CN106978192B - A kind of high birefringence liquid crystal compound and its preparation method and its composition - Google Patents
A kind of high birefringence liquid crystal compound and its preparation method and its composition Download PDFInfo
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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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- 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 compounds and preparation method thereof, and the composition containing this compound.Shown in the structure of liquid-crystal compounds such as general formula (I):Wherein X1、X2、X3For H or F, R be straight-chain alkenyl that carbon atom number is 2~5 or carbon atom number is one of 2~5 fluoro alkenyl.Liquid-crystal composition include less than or equal to 40% and be not zero I compound represented of general formula, 1%~40% general formula II shown in compound, 1%~30% general formula III shown in compound and 2%~50% general formulae IV shown in compound.Wherein, R1、R2、R3Be respectively carbon atom number be 1~7 alkyl, carbon atom number be 1~7 alkoxy or carbon atom number be one of 1~5 fluoroalkyl；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, was suitable for the fields such as spatial light modulator, laser detector and 3D display.
Description
Technical field
The invention belongs to liquid crystal material technical fields, and in particular to a kind of high birefringence rate liquid crystal compound and combinations thereof
Object is primarily adapted for use in laser detector, spatial light modulator, varifocal liquid crystal lens and microwave and mutually adjusts with the position in the field THz
Device processed and 3D display field etc..
Background technique
In recent years, with high birefringence rate liquid crystal material laser detector, spatial light modulator, liquid crystal grating and
Application in the novel liquid crystals such as varifocal liquid crystal lens optical device and 3D display, holographic technique is concerned.And liquid crystal light
Learning device application requirement must have certain Spatial transmission amount (λ of Δ nd >=1), if liquid crystal material have it is sufficiently large two-fold
It penetrates rate i.e. Δ n value to talk about, the smaller optical device of thickness of liquid crystal box can be prepared under identical modulation voltage, this can be mentioned significantly
The response speed of high device.The response time of phase-type liquid crystal light control device depends primarily on fall time, formula 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 to improve liquid crystal optical device overall performance, just must use simultaneously have high birefringence rate and it is low glue
Spend the liquid crystal material of characteristic.
For liquid-crystal compounds, to obtain 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 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 that will lead to formula in crystal formulations, which increase, even generates partial crystallization, these defects largely effect on compound and are being formulated
In additive amount.Tolans base isothiocyanates liquid-crystal compounds is viscous due to birefringence with higher and moderate rotation
Degree, is used widely in liquid crystal optical device, for improving the birefringence of formula, to promote the responsiveness of device
Energy.Therefore it in order to make mixed liquid crystal formula that there is faster response characteristic, while guaranteeing has high birefringence rate, selects as far as possible
It takes the liquid-crystal compounds with more low viscosity and more low melting point or low melt enthalpy as the main body component of formula, has to be formed
Low molten altogether and low viscosity good formulas.
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 the paper of crystals "
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 the paper of crystals "
Formula is as follows:
The phase transition temperature of report is Cr 96.7 (N 89.9) I, and 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 easy to cause low temperature in formula, there is partial crystallization phenomenon.
Summary of the invention
In order to overcome defect present in background technique or deficiency, the present invention provides a kind of high, fusing point with birefringence
With the melting liquid-crystal compounds and combinations thereof that enthalpy is low and rotary viscosity is small.
In order to realize that above-mentioned task, the present invention take following technical solution:
A kind of high birefringence rate liquid crystal compound, which is characterized in that shown in its general structure such as formula (I):
Wherein X1、X2、X3It is the straight-chain alkenyl that carbon atom number is 2~5 or the fluoro alkene that carbon atom number is 2~5 for H or F, R
One of base.
According to the present invention, the R is preferably the straight-chain alkenyl that carbon atom number is 3,4.
