CN1923951A - Diphenylacetylene liquid crystal compounds - Google Patents
Diphenylacetylene liquid crystal compounds Download PDFInfo
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- CN1923951A CN1923951A CN 200610140460 CN200610140460A CN1923951A CN 1923951 A CN1923951 A CN 1923951A CN 200610140460 CN200610140460 CN 200610140460 CN 200610140460 A CN200610140460 A CN 200610140460A CN 1923951 A CN1923951 A CN 1923951A
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Abstract
The invention discloses a diphenylacetylene LCD compound to increase negative dielectric aeolotropic value, which possesses structural formula as formula (I), wherein R is C1-9 straight chain normal paraffin; R' is C1-3 straight chain normal paraffin or alkoxy.
Description
Technical field
The present invention relates to a kind of diphenylacetylene liquid crystal compounds, be mainly used in liquid-crystal display.
Technical background
Along with the continuous development of lcd technology, liquid-crystal display has not only occupied most markets of tabletop display, and large-sized dull and stereotyped LCD TV is also popularized rapidly.Compare with tabletop display, large-sized dull and stereotyped LCD TV is in order to satisfy the requirement of high-speed motion picture, must have higher contrast gradient, wide as far as possible angle of visibility, quicker response.The technique of display of liquid crystal display television by using mainly contains TN-TFT, IPS and three kinds of display formats of VA-TFT at present.The TN-TFT pattern is a kind of display format of being used widely the earliest, and the visual angle is little, response speed waits problem slowly but exist.IPS pattern and VA-TFT pattern have wide visual angle, the fast characteristics of response speed, are the main display formats of LCD TV.
The VA-TFT pattern requires liquid crystal material to have big negative dielectric anisotropic value and low viscosity, to improve response speed, increase contrast gradient and to reduce driving voltage.And, as the TFT type of drive, also require liquid crystal material to have high voltage retention (V.H.R).
Driving voltage (the V of liquid-crystal display
Th) can be represented by the formula with the relation of liquid crystal material:
V
th＝π(K/ε
0Δε)
1/2
K is the elastic constant of liquid crystal material, ε
0Be permittivity of vacuum, Δ ε is the dielectric anisotropy value of liquid crystal material.As can be seen, elastic constant that can be by reducing liquid crystal material and increase the driving voltage that specific inductivity reduces liquid-crystal display.But the elastic constant of control liquid crystal material is difficulty very, so generally reduce driving voltage by the dielectric anisotropy value that increases liquid crystal material.
Dielectric radio in the liquid crystal molecule on the long axis direction is ε
∥, the dielectric radio of short-axis direction is ε
⊥, the difference of the two is dielectric anisotropy value Δ ε:
Δε＝ε
∥-ε
⊥
Traditional TN-TFT and IPS pattern all adopt the liquid crystal material of positive dielectric anisotropy, i.e. Δ ε＞0.In order to satisfy the requirement of Δ ε＞0, generally take on the long axis direction of liquid crystal molecule to introduce and have strong polar group.And the liquid crystal material that the VA-TFT pattern requires to be adopted has negative dielectric anisotropy＜0, need promptly introduce groups such as strong polar fluorine atom or cyano group on the side direction of molecule at the short-axis direction of molecule.Though it is bigger to contain the liquid crystalline cpd negative dielectric anisotropic value of side direction cyano group replacement, its resistivity is low, and application is restricted.The liquid crystalline cpd that the side direction fluorine atom replaces has resistivity height, characteristics that polarity is bigger, is suitable as the liquid crystal material of VA-TFT display format.
DE3906058 discloses a class and has had 2, and 3-difluorophenol esters liquid crystal compound is introduced 2 fluorine atoms in the molecule side direction, obtains bigger dielectric anisotropy.But esters liquid crystal compound resistivity is lower, and application is restricted.
US6348244 discloses has 2, the liquid crystalline cpd of 3-DfBP hexanaphthene:
This compounds resistivity height is stablized, and is used widely at present.But this compounds viscosity is higher relatively, causes liquid crystal response speed slower.
