CN102786456A - Liquid crystal compound containing isothiocyanic acid radical as well as preparation method and application thereof - Google Patents
Liquid crystal compound containing isothiocyanic acid radical as well as preparation method and application thereof Download PDFInfo
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- CN102786456A CN102786456A CN2012102616729A CN201210261672A CN102786456A CN 102786456 A CN102786456 A CN 102786456A CN 2012102616729 A CN2012102616729 A CN 2012102616729A CN 201210261672 A CN201210261672 A CN 201210261672A CN 102786456 A CN102786456 A CN 102786456A
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Abstract
The invention discloses a liquid crystal compound containing an isothiocyanic acid radical as well as a preparation method and an application thereof. The structural general formula of the liquid crystal compound containing the isothiocyanic acid radical is disclosed in a formula I. The compound containing the isothiocyanic acid radical is a liquid crystal monomer; the monomer of the class has bigger optical anisotropy (delta n); and after the monomer is added into mixed liquid crystal, the optical anisotropy of the mixed liquid crystal can be greatly increased so as to improve the property of the mixed liquid crystal. The formula I is as follows.
Description
Technical field
The invention belongs to liquid crystalline cpd and Application Areas, relate to a kind of liquid crystalline cpd that contains isosulfocyanate radical and preparation method thereof and application.
Background technology
LCD is divided into the type that dynamically shines, warping property TN, supertwist type STN and plane conversion hysteria IPS according to its display mode, though the used liquid-crystal compsn display characteristic of these LCD is different, following general character is arranged all:
1) under the change of environmental factorss such as water, air and light, keeps the stable of performance;
2) nematic temperature range of broad;
3) less viscosity;
4) lower driving voltage;
5) optical anisotropy (△ n) of the best.
In order to develop big specific refractory power liquid crystal, people have done a large amount of research, and this monomer liquid crystal of finding to contain isosulfocyanate radical is a stronger electron acceptor, have very strong moment of dipole (～3.59D), therefore this liquid crystal has very salient feature:
1. the liquid crystal that contains isosulfocyanate radical has extremely strong dipole moment, therefore can obtain bigger △ n through strengthening electron conjugated length;
2. the liquid crystal monomer that contains isosulfocyanate radical has bigger △ ε, though with respect to-CN is less, is more or less the same, and belongs to the liquid crystal monomer of big △ ε
3. the stability of this type liquid crystal monomer generally is higher than cyanogen class liquid crystal monomer, is the fabulous substitute of cyanogen class liquid crystal monomer, makes it in prescription is used, hold out broad prospects;
4. intermiscibility is preferably arranged during this type liquid crystal monomer low temperature,, do not influence the allotment of mixed crystal though therefore this type liquid crystal monomer fusing point is higher;
5. this type liquid crystal monomer has bigger resistivity.
Any demonstration all requires suitable TR with liquid crystal material, the mesomorphism temperature of broad, and advantages of higher stability, the viscosity that relatively is fit to has response speed faster to electric field.And some specific liquid crystal material also needs bigger optical anisotropy (△ n), higher resistivity (ρ), bigger dielectric anisotropy (△ ε) and reasonable low temperature intermiscibility.But single liquid crystal monomer can't satisfy all requirements, if but mix two or more liquid crystal monomer, being mixed becomes liquid crystal compound, just can obtain well behaved liquid crystal material.General TFT liquid crystal basically all is that more than 20 kind of monomer liquid crystal mixes.Therefore, also have very widely as this liquid crystal monomer that very big △ n, bigger viscosity arranged that contains isosulfocyanate radical and use.
Because its particular performances, the liquid crystal monomer that contains isosulfocyanate radical is widely used among various types of liquid crystal allotments, for example liquid crystal such as light scattering mode (RSM), PDLC, optical communication.These liquid crystal all have big △ n, and therefore the requirement of big △ ε also has bigger demand to the monomer liquid crystal that contains isosulfocyanate radical with this type character.
Summary of the invention
The purpose of this invention is to provide a kind of liquid crystalline cpd that contains isosulfocyanate radical and preparation method thereof and application.
The liquid crystalline cpd that contains isosulfocyanate radical provided by the invention, its general structure be suc as formula shown in the I,
Formula I
Among the said formula I, R is H, C
1-C
15Alkyl, C
1-C
15Alkoxyl group, C
1-C
15Thiazolinyl, C
1-C
15Alkene oxygen base, cyclohexyl, C
1-C
15The substituted cyclohexyl of alkyl, C
1-C
15The substituted cyclohexyl of alkoxyl group, C
1-C
15The cyclohexyl of alkenyl substituted, C
1-C
15At least one hydrogen in any group in substituted cyclohexyl of alkene oxygen base or the above-mentioned all kinds of group by at least a replacement in the halogen and group;
Above-mentioned containing-CH
2-any group in one or more non-conterminous-CH
2-can be replaced by at least a substituted group in the following group :-C ≡ C-,-C=C-,-O-,-COO-or-OCO-;
L
1And L
2Represent H or F independently of one another, but be not H simultaneously.
