CN106978192A - A kind of high birefringence rate liquid crystal compound and preparation method thereof with and combinations thereof - Google Patents
A kind of high birefringence rate liquid crystal compound and preparation method thereof with and combinations thereof Download PDFInfo
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- 0 *c1cc(C#Cc(cc2)ccc2O*)c(*)c(*)c1N=C=S Chemical compound *c1cc(C#Cc(cc2)ccc2O*)c(*)c(*)c1N=C=S 0.000 description 9
- AIGVEAVMTYQLAG-UHFFFAOYSA-N CCCCOc(cc1)ccc1C#Cc(cc1)cc(F)c1N=C=S Chemical compound CCCCOc(cc1)ccc1C#Cc(cc1)cc(F)c1N=C=S AIGVEAVMTYQLAG-UHFFFAOYSA-N 0.000 description 1
- VSMDINRNYYEDRN-UHFFFAOYSA-N Oc(cc1)ccc1I Chemical compound Oc(cc1)ccc1I VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 description 1
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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Abstract
The invention discloses a kind of high birefringence rate liquid crystal compound and preparation method thereof, and the composition containing this compound.Shown in the structure of liquid-crystal compounds such as formula (I)：Wherein X1、X2、X3It is one kind in the fluoro alkenyl that straight-chain alkenyl or carbon number that carbon number is 2~5 are 2~5 for H or F, R.Liquid-crystal composition includes compound less than or equal to 40% and shown in the formula I that is not zero, compound shown in 1%~40% formula II, compound shown in 1%~30% general formula III and compound shown in 2%~50% general formulae IV.Wherein, R1、R2、R3Be respectively carbon number be 1~7 alkyl, carbon number be 1~7 alkoxy or carbon number be 1~5 fluoroalkyl in one kind；X4~X9It is H or F respectively.The present invention had not only had the advantages that high two-fold rate but also had had low rotary viscosity, it is adaptable to which spatial light modulator, laser detector and 3D such as show at the field.
Description
Technical field
The invention belongs to liquid crystal material technical field, and in particular to a kind of high birefringence rate liquid crystal compound and combinations thereof
Thing, is primarily adapted for use in laser detector, spatial light modulator, varifocal liquid crystal lens and microwave and is mutually adjusted with the position in THz fields
Device and 3D display field processed etc..
Background technology
In recent years, the liquid crystal material with high birefringence rate laser detector, spatial light modulator, liquid crystal grating and
The novel liquid crystal such as varifocal liquid crystal lens optics and 3D are shown, the application in holographic technique receives much concern.And liquid crystal light
Device application requirement is learned it is necessary to have certain Spatial transmission amount (Δ nd >=1 λ), if liquid crystal material have it is sufficiently large two-fold
Rate i.e. Δ n values are penetrated to talk about, just can be with the smaller optics of the brilliant box thickness of preparation solution under identical modulation voltage, this can just be carried significantly
The response speed of high device.The response time of phase-type liquid crystal light control device depends primarily on fall time, and its formula is τf
=γ1d2/ π K, it can thus be seen that the rotary viscosity γ of material1Lower, thickness of liquid crystal box d is smaller, then the response time of device
It is shorter.Therefore want the overall performance of raising liquid crystal optical device, must just use while there is high birefringence rate and low viscous
Spend the liquid crystal material of characteristic.
For liquid-crystal compounds, to expect higher birefringence, the method for most effective method is to liquid crystal point
Unsaturated bonds such as benzene ring structure, double or triple bonds etc. are introduced in sub- rigid nuclear to increase its pi-electron conjugate length.But it is due to height
The conjugated structure of degree certainly will cause the fusing point of compound, melting enthalpy and viscosity etc. to be substantially increased, and be added to mixed liquor
The fusing point and viscosity of formula can be caused to raise or even produce partial crystallization in crystal formulations, these defects largely effect on compound in formula
In addition.Tolans base isothiocyanates liquid-crystal compounds is due to viscous with higher birefringence and moderate rotation
Degree, is used widely in liquid crystal optical device, the birefringence for improving formula, so that the response of boost device
Energy.Therefore in order that mixed liquid crystal formula has faster response characteristic, while ensureing to have high birefringence rate, select as far as possible
Take the liquid-crystal compounds with more low viscosity and more low melting point or low melt enthalpy as the main body component of formula, have to be formed
The good formulas of low molten altogether and low viscosity.
In periodical " Crystals, 2013,3：443-482 ", entitled " High birefringence liquid
The tolans base isothiocyanates liquid-crystal compounds containing butoxy, the following institute of structural formula are reported in crystals " paper
Show：
The phase transition temperature of report is Cr 112.7 (SmE 112.0) N 116I, and fusing point is up to 112.7 DEG C, and melting enthalpy is
25.6kJ/mol。
In periodical " Crystals, 2013,3：443-482 ", entitled " High birefringence liquid
The side fluorine substituted diphenyl acetylene base isothiocyanates liquid-crystal compounds containing butoxy, structure are reported in crystals " paper
Formula is as follows：
The phase transition temperature of report be Cr 96.7 (N 89.9) I, more a height of 96.7 DEG C of fusing point, melting enthalpy is also more a height of
35.6kJ/mol.Above-mentioned liquid-crystal compounds, which is added to when being easily caused low temperature in formula, there is partial crystallization phenomenon.
The content of the invention
In order to overcome defect present in background technology or deficiency, the present invention provides a kind of with birefringence height, fusing point
With melting enthalpy is low and rotary viscosity is small liquid-crystal compounds and combinations thereof.
In order to realize above-mentioned task, the present invention takes following technical solution：
A kind of high birefringence rate liquid crystal compound, it is characterised in that shown in its general structure such as formula (I)：
Wherein X1、X2、X3It is the fluoro alkene that straight-chain alkenyl or carbon number that carbon number is 2~5 are 2~5 for H or F, R
One kind in base.
