CN104593000A - Liquid crystal compound and liquid crystal display element comprising compound - Google Patents
Liquid crystal compound and liquid crystal display element comprising compound Download PDFInfo
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- CN104593000A CN104593000A CN201410854320.3A CN201410854320A CN104593000A CN 104593000 A CN104593000 A CN 104593000A CN 201410854320 A CN201410854320 A CN 201410854320A CN 104593000 A CN104593000 A CN 104593000A
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- 0 *c(cc1)c(C=C)cc1-c1ccc(C(*C2)OCC2C2CCCC2)cc1 Chemical compound *c(cc1)c(C=C)cc1-c1ccc(C(*C2)OCC2C2CCCC2)cc1 0.000 description 3
- BPUJUEKRCLQNIH-UHFFFAOYSA-N C=Cc1cc(-c2ccc(C3CCCC3)cc2)ccc1-c(cc1F)cc(F)c1OC(F)(F)F Chemical compound C=Cc1cc(-c2ccc(C3CCCC3)cc2)ccc1-c(cc1F)cc(F)c1OC(F)(F)F BPUJUEKRCLQNIH-UHFFFAOYSA-N 0.000 description 1
- COYJLFBVHNMRDN-UHFFFAOYSA-N Fc1cc(-c(cc2)ccc2-c2ccc(C3CCCC3)cc2)ccc1-c(cc1F)cc(F)c1F Chemical compound Fc1cc(-c(cc2)ccc2-c2ccc(C3CCCC3)cc2)ccc1-c(cc1F)cc(F)c1F COYJLFBVHNMRDN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a liquid crystal compound and a liquid crystal display element comprising the compound. The compound is high in dielectric anisotropy and high in refractive index anisotropy; more importantly, the compound is extremely high in response speed, high in clearing point and high in low-temperature intersolubility, and particularly suitable for TN-TFT, IPS and FFS liquid crystal displays with smaller cell thickness and higher response speed. The formula is shown in the specification.
Description
Technical field
The invention belongs to liquid crystalline cpd and Application Areas, be specifically related to a kind of liquid crystalline cpd and comprise the liquid crystal display device of this compound.
Background technology
The optical property of liquid crystal can be changed by the voltage applied, and therefore this material is mainly used as the dielectric medium in display equipment.In the middle of technical field of liquid crystal display, the electrooptics equipment based on liquid crystal known by technician is based on various effect.The pattern of this kind equipment mainly comprises dynamic scattering mode, DAP (distortion of aligned arrangement phase) pattern, guest/holotype, there is the TN pattern of twisted-nematic structure, STN (supertwist is to row) pattern, SBE (super birefringence effect) pattern, OMI (optical mode interference) pattern and OCB (optical compensation curved) pattern.
In the system of tft active matrix, mainly contain TN (Twisted Nematic, twisted-nematic structure) pattern, IPS (In-Plane Switching, plane conversion)/FFS (Fringe Field Switching, fringe field switching technology) the main display format such as pattern and VA (Vertical Alignment, vertical orientated) pattern.
For thin-film transistor technologies (TFT-LCD) Application Areas, accumulation through decades develops, technology is also ripe gradually, but people to the requirement of technique of display also in continuous raising, in order to pursue the superiority of image quality further, just require that liquid-crystal display can realize responding more fast, bright-colored, colour gamut is wider; In energy-conservation, reduce driving voltage to reduce the aspects such as power consumption.Liquid crystal material as one of important photoelectron material of liquid-crystal display, the effect important to the performance improving liquid-crystal display.
Liquid-crystal display is carrying out in Dynamic Announce process, as liquid-crystal display or LCD TV, in order to ensure that the picture of a upper width display no longer shows at next width, cause and occur ghost or conditions of streaking in picture handoff procedure, just require that liquid-crystal display has very fast response speed, and then require that the rotary viscosity of liquid crystal material is lower.In addition, in order to reduce equipment energy consumption, wish that the driving voltage of liquid crystal is low as far as possible, so the dielectric anisotropy △ ε improving liquid crystal is significant to mixed liquid crystal.
Liquid crystal material must have good chemistry and thermostability and the good stability to electric field and electromagnetic radiation.In addition, liquid crystal material should have low viscosity and produce short address-time, low threshold voltage and the high-contrast in screen.Liquid crystal generally uses as the mixture of several component, and importantly these components are easily miscible each other.Other performance, as electroconductibility, dielectric anisotropy and optical anisotropy, must meet the various requirement depending on this type and Application Areas.Such as, the material with the pattern of twisted nematic structure should have positive dielectric anisotropy and low electroconductibility.
