CN103214353A - Alkene-terminated polyfluorinated diaryl acetylene liquid crystal compound and preparation method thereof - Google Patents
Alkene-terminated polyfluorinated diaryl acetylene liquid crystal compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an alkene-terminated polyfluorinated diaryl acetylene liquid crystal compound and a synthesis method thereof. The compound is shown in the structural formula I as shown in the specification, wherein in the structural formula I, (F)m and (F)n both refer to fluorine atom substitutes; m and n refer to the substitute number of fluorine atoms, and the value thereof is 0-2; x refers to the number of connected methylene, and the value thereof is 0-3; and R refers to C1-C15 alkyls, C1-C15 alkenyls, C1-C15 alkoxy and C1-C15 enyloxy. According to the invention, because the compound is synthesized through adopting classic reactions such as nucleophilic substitution, coupling reaction, and the like, the operation is simple, and the yield and purity of products are high; and the compound has the advantages of large negative dielectric anisotropy, low melting point, wide liquid crystal phase interval, large double refraction, and the like, and can be applied to a dual-frequency liquid crystal display mode.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of end alkene polyfluoro diaryl ethine liquid crystal compound and preparation method thereof.
Background technology
Dual-frequency liquid crystal (DFLCs) can reduce the time of response T of liquid crystal simultaneously
OnWith relaxation time T
Off, have special advantages in the raising response speed of liquid crystal, aspect large screen television, have good application prospects.Dual-frequency liquid crystal material is to be the main body prescription with the negative dielectric anisotropic compound, adds positive dielectric anisotropy compound and forms.The side direction polyfluoro replaces terphenyl compounds, show bigger negative dielectric anisotropic, higher advantages such as double refraction, but its fusing point is higher, and narrower between the phase change zone, is difficult to satisfy the application in dual-frequency liquid crystal.Side direction polyfluoro substituted diaryl acetylene class liquid crystalline cpd shows big negative dielectric anisotropic, between high double refraction and wide phase change zone, can be applicable to the dual-frequency liquid crystal display format, and can obtain response speed faster.At present report use this maximum compounds mainly with alkyl or alkoxyl group be end group liquid crystalline cpd (Liq.Cryst.2012,39,957-963.), as following compound:
This compounds of development research at present, its dielectric anisotropy be big (5～-6), but fusing point and fusion enthalpy height, and viscosity is relatively large, needs to add low melting point, low viscous liquid crystal compound, reduces the fusing point and the viscosity of mixed crystal.And will cause liquid crystal clearing point and birefringent reduction like this, thereby influence between the phase change zone of liquid crystal and response speed.
Summary of the invention
(1) technical problem that will solve
The method that the technical problem to be solved in the present invention provides end alkene polyfluoro diaryl ethine liquid crystal compound and prepares above-claimed cpd.
(2) technical scheme
The present invention relates to a kind of end alkene polyfluoro diaryl ethine liquid crystal compound, the structural formula of this compound is suc as formula shown in the I:
(F) m, (F) n represent that all fluorine atom replaces in the formula, m, n represent the replacement number of fluorine atom, and its value is 0～2, and x represents to connect the number of methylene radical, its value is 0～3, and R represents C1～C15 alkyl, C1～C15 thiazolinyl, C1～C15 alkoxyl group, C1～C15 alkene oxygen base.
Passable in the end alkene polyfluoro diaryl ethine liquid crystal compound of the present invention, the value of m is 0, and the value of n is 0 or 2, and the value of x is 0 or 1.
Passable in the end alkene polyfluoro diaryl ethine liquid crystal compound of the present invention, the value of m is 2, and the value of n is 0 or 2, and the value of x is 0 or 1.
In the end alkene polyfluoro diaryl acetylene compound of the present invention, the carbon atom of R can be 2～5.
End alkene polyfluoro diaryl acetylene compound of the present invention, R can be the straight chained alkyl of C2～C5.