According to the present invention, described R is preferably the straight-chain alkenyl that carbon number is 3,4.
, according to the invention it is preferred to example be：Described high birefringence rate liquid crystal compound, concrete structure formula is as follows：
According to technical scheme, a kind of high birefringence rate liquid crystal compound is prepared using following synthetic route：
Specifically prepare according to the following steps：
1. under nitrogen protection, sequentially added into reaction bulb to iodophenol, raw material (A), K2CO3, ethanol, heating stirring, return
Stop stirring after stream reaction 2h, reaction solution is naturally cooling to room temperature, filters out insoluble matter, rotates after ethanol, adds normal heptane
Dissolved organic matter, is washed to neutrality, and anhydrous magnesium sulfate is filtered after drying, through column chromatography after filtrate revolving is dry, normal heptane elution, rotation
It is evaporated off after solvent obtaining intermediate (1), wherein the mol ratio to iodophenol, raw material (A) is 1:1~3；
2. under nitrogen protection, intermediate (1), triethylamine, triphenylphosphine, cuprous iodide, two (triphens are added in reaction bulb
Base phosphine) palladium chloride, in stirring a moment, heating is opened, keep that trimethylsilyl acetylene and triethylamine mixed solution, 40 are added dropwise at 40 DEG C
DEG C stirring 3 hours stop reaction, be cooled to after room temperature filter, rotate after add toluene dissolving, washing, dry, filtering, revolving after
Red liquid intermediate (2) is obtained, wherein intermediate (1), the mol ratio of trimethylsilyl acetylene are 1:1~5；
3. intermediate (2) is added in reaction bulb, and potassium hydroxide, water, ethanol are sequentially added, be stirred at room temperature 1 hour, stop
After only reacting, reaction solution is washed to neutrality after being extracted with normal heptane, and gained red liquid after solvent is evaporated off and uses high vacuum distillation
Purified, collect 60Pa vacuums it is lower 80 DEG C when cut, obtain intermediate (3), the intermediate (2), potassium hydroxide rub
You are than being 1:0.1~1；
4. under nitrogen protection, raw material (B), triethylamine, triphenylphosphine, cuprous iodide, palladium are sequentially added in there-necked flask and is urged
The mixed solution of intermediate (3) and triethylamine is added dropwise in agent, heating stirring when interior temperature rises to 70 DEG C, drips off latter 70 DEG C instead
4h is answered, stops filtering after reaction, revolving and removes triethylamine, toluene dissolved organic matter, washing, drying, filtering, filtrate revolving is added
Intermediate (4) is recrystallized to obtain with normal heptane afterwards, the Sonogashira coupling reactions reaction temperature is 0~90 DEG C, raw material (B),
Intermediate (3), the mol ratio of palladium catalyst are 1:1~1.5:0.1%~3%；
5. adding intermediate (4), water, acetone in there-necked flask, thiophosgene stirring a moment, room temperature reaction 2 are added dropwise at room temperature
Hour, TLC monitorings stop reacting without starting material left, rotate reaction solution, and gained crude product toluene dissolves, and is washed to neutrality, anhydrous
Magnesium sulfate is dried, filtering, and revolving is done and column chromatography purifying is carried out after dissolving, and the mixed solvent of normal heptane and toluene is eluted, and is washed
The crude product obtained after de- liquid revolving is recrystallized to give target compound (5) with normal heptane；The intermediate (4) is rubbed with thiophosgene
You are than being 1:1~4.
Further,
The mol ratio to iodophenol, raw material (A) described in step 1 is preferably 1:1~2；
Intermediate (1) described in step 2, the mol ratio of trimethylsilyl acetylene are preferably 1:1~2；
Intermediate (2) described in step 3, the mol ratio of potassium hydroxide are preferably 1:0.1~0.5；
The mol ratio of raw material (B), intermediate (3), palladium catalyst described in step 4 is preferably 1:1~1.2:0.3%
~1%；Its reaction temperature of Sonogashira coupling reactions is preferably 40~80 DEG C；Described palladium catalyst is to match somebody with somebody containing organophosphor
The palladium catalyst of body, preferably two (triphenylphosphine) palladium bichlorides or tetrakis triphenylphosphine palladium；
The mol ratio of intermediate (4) and thiophosgene described in step 5 is 1:1.2~2.
According to technical scheme, a kind of high birefringence rate liquid-crystal composition, including at least liquid shown in a kind of formula I
Crystallization compound, and weight percentage is less than or equal to 40% and is not zero.Also include chemical combination shown in 1%~40% formula II
Compound shown in compound shown in thing, 1%~30% general formula III and 2%~50% general formulae IV.
Wherein, R1、R2、R3Be respectively carbon number be 1~7 alkyl, carbon number be 1~7 alkoxy or carbon atom
Number is one kind in 1~5 fluoroalkyl；X1~X9It is-H or-F respectively.
Above-mentioned composition is preferred：Compound shown in formula II be compound shown in 5%~30%, general formula III be 5%~
25%th, compound shown in general formulae IV is 15%~46%.
Technological progress acquired by the present invention is：The liquid-crystal compounds of the present invention has high birefringence rate, low melt enthalpy
The advantage of value and low rotary viscosity, being added to the nematic phase liquid crystal composition formed in mixed liquid crystal formula has high pair
Refractive index, lower rotary viscosity and lower fusing point, the spatial light modulator that is particularly suitable for use in and 3D display fields.The present invention is also
A kind of preparation method of described high birefringence rate liquid crystal compound is given, its synthesis step is short, and the cost of raw material is low, experiment
Process is easy to operate, and aftertreatment technology is simple.
Embodiment
The present invention is described in further details below in conjunction with specific embodiment.