, according to the invention it is preferred to example be: the high birefringence rate liquid crystal compound, concrete structure formula are as follows:
Technical solution according to the invention, a kind of high birefringence rate liquid crystal compound are prepared using following synthetic route:
Specifically prepare according to the following steps:
1. under nitrogen protection, being sequentially added into reaction flask to iodophenol, raw material (A), K2CO3, ethyl alcohol, heating stirring, return
Stop stirring after stream reaction 2h, reaction solution is naturally cooling to room temperature, and after filtering out insoluble matter, rotating ethyl alcohol, normal heptane is added
Dissolved organic matter is washed to neutrality, filters after anhydrous magnesium sulfate is dry, chromatographs after filtrate revolving is dry through column, normal heptane elution, rotation
Intermediate (1) is obtained after solvent is evaporated off, wherein being 1:1~3 to the molar ratio of iodophenol, raw material (A)；
2. under nitrogen protection, intermediate (1), triethylamine, triphenylphosphine, cuprous iodide, two (triphens are added in reaction flask
Base phosphine) palladium chloride, in stirring a moment, heating is opened, keeps that trimethylsilyl acetylene and triethylamine mixed solution are added dropwise at 40 DEG C, 40
DEG C stirring reaction of stoppings in 3 hours, is cooled to filtering after room temperature, toluene dissolution is added after revolving, washing, dry, filtering, after rotating
Red liquid intermediate (2), wherein intermediate (1), trimethylsilyl acetylene molar ratio be 1:1~5；
3. intermediate (2) are added in reaction flask, and potassium hydroxide, water, ethyl alcohol are sequentially added, is stirred at room temperature 1 hour, stops
After only reacting, reaction solution is washed to neutrality after being extracted with normal heptane, and gained red liquid is using high vacuum distillation after solvent is evaporated off
Purified, collect 60Pa vacuum degree it is 80 DEG C lower when fraction, obtain intermediate (3), the intermediate (2), potassium hydroxide rub
You are than being 1:0.1~1；
4. under nitrogen protections, raw material (B), triethylamine, triphenylphosphine, cuprous iodide, palladium being 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, rotate and remove 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 reaction reaction temperature is 0~90 DEG C, raw material (B),
Intermediate (3), palladium catalyst molar ratio be 1:1~1.5:0.1%~3%；
5. intermediate (4), water, acetone are added in there-necked flask, thiophosgene stirring a moment, room temperature reaction 2 are added dropwise at room temperature
Hour, TLC monitoring stops reacting without starting material left, rotates reaction solution, and gained crude product is dissolved with toluene, is washed to neutrality, anhydrous
Magnesium sulfate dries, filters, and rotates and carries out column chromatographic purifying after doing dissolution, and the mixed solvent of normal heptane and toluene is eluted, and washes
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,
It is preferably 1:1~2 to the molar ratio of iodophenol, raw material (A) described in step 1；
Intermediate described in step 2 (1), trimethylsilyl acetylene molar ratio be preferably 1:1~2；
Intermediate described in step 3 (2), potassium hydroxide molar ratio be preferably 1:0.1~0.5；
Raw material described in step 4 (B), intermediate (3), palladium catalyst molar ratio be preferably 1:1~1.2:0.3%
~1%；Its reaction temperature of Sonogashira coupling reaction is preferably 40~80 DEG C；The palladium catalyst is to match containing organic phosphorus
The palladium catalyst of body, preferably two (triphenylphosphine) palladium chlorides or tetrakis triphenylphosphine palladium；
The molar ratio of intermediate described in step 5 (4) and thiophosgene is 1:1.2~2.
Technical solution according to the invention, a kind of high birefringence rate liquid-crystal composition include at least liquid shown in a kind of general formula I
Brilliant compound, and weight percentage is less than or equal to 40% and is not zero.It further include having chemical combination shown in 1%~40% general formula II
Object, 1%~30% general formula III shown in compound and 2%~50% general formulae IV shown in compound.
Wherein, R1、R2、R3Be respectively carbon atom number be 1~7 alkyl, carbon atom number be 1~7 alkoxy or carbon atom
One of the fluoroalkyl that number is 1~5；X1~X9It is-H or-F respectively.
Above-mentioned composition is preferred: compound shown in general formula II is 5%~30%, compound shown in general formula III be 5%~
25%, compound shown in general formulae IV is 15%~46%.
Technological progress obtained by the present invention is: liquid-crystal compounds of the invention has high birefringence rate, low melt enthalpy
The advantages 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, are particularly suitable for spatial light modulator and 3D display field.The present invention is also
A kind of preparation method of high birefringence rate liquid crystal compound is given, synthesis step is short, and raw material cost is low, experiment
Process is easy to operate, and aftertreatment technology is simple.
Specific embodiment
The present invention is described in further details below in conjunction with specific embodiment.
GC in embodiment indicates gas chromatographic purity (%), test equipment: the HP6820 type gas phase color of agilent company
Spectrum analysis instrument；1H-NMR indicates nuclear magnetic resonance spectroscopy, test equipment: the Advanced500MHz nuclear magnetic resonance of Bruker company
Instrument；GC-MS indicates gas chromatograph-mass spectrometer, test equipment: agilent company MS5975C type gas chromatograph-mass spectrometer.
