{ (trans, trans-dicyclohexyl)-4-yl } benzene of 5g (16.8mmol), the iodine of 3.05g (12mmol), Periodic acid two water complexs of 3.3g (14.5mmol).Add again 1 of the Glacial acetic acid of 8ml and 10ml, 2-ethylene dichloride, under agitation oil bath reflux 5h.After waiting and reacting completely, be cooled to room temperature, add 10% aqueous solution of sodium bisulfite 100ml, stir, eliminate residual iodine.With toluene extraction, obtain organic phase, with twice of salt washing.By organic phase dried over mgso.Removal of solvent under reduced pressure, obtains solid residue.With ethanol: ethyl acetate (10:1) mixing solutions recrystallization, obtains product 5g.Yield y:70%.
Synthesizing of the fluoro-4-oxyethyl group of 2,3-bis-iodobenzene
By 2 of 10g (0.063mol), 3, the tetrahydrofuran (THF) that-difluoroethoxy benzene and 70ml are dry adds in the there-necked flask of 250ml under nitrogen protection, mechanical stirring, be cooled to below-78 DEG C, drip the n-Butyl Lithium of 40ml (2M), 20min drips off, control temperature and react 1.5h between-70--80 DEG C, automatic heating drips 20g (0.079mol) iodine to-60 DEG C time and is dissolved in the solution of 50mlTHF, 40min drips off, control temperature and react 2h between-60--70 DEG C, stop, automatic heating is to normal temperature, add saturated aqueous ammonium chloride solution 200ml, layering, inorganic phase extracts twice by ethyl acetate, merge organic phase, and wash three times with aqueous solution of sodium bisulfite, wash twice, obtain organic phase anhydrous magnesium sulfate drying, water pump underpressure distillation is except desolventizing, oil pump underpressure distillation, collect 84-88 DEG C/2mmHg of cut, obtain thick product 9.5g, obtain white solid product 7.1g with sherwood oil recrystallization again.Y:39%.1,1-dimethyl-3-(the fluoro-4-phenetole of 2,3-bis-)-2-propine-1-alcohol synthetic
By 2 of 4g (0.014mol); 3-difluoro is to oxyethyl group iodobenzene; 1.5g (0.018mol) 1; 1 dimethyl-2-propine-1-alcohol; dichloro two (triphenyl phosphorus) palladium of 100mg; the cuprous iodide of 120mg and the triethylamine of 80ml add in the there-necked flask of 100ml under nitrogen protection; magnetic agitation, temperature is controlled at about 40 DEG C reaction 3h, and TLC follows the tracks of and reacts completely; cooling; suction filtration, solid is washed by ethyl acetate, obtains mother liquor pressure reducing and steaming solvent; cross pillar with the eluent of ethyl acetate: normal hexane=5:1, obtain yellow liquid product 3.2g.y:95%.
Synthesizing of the fluoro-4-phenetole of 2,3-bis-acetylene
By 1 of 3.29g (13.7mmol), 1-dimethyl-3-(2, the fluoro-4-phenetole of 3-bis-)-2-propine-1-alcohol, the potassium hydroxide of 0.9g (16.1mmol) and the toluene of 80ml add in the single port flask of 100ml, magnetic agitation, the lower reaction 3h that refluxes, TLC follows the tracks of and reacts completely, cooling, suction filtration, solid is washed with toluene, obtains mother liquor pressure reducing and steaming solvent, cross post with the eluent of sherwood oil: ethyl acetate=10:1, obtain yellow liquid, crystallisation by cooling, uses sherwood oil recrystallization, obtain white solid product 1.14g, y:46%.
1-[is trans, trans-4 '-n-propyl or ethyl (1,1 '-dicyclohexyl)-4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene ethynyl) benzene synthetic
By the 4-propyl group of 440mg (1.11mmol) or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2 of 182mg (0.83mmol), the fluoro-4-phenetole of 3-bis-acetylene, dichloro two (triphenyl phosphorus) palladium of 45mg, the cuprous iodide of 100mg and the triethylamine of 60ml add in the there-necked flask of 100ml under nitrogen protection, magnetic agitation, lower reaction 4h refluxes, TLC follows the tracks of and reacts completely, cooling, suction filtration, solid is washed by ethyl acetate, obtaining mother liquor washes with water three times, obtain organic phase anhydrous sodium sulfate drying, pressure reducing and steaming solvent, cross post with the eluent of sherwood oil: toluene=8:1, obtain white solid crude product ethanol/toluene recrystallization, obtain white solid product.