GC in embodiment represents gas chromatographic purity (%), tester：The HP6820 type gas phase colors of Agilent company
Spectrometer；1H-NMR represents proton nmr spectra, tester：The Advanced500MHz nuclear magnetic resonance of Bruker companies
Instrument；GC-MS represents gas chromatograph-mass spectrometer, tester：Agilent company MS5975C type gas chromatograph-mass spectrometers.
The quantitative measurement method of liquid-crystal compounds is as follows：
Clearing point (Tni)：Polarisation thermal station method：Liquid crystalline sample is coated on slide and is placed in cross-polarized light microscopic heating stand,
Setting heating rate is 3 DEG C/min, as temperature of the observation liquid crystalline sample by state of during blackening, clearing point.Differential scanning
Calorimetry：Under nitrogen protection, setting heating rate is 3 DEG C/min.
Basic components (P0) for liquid-crystal compounds quantitative measurement are as three kinds of liquid crystal lists shown in following structural formula
Body is according to 1:1:1 mass ratio is mixed.
Birefringence (Δ n) the method for testings of liquid-crystal compounds：It is added to basic components P0 according to 5% mass ratio
In, using abbe's refractometer, at 25 DEG C, the birefringence of test formulations under 589nm, extrapolation obtains the birefringence of monomeric compound
Rate.
Rotary viscosity (the γ of liquid-crystal compounds1) method of testing：It is added to basic components P0 according to 5% mass ratio
In, using liquid crystal comprehensive tester, the rotary viscosity of test formulations at 25 DEG C, the rotation that extrapolation obtains monomeric compound is glued
Degree.
Embodiment 1：
4- ((4- propenyloxy groups) phenyl) acetenyl) the fluoro- 1- isothiocyanos benzene of -2- synthesis：
Concrete structure is as follows：
Preparation process is as follows：
Step 1:The synthesis of 1- (propenyloxy group) -4- iodobenzenes
Under nitrogen protection, sequentially added in 2L reaction bulbs to iodophenol (176.08g, 0.8mol), the bromo- 1- propylene of 3-
(145.2g, 1.2mol), K2CO3(221g, 1.6mol), ethanol 800mL.Open heating and stir, stop stirring after back flow reaction 2h
Mix, be naturally cooling to room temperature and post-processed.Insoluble matter is filtered out, is rotated after ethanol, normal heptane dissolved organic matter, water is added
Neutrality is washed till, anhydrous magnesium sulfate is filtered after drying, through column chromatography after filtrate revolving is dry, and normal heptane elution, eluent revolving is removed
It is intermediate 1- (propenyloxy group) -4- iodobenzenes that 201g colourless liquids are obtained after solvent.GC purity is 98.26%.
Step 2：The synthesis of ((4- (propenyloxy group) phenyl) acetenyl) trimethyl silicane alkynes
Under nitrogen protection, compound 1-1 (201g, 0.77mol), PdCl are added in 2L reaction bulbs2(PPh3)2(2.7g,
0.5%mol), CuI (2.2g, 1.5%mol), PPh3(3.1g, 1.5%mol), Et3N 1.6L.Heating is opened, interior temperature rise is treated extremely
Start the mixed solution of dropwise addition TMSA (154g, 1.92mol) triethylamine at 40 DEG C.Stop after completion of dropping after 40 DEG C of reaction 3h
Heating, is down to after room temperature and is post-processed naturally.Triethylamine is removed after filtering, filtrate revolving, normal heptane dissolved organic matter is added,
Neutrality is washed to after the aqueous solution washing of saturated ammonium chloride, anhydrous magnesium sulfate is filtered after drying, and filtrate revolving is removed and obtained after solvent
Red liquid 191g as intermediates are obtained after carrying out column chromatography purifying, normal heptane elution, eluent revolving to red liquid
((4- (propenyloxy group) phenyl) acetenyl) trimethyl silicane alkynes.
Step 3：The synthesis of 1- (propenyloxy group) -4- acetylenylbenzenes
The red liquid that upper step is obtained is added in 1L reaction bulbs, adds KOH (23.2g, 0.41mol), absolute ethyl alcohol
Stop stirring after 200ml, room temperature reaction 1h to be post-processed.Solvent is rotated, normal heptane dissolved organic matter is added, in being washed to
Property, anhydrous magnesium sulfate is dried.Filtering, filtrate, which rotates, obtains red liquid 120.47g after organic solvent.Using high vacuum distillation
Purified, cut 88g when collection 60Pa vacuums are lower 80 DEG C is intermediate 1- (propenyloxy group) -4- acetylenylbenzenes, GC
Purity 98.16%.
Step 4：The synthesis of 4- ((4- (propenyloxy group) phenyl) acetenyl) -2- fluorine
Under nitrogen protection, the fluoro- 4- Iodoanilines (25.36g, 0.107mol) of 3-, PdCl are added in 500mL reaction bulbs2
(PPh3)2(0.75g, 1%mol), CuI (0.61g, 3%mol), PPh3(0.84g, 3%mol), Et3N 150mL.Open and add
Heat, starts that the triethylamine for the intermediate (3) (18.59g, 0.118mol) that upper step reaction is obtained is added dropwise when interior temperature rise is to 70 DEG C
Mixed solution.Stop heating after 70 DEG C of reaction 4h after completion of dropping, be naturally cooling to be post-processed after room temperature.Filtering, filtrate
Triethylamine is removed after revolving, toluene 150mL dissolved organic matters are added, the aqueous solution for adding saturated ammonium chloride is washed 2 times, then is washed
To neutral, filtering after anhydrous magnesium sulfate is dried, filtrate revolving, which is removed, obtains khaki solid 13g after solvent.It is pure using column chromatography
Change, toluene：Normal heptane (volume ratio)=1：1 mixed solvent is eluted, and obtaining crude product normal heptane after eluent revolving recrystallizes 2 times
It is intermediate 4- ((4- (propenyloxy group) phenyl) acetenyl) -2- fluorine, GC purity to obtain the light yellow flat crystals of 10.5g
99.06%.