The quantitative measurement method of liquid-crystal compounds is as follows:
Clearing point (Tni): polarisation thermal station method: liquid crystalline sample being coated on glass slide and is placed in cross-polarized light microscopic heating stand,
Setting heating rate is 3 DEG C/min, observes temperature of the liquid crystalline sample by illuminated state when blackening, as clearing point.Differential scanning
Calorimetry: under nitrogen protection, setting heating rate is 3 DEG C/min.
Basic components (P0) three kinds of liquid crystal lists as shown in following structural formula for liquid-crystal compounds quantitative measurement
Body is mixed according to 1:1:1 mass ratio.
It (Δ n) test method: is added to basic components P0 according to 5% mass ratio by the birefringence of liquid-crystal compounds
In, using abbe's refractometer, at 25 DEG C, the birefringence of test formulations under 589nm, extrapolation obtains the birefringent of monomeric compound
Rate.
Rotary viscosity (the γ of liquid-crystal compounds1) test method: 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 group) phenyl) acetenyl) the fluoro- 1- isothiocyano benzene of -2- synthesis:
Specific structure is as follows:
Preparation process is as follows:
The synthesis of step 1:1- (propenyloxy group) -4- iodobenzene
Under nitrogen protection, sequentially added in 2L reaction flask to iodophenol (176.08g, 0.8mol), the bromo- 1- propylene of 3-
(145.2g, 1.2mol), K2CO3(221g, 1.6mol), ethyl alcohol 800mL.Heating and stirring are opened, stop stirring after back flow reaction 2h
It mixes, is naturally cooling to room temperature and is post-processed.Insoluble matter is filtered out, after rotating ethyl alcohol, normal heptane dissolved organic matter, water is added
It is washed till neutrality, is filtered after anhydrous magnesium sulfate is dry, is chromatographed after filtrate revolving is dry through column, normal heptane elution, eluent revolving is removed
It is intermediate 1- (propenyloxy group) -4- iodobenzene that 201g colourless liquid is obtained after solvent.GC purity is 98.26%.
Step 2:((4- (propenyloxy group) phenyl) acetenyl) trimethyl silicane alkynes synthesis
Under nitrogen protection, compound 1-1 (201g, 0.77mol), PdCl are added in 2L reaction flask2(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, extremely to interior temperature rise
Start the mixed solution that the triethylamine of TMSA (154g, 1.92mol) is added dropwise at 40 DEG C.Stop after 40 DEG C of reaction 3h after being added dropwise
Heating, is cooled to room temperature naturally and is post-processed.Triethylamine is removed after filtering, filtrate revolving, normal heptane dissolved organic matter is added,
It is washed to neutrality after the aqueous solution washing of saturated ammonium chloride, is filtered after anhydrous magnesium sulfate is dry, filtrate revolving obtains after removing solvent
Column chromatographic purifying is carried out to red liquid, normal heptane elution, it is intermediate that eluent, which obtains red liquid 191g after rotating,
((4- (propenyloxy group) phenyl) acetenyl) trimethyl silicane alkynes.
The synthesis of step 3:1- (propenyloxy group) -4- acetylenylbenzene
The red liquid that upper step is obtained is added in 1L reaction flask, is added KOH (23.2g, 0.41mol), dehydrated alcohol
200ml, stopping stirring being post-processed after reacting at room temperature 1h.It rotates solvent, normal heptane dissolved organic matter is added, be washed to
Property, anhydrous magnesium sulfate is dry.Filtering, filtrate obtain red liquid 120.47g after rotating organic solvent.Using high vacuum distillation
It is purified, fraction 88g when collection 60Pa vacuum degree is 80 DEG C lower is intermediate 1- (propenyloxy group) -4- acetylenylbenzene, GC
Purity 98.16%.