DE4444813 discloses has 2, and the diphenylacetylene liquid crystal compounds that the 3-difluoro replaces is introduced acetylene bond in this compounds molecular skeleton, and viscosity is low, and the mesomorphic phase temperature range is big, but its negative dielectric anisotropic value is less than normal, uses and is subjected to certain restriction.
Summary of the invention
The objective of the invention is provides a kind of negative dielectric anisotropic value big diphenylacetylene liquid crystal compounds in order to solve known tolane liquid crystal negative dielectric anisotropic defective less than normal.
In order to realize purpose of the present invention, Molecular Structure Design of the present invention adopts in the two fluorine substituted diphenyl acetylene structures of side direction and introduces the 3rd side direction fluorine atom, make and obtain bigger dielectricity ε ⊥ on the short-axis direction of molecule, to increase the purpose of its negative dielectric anisotropic value, has the wide advantage of mesomorphic phase temperature range simultaneously.The The compounds of this invention structure is represented with following general formula:
Wherein R is the straight chained alkyl of carbon number 1～9, for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-heptyl, n-octyl or n-nonyl.R is preferably the straight chained alkyl of carbon number 2～7, the straight chained alkyl of carbon number 2～5, and R is ethyl more preferably.
Wherein R ' is the straight chained alkyl or the alkoxyl group of carbon number 1～3, for example methyl, ethyl, n-propyl or methoxyl group, oxyethyl group, positive propoxy.R ' is preferably the alkyl or the alkoxyl group of carbon number 1～2, and R ' is the alkoxyl group of carbon number 1～2 more preferably, and R ' is methoxyl group more preferably.
The preferred diphenylacetylene liquid crystal compounds of the present invention, R are ethyl, and R ' is a methoxyl group.
Liquid crystalline cpd mesomorphic phase a wider range of the present invention, the negative dielectric anisotropic value is big, will be used widely in liquid-crystal display and optical communication technology field.
The present invention adopts synthetic route as follows:
(1) preparation of intermediate 4-(trans-the 4-alkyl-cyclohexyl)-2-fluorine iodobenzene
(2) intermediate 4-alkyl-2,3-difluoro phenylacetylene and 4-alkoxyl group-2, the preparation of 3-difluoro phenylacetylene:
R ' is an alkyl:
R ' is an alkoxyl group:
(3) target product
Embodiment
Below in conjunction with specific embodiment the present invention is described in further details.
Embodiment 1
4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoroanisole synthetic
(1) 4-(trans-4-ethyl cyclohexyl)-2-fluorine iodobenzene is synthetic
3-(trans-the 4-alkyl-cyclohexyl) fluorobenzene prepares according to EP 0194879 disclosed method.
3-(trans-4-ethyl cyclohexyl) fluorobenzene 40g and 43.5g potassium tert.-butoxide are put into exsiccant 1L four-hole bottle; under nitrogen protection, add 150mL exsiccant tetrahydrofuran (THF); be cooled to-80 ℃ with cooled with liquid nitrogen, begin to drip the hexane solution of 103mL 2.25mol/L n-Butyl Lithium, about 1h drips off.Drip off the back and keep stirring reaction 2.5h under this temperature, remain on then and slowly drip the mixing solutions of the 100mL exsiccant tetrahydrofuran (THF) of refrigerative 51.2g iodine in advance under-85～-90 ℃, drip off the back and be warming up to room temperature naturally.Add the washing of 100ml 10% sodium thiosulfate solution, get organic layer, use anhydrous magnesium sulfate drying.Remove solvent under reduced pressure, get yellow liquid 42g, yield 65%.
Structure is identified:
Ultimate analysis:
Theoretical value: C50.62, H5.46, F5.72, I38.20
Measured value: C50.65, H5.49, F5.70, I38.16
IR (pressing potassium bromide troche, wave number): 3021,2959,1632,1521,1479,1296,994,806,821,704
1H-NMR(500MHz，CDCl
3，δ)：0.91(3H，t)；0.99～1.07(2H，m)；1.16～1.29(2H，m)；1.37～1.45(2H，m)；1.53～1.65(1H，m)；1.88～1.90(4H，d)；2.47(1H，tt)；6.9(1H，td)；7.3(1H，td)；7.5(1H，t)。
MS：332.04(M
+)。
Confirmed that the material that above-mentioned reaction obtains is 4-(trans-4-ethyl cyclohexyl)-2-fluorine iodobenzene really.