Step 5：4- ((propenyloxy group) phenyl) acetenyl) the fluoro- 1- isothiocyanos benzene of -2- synthesis
In 250mL reaction bulbs add intermediate 4- ((4- (propenyloxy group) phenyl) acetenyl) -2- fluorine (10.3g,
0.0386mol)、CSCl2(5.8g, 0.05mol), acetone 50mL, water 5mL.Stop reaction after reaction being stirred at room temperature 1 hour to carry out
Post processing.Revolving removes addition toluene dissolved organic matter after organic solvent, is washed to neutrality, and anhydrous magnesium sulfate is dried, filtering, plus
The normal heptane for entering 10 times carries out column chromatography purifying, and the mixed solvent of normal heptane and toluene is eluted, and eluent is obtained after rotating
Crude product, it is compound target compound 4- ((propylene oxygen that 1 time is recrystallized with 10 times of normal heptanes and obtains 9.8g white needle-like crystals
Base) phenyl) acetenyl) the fluoro- 1- isothiocyanos benzene of -2-, GC purity 99.60%.
Structural Identification data：1H-NMR (δ, CDCl3)：4.557-4.573(m,2H),5.302-5.325(m,1H),
5.405-5.443(m,1H),6.025-6.081(m,1H),6.891-6.909(m,2H),7.119-7.151(t,2H),
7.224-7.285(m,2H),7.437-7.455(m,2H)；MS (70eV) m/z (%)：309.0(M+,66),267.9(100),
239.9(23),208(10),182(17)。
The compound gone out synthesized by above Structural Identification as shown by data is strictly 4- ((propenyloxy group) phenyl) acetenyl)-
The fluoro- 1- isothiocyanos benzene of 2-.
With DSC with 3 DEG C/min condition heating test 4- ((propenyloxy group) phenyl) acetenyl) the fluoro- 1- isothiocyanos of -2-
The phase transition temperature of benzene, as a result for：Cr 87.55 (28.92) I, fusing point is 87.55 DEG C, and melting enthalpy is 28.92kJ/mol.By the list
The brilliant mass percent with 5% of body fluid, which is added in basic components P0, forms mixed liquid crystal, and test formulations is physical at 25 DEG C
Can, data are shown in Table 1.
The test data of table 1
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 1+P0 | 0.0971 | 149.3 |
Add after the compound of embodiment 1, the birefringence of mixed liquid crystal increases 24%, rotary viscosity reduction.According to adding
The birefringence value of the method principle extrapolation compound of embodiment 1 is 0.4744, and rotary viscosity is 61.6mPaS.Prove the compound
Have the advantages that birefringence is high and rotary viscosity is low.
Embodiment 2：
The synthesis of 4- ((4- (2,2- difluoroethylenes base) phenyl) acetenyl) fluoro- isothiocyano benzene of -2-：
The fluoro- 4- Iodoanilines of 2- in the step of embodiment 1 (4) are replaced using 4- Iodoanilines, using side similarly to Example 1
Method synthesizes 1- (propenyloxy group) -4- ((4- isothiocyanatophenyls) acetenyl) benzene.
Structural Identification：
1H-NMR (δ, CDCl3)：4.552-4.568(m,2H),5.296-5.320(m,1H),5.434-5.443(m,1H),
6.013-6.090(m,1H),6.879-6.908(m,2H),7.170-7.192(m,2H),7.433-7.482(m,4H)；MS
(70eV) m/z (%):290.9(M+,63),221.9.0(19),189.9(8),162.9(17),149.9(100)。
The compound gone out synthesized by above Structural Identification as shown by data is strictly 1- (propenyloxy group) -4- ((4- isothiocyanos
Phenyl) acetenyl) benzene.
With DSC with 3 DEG C/min condition heating test 1- (propenyloxy group) -4- ((4- isothiocyanatophenyls) acetenyl) benzene
Liquid-crystal phase-transition temperature, as a result for：Cr 104.8I, melting enthalpy is 21.35kJ/mol.By monomer liquid crystal with 5% quality hundred
Divide and form mixed liquid crystal than being added in basic components P0, the physical property of test formulations at 25 DEG C, data are shown in Table 2.
The test data of table 2
| Mixed crystal code name | Δn(589nm) |
| P0 | 0.0784 |
| Embodiment 2+P0 | 0.0990 |
Add after the compound of embodiment 2, the birefringence of mixed liquid crystal increases 26%.Extrapolated and implemented according to addition principle
The birefringence value of the compound of example 2 is 0.4904.Prove that the compound has the advantages that birefringence is high.
Embodiment 3：
The synthesis of 1- ((4- (propenyloxy group) phenyl) acetenyl) fluoro- 4- isothiocyanos benzene of -2-：
The fluoro- 4- Iodoanilines of 2- in the step of embodiment 1 (4) are replaced using the fluoro- 4- Iodoanilines of 3-, using same with embodiment 1
The method of sample synthesizes 1- ((4- (propenyloxy group) phenyl) acetenyl) fluoro- 4- isothiocyanos benzene of -2-.
Structural Identification：
1H-NMR (δ, CDCl3)：4.555-4.571(m,2H),5.297-5.321(q,1H),5.403-5.440(q,1H),
6.012-6.089(m,1H),6.884-6.912(m,2H),6.953-7.007(m,2H),7.437-7.487(m,3H)；MS
(70eV) m/z (%):308.9(M+,66),267.9(100),239.9(22),207.9(8),182(16),156(2).
The compound gone out synthesized by above Structural Identification as shown by data is strictly 1- ((4- (propenyloxy group) phenyl) acetylene
Base) the fluoro- 4- isothiocyanos benzene of -2-.