The invention still further relates to the concrete liquid crystalline cpd of a plurality of end alkene polyfluoro diaryl acetylenes, for, 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-propyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-butyl phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-amyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-ethylphenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-propyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-butyl phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-ethylphenyl-4 '-[3,3-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene; 4-ethylphenyl-4 '-[1,1-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
(3) beneficial effect
Performances such as containing the side direction polyfluoro diaryl acetylene compound of holding alkene and have that fusing point is low, clearing point is high, the interval broad of mesomorphic phase, double refraction are big is introduced the negative dielectric anisotropic that fluorine atom can further improve liquid crystal at the alkene end.This compounds can directly dispose liquid crystal compound, is not adding any low melting point, under the situation of low viscosity liquid crystal compound, realizes between the temperature range-20 ℃ of mixed liquid crystal～100 ℃.
The method for preparing end alkene polyfluoro diaryl ethine liquid crystal compound among the present invention adopts classical reaction such as nucleophilic substitution, linked reaction, and is simple to operate, product yield and purity height.
Description of drawings
Fig. 1 is the liquid crystalline cpd of embodiment 1 preparation
13The C nmr spectrum.
Fig. 2 is the liquid crystalline cpd of embodiment 1 preparation
1The H nmr spectrum.
Fig. 3 is the differential scanning calorimetric curve of the liquid crystalline cpd of embodiment 1 preparation.
Fig. 4 is the schlieren texture figure in the time of 153 ℃ in the liquid crystalline cpd temperature-fall period of embodiment 1 preparation.
Fig. 5 is the liquid crystalline cpd of embodiment 2 preparation
13The C nmr spectrum.
Fig. 6 is the liquid crystalline cpd of embodiment 2 preparation
1The H nmr spectrum.
Fig. 7 is the differential scanning calorimetric curve of the liquid crystalline cpd of embodiment 2 preparations.
Fig. 8 is the schlieren texture figure in the time of 147 ℃ in the liquid crystalline cpd temperature-fall period of embodiment 2 preparation.
Embodiment
For making purpose of the present invention, content and advantage clearer,, the specific embodiment of the present invention is described in further detail below in conjunction with drawings and Examples.
With preparation 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C2, the value of m, n is 0, the value of x is 0, and is raw materials used and preparation method thereof as follows:
Synthesizing of step 1:4-ethylbenzene boric acid: under nitrogen protection; in the 500mL there-necked flask that constant pressure funnel, thermometer and magnetic stir bar are housed, add 4-ethyl bromobenzene 55.2g (0.30mol); in reaction flask, inject 250mL exsiccant tetrahydrofuran (THF) respectively and inject 144mL (2.5mol/L, 0.36mol) n-butyllithium solution by syringe to constant pressure funnel.Reaction system is cooled to-78 ℃ with liquid nitrogen, begin to drip n-butyllithium solution, dropwise the back and under this temperature, continue reaction 1h, dropwise drip 69.0g (0.30mol) tri-n-butyl borate, the control rate of addition, system temperature is controlled at below-75 ℃, dropwises the back and continue reaction 1h, be warming up to room temperature naturally at-75 ℃.Drip the hydrochloric acid of 150mL10%, continue to stir 1h.Tell organic layer, water layer ethyl acetate extraction 3 times merge organic phase, and are washed to neutrality, and anhydrous magnesium sulfate drying filters, and removes solvent under reduced pressure, gets the white powder solid.
Step 2:4-ethyl-2 '; 3 '-two fluoro-1; 1 '-biphenyl synthetic: under nitrogen protection; in the 500mL there-necked flask that thermometer, prolong and magnetic stir bar are housed, add 33.0g (0.21mol) 4-ethylbenzene boric acid, 38.6g (0.20mol) 2; 3-difluoro bromobenzene, 58.0g (0.42mol) salt of wormwood, 240mL N, dinethylformamide and 80mL H
2O is warming up to 80 ℃, treat that solid dissolves fully after, add 2.3g (2mmol) four triphenylphosphines and close palladium, 80 ℃ of reaction 8h add the sherwood oil dilution, tell organic phase, water layer petroleum ether extraction three times merge organic phase, and be washed to neutrality, anhydrous magnesium sulfate drying filters, and removes solvent under reduced pressure, collect 110～115 ℃/40Pa cut, get colorless oil.