The synthesis of step 4:4- ((4- (propenyloxy group) phenyl) acetenyl) -2- fluorine
Under nitrogen protection, the fluoro- 4- Iodoaniline (25.36g, 0.107mol) of 3-, PdCl are added in 500mL reaction flask2
(PPh3)2(0.75g, 1%mol), CuI (0.61g, 3%mol), PPh3(0.84g, 3%mol), Et3N 150mL.It opens and adds
Heat starts the triethylamine that the intermediate (3) (18.59g, 0.118mol) that upper step is reacted is added dropwise when interior temperature rise is to 70 DEG C
Mixed solution.Stop heating after being added dropwise after 70 DEG C of reaction 4h, is post-processed after being naturally cooling to room temperature.Filtering, filtrate
Triethylamine is removed after revolving, toluene 150mL dissolved organic matter is added, and the aqueous solution that saturated ammonium chloride is added washs 2 times, then washes
It to neutrality, is filtered after anhydrous magnesium sulfate is dry, filtrate revolving obtains khaki solid 13g after removing solvent.It is chromatographed using column pure
Change, toluene: normal heptane (volume ratio)=1:1 mixed solvent elution, eluent obtain crude product normal heptane and recrystallize 2 times after rotating
Obtaining the light yellow flat crystal of 10.5g is intermediate 4- ((4- (propenyloxy group) phenyl) acetenyl) -2- fluorine, GC purity
99.06%.
Step 5:4- ((propenyloxy group) phenyl) acetenyl) the fluoro- 1- isothiocyano benzene of -2- synthesis
In 250mL reaction flask be added 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 being stirred at room temperature reaction 1 hour to carry out
Post-processing.Toluene dissolved organic matter is added after removing organic solvent in revolving, is washed to neutrality, anhydrous magnesium sulfate dries, filters, and adds
Enter 10 times of normal heptane and carry out column chromatographic purifying, the mixed solvent of normal heptane and toluene is eluted, and is obtained after eluent revolving
Crude product, recrystallizing 1 time to obtain 9.8g white needle-like crystals with 10 times of normal heptanes is compound target compound 4- ((propylene oxygen
Base) phenyl) acetenyl) the fluoro- 1- isothiocyano 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 4- ((propenyloxy group) phenyl) acetenyl)-
The fluoro- 1- isothiocyano benzene of 2-.
With DSC with condition heating test 4- ((propenyloxy group) phenyl) acetenyl of 3 DEG C/min) the fluoro- 1- isothiocyano of -2-
The phase transition temperature of benzene, as a result are as follows: Cr 87.55 (28.92) I, fusing point are 87.55 DEG C, melting enthalpy 28.92kJ/mol.By the list
Body fluid crystalline substance is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, and test formulations is physical at 25 DEG C
Can, data are shown in Table 1.
1 test data of table
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 1+P0 | 0.0971 | 149.3 |
After 1 compound of embodiment is added, the birefringence of mixed liquid crystal increases 24%, and rotary viscosity reduces.According to adding
The birefringence value of method principle extrapolation 1 compound of embodiment is 0.4744, rotary viscosity 61.6mPaS.Prove the compound
Have the advantages that birefringence height and rotary viscosity are low.
Embodiment 2:
The synthesis of 4- ((4- (2,2- difluoroethylene base) phenyl) acetenyl) fluoro- isothiocyano benzene of -2-:
The fluoro- 4- Iodoaniline of 2- in 1 step of embodiment (4) is replaced using 4- Iodoaniline, using side similarly to Example 1
Method synthesizes 1- (propenyloxy group) -4- ((4- isothiocyanatophenyl) 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 1- (propenyloxy group) -4- ((4- isothiocyano
Phenyl) acetenyl) benzene.
With DSC with condition heating test 1- (propenyloxy group) -4- ((4- isothiocyanatophenyl) acetenyl) benzene of 3 DEG C/min
Liquid-crystal phase-transition temperature, as a result are as follows: Cr 104.8I, melting enthalpy be 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.
2 test data of table
| Mixed crystal code name | Δn(589nm) |
| P0 | 0.0784 |
| Embodiment 2+P0 | 0.0990 |
After 2 compound of embodiment is added, the birefringence of mixed liquid crystal increases 26%.It is extrapolated and is implemented according to addition principle
The birefringence value of 2 compound of example 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- isothiocyano benzene of -2-:
The fluoro- 4- Iodoaniline of 2- in 1 step of embodiment (4) is replaced using the fluoro- 4- Iodoaniline of 3-, using same with embodiment 1
The method of sample synthesizes 1- ((4- (propenyloxy group) phenyl) acetenyl) fluoro- 4- isothiocyano 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 1- ((4- (propenyloxy group) phenyl) acetylene
Base) the fluoro- 4- isothiocyano benzene of -2-.