With DSC with 3 DEG C/min condition heating test 1- ((4- (propenyloxy group) phenyl) acetenyl) different sulphur of the fluoro- 4- of -2-
The liquid-crystal phase-transition temperature of cyano group benzene, as a result for：The I of 66.35 N of Cr 81.35, fusing point is 66.35 DEG C, and melting enthalpy is
21.35kJ/mol, nematic phase warm area is 15 DEG C.The compound has relatively low fusing point, relatively low melting enthalpy and wider
Nematic phase temperature range.The monomer liquid crystal is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, 25
The physical property of test formulations at DEG C, data are shown in Table 3.
The test data of table 3
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 3+P0 | 0.0972 | 149.5 |
Add after the compound of embodiment 3, the birefringence of mixed liquid crystal increases 24%, and rotary viscosity is also reduced.According to
The birefringence value of the addition principle extrapolation compound of embodiment 3 is 0.4544, and rotary viscosity is 62mPaS.Prove the compound
Have the advantages that birefringence height, rotary viscosity are low.
Embodiment 4：
The synthesis of 5- ((4- (propenyloxy group) phenyl) acetenyl) fluoro- 2- isothiocyanos benzene of -1,3- two：
Using the fluoro- 4- Iodoanilines of 2,6- bis- replace the step of embodiment 1 (4) in the fluoro- 4- Iodoanilines of 2-, using with embodiment
1 same method synthesizes 5- ((4- (propenyloxy group) phenyl) acetenyl) fluoro- 2- isothiocyanos benzene of -1,3- two.
Structural Identification：
1H-NMR (δ, CDCl3)：2.534-2.580(m,2H),4.026-4.053(t,2H),5.109-5.201(m,2H),
5.859-5.940(m,1H),6.868-6.897(m,2H),7.057-7.095(t,2H),7.423-7.451(m,2H)；MS(70
EV) m/z (%):340.9(M+,73),286.9(100),254.9(6),225.9(6),199.9(7),55.1(7)。
The compound gone out synthesized by above Structural Identification as shown by data is strictly 5- ((4- (propenyloxy group) phenyl) acetylene
Base) the fluoro- 2- isothiocyanos benzene of -1,3- two.
With DSC with the 3 DEG C/min fluoro- 2- of condition heating test 5- ((4- (propenyloxy group) phenyl) acetenyl) -1,3- two
The liquid-crystal phase-transition temperature of isothiocyano benzene, as a result for：Cr 86.90I, fusing point is 86.90 DEG C, and melting enthalpy is 27.44kJ/
mol.The monomer liquid crystal is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, test is matched somebody with somebody at 25 DEG C
The physical property of side, data are shown in Table 4.
The test data of table 4
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 4+P0 | 0.0970 | 145.7 |
Add after the compound of embodiment 4, the birefringence of mixed liquid crystal increases 19%, and rotary viscosity is also reduced.According to
The birefringence value of the addition principle extrapolation compound of embodiment 4 is 0.4504, and rotary viscosity is 37.4mPaS.Prove the chemical combination
Thing has the advantages that birefringence height, rotary viscosity are low.
Embodiment 5
The preparation of 1- (3- butenyloxies) -4- ((4- isothiocyanatophenyls) acetenyl) benzene
The bromo- 1- propylene of 3- in the step of embodiment 1 (1) is replaced using the bromo- 1- butylene of 4-, replaces implementing using 4- Iodoanilines
The fluoro- 4- Iodoanilines of 2- in the step of example 1 (4), synthesize 1- (3- butenyloxies) -4- using method similarly to Example 1
((4- isothiocyanatophenyls) acetenyl) benzene.
Structural Identification：
1H-NMR (δ, CDCl3)：2.534-2.579(m,2H),4.021-4.028(t,2H),4.974-5.269(m,2H),
5.862-5.944(m,1H),6.862-6.891(m,2H),7.172-7.198(m,2H),7.432-7.479(m,4H)；MS
(70eV) m/z (%):305.0(M+,77),251.0(100),222.0(7),190.0(6),163.0(9),55.1(3).
The compound gone out synthesized by above Structural Identification as shown by data is strictly 1- (3- butenyloxies) -4- ((different sulphur cyanogen of 4-
Base phenyl) acetenyl) benzene.
With DSC with 3 DEG C/min condition heating test 1- (3- butenyloxies) -4- ((4- isothiocyanatophenyls) acetenyl)
The liquid-crystal phase-transition temperature of benzene, as a result for：Cr 104.13I, fusing point is 104.13 DEG C, and melting enthalpy is 21.78kJ/mol.Should
Monomer liquid crystal is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, the physics of test formulations at 25 DEG C
Performance, data are shown in Table 5.
The test data of table 5
Add after the compound of embodiment 5, the birefringence of mixed liquid crystal increases 26%, and rotary viscosity is also reduced.According to
The birefringence value of the addition principle extrapolation compound of embodiment 5 is 0.4824, and rotary viscosity is 28.4mPaS.Prove the chemical combination
Thing has the advantages that birefringence height, rotary viscosity are low.
Embodiment 6
The preparation of 4- ((- (3- butenyloxies) phenyl) acetenyl) fluoro- 1- isothiocyanos benzene of -2-
3- bromo- 1- propylene in the step of embodiment 1 (1) is replaced using the bromo- 1- butylene of 4-, using similarly to Example 1
Method synthesizes 4- ((- (3- butenyloxies) phenyl) acetenyl) fluoro- 1- isothiocyanos benzene of -2-.
Structural Identification：
1H-NMR (δ, CDCl3)：2.537-2.577(m,2H),4.025-4.052(t,2H),5.111-5.201(m,2H),
5.861-5.943(m,1H),6.866-6.895(m,2H),7.117-7.148(t,1H),7.221-7.298(m,2H),
7.428-7.456(m,2H)；MS (70eV) m/z (%):323(M+,72),269(100),239.9(7),208(7),181(8),
55.1(5)。
The compound gone out synthesized by above Structural Identification as shown by data is strictly 4- ((- (3- butenyloxies) phenyl) acetylene
Base) the fluoro- 1- isothiocyanos benzene of -2-.