Preferably, R is C
1-C
7Alkyl, C
1-C
7Alkoxyl group, C
2-C
7Thiazolinyl or C
1-C
7The substituted cyclohexyl of alkyl.
Compound specifically can be shown in the said formula I
Wherein, R is C
1-C
7Alkyl, C
1-C
7Alkoxyl group, C
2-C
7Thiazolinyl, C
1-C
7The substituted cyclohexyl of alkyl.
The method for preparing the said compound of formula I provided by the invention comprises the steps:
1) biphenyl, concentrated nitric acid and iodine mixing are carried out nitration reaction; Obtain behind the iodo nitrobiphenyl; Gained is reduced back flow reaction to iodo nitrobiphenyl and Hydrazine Hydrate 80 under the condition that catalyzer a exists; Reaction finishes and obtains iodo amido biphenyl; Gained is carried out the coupling back flow reaction to iodo amido biphenyl and 2-methyl isophthalic acid-alkynes-Ding-2-alcohol under the condition of acid binding agent and catalyzer b existence; Reaction finishes and obtains
and again gained
and alkali are taken off the acetone back flow reaction, and reaction finishes and obtains iodo amido biphenyl acetylene
2)
carried out adding iodine again behind the lithiation with n-Butyl Lithium and react, reaction finishes and obtains
3) with said step 1) gained to iodo amido biphenyl acetylene
and said step 2) gained
mixing carries out linked reaction, obtains
4) with said step 3) gained
With thiophosgene (CSCl
2) and the carbonate mixing react and obtain compound shown in the said formula I;
Said
In, said R, L
1And L
2Definition with aforementioned identical.
The reaction process of this method is as follows:
In the said step 1) of aforesaid method, said catalyzer a is selected from least a in iron trichloride, titanium tetrachloride and the palladium carbon;
Said catalyzer b is the mixture that tetrakis triphenylphosphine palladium, cuprous iodide and triphenylphosphine are formed; Wherein, the mass ratio of said tetrakis triphenylphosphine palladium, cuprous iodide and triphenylphosphine is: 1: (3-5): (3-8), and preferred 1.5:5:8;
Said alkali is selected from least a in Pottasium Hydroxide, sodium hydride and the sodium hydroxide;
The mass percentage concentration of said concentrated nitric acid is 50%-68%, preferred 68%;
The amount ratio of said biphenyl, concentrated nitric acid and iodine is 1mol:100-500ml:0.8-2mol, preferred 1mol:200ml:1.1mol;
Said amount ratio to iodo nitrobiphenyl, Hydrazine Hydrate 80 and catalyzer a is 1mol:100-200ml:4-10g, preferred 1mol:120ml:6g;
Said amount ratio to iodo amido biphenyl, 2-methyl isophthalic acid-alkynes-Ding-2-alcohol, acid binding agent and catalyzer b is 1mol:1.5-2mol:300-1000ml:2-15g, preferred 1mol:2mol:757ml:14.5g;
Said
is 1mol:0.8-1.5mol with the amount ratio of alkali, preferred 1mol:1.05mol;
In the said nitration reaction step, temperature is 50-80 ℃, and the time is 2-6 hour;
In the said reduction backflow reactions step, the time is 1-6 hour;
In the said coupling back flow reaction step, the time is 3-10 hour;
Said taking off in the acetone back flow reaction step, the time is 0.5-3 hour;
Step 2) in; Said
is 1mol:1-1.3mol with the amount ratio of n-Butyl Lithium, preferred 1mol:1.15mol;
In the said lithiation step, temperature is-60--90 ℃, and the time is 20-60 minute; The said iodine that adds again carries out in the reactions step, and temperature is-60--90 ℃, the time is 1-3 hour;
In the step 3); Said step 1) gained is to iodo amido biphenyl acetylene
and said step 2) amount ratio of gained
is 1mol:1-1.2mol, preferred 1:1.1;
In the said coupling back flow reaction step, the time is 4-10 hour;
In the said step 4), said carbonate is selected from least a in lime carbonate, yellow soda ash and the salt of wormwood; Said step 3) gained
Thiophosgene CSCl
2With the amount ratio of carbonate be 1mol:1-2mol:0.5-4mol, preferred 1mol:1.5mol:2mol;
In the said reactions step, temperature is 0-40 ℃, and the time is 1-4 hour;
The said reaction of said step 1) to step 4) is all carried out in solvent; Said solvent is selected from least a in THF, toluene and the chloroform.
At least a liquid crystal compound in the compound also belongs to protection scope of the present invention shown in the formula I that the invention described above provides, and is concrete, contains any one to the five kind of compound in the said compound of formula I in the said liquid crystal compound.Such liquid crystal compound has following at least a characteristic: bigger △ n, bigger △ ε, higher clearing point.
More specifically, said liquid crystal compound is any one among the following liquid crystal compound a to c:
Liquid crystal compound a:
Liquid crystal compound b:
Liquid crystal compound c:
Among the above-mentioned liquid crystal compound a to c, each components contents is the quality percentage composition.
The gross weight of compound accounts for the 1-95% of said liquid crystal compound shown in the said formula I, preferred 5-60%, more preferably 5-40%.