With DSC with condition heating test 1- ((4- (propenyloxy group) phenyl) acetenyl) different sulphur of the fluoro- 4- of -2- of 3 DEG C/min
The liquid-crystal phase-transition temperature of cyano benzene, as a result are as follows: 66.35 N of Cr, 81.35 I, fusing point are 66.35 DEG C, and melting enthalpy is
21.35kJ/mol, nematic phase warm area are 15 DEG C.The compound has lower fusing point, lower 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, data are shown in Table 3 at DEG C.
3 test data of table
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 3+P0 | 0.0972 | 149.5 |
After 3 compound of embodiment is added, the birefringence of mixed liquid crystal increases 24%, and rotary viscosity also reduces.According to
The birefringence value of addition principle extrapolation 3 compound of embodiment is 0.4544, rotary viscosity 62mPaS.Prove the compound
Have the advantages that birefringence is high, rotary viscosity is low.
Embodiment 4:
The synthesis of the fluoro- 2- isothiocyano benzene of 5- ((4- (propenyloxy group) phenyl) acetenyl) -1,3- two:
The fluoro- 4- Iodoaniline of 2- in 1 step of embodiment (4), use and embodiment are replaced using the fluoro- 4- Iodoaniline of 2,6- bis-
1 same method synthesizes the fluoro- 2- isothiocyano benzene of 5- ((4- (propenyloxy group) phenyl) acetenyl) -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 above Structural Identification is statistics indicate that synthesized compound out is strictly 5- ((4- (propenyloxy group) phenyl) acetylene
Base) two fluoro- 2- isothiocyano benzene of -1,3-.
With DSC with the condition heating test fluoro- 2- of 5- ((4- (propenyloxy group) phenyl) acetenyl) -1,3- two of 3 DEG C/min
The liquid-crystal phase-transition temperature of isothiocyano benzene, as a result are as follows: Cr 86.90I, fusing point are 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 at 25 DEG C
The physical property of side, data are shown in Table 4.
4 test data of table
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 4+P0 | 0.0970 | 145.7 |
After 4 compound of embodiment is added, the birefringence of mixed liquid crystal increases 19%, and rotary viscosity also reduces.According to
The birefringence value of addition principle extrapolation 4 compound of embodiment is 0.4504, rotary viscosity 37.4mPaS.Prove the chemical combination
Object has the advantages that birefringence is high, rotary viscosity is low.
Embodiment 5
The preparation of 1- (3- butenyloxy) -4- ((4- isothiocyanatophenyl) acetenyl) benzene
The bromo- 1- propylene of 3- in 1 step of embodiment (1) is replaced using the bromo- 1- butylene of 4-, replaces implementing using 4- Iodoaniline
The fluoro- 4- Iodoaniline of 2- in 1 step of example (4) synthesizes 1- (3- butenyloxy) -4- using method similarly to Example 1
((4- isothiocyanatophenyl) 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 1- (3- butenyloxy) -4- ((different sulphur cyanogen of 4-
Base phenyl) acetenyl) benzene.
With DSC with condition heating test 1- (3- butenyloxy) -4- ((4- isothiocyanatophenyl) acetenyl) of 3 DEG C/min
The liquid-crystal phase-transition temperature of benzene, as a result are as follows: Cr 104.13I, fusing point are 104.13 DEG C, and melting enthalpy is 21.78kJ/mol.It 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.
5 test data of table
After 5 compound of embodiment is added, the birefringence of mixed liquid crystal increases 26%, and rotary viscosity also reduces.According to
The birefringence value of addition principle extrapolation 5 compound of embodiment is 0.4824, rotary viscosity 28.4mPaS.Prove the chemical combination
Object has the advantages that birefringence is high, rotary viscosity is low.
Embodiment 6
The preparation of 4- ((- (3- butenyloxy) phenyl) acetenyl) fluoro- 1- isothiocyano benzene of -2-
3- bromo- 1- propylene in 1 step of embodiment (1) is replaced using the bromo- 1- butylene of 4-, using similarly to Example 1
Method synthesizes 4- ((- (3- butenyloxy) phenyl) acetenyl) fluoro- 1- isothiocyano 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 4- ((- (3- butenyloxy) phenyl) acetylene
Base) the fluoro- 1- isothiocyano benzene of -2-.
With DSC with condition heating test 4- ((- (3- butenyloxy) phenyl) acetenyl) different sulphur of the fluoro- 1- of -2- of 3 DEG C/min
The liquid-crystal phase-transition temperature of cyano benzene, as a result are as follows: Cr 88.39I, fusing point are 88.39 DEG C, and melting enthalpy is 33.42kJ/mol.It will
The monomer liquid crystal is added in basic components P0 with 5% mass percent and forms mixed liquid crystal, the object of test formulations at 25 DEG C
Rationality energy, data are shown in Table 6.