With DSC with 3 DEG C/min condition heating test 4- ((- (3- butenyloxies) phenyl) acetenyl) different sulphur of the fluoro- 1- of -2-
The liquid-crystal phase-transition temperature of cyano group benzene, as a result for：Cr 88.39I, fusing point is 88.39 DEG C, and melting enthalpy is 33.42kJ/mol.Will
The monomer liquid crystal is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, the thing of test formulations at 25 DEG C
Rationality energy, data are shown in Table 6.
The test data of table 6
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 6+P0 | 0.0971 | 141.1 |
Add after the compound of embodiment 6, the birefringence of mixed liquid crystal increases 24%, and rotary viscosity is also reduced.According to
The birefringence value of the addition principle extrapolation compound of embodiment 6 is 0.4524, and rotary viscosity is 19.7mPaS.Prove the chemical combination
Thing has the advantages that birefringence height, rotary viscosity are low.
Embodiment 7
The preparation of 1- ((4- (3- butenyloxies) phenyl) acetenyl) fluoro- 4- isothiocyanos benzene of -2-
The bromo- 1- propylene of 3- in the step of embodiment 1 (1) is replaced using the bromo- 1- butylene of 4-, replaced using the fluoro- 4- iodobenzenes of 3-
The fluoro- 4- iodobenzenes of 2- in embodiment step (4), synthesize 1- ((4- (3- butenyloxies) using method similarly to Example 1
Phenyl) acetenyl) the fluoro- 4- isothiocyanos benzene of -2-.
Structural Identification：
1H-NMR (δ, CDCl3)：2.536-2.576(m,2H),4.024-4.051(t,2H),5.110-5.200(m,2H),
5.861-5.942(m,1H),6.865-6.894(m,2H),6.952-7.007(m,2H),7.436-7.484(m,3H)；MS
(70eV) m/z (%):323.0(M+,74),262.0(100),240.0(7),208.0(7),182.0(8),55.1(3)。
The compound gone out synthesized by above Structural Identification as shown by data is strictly 1- ((4- (3- butenyloxies) phenyl) acetylene
Base) the fluoro- 4- isothiocyanos benzene of -2-.
It is different with 3 DEG C/min condition heating test 1- ((4- (3- butenyloxies) phenyl) acetenyl) fluoro- 4- of -2- with DSC
The liquid-crystal phase-transition temperature of thiocyanogen benzene, as a result for：Cr 69.75I, fusing point is 69.75 DEG C.By monomer liquid crystal with 5% quality hundred
Divide and form mixed liquid crystal than being added in basic components P0, the physical property of test formulations at 25 DEG C, data are shown in Table 7.
The test data of table 7
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 7+P0 | 0.0966 | 144.7 |
Add after the compound of embodiment 7, the birefringence of mixed liquid crystal increases 23%, and rotary viscosity is also reduced.According to
The birefringence value of the addition principle extrapolation compound of embodiment 7 is 0.4424, and rotary viscosity is 32.6mPaS.Prove the chemical combination
Thing has the advantages that birefringence height, rotary viscosity are low.
Embodiment 8
Liquid-crystal composition (being shown in Table 8) containing the structure of embodiment 1,3,6,7, including following composition：Wherein " % " expression " matter
It is as follows that characteristic is determined in amount percentage ", embodiment：Δn:25 DEG C, birefringence anisotropy under 589nm；Tm.p.:It is molten
Point；Tni:Clearing point；γ1:Rotary viscosity.
The composition of 8 embodiment of table 8 and performance
Embodiment 9：
Liquid-crystal composition containing the structure of embodiment 1,3,6,7, as shown in table 9.
The composition of 9 embodiment of table 9 and performance
Comparative example 1：
Synthesize following structural compounds according to literature method：
Its phase transition temperature is tested with the heating of 3 DEG C/min condition with DSC, as a result for：Cr 88.75I, fusing point is 88.75
DEG C, melting enthalpy is 31.13kJ/mol.And be added to it in basic components P0 with 5% mass ratio, test formulations at 25 DEG C
Physical property, data are shown in Table 10.
The test data of table 10
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 1+P0 | 0.0969 | 150.3 |
Its birefringence of extrapolating is 0.4484, and rotary viscosity is 69.7mPaS.And the compound structure of above-described embodiment 1
I.e.：
Its phase transition temperature is：Cr 87.55I, melting enthalpy is 28.92kJ/mol.
With the compound phase ratio of comparative example 1, its fusing point reduces 1.2 DEG C, and melting enthalpy reduces 2.2kJ/mol, double
Refractive index improves 6%, and rotary viscosity declines 12%.It can be seen that, the liquid-crystal compounds fusing point of the present embodiment is lower, melting enthalpy
Lower, birefringence bigger, rotary viscosity is lower, further demonstrates the advantage of the compound.
Comparative example 2：
Periodical " Liquid crystals, 2003,30 (2)：191-198 ", entitled " Synthesis, mesomorphic
And optical propertities of isothiocyanatotolanes " paper reports following structure liquid crystal material
Material：
Its phase transition temperature is Cr 125.3I, and melting enthalpy is 23.7kJ/mol.
Synthesize the compound according to literature method, and it is added in basic components P0 with 5% mass ratio, 25 DEG C
The physical property of lower test formulations, data are shown in Table 11.
The test data of table 11
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 2+P0 | 0.0987 | 150.5 |
The birefringence value for the compound of comparative example 2 of extrapolating is 0.4844, and rotary viscosity is 71.6mPaS.And it is above-mentioned
The compound structure of embodiment 2 is：
Its phase transition temperature is：Cr 104.8I, melting enthalpy is 21.35kJ/mol.