Use 4-(trans-4-n-propyl cyclohexyl)-2-fluorine iodobenzene, 4-(trans-4-normal-butyl cyclohexyl)-2-fluorine iodobenzene, 4-(trans-4-n-pentyl cyclohexyl)-2-fluorine iodobenzene, 4-(trans-4-n-hexyl cyclohexyl)-2-fluorine iodobenzene or 4-(trans-4-n-octyl cyclohexyl)-2-fluorine iodobenzene to substitute 4-(trans-4-ethyl cyclohexyl)-2-fluorine iodobenzene respectively, adopting uses the same method synthesizes:
4-(trans-4-n-propyl cyclohexyl)-2-fluorine iodobenzene;
4-(trans-4-normal-butyl cyclohexyl)-2-fluorine iodobenzene;
4-(trans-4-n-pentyl cyclohexyl)-2-fluorine iodobenzene;
4-(trans-4-n-hexyl cyclohexyl)-2-fluorine iodobenzene;
4-(trans-4-n-octyl cyclohexyl)-2-fluorine iodobenzene.
Synthesizing of (2) 2,3-two fluorobenzoic boric acids
In the 500mL there-necked flask that thermometer, agitator are housed, add exsiccant tetrahydrofuran (THF) 200ml, exsiccant Tetramethyl Ethylene Diamine 50ml, 1,2-Difluorobenzene 23g, cooled with liquid nitrogen is cooled to-78 ℃, and dripping concentration is the n-Butyl Lithium hexane solution 100mL of 2.2M, drips off back insulation reaction 2 hours.Dropping is dissolved with the 150mL dry tetrahydrofuran solution of 70g tributyl borate, drips off the back and is warming up to room temperature naturally.Add 10% hydrochloric acid 100ml, stirred 1 hour.Get organic layer, remove solvent under reduced pressure, get white solid 28.5g, yield 91%.
Synthesizing of (3) 2,3-difluorophenols
In the 500mL there-necked flask that thermometer, agitator, reflux condensing tube are housed, add 2,3-two fluorobenzoic boric acid 32g, ether 200ml drips 10% hydrogen peroxide 50ml, back flow reaction 2 hours.Tell organic layer, water layer 100ml extracted with diethyl ether.Merge organic layer, the anhydrous magnesium sulfate drying organic layer.Steaming desolventizes, and underpressure distillation is collected 80～82 ℃/75mmHg cut, yield 82%.
Synthesizing of (4) 2,3-difluoroanisoles
In the 500mL there-necked flask that thermometer, agitator, reflux condensing tube are housed, add 2,3-difluorophenol 26g, 50% aqueous sodium hydroxide solution drips methyl-sulfate 25g, back flow reaction 2 hours.Add the 100ml petroleum ether extraction, be washed to neutrality, anhydrous magnesium sulfate drying.Steaming desolventizes, and underpressure distillation is collected 88～90 ℃/37mmHg cut, yield 88%.
Synthesizing of (5) 2,3-difluoro ethers
In the 500mL there-necked flask that thermometer, agitator, reflux condensing tube are housed, add 2,3-difluorophenol 26g, monobromethane 32g, Anhydrous potassium carbonate 48g, dehydrated alcohol 200ml, back flow reaction 8 hours.Cooling is filtered, and steams and removes ethanol, gets oily liquids.Underpressure distillation is collected 97～99 ℃/37mmHg cut, productive rate 86%.
Replace monobromethane with n-propyl bromide, adopting uses the same method synthesizes 2, the positive propyl phenyl ether of 3-difluoro.