6 test data of table
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 6+P0 | 0.0971 | 141.1 |
After 6 compound of embodiment is added, the birefringence of mixed liquid crystal increases 24%, and rotary viscosity also reduces.According to
The birefringence value of addition principle extrapolation 6 compound of embodiment is 0.4524, rotary viscosity 19.7mPaS.Prove the chemical combination
Object has the advantages that birefringence is high, rotary viscosity is low.
Embodiment 7
The preparation of 1- ((4- (3- butenyloxy) phenyl) acetenyl) fluoro- 4- isothiocyano benzene of -2-
The bromo- 1- propylene of 3- in 1 step of embodiment (1) is replaced using the bromo- 1- butylene of 4-, is replaced using the fluoro- 4- iodobenzene of 3-
The fluoro- 4- iodobenzene of 2- in embodiment step (4) synthesizes 1- ((4- (3- butenyloxy) using method similarly to Example 1
Phenyl) acetenyl) the fluoro- 4- isothiocyano 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 above Structural Identification is statistics indicate that synthesized compound out is strictly 1- ((4- (3- butenyloxy) phenyl) acetylene
Base) the fluoro- 4- isothiocyano benzene of -2-.
It is different with condition heating test 1- ((4- (3- butenyloxy) phenyl) acetenyl) fluoro- 4- of -2- of 3 DEG C/min with DSC
The liquid-crystal phase-transition temperature of thiocyanogen benzene, as a result are as follows: Cr 69.75I, fusing point are 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.
7 test data of table
| Mixed crystal code name | Δn(589nm) | γ1/mPa·S |
| P0 | 0.0784 | 156.5 |
| Embodiment 7+P0 | 0.0966 | 144.7 |
After 7 compound of embodiment is added, the birefringence of mixed liquid crystal increases 23%, and rotary viscosity also reduces.According to
The birefringence value of addition principle extrapolation 7 compound of embodiment is 0.4424, rotary viscosity 32.6mPaS.Prove the chemical combination
Object has the advantages that birefringence is high, rotary viscosity is low.
Embodiment 8
Liquid-crystal composition (being shown in Table 8) containing 1,3,6,7 structure of embodiment, including following ingredient: wherein " % " expression " matter
Measure percentage ", measurement characteristic is as follows in embodiment: n:25 DEG C of Δ, birefringence anisotropy under 589nm；Tm.p.: it is molten
Point；Tni: clearing point；γ1: rotary viscosity.
8 embodiment of table, 8 composition and performance
Embodiment 9:
Liquid-crystal composition containing 1,3,6,7 structure of embodiment, as shown in table 9.
9 embodiment of table, 9 composition and performance
Comparative example 1:
Synthesize following structural compounds according to literature method:
Its phase transition temperature is tested with the condition heating of 3 DEG C/min with DSC, as a result are as follows: Cr 88.75I, fusing point 88.75
DEG C, melting enthalpy is 31.13kJ/mol.And it is added in basic components P0 with 5% mass ratio, test formulations at 25 DEG C
Physical property, data are shown in Table 10.
10 test data of table
| 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, rotary viscosity 69.7mPaS.And 1 compound structure of above-described embodiment
That is:
Its phase transition temperature are as follows: Cr 87.55I, melting enthalpy are 28.92kJ/mol.
Compared with 1 compound of comparative example, fusing point reduces 1.2 DEG C, and melting enthalpy reduces 2.2kJ/mol, double
Refractive index improves 6%, rotary viscosity decline 12%.As can be seen, the liquid-crystal compounds fusing point of the present embodiment is lower, melting enthalpy
The advantages of lower, birefringence is bigger, rotary viscosity is lower, further demonstrates the compound.
Comparative example 2:
Periodical " Liquid crystals, 2003,30 (2): 191-198 ", entitled " Synthesis, mesomorphic
The paper of and optical propertities of isothiocyanatotolanes " 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.
11 test data of table
| 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 of extrapolation 2 compound of comparative example is 0.4844, rotary viscosity 71.6mPaS.And it is above-mentioned
2 compound structure of embodiment is i.e.:
Its phase transition temperature are as follows: Cr 104.8I, melting enthalpy are 21.35kJ/mol.
Compared with 2 compound of comparative example, the birefringence of 1 compound of embodiment 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 is bigger, fusing point is lower, melting enthalpy
The advantages of value is smaller, further demonstrates the compound.