With the compound phase ratio of comparative example 2, the birefringence of the compound of embodiment 1 increases, and fusing point reduces 20.4 DEG C, melting
Enthalpy reduces 2.4kJ/mol.As can be seen that the liquid-crystal compounds birefringence of the present embodiment bigger, fusing point is lower, melting enthalpy
Value is smaller, further demonstrates the advantage of the compound.
Comparative example 3：
Synthesize following structural compounds according to literature method：
Its phase transition temperature is tested with the heating of 3 DEG C/min condition with DSC, as a result for：Cr 72.51N 82.55I, fusing point is
72.51 DEG C, melting enthalpy is 22.56kJ/mol, and nematic temperature range is 10 DEG C.By the monomer liquid crystal with 5% quality hundred
Divide and form mixed liquid crystal than being added in basic components P0, the physical property of test formulations at 25 DEG C, data are shown in Table 12.
The test data of table 12
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 3+P0 | 0.0961 | 150.9 |
The birefringence value for the compound of comparative example 3 of extrapolating is 0.4324, and rotary viscosity is 75.5mPaS.And it is above-mentioned
The compound structure of embodiment 3 is：
With the compound phase ratio of comparative example 3, fusing point reduces 6.2 DEG C, and melting enthalpy reduces 1.2kJ/mol, nematic
Phase temperature has widened 5 DEG C, and birefringence improves 5%, and viscosity have dropped 18%, further demonstrates the advantage of the compound.
Comparative example 4：
Periodical " Liquid crystals, 2004,31 (4):541-555 ", entitled " Tailoring the
physical properties of some high birefringence isothiocyanato-based liquid
The liquid crystal material of following structure is reported in crystals " paper：
Its phase transition temperature is：The I of C 86.8, melting enthalpy is 32.56 kJ/mol.
Synthesize the compound according to literature method, and it is added in basic components P0 with 5% mass ratio, 25 DEG C
The physical property of lower test formulations, data are shown in Table 13.
The test data of table 13
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 4+P0 | 0.0958 | 147.5 |
The birefringence value for the compound of comparative example 4 of extrapolating is 0.4264, and rotary viscosity is 47.9mPaS.And it is above-mentioned
The compound structure of embodiment 4 is：
Its phase transition temperature, as a result for：The I of Cr 86.90, fusing point is 86.90 DEG C, and melting enthalpy is 27.44kJ/mol,
With the compound phase ratio of comparative example 4, it melts enthalpy and reduces 5.1kJ/mol, and birefringence improves 6%, rotation
Turn viscosity and decline 22%.It can be seen that, the liquid-crystal compounds of the present embodiment melting enthalpy is lower, birefringence is bigger, rotation is viscous
Degree is lower, further demonstrates the advantage of the compound.
Comparative example 5：
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
Crystals " paper reports the liquid crystal material of following structure：
Its phase transition temperature is the I of Cr 112.7 (SmE 112.0) N 116, melting enthalpy 25.6kJ/mol.
Synthesize the compound according to literature method, and it is added in basic components P0 with 5% mass ratio, 25 DEG C
The physical property of lower test formulations, data are shown in Table 14.
The test data of table 14
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 5+P0 | 0.0974 | 150.9 |
The birefringence value for the compound of comparative example 5 of extrapolating is 0.4584, and rotary viscosity is 75.7mPaS.And it is above-mentioned
The compound structure of embodiment 5 is：
With the compound phase ratio of comparative example 5, fusing point reduces 8.6 DEG C, melts enthalpy 4kJ/mol, and birefringence is improved
5%, viscosity have dropped 62%, further demonstrate the advantage of the compound.
Comparative example 6
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
Crystals " paper reports the liquid crystal material of following structure：
Its phase transition temperature is Cr 96.7I, melting enthalpy 35.6kJ/mol.
Synthesize the compound according to literature method, and it is added in basic components P0 with 5% mass ratio, 25 DEG C
The physical property of lower test formulations, data are shown in Table 15.
The test data of table 15
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 6+P0 | 0.0962 | 151.1 |
The birefringence value for the compound of comparative example 6 of extrapolating is 0.4284, and rotary viscosity is 78.6mPaS.And it is above-mentioned
The compound structure of embodiment 6 is：
With the compound phase ratio of comparative example 6, fusing point reduces 8.4 DEG C, and melting enthalpy reduces 2.2kJ/mol, birefringence
4% is increased, rotary viscosity reduces 75%.Further demonstrate the advantage of the compound.
Comparative example 7：
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
Crystals " paper reports the liquid crystal material of following structure：
Its phase transition temperature, as a result for：Cr 70.3N 94.4I, fusing point is 70.3 DEG C.By the monomer liquid crystal with 5% quality
Percentage, which is added in basic components P0, forms mixed liquid crystal, and the physical property of test formulations at 25 DEG C, data are shown in Table 16.
The test data of table 16
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Comparative example 7+P0 | 0.0959 | 151.1 |
The birefringence value for the compound of comparative example 7 of extrapolating is 0.4284, and rotary viscosity is 77.5mPaS.And it is above-mentioned
The compound structure of embodiment 7 is：
With the compound phase ratio of comparative example 6, fusing point reduces 0.6 DEG C, and birefringence improves 3%, and rotary viscosity have dropped
58%.
Comparative example 8：
Liquid-crystal composition containing the structure of comparative example 1,3,6,7, such as table 17.
The composition of 17 comparative example of table 8 and performance
The performance data of comparison sheet 8 and table 17 is found：Identical system, the compound of addition embodiment 1,3,6,7 is formed
Composition, its birefringence is higher, fusing point is lower, rotary viscosity is lower, and low temperature intermiscibility is more preferable.