Step 3:4-ethyl-2 '; 3 '-two fluoro-4 '-iodo-1; 1 '-biphenyl synthetic: under argon shield; in the 500mL there-necked flask that constant pressure funnel, thermometer and magnetic stir bar are housed, add 34.1g (0.15mol) 4-ethyl-2 '; 3 '-two fluoro-1; 1 '-biphenyl, in reaction flask, inject 200mL exsiccant tetrahydrofuran (THF) respectively and inject 72mL (2.5mol/L, 0.36mol) n-butyllithium solution by syringe to constant pressure funnel.Reaction system is cooled to-78 ℃ with liquid nitrogen, begin to drip n-butyllithium solution, dropwise the back and under this temperature, continue reaction 1h, dropwise drip the 150mL dry tetrahydrofuran solution that is dissolved with 45.7g (0.18mol) iodine, the control rate of addition, system temperature is controlled at below-75 ℃, dropwises the back and continue reaction 1h, be warming up to room temperature naturally at-75 ℃.Reaction solution is slowly injected frozen water, solution is transferred to neutrality, add petroleum ether extraction, water layer petroleum ether extraction three times with S-WAT, merge organic layer, and be washed to neutrality, anhydrous magnesium sulfate drying, filter, remove solvent under reduced pressure, crude product gets white solid with ethyl alcohol recrystallization.
Step 4:4-[(2-tetrahydropyrans) oxygen] bromobenzene synthetic: in the 500mL there-necked flask that thermometer, magnetic stir bar, prolong are housed, add 52.0g (0.25mol) 4-bromo-2,3-difluorophenol, 31.9g (0.38mol) 3,4-2H-dihydropyrane, 5.0g (0.02mol) 4-toluene sulfonic acide pyridine and 250mL anhydrous methylene chloride, stirring at normal temperature reaction 4h.Be cooled to room temperature, thin up is told organic layer, and water layer dichloromethane extraction three times merge organic phase, and are washed to neutrality, and anhydrous magnesium sulfate drying filters, and removes solvent under reduced pressure, gets oily liquids.
Step 5:4-[(2-tetrahydropyrans) oxygen]-2; synthesizing of 3-difluoro phenylacetylene: under nitrogen protection; in the 500mL there-necked flask that thermometer, prolong, magnetic stir bar are housed; add 58.4g (0.2mol) 4-[(2-tetrahydropyrans) oxygen] bromobenzene, 20.2g (0.24mol) 2-methyl-3-butyne-2-alcohol, 1.9g (10mmol) cuprous iodide, 4.2g (16mmol) triphenylphosphine and 250mL triethylamine; be warming up to 80 ℃; add 2.3g (2mmol) four triphenylphosphines and close palladium, 80 ℃ are continued stirring reaction 8h down.Question response liquid is cooled to room temperature, uses the dichloromethane extraction reaction solution, and water layer dichloromethane extraction three times merge organic phase, and with saturated ammonium chloride solution washing 3 times, anhydrous magnesium sulfate drying filters.Remove solvent under reduced pressure, get the oily crude product.Crude product is joined in the single port flask that prolong is housed, add 200mL toluene again, 4.0g (0.1mol) sodium hydroxide and 0.4g (2mmol) 2, the 6-ditertbutylparacresol, 100 ℃ are reacted 4h down, change reaction unit into water distilling apparatus, normal pressure steams toluene, 110～115 ℃/10Pa cut is collected in underpressure distillation again, gets colourless oil liquid.