The application in preparation liquid crystal display material or electrooptics display material of compound shown in the formula I that the invention described above provides or foregoing liquid crystal mixture; And contain the liquid crystal display material or the electrooptics display material of compound shown in the said formula I or foregoing liquid crystal mixture, also belong to protection scope of the present invention.
The compound that contains isosulfocyanate radical shown in the formula I provided by the invention is a kind of liquid crystal monomer; This type of monomer has bigger optical anisotropy (△ n); Being added in the mixed liquid crystal to increase the optical anisotropy of mixed liquid crystal greatly, thereby improves the character of mixed liquid crystal.
Description of drawings
Fig. 1 is the mass spectrum of embodiment 1 preparation products therefrom.
Fig. 2 is the mass spectrum of embodiment 2 preparation products therefroms.
Fig. 3 is the mass spectrum of embodiment 13 preparation products therefroms.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is ordinary method if no special instructions.Said reaction raw materials all can get from open commercial sources if no special instructions.
Product shown in the following embodiment gained formula I all utilizes gc and GC-MS gained mass spectrum to identify and confirms structural correctness.GC is measured by the HP6820 type gas chromatographicanalyzer of Agilent company, and GC-MS assay determination device is the MS5975C type of Agilent company, and the micro-thermal analyzer of WRX-1S is used in fusing point test, and setting temperature rise rate is 3 ℃/min.
The rerum natura of product all uses dual mode to measure shown in the following embodiment gained formula I: compound itself is measured as sample and compound mixed as sample with the parent liquid crystal measure.Compound is mixed the mode of measuring the compound rerum natura as sample with the parent liquid crystal be: at first 15% liquid crystalline cpd is mixed with 85% parent liquid crystal and make sample; Then according to the measured value of gained sample; Extrapotation according to shown in the following formula is calculated extrapolated value
The weight percent of extrapolated value=[100 * (measured value of sample)-(weight percent of parent liquid crystal) * (measured value of parent liquid crystal)]/compound,
Thereby draw the rerum natura of monomer liquid crystal compound.
Used parent liquid crystal is formed as follows:
The physical property measurement method of compound:
Phase structure and transmit temperature (℃) mensuration
1. possessing polarizing microscope fusing point appearance [plum Teller (Mettler) FP-52 of company type], place compound on the hot-plate, on one side with the heating of 3 ℃/min speed, utilize polarizing microscope to observe phase-state change on one side, thereby confirm the phase kind.
2. utilize the differential calorimetric of Mei Tele company to turn round scanner DSC822e, heat up or cooling, utilize extrapotation to obtain to follow heat absorption crest or the starting point of heating crest of the phase change of sample, thereby confirm tansition temperatures with the speed of 1 ℃/min.
Crystallization is expressed as C, and smectic phase is S, and nematic phase is N, and liquid is I.
2. viscosity (η measures mPa.s down at 20 ℃) is used E type rotary viscosity design determining.
3. optical anisotropy (the specific refractory power anisotropy is measured △ n down at 25 ℃) is determined under 25 ℃, with the light of wavelength 589nm, uses Abbe refractometer to measure △ n.After a direction rubs to the surface of headprism (Pri3m), sample is added drop-wise on the headprism.Specific refractory power (n
11) be when polarization direction is parallel with frictional direction, to measure institute's value, specific refractory power (n
⊥) be when polarization direction is vertical with frictional direction, to measure institute's value, the value of optical anisotropy (△ n) is by △ n=n
11-n
⊥Calculate.
4. dielectric constant anisotropy (△ ε measures down at 25 ℃) is measured by the accurate LCR tester of the HP4284a of Hewlett-Packard.Measure the DIELECTRIC CONSTANTS of liquid crystal molecule at long axis direction
||, measure the specific inductivity (ε of liquid crystal molecule at short-axis direction
⊥), dielectric anisotropy △ ε is through △ ε=ε
||-ε
⊥Calculate.
The preparation of
Step 1) a, to the preparation of iodo nitrobiphenyl
Add 254g (1mol) biphenyl (solvent) and 280g (1.1mol) iodine grain (reactant) in the 1L there-necked flask, being heated to 70 ℃ of left and right sides molten states, to drip the 200ml mass percentage concentration be 68% concentrated nitric acid (reactant), keeps temperature of reaction between 65 ℃-75 ℃, occurs red gas during reaction; Import the alkali bottle and remove, be cooled to about 40 ℃ after dropwising, add 40ml methylene dichloride (solvent); Be heated to backflow once more, backflow 4h, reaction finishes; Reduce to room temperature, filter and obtain brown solid, 500ml deionized water (solvent) washing leaching cake; Add 500ml toluene (solvent) after draining solid is boiled about 30min, filter after cooling, oven dry; Obtain yellow solid product 322g, GC:92.4%, yield 91.5%.