obtain 0.30g.Productive rate: 63%.MS(m/z,%):464.3.3(M+,100.00),464.3(100.00);
1H?NMR(400MHz,CDCl3):δ0.81(t,J＝7.2Hz,5H),0.88-1.01(m,3H),1.08-1.09(m,6H),1.18-1.27(m,2H),1.33-1.41(m,5H),1.65-1.85(m,8H),2.34-2.42(m,1H),4.07(q,J＝7.0Hz,2H),6.60-6.64(m,1H),7.08-7.12(m,3H),7.38(d,J＝8.0Hz,2H)。
The mesomorphic phase temperature (using warm table polarized light microscope observing) of A compound:
Cr154.8℃N303.3℃I300.0℃N142.5℃Cr。
1-[is trans, trans-4 '-ethyl (1,1 '-dicyclohexyl)-4-yl]-4-(4-oxyethyl group-2,3-difluorobenzene ethynyl) benzene (A)
obtain 0.25g, productive rate 59%.MS(m/z,%):450.3(M+,100.00),450.3(100.00);
1H?NMR(400MHz,CDCl3):δ0.78-0.82(m,5H),0.89-1.03(m,3H),1.08-1.19(m,6H),1.33-1.42(m,5H),1.66-1.86(m,8H),2.35-2.42(m,1H),4.07(q,J=7.0Hz,2H),6.60-6.64(m,1H),7.08-7.13(m,3H),7.38(d,J＝8.4Hz,2H)。
The mesomorphic phase temperature (using warm table polarized light microscope observing) of B compound:
Cr146.20℃N298.5℃I293.4℃N133.82℃Cr。
Claims (4)
1. the fluorine-containing negative liquid crystal compound in Fourth Ring, has following molecular formula:
2. a synthetic method for the fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 1, is characterized in that obtaining by the following method:
By 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 2, the fluoro-4-phenetole of 3-bis-acetylene, dichloro two (triphenyl phosphorus) palladium, cuprous iodide and triethylamine flow down reaction 1～5h next time in nitrogen protection;
2 of described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene, 0.83mmol, the mol ratio of 3-bis-fluoro-4-phenetole acetylene and triethylamine is 1～1.2:0.8～1.0:1～100; Described 4-propyl group or ethyl-{ (trans, trans-dicyclohexyl)-4-yl } iodobenzene mmole, dichloro two (triphenyl phosphorus) palladium milligram weight and cuprous iodide milligram weight ratio are 1:45～60:50～100.
3. a synthetic method for the fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 2, it is characterized in that product through filtering, washing, dry, concentrated, column chromatography and recrystallization purifying processing.
4. a purposes for the fluorine-containing negative liquid crystal compound in Fourth Ring as claimed in claim 1, is characterized in that the high-temperature component as mixed liquid crystal, the negative liquid crystal of very wide thermally-stabilised, the high birefringence rate of preparation work temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210585813.2A CN103012083B (en) | 2012-12-28 | 2012-12-28 | Dicyclohexyl fluorinated tolane negative liquid crystal, and synthesis method and application thereof |
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| CN1911888A (en) * | 2005-08-12 | 2007-02-14 | 石家庄永生华清液晶有限公司 | 2,3,2,'3' tetrafluoro diphenyl acetylene derivative, its composition, preparation method and use |
| CN1923951A (en) * | 2006-10-09 | 2007-03-07 | 西安近代化学研究所 | Diphenylacetylene liquid crystal compounds |
| CN102408284A (en) * | 2010-09-21 | 2012-04-11 | 江苏广域化学有限公司 | Method for converting cis-substituted cyclohexyl in organic molecule into trans-substituted cyclohexyl |
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| CN1923951A (en) * | 2006-10-09 | 2007-03-07 | 西安近代化学研究所 | Diphenylacetylene liquid crystal compounds |
| CN102408284A (en) * | 2010-09-21 | 2012-04-11 | 江苏广域化学有限公司 | Method for converting cis-substituted cyclohexyl in organic molecule into trans-substituted cyclohexyl |
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