Step 6:4-ethylphenyl-4 '-[(2-tetrahydropyrans) oxygen]-2; 3; 2 '; 3 '-tetrafluoro diphenyl acetylene synthetic: under nitrogen protection; to thermometer is housed; prolong; in the 250mL there-necked flask of magnetic stir bar; add 2.38g (10mmol) 4-[(2-tetrahydropyrans) oxygen]-2; 3-difluoro phenylacetylene; 4.12g (12mmol) 4-ethyl-2 '; 3 '-two fluoro-4 '-iodo-1; 1 '-biphenyl; 0.10g (0.5mmol) cuprous iodide; 0.52g (2mmol) triphenylphosphine and 25mL triethylamine; be warming up to 80 ℃, add 0.29g (0.25mmol) four triphenylphosphines and close palladium, 80 ℃ are continued reaction 8h down.Question response liquid is cooled to room temperature, uses the dichloromethane extraction reaction solution, and water layer dichloromethane extraction three times merge organic phase, and with saturated ammonium chloride solution washing 3 times, anhydrous magnesium sulfate drying filters, and removes solvent under reduced pressure, gets the white solid crude product.With the sherwood oil is eluent, and chromatography column separates purifies, and the sherwood oil recrystallization gets the white powder solid.
Step 7:4-ethylphenyl-4 '-hydroxyl-2; 3; 2 '; 3 '-tetrafluoro diphenyl acetylene synthetic: under nitrogen protection, in the 125mL there-necked flask that thermometer, prolong, magnetic stir bar are housed, add 3.63g (8mmol) 4-ethylphenyl-4 '-[(2-tetrahydropyrans) oxygen]-2; 3; 2 ', 3 '-tetrafluoro diphenyl acetylene, 0.09g (0.8mmol) trifluoroacetic acid and 30mL anhydrous methylene chloride, ice bath stirring reaction 2h.Reaction solution is eluent with the methylene dichloride, and the flash chromatography post separates removes trifluoroacetic acid.With the sherwood oil is eluent, add depress rapid column chromatography separate remove raw material after, be that eluent separation and purification reaction solution is eluent with the methylene dichloride again with the methylene dichloride, remove solvent under reduced pressure under the normal temperature after, white solid.
Step 8:4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene synthetic: in the 125mL there-necked flask that thermometer, prolong, magnetic stir bar are housed, adding 1.85g (5mmol) 4-ethylphenyl-4 '-hydroxyl-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene, 1.38g (10mmol) Anhydrous potassium carbonate, 0.91g (7.5mmol) 3-bromopropylene, 10mL tetrahydrofuran (THF) and water 10mL, 65 ℃ of stirring reaction 4h.Question response liquid is cooled to room temperature, and dichloromethane extraction is told organic layer, and water layer merges organic layer with dichloromethane extraction 3 times, and anhydrous magnesium sulfate drying filters, steam desolventize the crude product sample.With the sherwood oil is eluent, and chromatography column separates purifies, and the sherwood oil recrystallization gets white crystal.
Gained 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene carries out structure, performance with the hot platform polarizing microscope of Avance300MHz type nuclear magnetic resonance analyser, DSC-60 type differential scanning calorimeter and XPN-300E type and liquid crystal state texture characterizes, and the results are shown in Figure 1～5.
13C-NMR (CDCl
3Be solvent, in be designated as TMS, 75MHz, ppm): 15,28,70,86,88,105,109,112,118,124,127,127,127,127,128,128,131,131,132,139,142,144,146,149,150,150,153,153.
1H-NMR (CDCl
3Be solvent, in be designated as TMS, 300MHz, ppm): 1.24,2.65,4.61,5.31,5.96,6.68,7.12,7.45.
Fig. 1's
13In the C nuclear magnetic resonance map, 153,153,150,150,149,146,142, the existence of four C-F of eight peaks explanations of 139ppm, and coupling constant meets carbon fluorine coupling rule, itself and 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene in the carbon-fluorine bond number conform to, 144,118ppm is ethylene linkage two peaks of allyloxy, and 70ppm is the methylene peak of allyloxy.Fig. 2's
1In the H nuclear magnetic resonance map, 7.45,7.12,6.68ppm three peaks are fragrant hydrogen absorption peak, 5.96,5.31ppm is the hydrogen absorption peak of allyloxy ethylene linkage, 4.61ppm is the hydrogen absorption peak of methylene radical in the allyloxy.In conjunction with the analytical results of Fig. 1 and Fig. 2, the compound that embodiment 1 preparation is described be 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
As seen from Figure 3, prepared 4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 ' tetrafluoro diphenyl acetylene has mesomorphic phase, and the mesomorphic phase interval is 68～178 ℃; As seen from Figure 4, this compound has typical nematic phase.