B, to the preparation of iodo amido biphenyl
Add aforementioned preparation gained 322g (0.915mol) in the 1L there-necked flask to iodo nitrobiphenyl (reactant) and 600mlTHF (solvent), be heated to material dissolution, reduce to room temperature afterwards, add 30g gac (sorbent material) and 5g iron trichloride (catalyzer); Be heated to backflow, stir and drip 100ml Hydrazine Hydrate 80 (reactant) down, the control rate of addition makes its gentle reflux; After dropwising, backflow 4h, filtered while hot, elimination gac; Get upper organic phase, revolve to steam to remove and desolvate, add 200ml toluene recrystallization, filter after the freezing 4h of refrigerator; Obtain light yellow product 271g (0.88mol), detect GC:95.4%, yield 96.2%.
C, to the preparation of iodo amido biphenyl acetylene
The 102g (0.33mol) that a last step of adding obtains in the 1L there-necked flask under nitrogen protection, is heated to backflow to iodo amido biphenyl (reactant), 56g (0.66mol) 2-methyl isophthalic acid-alkynes-Ding-2-alcohol (reactant), 250ml triethylamine (acid binding agent), 250ml toluene (solvent), 1.5g tetrakis triphenylphosphine palladium (catalyzer) and 5g cuprous iodide (catalyzer), 8g triphenylphosphine (catalyzer); Refluxed 6 hours, and reacted the cool to room temperature that finishes, filter; 200ml toluene (solvent) washing leaching cake; Filtrating is revolved steaming except that desolvating, and 100ml toluene (solvent) dissolves thick product, crosses 10cm silica gel pillar and purifies; Revolve to steam to remove and desolvate, subsequent use.
Reaction product and 20g (0.35mol) Pottasium Hydroxide (reactant), the 200ml toluene (solvent) that added a lasted step in the 500ml there-necked flask, reflux 1h changes back afterwards that to heat up in a steamer be to distill; Steam low-boiling-point substance and about 50ml toluene, reduce to room temperature after reaction finishes, in the bottle a small amount of mud shape insolubles is arranged; Cross and filter out 100ml toluene (solvent) washing leaching cake, the 10cm silicagel column of will filtrating; Obtain red liquid, revolve to steam to remove and desolvate, add 100ml toluene recrystallization; Obtain 57g yellow solid (0.28mol), detect GC:96.2%, yield 85.2%.
2) 4-iodo-3, the preparation of 5-difluoro ethylbenzene:
Add 3 of 44g (0.31mol) in the 250ml there-necked flask, 5-difluoro ethylbenzene (reactant) and the dried THF of 100ml (solvent) under nitrogen protection, are cooled to-70 ℃; Drip 48ml (0.36mol) n-Butyl Lithium (2.5M) (reactant), keep temperature-70--80 ℃, after dropwising, keep low-temp reaction 30min; Drip 50mlTHF (solvent) solution dissolved 102g (0.4mol) iodine (reactant) again, maintenance-70--80 ℃ 2 hours, after dropwising; Naturally heat up, add the saturated aqueous solution of sodium bisulfite hydrolysis of 50ml, separatory about 0 ℃; Get upper organic phase, revolve to steam to remove and desolvate, obtain product weak yellow liquid 82g (0.29mol); GC:95.1%, yield: 93.8%, subsequent use.
3) preparation of 4'-((4-ethyl-2,6-fluorophenyl) ethynyl) biphenyl-4-amine:
The 250ml there-necked flask adds 9.65g (0.048mol) step 1) gained to iodo phenylaniline acetylene (reactant) and 14.44g (0.051mol) step 2) gained 4-iodo-3,5-difluoro ethylbenzene (reactant), 0.2g tetrakis triphenylphosphine palladium (catalyzer), 1g cuprous iodide (catalyzer), 1.5g triphenylphosphine (catalyzer), 50ml triethylamine (acid binding agent), 100ml toluene (solvent), nitrogen protection; Be heated to backflow, back flow reaction 6h, reaction finishes and reduces to room temperature; Filter; 50ml toluene wash filter cake, the 10cm silica gel pillar of will filtrating revolves afterwards to steam to remove and desolvates; Add 30ml toluene recrystallization; Obtain 13.65g (0.041mol) light yellow crystal, GC:99.0%, yield 84.5%.
4) preparation of compound 4'-shown in thiophosgene and the formula I ((4-ethyl-2,6-difluorophenyl) ethynyl) biphenyl-4-lsothiocyanates:
2L there-necked flask and 1L tap funnel are respectively charged into 122.5g (1mol) Potcrate (reactant) and 600ml (7.2mol) concentrated hydrochloric acid (reactant), are assembled into the chlorine generating unit, add 38g (0.5mol) dithiocarbonic anhydride (reactant) in the 500ml there-necked flask; The ice bath cooling drips concentrated hydrochloric acid, generates chlorine; Through reacting in the dry back feeding of the vitriol oil (siccative) dithiocarbonic anhydride, keep slowly dripping, make to react completely; Reaction finishes about about 20h; 142 ℃ of cuts are afterwards got in the distillation of reaction back, and adding 10g sodium sulfate (siccative) back is subsequent use.