Synthesizing of (6) 2,3-two fluoro-4-iodanisols
In the 500mL there-necked flask that thermometer, feed hopper, agitator are housed; nitrogen protection adds exsiccant tetrahydrofuran (THF) 200ml down; exsiccant Tetramethyl Ethylene Diamine 50ml; 2; 3-difluoroanisole 29g; liquid nitrogen cooling is to-78 ℃, and dripping concentration is the n-Butyl Lithium hexane solution 100mL of 2.2M, drips off back insulation reaction 2 hours.Dropping is dissolved with the 150mL dry tetrahydrofuran solution of 50g iodine, drips off the back and is warming up to room temperature naturally.Add the washing of 100ml 10% sodium thiosulfate solution, tell organic layer, anhydrous magnesium sulfate drying.Remove solvent under reduced pressure, ethyl alcohol recrystallization gets pale yellow crystals 40g, yield 74%.
Use 2 respectively, 3-difluoro ether or 2, the positive propyl phenyl ether of 3-difluoro replaces 2, the 3-difluoroanisole, same method synthesizes:
2,3-two fluoro-4-iodobenzene ether;
2, the positive propyl phenyl ether of 3-two fluoro-4-iodine.
(7) phenyl 4-[(4-methoxyl group-2,3-difluoro)]-2-methyl-3-butyne-2-alcohol synthetic
In the 250mL there-necked flask that thermometer, prolong, agitator are housed, add 2,3-two fluoro-4-iodanisol 10.8g under the argon shield; two (triphenylphosphine) Palladous chloride 0.160g, cuprous iodide 0.08g, triphenylphosphine 0.3g; triethylamine 100ml, stirring and refluxing reaction 10 hours.Be cooled to room temperature, filter, add the 100ml methylene dichloride; Saturated aqueous ammonium chloride is washed till neutrality.Anhydrous magnesium sulfate drying removes solvent under reduced pressure, and the sherwood oil recrystallization gets faint yellow solid 6.4g, yield 72%.
Use 2 respectively, 3-two fluoro-4-iodobenzene ether, 2, the positive propyl phenyl ether of 3-two fluoro-4-iodine replaces 2, and 3-two fluoro-4 iodanisols adopt to synthesize with quadrat method:
4-[(4-oxyethyl group-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol;
4-[(4-positive propoxy-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol.
(8) 4-methoxyl group-2,3-difluoro phenylacetylene synthetic
In the 250mL there-necked flask that thermometer, prolong, agitator are housed, add 4-[(4-methoxyl group-2, the 3-difluoro under the nitrogen protection) phenyl]-2-methyl-3-butyne-2-alcohol 6.4g, toluene 120ml; Slowly add 2.4gNaH (dispersion of 70% fluid) under stirring, added the back back flow reaction 4 hours.Be cooled to room temperature, filter, pour in 100g ice and the 20ml concentrated hydrochloric acid, tell organic layer, saturated sodium-chloride water solution is washed till neutrality.Drying removes solvent under reduced pressure.(eluent: sherwood oil: ethyl acetate=10: 1), get faint yellow solid, the sherwood oil recrystallization gets white crystal 3.3g to the silicagel column purifying, yield 68%.Structure is identified:
Ultimate analysis:
Theoretical value: C64.29, H3.60, F22.60, O9.51
Actual value: C64.26, H3.59, F22.61, O9.54
IR (pressing potassium bromide troche, wave number): 3299,2847,2600,1631,1512,1301,1093,986,928,715,681
1H-NMR(500MHz，CDCl
3，δ)：3.27(1H，s)；3.93(3H，s)；6.68～6.72(1H，m)；7.18～7.21(1H，m)。
Use 4-[(4-oxyethyl group-2 respectively, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol, 4-[(4-positive propoxy-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol replacement 4-[(4-methoxyl group-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol, adopting uses the same method synthesizes:
4-oxyethyl group-2,3-difluoro phenylacetylene;
4-positive propoxy-2,3-difluoro phenylacetylene.