Comparative example 3:
Synthesize following structural compounds according to literature method:
Its phase transition temperature is tested with the condition heating of 3 DEG C/min with DSC, as a result are as follows: Cr 72.51N 82.55I, fusing point are
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.
12 test data of table
| 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 of extrapolation 3 compound of comparative example is 0.4324, rotary viscosity 75.5mPaS.And it is above-mentioned
3 compound structure of embodiment is i.e.:
Compared with 3 compound of comparative example, fusing point reduces 6.2 DEG C, and melting enthalpy reduces 1.2kJ/mol, nematic
The advantages of phase temperature has widened 5 DEG C, and birefringence improves 5%, and viscosity has dropped 18%, further demonstrates 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 such as flowering structure is reported in the paper of crystals ":
Its phase transition temperature are as follows: 86.8 I of C, melting enthalpy are 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.
13 test data of table
| 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 of extrapolation 4 compound of comparative example is 0.4264, rotary viscosity 47.9mPaS.And it is above-mentioned
4 compound structure of embodiment is i.e.:
Its phase transition temperature, as a result are as follows: 86.90 I of Cr, fusing point are 86.90 DEG C, and melting enthalpy is 27.44kJ/mol,
Compared with 4 compound of comparative example, melting enthalpy reduces 5.1kJ/mol, and birefringence improves 6%, rotation
Turn viscosity decline 22%.As can be seen, the liquid-crystal compounds melting enthalpy of the present embodiment is lower, birefringence is bigger, rotation is viscous
The advantages of degree is lower, further demonstrates the compound.
Comparative example 5:
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
The paper of crystals " reports the liquid crystal material such as flowering structure:
Its phase transition temperature is 116 I of Cr 112.7 (SmE 112.0) N, melts 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.
14 test data of table
| 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 of extrapolation 5 compound of comparative example is 0.4584, rotary viscosity 75.7mPaS.And it is above-mentioned
5 compound structure of embodiment is i.e.:
Compared with 5 compound of comparative example, fusing point reduces 8.6 DEG C, melts enthalpy 4kJ/mol, and birefringence improves
The advantages of 5%, viscosity has dropped 62%, further demonstrates the compound.
Comparative example 6
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
The paper of crystals " reports the liquid crystal material such as flowering structure:
Its phase transition temperature is Cr 96.7I, melts 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.
15 test data of table
| 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 of extrapolation 6 compound of comparative example is 0.4284, rotary viscosity 78.6mPaS.And it is above-mentioned
6 compound structure of embodiment is i.e.:
Compared with 6 compound of comparative example, fusing point reduces 8.4 DEG C, and melting enthalpy reduces 2.2kJ/mol, birefringence
4% is increased, rotary viscosity reduces 75%.The advantages of further demonstrating the compound.
Comparative example 7:
Periodical " Crystals, 2013,3:443-482 ", entitled " High birefringence liquid
The paper of crystals " reports the liquid crystal material such as flowering structure:
Its phase transition temperature, as a result are as follows: Cr 70.3N 94.4I, fusing point are 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, data are shown in Table 16 at 25 DEG C.
16 test data of table
| 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 of extrapolation 7 compound of comparative example is 0.4284, rotary viscosity 77.5mPaS.And it is above-mentioned
7 compound structure of embodiment is i.e.:
Compared with 6 compound of comparative example, fusing point reduces 0.6 DEG C, and birefringence improves 3%, and rotary viscosity has dropped
58%.
Comparative example 8:
Liquid-crystal composition containing 1,3,6,7 structure of comparative example, such as table 17.
17 comparative example of table, 8 composition and performance
The discovery of the performance data of comparison sheet 8 and table 17: the compound of identical system, addition embodiment 1,3,6,7 is formed
Composition, 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 1,3,6,7 structure of comparative example, such as table 18.
18 comparative example of table, 9 composition and performance
The discovery of the performance data of comparison sheet 9 and table 18: the compound of identical system, addition embodiment 1,3,6,7 is formed
Composition, 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, which is characterized in that shown in general structure such as formula (I):
Wherein X1、X2、X3It is in the straight-chain alkenyl that carbon atom number is 2~5 or the fluoro alkenyl that carbon atom number is 2~5 for H or F, R
One kind.
2. liquid-crystal compounds according to claim 1, which is characterized in that the R is the straight chain that carbon atom number is 3~4
Alkenyl.