Add 60g (0.5mol) metallic tin (reactant) in the 500ml there-necked flask, add 200ml hydrochloric acid (reactant), be heated to backflow; Stirring reaction 1h reacts completely it, single step reaction thing in the dropping, room temperature reaction 1h; After reaction finishes, change distillation into, get 72-76 ℃ of cut; Obtain red liquid 46g (0.4mol), yield 80%.
100ml single port bottle adds step 3) gained 3.36g (0.01mol) 4'-((4-ethyl-2,6-difluorophenyl) ethynyl) biphenyl-4-amine (reactant), 2g (0.02mol) lime carbonate (reactant), 30ml chloroform (solvent); Add 1.7g (0.015mol) thio phosgene (reactant), stirring at room 2h, reaction finishes and adds 20ml deionized water (solvent) hydrolysis; Separatory takes off a layer organic phase, revolves to steam to remove to desolvate; Add 50ml toluene (solvent) and use silica gel column chromatography to purify, revolve to steam to remove and desolvate, use 5 times of toluene recrystallizations 3 times; Obtain white crystal 3.02g (0.008mol), yield 80%.
Test result is following:
(1)GC：99.6%；
(2) mass spectrum: as shown in Figure 1;
(3) the compound phase-variable temperature (℃): Cr143.52S
A183.82N268.55I;
(4) compound itself is measured as sample, directly tested the optical anisotropy and the dielectric anisotropy of the liquid crystal monomer shown in the formula 1-1, the fitting parameter of gained is Δ n=0.528, Δ ε=22.9;
(5) liquid crystal monomer shown in the formula 1-1 and parent liquid crystal proportional mixing are measured optical anisotropy and dielectric anisotropy as sample, gained result such as table 1:
Table 1, test data tabulation
By on can know that this compound structure is correct, be the target compound shown in the formula 1-1.And can find out by the rerum natura of above-claimed cpd; Present embodiment prepares gained compound 1-1 and has the necessary characteristic as liquid crystal display material; Can effectively improve the optical anisotropy (Δ n) of mixed liquid crystal; Have bigger dielectric anisotropy (Δ ε), can be used as a kind of in the liquid crystal display material, be used for the Δ n and the Δ ε of regulator solution crystal composite.
Embodiment 2
The preparation of
Step 1) is according to preparing iodo amido biphenyl acetylene with embodiment 1 identical step
Step 2) 4-iodo-3, the preparation of 5-difluoro propylbenzene:
Add 3 of 27g (0.173mol) in the 250ml there-necked flask, 5-difluoro propylbenzene (reactant) and the dried THF of 100ml (solvent) under nitrogen protection, are cooled to-70 ℃; Drip 27ml (0.2mol) n-Butyl Lithium (2.5M) (solvent), keep temperature-70--80 ℃, after dropwising, keep low-temp reaction 30min; Drip 50mlTHF (solvent) solution that has dissolved 53.5g iodine (0.21mol) (reactant) again, maintenance-70--80 ℃, after dropwising; Naturally heat up, add the saturated sodium sulfite anhy 96 of 50ml (reductive agent) aqueous hydrolysis, separatory about 0 ℃; Get upper organic phase, revolve to steam to remove and desolvate, obtain product weak yellow liquid 46g (0.155mol); GC:95.1%, yield: 89.7%, subsequent use.
The preparation of step 3) 4'-((4-propyl group-2,6-difluorophenyl) ethynyl) biphenyl-4-amine:
The 250ml there-necked flask adds 9.65g (0.048mol) step 1) gained to iodo amido biphenyl acetylene (reactant) and 15.1g (0.051mol) step 2) gained 4-iodo-3,5-difluoro propylbenzene (reactant), 0.2g tetrakis triphenylphosphine palladium (catalyzer), 1g cuprous iodide (catalyzer), 1.5g triphenylphosphine (catalyzer), 50ml triethylamine (acid binding agent), 100ml toluene (solvent), nitrogen protection; Be heated to backflow, back flow reaction 6h, reaction finishes and reduces to room temperature; Filter; 50ml toluene (solvent) washing leaching cake, the 10cm silica gel pillar of will filtrating revolves afterwards to steam to remove and desolvates; Add 30ml toluene recrystallization; Obtain 14.6g (0.042mol) light yellow crystal, GC:99.1%, yield 86.9%.
The preparation of compound 4'-shown in the step 4) formula I ((4-propyl group-2,6-difluorophenyl) ethynyl) biphenyl-4-lsothiocyanates:
100ml single port bottle adds 3.5g (0.01mol) mol4'-((4-propyl group-2,6-difluorophenyl) ethynyl) biphenyl-4-amine (reactant), 2g (0.02mol) lime carbonate (reactant), 30ml chloroform (solvent); Add 1.7g (0.015mol) thiophosgene (reactant) (its preparation method is with embodiment 1 step 4)), stirring at room 2h, reaction finishes and adds 20ml deionized water (solvent) hydrolysis; Separatory takes off a layer organic phase, revolves to steam to remove to desolvate; Add 50ml toluene (solvent) and use silica gel column chromatography to purify, revolve to steam to remove and desolvate, use 5 times of toluene recrystallizations 3 times; Obtain white crystal 3.19g, yield 81.5%.