(9) 4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoroanisole synthetic
Under the argon shield in the 250mL there-necked flask that thermometer, prolong, agitator are housed; add 4-methoxyl group-2; 3-difluoro phenylacetylene 3.3g; 4-(trans-4-ethyl cyclohexyl) 2-fluorine iodobenzene 6.6g; two (triphenylphosphine) Palladous chloride 0.08g, cuprous iodide 0.04g, triphenylphosphine 0.16mg; triethylamine 100ml, stirring and refluxing reaction 10 hours.Be cooled to room temperature, reactant is poured in 100g ice and the 30ml concentrated hydrochloric acid, use petroleum ether extraction, be washed to neutrality.Drying removes solvent under reduced pressure, and residue is with sherwood oil: methylene dichloride=10: 1 is that eluent carries out column chromatography, dehydrated alcohol recrystallization twice, white solid 5.3, yield 71%, gas chromatographic purity 99%.
Structure is identified:
Ultimate analysis:
Theoretical value C74.18; H6.22; F15.30; O4.30
Measured value C74.54; H6.34; F15.02; O4.10
IR (pressing potassium bromide troche, wave number): 3074,2959,2219,1632,1519,1481,1297,994,806,821,704
1H-NMR(500MHz，CDCl
3，δ)：0.91(3H，t)；0.99～1.07(2H，m)；1.16～1.29(2H，m)；1.37～1.45(2H，m)；1.53～1.65(1H，m)；1.88～1.90(4H，d)；2.47(1H，tt)；3.92(3H，s)；6.7(1H，td)；6.9(2H，td)；7.2(1H，td)；7.4(1H，t)。
MS：372(M
+)。
Confirmed that the material that above-mentioned reaction obtains is 4-{2-[4-(trans-4-second cyclohexyl)-2-fluorophenyl really] acetylene }-2, the 3-difluoroanisole.
Corresponding with 4-(trans-the 4-alkyl-cyclohexyl)-2-fluorine iodobenzene and 4-positive alkoxyl group-2,3-difluoro phenylacetylene, adopting uses the same method synthesizes following compound:
4-{2-[4-(trans-4-n-propyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoroanisole;
4-{2-[4-(trans-4-normal-butyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoroanisole;
4-{2-[4-(trans-4-n-pentyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoroanisole;
4-{2-[4-(trans-4-n-octyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoroanisole;
4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the positive propyl phenyl ether of 3-difluoro;
4-{2-[4-(trans-4-n-propyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the positive propyl phenyl ether of 3-difluoro;
4-{2-[4-(trans-4-normal-butyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the positive propyl phenyl ether of 3-difluoro;
4-{2-[4-(trans-4-n-pentyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the positive propyl phenyl ether of 3-difluoro;
4-{2-[4-(trans-4-n-octyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the positive propyl phenyl ether of 3-difluoro.
Embodiment 2
4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro toluene synthetic
Synthesizing of (1) 2,3-difluoro toluene
In the 500mL there-necked flask of thermometer, agitator is housed, add exsiccant tetrahydrofuran (THF) 200ml, exsiccant Tetramethyl Ethylene Diamine 50ml, 1,2-Difluorobenzene 23g, liquid nitrogen cooling is to-78 ℃, and dripping concentration is the n-Butyl Lithium hexane solution 100mL of 2.2M, drips off back insulation reaction 2 hours.Dropping is dissolved with the 50mL 1 of 28g methyl iodide, and 3-dimethyl-imidazolinone solution drips off the back and is warming up to room temperature naturally.Pour in the water, the 200ml n-hexane extraction is told organic layer, drying.110～115 ℃ cut is collected in distillation, gets colourless liquid 18g, yield 70%.
Use iodoethane, propyl iodide replaces methyl iodide, and adopting uses the same method closes out 2,3-difluoro ethylbenzene and 2,3-difluoro n-propylbenzene.
Synthesizing of (2) 2,3-two fluoro-4-toluene iodides
In the 500mL there-necked flask of thermometer, agitator is housed; nitrogen protection adds exsiccant tetrahydrofuran (THF) 200ml down; exsiccant Tetramethyl Ethylene Diamine 50ml; 2; 3-difluoro toluene 18g; liquid nitrogen cooling is to-78 ℃, and dripping concentration is the n-Butyl Lithium hexane solution 70mL of 2.2M, drips off back insulation reaction 2 hours.Dropping is dissolved with the 50mL tetrahydrofuran solution of 35g iodine, drips off the back and is warming up to room temperature naturally.Pour in the water, use the 200ml n-hexane extraction, tell organic layer, anhydrous magnesium sulfate drying.Underpressure distillation, the cut of 80～82 ℃/200Pa of collection gets colourless liquid 18g, yield 70%.