With preparation 4-propyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C3, the value of m, n is 0, the value of x is 0, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-propyl group bromobenzene, and other steps are identical with corresponding embodiment, be prepared into 4-propyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-propyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-transformation temperature of tetrafluoro diphenyl acetylene is: Cr62.9N191.7I.
With preparation 4-butyl phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C4, the value of m, n is 0, the value of x is 0, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-butyl bromobenzene, and other steps are identical with corresponding embodiment, are prepared into 4-butyl phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-butyl phenyl-4 '-allyloxy-2,3, the transformation temperature of 2 ', 3 '-tetrafluoro diphenyl acetylene is: Cr40.6N168.2I.
With preparation 4-amyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C5, the value of m, n is 0, the value of x is 0, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-amylic phenyl-bromide, and other steps are identical with corresponding embodiment, is prepared into 4-amyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-amyl group phenyl-4 '-allyloxy-2,3, the transformation temperature of 2 ', 3 '-tetrafluoro diphenyl acetylene is: Cr44.8N170.6I.
With preparation 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C5, the value of m, n is 0, the value of x is 1, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-amylic phenyl-bromide, and the 3-bromopropylene is replaced with equimolar 4-bromo-1-butylene, other steps are identical with embodiment 1, be prepared into 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
Gained 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene Avance300MHz type nuclear magnetic resonance analyser, DSC-60 type differential scanning calorimeter and the hot platform polarizing microscope of XPN-300E type carry out structure, performance and liquid crystal state texture and characterize, and the results are shown in Figure 5～8.
13C-NMR (CDCl
3Be solvent, in be designated as TMS, 75MHz, ppm): 14,23,31,32,33,36,69,86,88,105,109,112,118,125,127,127,127,127,128,128,131,131,134,139,142,143,146,149,150,150,153,153.
1H-NMR (CDCl
3Be solvent, in be designated as TMS, 300MHz, ppm): 0.88,1.34,1.62,2.56,4.06,5.11,5.81,6.66,7.12,7.44.
Fig. 5's
13In the C nuclear magnetic resonance map, 153,153,150,150,149,146,142, the existence of four C-F of eight peaks explanations of 139ppm, and coupling constant meets carbon fluorine coupling rule, itself and 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene in the carbon-fluorine bond number conform to, 143,118ppm is ethylene linkage two peaks of allyloxy, and 69ppm is the methylene peak of allyloxy.Fig. 6's
1In the H nuclear magnetic resonance map, 7.44,7.12,6.66ppm three peaks are fragrant hydrogen absorption peak, 5.81,5.11ppm is the hydrogen absorption peak of allyloxy ethylene linkage, 4.06ppm is the hydrogen absorption peak of methylene radical in the allyloxy.In conjunction with the analytical results of Fig. 5 and Fig. 6, the compound that embodiment 2 preparation is described be 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
As seen from Figure 7, prepared 4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene has mesomorphic phase, and the mesomorphic phase interval is 48～165 ℃; As seen from Figure 8, this compound has typical nematic phase.
With preparation 4-ethylphenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C2, the value of m, n is 0, the value of x is 1, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 3-bromopropylene is replaced with equimolar 4-bromo-1-butylene, and other steps are identical with embodiment 1, be prepared into 4-ethylphenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-ethylphenyl-4 '-alkene butoxy-2,3,2 ', 3 '-transformation temperature of tetrafluoro diphenyl acetylene is: Cr77.6N166.1I.