Test result is following:
(1)GC：99.4%；
(2) mass spectrum: as shown in Figure 2;
(3) the compound phase-variable temperature (℃): Cr137.71S
A195.29N272.93I;
(4) compound itself is measured as sample, directly tested the optical anisotropy and the dielectric anisotropy of the liquid crystal monomer shown in the formula 1-1, the fitting parameter of gained is Δ n=0.526, Δ ε=20.5.
Embodiment 3-4
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 3 respectively, 5-difluoro butylbenzene-, 3,5-difluoro amylbenzene, other are operated with embodiment 1, prepare following compound.
The rerum natura of test liquid crystal monomer 1-3 and 1-4 obtains following result:
The liquid crystal applications character data of table 2 liquid crystal monomer
Embodiment 5-8
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 3-fluoro ethyl benzene, 3-fluoropropyl benzene, 3-fluorine butylbenzene-, 3-fluorine amylbenzene respectively, and other are operated with embodiment 1, prepare following compound.
The test gained is the liquid crystal property of structural formula compound as above, and gained data and embodiment 1-4 do not have substantive difference, repeat no more here.
Embodiment 9-12
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 1 respectively; 3-two fluoro-5-anisoles, 1,3-two fluoro-5-phenetoles, 1,3-two fluoro-5-butyl phenyl ethers, 1; 3-two fluoro-5-amyl phenyl ethers, other are operated with embodiment 1, prepare following compound.
The test gained is the liquid crystal property of structural formula compound as above, and gained data and embodiment 1-4 do not have substantive difference, repeat no more here.
Embodiment 13
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 1,3-two fluoro-5-propoxy-benzene, other are operated with embodiment 1, prepare following compound.
(1)GC：99.4%；
(2) mass spectrum: as shown in Figure 3;
(3) the compound phase-variable temperature (℃): Cr124.87N290.43I;
(4) compound itself is measured as sample, directly tested the optical anisotropy and the dielectric anisotropy of the liquid crystal monomer shown in the formula 1-1, the fitting parameter of gained is Δ n=0.537, Δ ε=24.2.
Embodiment 14-18
Present embodiment reference example 1; With 3 in the step 4; 5-difluoro ethylbenzene replaces with 1-methoxyl group-3-fluorobenzene, 1-oxyethyl group-3-fluorobenzene, 1-propoxy--3-fluorobenzene, 1-butoxy-3-fluorobenzene, 1-pentyloxy-3-fluorobenzene respectively, and other are operated with embodiment 1, prepare following compound.
The test gained is the liquid crystal property of structural formula compound as above, and gained data and embodiment 1-4 do not have substantive difference, repeat no more here.
Embodiment 19-22
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 1-(4-ethyl cyclohexyl)-3 respectively; 5-fluorobenzene, 1-(4-propyl group cyclohexyl)-3; 5-fluorobenzene, 1-(4-butyl cyclohexyl)-3,5-fluorobenzene, 1-(4-amyl group cyclohexyl)-3,5-fluorobenzene; Other operations prepare following compound with embodiment 1.
The test gained is the liquid crystal property of structural formula compound as above, and gained data and embodiment 1-4 do not have substantive difference, repeat no more here.
Embodiment 23-27
Present embodiment reference example 1, with 3 in the step 4,5-difluoro ethylbenzene replaces with 1 respectively; 3-two fluoro-5-(4-methoxyl group cyclohexyl) benzene, 1,3-two fluoro-5-(4-oxyethyl group cyclohexyl) benzene, 1,3-two fluoro-5-(4-propoxy-cyclohexyl) benzene, 1; 3-two fluoro-5-(4-butoxy cyclohexyl) benzene, 1; 3-two fluoro-5-(4-pentyloxy cyclohexyl) benzene, other are operated with embodiment 1, prepare following compound.
The test gained is the liquid crystal property of structural formula compound as above, and gained data and embodiment 1-4 do not have substantive difference, repeat no more here.
Embodiment 28
According to following each compound ratio allotment mixed crystal, and the optical anisotropy and the dielectric anisotropy of mensuration mixed crystal.
The performance of gained liquid crystal compound is following:
Physical properties: cp=97 ℃
Δn=0.30
Δε=4.5
Can know, be to be added in the mixed liquid crystal to increase the optical anisotropy of mixed liquid crystal greatly with the compound that contains isosulfocyanate radical shown in the formula I provided by the invention, thereby improve the character of mixed liquid crystal.
According to following each compound ratio allotment mixed crystal, and the optical anisotropy and the dielectric anisotropy of mensuration mixed crystal.
The performance of gained liquid crystal compound is following:
Physical properties: cp=95 ℃
Δn=0.35
Δε=10
Can know, be to be added in the mixed liquid crystal to increase the optical anisotropy of mixed liquid crystal greatly with the compound that contains isosulfocyanate radical shown in the formula I provided by the invention, thereby improve the character of mixed liquid crystal.
Embodiment 30
According to following each compound ratio allotment mixed crystal, and the optical anisotropy and the dielectric anisotropy of mensuration mixed crystal.