Monomeric liquid crystal material performance superior, directly determine the superior performance of mixed liquid crystal material, therefore developing the superior monomeric liquid crystal material of a over-all properties is a very important thing.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides one type of liquid crystal compound, for MLC, IPS, during TN or STN indicating meter, not there is above-mentioned shortcoming or only compared with low degree having above-mentioned shortcoming, there is very high resistivity value and high dielectric anisotropic simultaneously, also there is high clearing point and low rotary viscosity in addition.
Liquid crystalline cpd shown in formula I provided by the present invention
Wherein, Cycloalkyl representative ring butyl, cyclopentyl or suberyl;
Z
1, Z
2represent singly-bound ,-CH independently of one another
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
Y
1, Y
2, Y
3, Y
4, Y
5, Y
6represent H or F independently of one another;
X
0represent alkyl that F, Cl, carbonatoms are 1-6, halogenated alkoxy that haloolefin that haloalkyl that carbonatoms is 1-6, carbonatoms are 2-6, carbonatoms are 1-6 or carbonatoms are arbitrary group in the haloalkene oxygen base of 2-6;
M represents 0,1 or 2, m when representing 2,
may be the same or different;
represent
and/or
in one or more groups.
The each element forming this compound can comprise its isotropic substance.
Preferably when described m represents 0 or 1, described Z
1, Z
2represent singly-bound.
As another preferred version, described Y
3, Y
4represent F.As more preferably scheme, described Y
2, Y
3, Y
4represent F.
Liquid crystalline cpd shown in formula I provided by the present invention, the compound of preferred Cycloalkyl representative ring butyl, cyclopentyl or suberyl.
Liquid crystalline cpd shown in formula I is specifically preferably liquid crystalline cpd shown in following formula I A, I B, I C, I D or I E,
Shown in described formula I A, liquid crystalline cpd is preferably compound shown in following formula I A-1 to I A-17,
Shown in described formula I B, liquid crystalline cpd is preferably compound shown in following formula I B-1 to I B-8,
Shown in described formula I C, liquid crystalline cpd is preferably compound shown in following formula I C-1 to I C-18,
Shown in described formula I D, liquid crystalline cpd is preferably compound shown in following formula I D-1 to I D-8,
Shown in described formula I E, liquid crystalline cpd is preferably compound shown in following formula I E-1 to I E-25,
Liquid crystalline cpd provided by the present invention can also the compound shown in preferred formula I F-1
Liquid crystalline cpd provided by the present invention has quick response, low viscosity, the feature of high dielectric, there is higher use value, meanwhile, low box is thick can reduce the time of response equally, and higher specific refractory power and higher clearing point monomer can meet the requirement of electro-optic display cell.The compound with cycloalkyl not only has higher dielectric anisotropic, adds this type of material simultaneously, can reduce the rotary viscosity of this type of material, improve overall clearing point in mixed crystal formula.
Comprise the above any one or the liquid crystal display device of plurality of liquid crystals compound there is excellent performance and the use value of Geng Gao.
Present invention also offers the method preparing compound described in structural formula I, is any one in following method 1 to method 3;
Method 1
This method is applicable to the compound of the claim 1 prepared containing amylene oxide ring
Method 2
This kind of method is suitable for claim 1 compound prepared containing dioxane
Method 3
This method is applicable to the compound of the claim 1 of synthesizing containing hexamethylene ring
Above-mentioned methodical reaction is in steps carried out all in a solvent; Described solvent is all selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO), ethanol and toluene.
The liquid crystal compound of the compound described in the application prepared in liquid crystal compound, liquid crystal display device material or electro-optical display part material and contained I of compound shown in the formula I that the invention described above provides, liquid crystal display device material or electro-optical display part material, also belong to protection scope of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.In embodiment, GC represents gas chromatographic purity below, and MP represents fusing point, and CP represents clearing point, and MS represents mass spectrum, and △ ε represents dielectric anisotropy, and △ n represents optical anisotropy.The method measuring GC, MP, CP, MS, △ ε and △ n is ordinary method.