Use 2 respectively, 3-difluoro ethylbenzene or 2,3-difluoro n-propylbenzene replaces 2, the 3-difluoro toluene, adopting uses the same method closes out 2,3-two fluoro-4-iodine ethylbenzenes and 2,3-two fluoro-4-iodine n-propylbenzene.
(3) phenyl 4-[(4-methyl-2,3-difluoro)]-2-methyl-3-butyne-2-alcohol synthetic
In the 250mL there-necked flask that thermometer, prolong, agitator are housed, add 2,3-two fluoro-4-toluene iodide 10.2g under the argon shield; two (triphenylphosphine) Palladous chloride 0.160g, cuprous iodide 0.08g, triphenylphosphine 0.3g; triethylamine 100ml, stirring and refluxing reaction 8 hours.Be cooled to room temperature, filter, add the 100ml methylene dichloride, saturated aqueous ammonium chloride is washed till neutrality.Anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent, the sherwood oil recrystallization gets white solid 6.1g, yield 73% twice.
Use 2 respectively, 3-two fluoro-4-iodine ethylbenzenes or 2,3-two fluoro-4-iodine n-propylbenzene replace 2,3-two fluoro-4-toluene iodides, adopting uses the same method closes out
4-[(4-ethyl-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol;
4-[(4-n-propyl-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol.
(4) 4-methyl-2,3-difluoro phenylacetylene synthetic
In the 250mL there-necked flask that thermometer, prolong, agitator are housed, add 4-[(4-methyl-2, the 3-difluoro under the nitrogen protection) phenyl]-2-methyl-3-butyne-2-alcohol 6.1g, toluene 120ml; Slowly add 2.4gNaH (dispersion of 70% fluid) under stirring, added the back back flow reaction 4 hours.Be cooled to room temperature, filter, pour in 100g ice and the 20ml concentrated hydrochloric acid, separatory, saturated sodium-chloride water solution is washed till neutrality.Drying removes solvent under reduced pressure.(eluent: sherwood oil: ethyl acetate=20: 1), get faint yellow solid, the sherwood oil recrystallization gets white crystal 2.8g to the silicagel column purifying, yield 62%.
Use 4-[(4-ethyl-2 respectively, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol and 4-[(4-n-propyl-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol replacement 4-[(4-methyl-2, the 3-difluoro) phenyl]-2-methyl-3-butyne-2-alcohol, adopting uses the same method closes out
4-ethyl-2,3-difluoro phenylacetylene;
4-n-propyl-2,3-difluoro phenylacetylene.
(5) 4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro toluene synthetic
Under the argon shield in the 250mL there-necked flask that thermometer, prolong, agitator are housed; add 4-methyl-2; 3-difluoro phenylacetylene 2.8g; 4-(trans-4-ethyl cyclohexyl)-2-fluorine iodobenzene 5.3g; two (triphenylphosphine) Palladous chloride 0.08g, cuprous iodide 0.04g, triphenylphosphine 0.16g; triethylamine 100ml, stirring and refluxing reaction 10 hours.Be cooled to room temperature, reactant is poured in 100g ice and the 30ml concentrated hydrochloric acid, use petroleum ether extraction, organic layer is washed to neutrality.Anhydrous magnesium sulfate drying removes solvent under reduced pressure, and residue is with sherwood oil: methylene dichloride=10: 1 is that eluent carries out column chromatography, dehydrated alcohol recrystallization twice, white solid 4.1, yield 73%, gas chromatographic purity 99%.
Structure is identified:
Ultimate analysis:
Theoretical value C77.50; H6.51; F15.99;
Measured value C77.46; H6.53; F16.01;
IR (pressing potassium bromide troche, wave number): 3029,2848,2219,1739,1627,1508,1481,994,806,821,786.