The performance of gained liquid crystal compound is following:
Physical properties: cp=80 ℃
Δn=0.21
Δε=1
Can know, be to be added in the mixed liquid crystal to increase the optical anisotropy of mixed liquid crystal greatly with the compound that contains isosulfocyanate radical shown in the formula I provided by the invention, thereby improve the character of mixed liquid crystal.
Claims (10)
1. compound shown in the formula I,
Formula I
Among the said formula I, R is H, C
1-C
15Alkyl, C
1-C
15Alkoxyl group, C
1-C
15Thiazolinyl, C
1-C
15Alkene oxygen base, cyclohexyl, C
1-C
15The substituted cyclohexyl of alkyl, C
1-C
15The substituted cyclohexyl of alkoxyl group, C
1-C
15The cyclohexyl of alkenyl substituted, C
1-C
15At least one hydrogen in any group in substituted cyclohexyl of alkene oxygen base or the above-mentioned all kinds of group by at least a replacement in the halogen and group;
R also is above-mentioned containing-CH
2-any group in one or more non-conterminous-CH
2-by at least a replacement in the following group and group :-C ≡ C-,-C=C-,-O-,-COO-or-OCO-;
L
1And L
2Represent H or F independently of one another, but be not H simultaneously.
2. compound according to claim 1 is characterized in that: among the said formula I, R is C
1-C
7Alkyl, C
1-C
7Alkoxyl group, C
2-C
7Thiazolinyl or C
1-C
7The substituted cyclohexyl of alkyl.
3. compound according to claim 1 and 2 is characterized in that: compound shown in the said formula I is a compound shown in compound shown in the formula I1 or the formula I2:
Formula I1
Formula I2
Among said formula I1 and the formula I2, R is C
1-C
7Alkyl, C
1-C
7Alkoxyl group, C
2-C
7Thiazolinyl or C
1-C
7The substituted cyclohexyl of alkyl.
4. a method for preparing the arbitrary said compound of claim 1-3 comprises the steps:
1) biphenyl, concentrated nitric acid and iodine mixing are carried out nitration reaction; Obtain behind the iodo nitrobiphenyl; Gained is reduced back flow reaction to iodo nitrobiphenyl and Hydrazine Hydrate 80 under the condition that catalyzer a exists; Reaction finishes and obtains iodo amido biphenyl; Gained is carried out the coupling back flow reaction to iodo amido biphenyl and 2-methyl isophthalic acid-alkynes-Ding-2-alcohol under the condition of acid binding agent and catalyzer b existence; Reaction finishes and obtains
and again gained
and alkali are taken off the acetone back flow reaction, and reaction finishes and obtains iodo amido biphenyl acetylene
2)
carried out adding iodine again behind the lithiation with n-Butyl Lithium and react, reaction finishes and obtains
3) with said step 1) gained to iodo amido biphenyl acetylene
and said step 2) gained
mixing carries out linked reaction, obtains
4) with said step 3) gained
With thiophosgene CSCl
2React with the carbonate mixing and to obtain compound shown in the said formula I;
Said
In, said R, L
1And L
2Definition all identical with claim 1.
5. method according to claim 4 is characterized in that: in the said step 1), said catalyzer a is selected from least a in iron trichloride, titanium tetrachloride and the palladium carbon;
Said catalyzer b is the mixture that tetrakis triphenylphosphine palladium, cuprous iodide and triphenylphosphine are formed; Wherein, the mass ratio of said tetrakis triphenylphosphine palladium, cuprous iodide and triphenylphosphine is: 1: (3-5): (3-10), and preferred 1.5:5:8;
Said alkali is selected from least a in Pottasium Hydroxide, sodium hydride and the sodium hydroxide;
The mass percentage concentration of said concentrated nitric acid is 50%-68%, preferred 68%;
The amount ratio of said biphenyl, concentrated nitric acid and iodine is 1mol:100-500ml:0.8-2mol, preferred 1mol:200ml:1.1mol;
Said amount ratio to iodo nitrobiphenyl, Hydrazine Hydrate 80 and catalyzer a is 1mol:100-200ml:4-10g, preferred 1mol:110ml:5.5g;
Said amount ratio to iodo amido biphenyl, 2-methyl isophthalic acid-alkynes-Ding-2-alcohol, acid binding agent and catalyzer b is 1mol:1.5-2mol:300-1000ml:2-15g, preferred 1mol:2mol:757ml:14.5g;
Said
is 1mol:0.8-1.5mol with the amount ratio of alkali, preferred 1mol:1.05mol;
In the said nitration reaction step, temperature is 50-80 ℃, and the time is 2-6 hour; Be preferably 70 ℃, the reaction times is 4 hours;
In the said reduction backflow reactions step, the time is 1-6 hour; Be preferably 4 hours;
In the said coupling back flow reaction step, the time is 3-10 hour; Be preferably 6 hours;
Said taking off in the acetone back flow reaction step, the time is 0.5-3 hour; Be preferably 1 hour;
Said step 2) in; Said
is 1mol:1-1.3mol with the amount ratio of n-Butyl Lithium, preferred 1mol:1.15mol;
In the said lithiation step, temperature is-60--90 ℃, and the time is 20-60 minute; Be preferably-70 ℃, the time is 30 minutes, and the said iodine that adds again carries out in the reactions step, temperature is-and 60--90 ℃, the time is 1-3 hour, is preferably-80 ℃, the time is 2 hours;
In the said step 3); Said step 1) gained is to iodo amido biphenyl acetylene
and said step 2) amount ratio of gained
is 1mol:1-1.2mol, preferred 1:1.05;
In the said coupling back flow reaction step, the time is 4-10 hour; Be preferably 6 hours;
In the said step 4), said carbonate is selected from least a in lime carbonate, yellow soda ash and the salt of wormwood; Said step 3) gained
Thiophosgene CSCl
2With the amount ratio of carbonate be 1mol:1-2mol:0.5-4mol, preferred 1mol:1.5mol:2mol;
In the said reactions step, temperature is 0-40 ℃, and the time is 1-4 hour; Be preferably 10 ℃, the time is 2 hours
The said reaction of said step 1) to step 4) is all carried out in solvent; Said solvent is selected from least a in THF, toluene and the chloroform.