3. liquid-crystal compounds according to claim 2, which is characterized in that the 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 general formula described in claim 1 (I), which is characterized in that synthetic route are as follows:
Specific step is as follows:
A, it under nitrogen protection, is sequentially added into reaction flask to iodophenol, raw material (A), K2CO3, ethyl alcohol, heating stirring, reflux is anti-
Stop stirring after answering 2h, reaction solution is naturally cooling to room temperature, and after filtering out insoluble matter, rotating ethyl alcohol, normal heptane dissolution is added
Organic matter is washed to neutrality, filters after anhydrous magnesium sulfate is dry, chromatographs after filtrate revolving is dry through column, and normal heptane elution, revolving is removed
Intermediate (1) is obtained after falling solvent, wherein being 1:1~3 to the molar ratio of iodophenol, raw material (A)；
B, under nitrogen protection, intermediate (1), triethylamine, triphenylphosphine, cuprous iodide, two (triphenyls are added in reaction flask
Phosphine) palladium chloride, in stirring a moment, heating is opened, keeps that trimethylsilyl acetylene and triethylamine mixed solution are added dropwise at 40 DEG C, 40 DEG C
The reaction of stopping in 3 hours is stirred, filtering after room temperature is cooled to, toluene dissolution is added after revolving, after washing, dry, filtering, revolving
Red liquid intermediate (2), wherein intermediate (1), trimethylsilyl acetylene molar ratio be 1:1~5；
C, intermediate (2) are added in reaction flask, and sequentially add potassium hydroxide, water, ethyl alcohol, be stirred at room temperature 1 hour, stopped anti-
Ying Hou, reaction solution are washed to neutrality after being extracted with normal heptane, and gained red liquid is carried out using high vacuum distillation after solvent is evaporated off
Purification, collect 60Pa vacuum degree it is 80 DEG C lower when fraction, obtain intermediate (3), the intermediate (2), potassium hydroxide molar ratio
For 1:0.1~1；
D, under nitrogen protection, raw material (B), triethylamine, triphenylphosphine, cuprous iodide, palladium catalyst are sequentially added in there-necked flask,
The mixed solution of intermediate (3) and triethylamine is added dropwise in heating stirring when interior temperature rises to 70 DEG C, 70 DEG C of reaction 4h after dripping off,
Stop filtering after reaction, rotate and remove triethylamine, toluene dissolved organic matter, washing, drying, filtering is added, is used after filtrate revolving
Normal heptane recrystallizes to obtain intermediate (4), and the Sonogashira coupling reaction reaction temperature is 0~90 DEG C, raw material (B), centre
Body (3), palladium catalyst molar ratio be 1:1~1.5:0.1%~3%；
E, intermediate (4), water, acetone are added in there-necked flask, thiophosgene stirring a moment is added dropwise at room temperature, reacts at room temperature 2 hours,
TLC monitoring stops reacting without starting material left, rotates reaction solution, and gained crude product is dissolved with toluene, is washed to neutrality, anhydrous magnesium sulfate
It dries, filters, rotates and carry out column chromatographic purifying after doing dissolution, 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 molar ratio of thiophosgene are
1:1~4.
5. the preparation method according to claim 4, it is characterised in that:
It is 1:1~2 to the molar ratio of iodophenol, raw material (A) described in step a；
Intermediate described in step b (1), trimethylsilyl acetylene molar ratio be 1:1~2；
Intermediate described in step c (2), potassium hydroxide molar ratio be 1:0.1~0.5；
Raw material described in step d (B), intermediate (3), palladium catalyst molar ratio be 1:1~1.2:0.3%~1%；
Sonogashira coupling reaction reaction temperature is 40~80 DEG C；The palladium catalyst is two (triphenylphosphine) palladium chlorides or four (three
Phenylphosphine) palladium；
The molar ratio of intermediate described in step e (4) and thiophosgene is 1:1.2~2.
6. a kind of liquid-crystal composition, which is characterized in that include at least liquid-crystal compounds shown in a kind of general 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 the general formula for being less than or equal to 40% and being not zero
I compound represented, 1%~40% general formula II shown in compound, 1%~30% general formula III shown in compound and 2%~
Compound shown in 50% general formulae IV,
Wherein, R1、R2、R3Be respectively carbon atom number be 1~7 alkyl, carbon atom number be 1~7 alkoxy or carbon atom number be
One of 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 general formula II is 5%~30%, general formula
Compound shown in III is 5%~25%, compound shown in general formulae IV is 15%~46%.
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