1H-NMR(500MHz，CDCl
3，δ)：0.93(3H，t)；0.94～1.08(2H，m)；1.16～1.29(2H，m)；1.37～1.45(2H，m)；1.53～1.65(1H，m)；1.88～1.90(4H，d)；2.47(1H，tt)；2.47(3H，s)；6.7(1H，td)；6.9(2H，td)；7.2(1H，td)；7.4(1H，t)。
MS：356(M
+)。
The material that confirmation obtains through above-mentioned reaction is 4-{2-[4-(trans-4-second cyclohexyl)-2-fluorophenyl really] acetylene }-2, the 3-difluoro toluene.
With corresponding 4-(the positive alkyl-cyclohexyl of trans-4-)-2-fluorine iodobenzene, 4-methyl-2,3-difluoro phenylacetylene, adopting uses the same method synthesizes following compound:
4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoro toluene;
4-{2-[4-(trans-4-n-propyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoro toluene;
4-{2-[4-(trans-4-normal-butyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoro toluene;
4-{2-[4-(trans-4-n-pentyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoro toluene;
4-{2-[4-(trans-4-n-octyl cyclohexyl)-2-fluorophenyl] acetylene }-2, the 3-difluoro toluene.
With corresponding 4-(the positive alkyl-cyclohexyl of trans-4-)-2-fluorine iodobenzene, 4-n-propyl-2,3-difluoro phenylacetylene, adopting uses the same method synthesizes following compound:
4-{2-[4-(trans-4-ethyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro n-propylbenzene;
4-{2-[4-(trans-4-n-propyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro n-propylbenzene;
4-{2-[4-(trans-4-normal-butyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro n-propylbenzene;
4-{2-[4-(trans-4-n-pentyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro n-propylbenzene;
4-{2-[4-(trans-4-n-octyl cyclohexyl)-2-fluorophenyl] acetylene }-2,3-difluoro n-propylbenzene.
Claims (4)
1, a kind of diphenylacetylene liquid crystal compounds, (I) is as follows for its general structure:
Wherein to represent carbon number be 1～9 straight chained alkyl to R, and it is 1～3 straight chained alkyl or alkoxyl group that R ' represents carbon number.
2, according to claims 1 described diphenylacetylene liquid crystal compounds, wherein to represent carbon number be 2～7 straight chained alkyl to R, and it is 1～2 alkyl or alkoxyl group that R ' represents carbon number.
3, according to claims 2 described diphenylacetylene liquid crystal compounds, wherein to represent carbon number be 2～5 straight chained alkyl to R, and it is 1～2 alkoxyl group that R ' represents carbon number.
4, according to claims 3 described diphenylacetylene liquid crystal compounds, wherein R represents ethyl, R ' representation methoxy.
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| CN 200610140460 CN1923951A (en) | 2006-10-09 | 2006-10-09 | Diphenylacetylene liquid crystal compounds |
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| CN 200610140460 CN1923951A (en) | 2006-10-09 | 2006-10-09 | Diphenylacetylene liquid crystal compounds |
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| CN104087308A (en) * | 2014-07-21 | 2014-10-08 | 西安近代化学研究所 | Trifluoromethoxy terminal-substituent diaryl acetylene liquid crystal compounds and synthetic method thereof |
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| CN102633596A (en) * | 2012-03-13 | 2012-08-15 | 石家庄诚志永华显示材料有限公司 | Side difluorine substituted diphenylacetylene liquid crystal compound, preparation method for same and application thereof |
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| CN108192640A (en) * | 2018-01-25 | 2018-06-22 | 西京学院 | Monomer liquid crystal of the huge electrocaloric effect of difluoro methoxy bridge bond low viscosity and preparation method thereof |
| CN108192640B (en) * | 2018-01-25 | 2021-05-28 | 西京学院 | Monomer liquid crystal with difluoromethoxy bridge bond low-viscosity giant electrothermal effect and preparation method thereof |
| CN108517217A (en) * | 2018-07-05 | 2018-09-11 | 西安近代化学研究所 | A kind of alkynes liquid crystal compounds, preparation method and the composition containing this compound and the high frequency assembly comprising this liquid crystal media |
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