6. contain at least a liquid crystal compound in the arbitrary said compound of claim 1-3.
7. liquid crystal compound according to claim 6 is characterized in that: contain the arbitrary said compound of 1-5 kind claim 1-3 in the said liquid crystal compound.
8. according to claim 6 or 7 described liquid crystal compounds, it is characterized in that: the gross weight of the arbitrary said compound of said claim 1-3 accounts for the 1-95% of said liquid crystal compound, preferred 5-60%, more preferably 5-40%.
9. arbitrary said compound of claim 1-3 or the arbitrary said liquid crystal compound of the claim 6-8 application in preparation liquid crystal display material or electrooptics display material.
10. the liquid crystal display material or the electrooptics display material that contain arbitrary said compound of claim 1-3 or the arbitrary said liquid crystal compound of claim 6-8.
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Cited By (8)
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| CN103880735A (en) * | 2014-03-27 | 2014-06-25 | 清华大学 | Smectic-phase liquid crystal compound as well as preparation method and application thereof |
| CN104087310A (en) * | 2014-07-21 | 2014-10-08 | 西安近代化学研究所 | High-birefringence liquid crystal compound and composition thereof |
| CN106397288A (en) * | 2015-07-31 | 2017-02-15 | 深圳超多维光电子有限公司 | Preparation method of biphenyl liquid crystal material |
| CN108431174A (en) * | 2015-12-21 | 2018-08-21 | 依视路国际公司 | Include the birefringence liquid crystal composition of alkyl alkylthio base aryl isosulfocyanate radical tolane compound |
| CN109825313A (en) * | 2019-03-06 | 2019-05-31 | 张富山 | One kind having optically anisotropic liquid-crystal composition |
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| EP1054001A1 (en) * | 1999-05-19 | 2000-11-22 | MERCK PATENT GmbH | Isothiocyanate tolanes and liquid crystal mixtures containing them |
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| CN103880735A (en) * | 2014-03-27 | 2014-06-25 | 清华大学 | Smectic-phase liquid crystal compound as well as preparation method and application thereof |
| CN103880735B (en) * | 2014-03-27 | 2016-03-30 | 清华大学 | A kind of smectic liquid crystal compound and preparation method thereof and application |
| CN104087310A (en) * | 2014-07-21 | 2014-10-08 | 西安近代化学研究所 | High-birefringence liquid crystal compound and composition thereof |
| CN104087310B (en) * | 2014-07-21 | 2016-08-17 | 西安近代化学研究所 | A kind of high birefringence rate liquid crystal compound and combinations thereof thing |
| CN106397288A (en) * | 2015-07-31 | 2017-02-15 | 深圳超多维光电子有限公司 | Preparation method of biphenyl liquid crystal material |
| CN108431174A (en) * | 2015-12-21 | 2018-08-21 | 依视路国际公司 | Include the birefringence liquid crystal composition of alkyl alkylthio base aryl isosulfocyanate radical tolane compound |
| CN108431174B (en) * | 2015-12-21 | 2022-08-26 | 依视路国际公司 | Birefringent liquid crystal compositions comprising alkylsulfanyl aryl isothiocyanatodiphenylacetylene compounds |
| CN109825313A (en) * | 2019-03-06 | 2019-05-31 | 张富山 | One kind having optically anisotropic liquid-crystal composition |
| CN111234843A (en) * | 2020-03-02 | 2020-06-05 | 中节能万润股份有限公司 | Preparation method of alkoxy difluoro (trans-4-alkylcyclohexyl) phenylethynyl benzene liquid crystal monomer |
| WO2022030344A1 (en) * | 2020-08-06 | 2022-02-10 | Dic株式会社 | Liquid crystal composition, and liquid crystal display element, sensor, liquid crystal lens, optical communication equipment, and antenna using same |
| WO2022234709A1 (en) * | 2021-05-06 | 2022-11-10 | Dic株式会社 | Compound, liquid crystal composition, and liquid crystal display element, sensor, liquid crystal lens, optical communication device and antenna each using same |
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