Comparative example 9：
Liquid-crystal composition containing the structure of comparative example 1,3,6,7, such as table 18.
The composition of 18 comparative example of table 9 and performance
The performance data of comparison sheet 9 and table 18 is found：Identical system, the compound of addition embodiment 1,3,6,7 is formed
Composition, its birefringence is higher, fusing point is lower, rotary viscosity is lower, low temperature intermiscibility is more preferable.
Claims (8)
1. a kind of high birefringence rate liquid crystal compound, it is characterised in that shown in general structure such as formula (I)：
Wherein X1、X2、X3In for H or F, R being the fluoro alkenyl that straight-chain alkenyl or carbon number that carbon number is 2~5 are 2~5
One kind.
2. liquid-crystal compounds according to claim 1, it is characterised in that described R is the straight chain that carbon number is 3~4
Alkenyl.
3. liquid-crystal compounds according to claim 2, it is characterised in that described liquid-crystal compounds is formula 1-1 to formula 1-
Any one in compound shown in 12.
4. the preparation method of the liquid-crystal compounds of formula described in claim 1 (I), it is characterised in that synthetic route is：
Comprise the following steps that：
Under a, nitrogen protection, sequentially added into reaction bulb to iodophenol, raw material (A), K2CO3, ethanol, heating stirring, backflow is anti-
Answer and stop stirring after 2h, reaction solution is naturally cooling to room temperature, filters out insoluble matter, rotates after ethanol, add normal heptane dissolving
Organic matter, is washed to neutrality, and anhydrous magnesium sulfate is filtered after drying, through column chromatography after filtrate revolving is dry, and normal heptane elution, revolving is removed
Fall and intermediate (1) is obtained after solvent, wherein the mol ratio to iodophenol, raw material (A) is 1:1~3；
Under b, nitrogen protection, intermediate (1), triethylamine, triphenylphosphine, cuprous iodide, two (triphenyls are added in reaction bulb
Phosphine) palladium chloride, in stirring a moment, heating is opened, keep that trimethylsilyl acetylene and triethylamine mixed solution, 40 DEG C are added dropwise at 40 DEG C
Stirring 3 hours stop reaction, be cooled to after room temperature filter, rotate after add toluene dissolving, washing, dry, filtering, revolving after
Red liquid intermediate (2), wherein intermediate (1), the mol ratio of trimethylsilyl acetylene are 1:1~5；
C, intermediate (2) added in reaction bulb, and sequentially add potassium hydroxide, water, ethanol, be stirred at room temperature 1 hour, stop anti-
Ying Hou, reaction solution is washed to neutrality after being extracted with normal heptane, and gained red liquid after solvent is evaporated off and is carried out using high vacuum distillation
Purification, cut when collection 60Pa vacuums are lower 80 DEG C, obtains intermediate (3), the intermediate (2), the mol ratio of potassium hydroxide
For 1:0.1~1；
Under d, nitrogen protection, raw material (B), triethylamine, triphenylphosphine, cuprous iodide, palladium catalyst are sequentially added in there-necked flask,
Heating stirring, is added dropwise the mixed solution of intermediate (3) and triethylamine when interior temperature rises to 70 DEG C, 70 DEG C of reaction 4h after dripping off,
Stop filtering after reaction, revolving and remove triethylamine, used after adding toluene dissolved organic matter, washing, drying, filtering, filtrate revolving
Normal heptane recrystallizes to obtain intermediate (4), and the Sonogashira coupling reactions reaction temperature is 0~90 DEG C, raw material (B), centre
Body (3), the mol ratio of palladium catalyst are 1:1~1.5:0.1%~3%；
E, addition intermediate (4), water, acetone in there-necked flask, are added dropwise thiophosgene stirring a moment, react at room temperature 2 hours at room temperature,
TLC monitorings stop reacting without starting material left, rotate reaction solution, and gained crude product toluene dissolves, and is washed to neutrality, anhydrous magnesium sulfate
Dry, filtering, revolving is done and column chromatography purifying is carried out after dissolving, the mixed solvent of normal heptane and toluene is eluted, eluent rotation
The crude product obtained after steaming is recrystallized to give target compound (5) with normal heptane；The intermediate (4) and the mol ratio of thiophosgene are
1:1~4.
5. preparation method according to claim 4, it is characterised in that：
The mol ratio to iodophenol, raw material (A) described in step a is 1:1~2；
The mol ratio of intermediate (1), trimethylsilyl acetylene described in step b is 1:1~2；
The mol ratio of intermediate (2), potassium hydroxide described in step c is 1：0.1~0.5；
The mol ratio of raw material (B), intermediate (3), palladium catalyst described in step d is 1:1~1.2:0.3%~1%；
Sonogashira coupling reactions reaction temperature is 40~80 DEG C；The palladium catalyst is two (triphenylphosphine) palladium bichlorides or four (three
Phenylphosphine) palladium；
The mol ratio of intermediate (4) and thiophosgene described in step e is 1:1.2~2.
6. a kind of liquid-crystal composition, it is characterised in that including at least liquid-crystal compounds shown in a kind of formula (I), and weight percent
Content is less than or equal to 40% and is not zero.
7. liquid-crystal composition according to claim 6, it is characterised in that：Including less than or equal to 40% and the formula that is not zero
Compound shown in compound, 1%~40% formula II shown in I, compound shown in 1%~30% general formula III and 2%~
Compound shown in 50% general formulae IV,
Wherein, R1、R2、R3Be respectively carbon number be 1~7 alkyl, carbon number be 1~7 alkoxy or carbon number be
One kind in 1~5 fluoroalkyl；X1~X9It is-H or-F respectively.
8. liquid-crystal composition according to claim 7, it is characterised in that：Compound shown in formula II is 5%~30%, formula
Compound shown in III is that compound shown in 5%~25%, general formulae IV is 15%~46%.
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