With preparation 4-propyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C3, the value of m, n is 0, the value of x is 1, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-propyl group bromobenzene, and the 3-bromopropylene is replaced with equimolar 4-bromo-1-butylene, other steps are identical with embodiment 1, be prepared into 4-propyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-propyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-transformation temperature of tetrafluoro diphenyl acetylene is: Cr53.6N177.1I.
With preparation 4-butyl phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C4, the value of m, n is 0, the value of x is 1, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 4-ethyl bromobenzene is replaced with equimolar 4-butyl bromobenzene, and the 3-bromopropylene is replaced with equimolar 4-bromo-1-butylene, other steps are identical with embodiment 1, be prepared into 4-butyl phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
4-butyl phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-transformation temperature of tetrafluoro diphenyl acetylene is: Cr48.3N163.1I.
Embodiment 9
With preparation 4-ethylphenyl-4 '-[3,3-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C2, the value of m is 2, the value of n is 0, the value of x is 0, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 3-bromopropylene is with equimolar 3-bromo-3, and 3-difluoro propylene is replaced, and other steps are identical with embodiment 1, be prepared into 4-ethylphenyl-4 '-[3,3-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
Embodiment 10
With preparation 4-ethylphenyl-4 '-[1,1-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene is an example, wherein R is the straight chained alkyl of C2, the value of m is 0, the value of n is 2, the value of x is 0, and is raw materials used and preparation method thereof as follows:
In embodiment 1, used 3-bromopropylene is with equimolar 3-bromo-1, and 1-difluoro propylene is replaced, and other steps are identical with corresponding embodiment, be prepared into 4-ethylphenyl-4 '-[1,1-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvement and distortion, these improvement and distortion also should be considered as protection scope of the present invention.
Claims (6)
1. hold alkene polyfluoro diaryl ethine liquid crystal compound, it is characterized in that the structural formula of this compound is suc as formula shown in the I:
(F) m, (F) n represent that all fluorine atom replaces in the formula, and m, n represent the replacement number of fluorine atom, and its value is 0～2, and x represents to connect the number of methylene radical, and its value is 0～3, and R represents C
1～C
15Alkyl, C
1～C
15Thiazolinyl, C
1～C
15Alkoxyl group, C
1～C
15Alkene oxygen base.
2. end alkene polyfluoro diaryl ethine liquid crystal compound according to claim 1, it is characterized in that: the value of described m is 0, and the value of n is 0 or 2, and the value of x is 0 or 1.
3. end alkene polyfluoro diaryl ethine liquid crystal compound according to claim 1, it is characterized in that: the value of described m is 2, and the value of n is 0 or 2, and the value of x is 0 or 1.
4. according to any described end alkene polyfluoro diaryl acetylene compound in the claim 1～3, it is characterized in that: the carbon atom of described R is 2～5.
5. according to the end alkene polyfluoro diaryl acetylene compound shown in the claim 4, it is characterized in that: described R is C
2～C
5Straight chained alkyl.
6. hold alkene polyfluoro diaryl ethine liquid crystal compound, for,
4-ethylphenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-propyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-butyl phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-amyl group phenyl-4 '-allyloxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-ethylphenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-propyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-butyl phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-amyl group phenyl-4 '-alkene butoxy-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-ethylphenyl-4 '-[3,3-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene;
4-ethylphenyl-4 '-[1,1-difluoro allyloxy]-2,3,2 ', 3 '-tetrafluoro diphenyl acetylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105294526A (en) * | 2015-09-10 | 2016-02-03 | 西安近代化学研究所 | High-birefringence liquid crystal compound, preparing method and composition of high-birefringence liquid crystal compound |
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| JP2019525462A (en) * | 2016-07-07 | 2019-09-05 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Electronic switching element |
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| US11522141B2 (en) | 2016-07-07 | 2022-12-06 | Merck Patent Gmbh | Electronic switching element |
| WO2021253624A1 (en) * | 2020-06-16 | 2021-12-23 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition and liquid crystal display element or liquid crystal display |
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