Compound 1D-1 shown in embodiment 1, formula I
Step 1
146g (0.62mol) paradibromobenzene is added in 2L there-necked flask, 1L tetrahydrofuran (THF), stirring makes dissolution of solid, inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-80 DEG C, drip 2.5M butyllithium aqueous solution 250ml (0.62) mol, within one hour, add, solid is had to separate out in dropping process, after half an hour, the 50ml tetrahydrofuran solution of 52g (0.62mol) cyclopentanone is still dripped at-80 DEG C, half an hour adds, obtain clear solution, remove cryostat, when being naturally warming up to-50 DEG C (2 hours used times) pour in the 500ml water of 80ml hydrochloric acid and be hydrolyzed, separatory, aqueous phase with 200ml methylbenzene extraction once, merge organic layer, be washed to neutrality.Steam neat solvent under decompression, add 400ml toluene, 2g tosic acid, reflux water-dividing together, no longer includes moisture after 4 hours and goes out, and steams neat solvent under decompression, with petroleum ether dissolution, cross preheated silicagel column, sherwood oil washes down, and concentrated chromatographic solution is to 300ml, freezing and crystallizing, filtration obtains pale yellow crystals (1-a) 105g, Gc:96.8%, yield: 76%.
Step 2
Add in 2L there-necked flask 90g (0.4mol) (1-a), 61.5g (0.44mol) 3-fluorobenzoic boric acid, 300ml toluene, 300ml ethanol, 300ml water, 53g (0.5mol) sodium carbonate, inflated with nitrogen displaced air, add 3.0g tetra-triphenylphosphine and close palladium, reflux 5 hours.Separate the organic phase in reaction solution, aqueous phase 100ml methylbenzene extraction, merge organic phase, be washed to neutrality, neat solvent is steamed, 300ml petroleum ether dissolution, overheated silicagel column under decompression, sherwood oil washes down, decompression is lower steams clean sherwood oil, uses 300ml ethyl alcohol recrystallization, obtains 90g pale yellow crystals (1-b), Gc:98.3%, yield: 93%
Step 3
90g pale yellow crystals (1-b) is added in 2L single port bottle, 200ml toluene, 100ml ethanol, 19g Raney's nickel catalyst, shakes hydrogenation 6 hours under normal temperature and pressure, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steams neat solvent under filtrate decompression, obtains 91g white solid (1-c), Gc:98.0%, yield: 96.8%
Step 4
Add in 1L there-necked flask 60g (0.25mol) (1-c), 300ml tetrahydrofuran (THF), inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-60 DEG C, drip 2.5M butyllithium aqueous solution 110ml (0.275mol), within one hour, add, after half an hour, the 100ml tetrahydrofuran solution of 76g (0.3mol) iodine is still dripped at-60 DEG C, half an hour adds, obtain clear solution, remove cryostat, naturally being warming up to-40 DEG C (2 hours used times) pours in the 500ml water of 27ml hydrochloric acid and is hydrolyzed, separatory, aqueous phase with 200ml Petroleum ether extraction once, merge organic layer, salt is washed to neutrality.Steam neat solvent under decompression, obtain yellow liquid, petroleum ether dissolution crosses silicagel column, and steaming desolventizes, and obtains 88g light yellow solid (1-d), Gc:72.3%
Step 5
Add in 1L there-necked flask 65g (0.128mol) (1-d), 24.6g (0.14mol) 3,4,5-trifluoro-benzene boric acid, 35.9g (0.26mol) salt of wormwood, 500ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 1L water, 150ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 150ml sherwood oil recrystallization 4 times, obtains white crystal (1-e) 37g.
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.92%; MP:80 DEG C; CP:66 DEG C; MS:m/z (%): 370.13 (100.0%), 371.14 (25.1%), 372.14 (3.0%); Δ n [589nm, 20 DEG C]: 0.195; Δ ε [1KHz, 20 DEG C]: 21.1.As from the foregoing, this product structure is correct, is the 1-e of compound shown in formula I.
Prepare compound 1-e shown in gained formula I to this embodiment and carry out liquid crystal property test, concrete steps comprise: prepared by this embodiment compound 1-e shown in gained formula I with 10% ratio to be dissolved in clearing point CP be in the parent A of 80 DEG C
In above-mentioned test, in parent A used the structural formula of each component composition and parts by weight as follows:
The clearing point CP of test gained liquid crystal compound, acquired results CP is 66.0 DEG C;
As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.
Adopt the synthetic method of embodiment 1, use the raw material of different substituents instead, liquid crystalline cpd (physico-chemical property of product and structure confirmation data are listed in thereafter respectively) shown in the formula I obtaining following structural formula respectively:
Gc：99.95％；MP：71℃；CP：59℃；m/z(％):406.12(100.0％),407.12(25.1％),408.12(3.0％)Δn[589nm,20℃]：0.190；ε[1KHz,20℃]:.20.1；
Gc：99.97％；MP：83℃；CP:71℃；MS：m/z(％):352.14(100.0％),353.15(25.1％),354.15(3.0％)；Δn[589nm,20℃]：0.192；ε[1KHz,20℃]:18.9
Gc：99.97％；MP：83℃；CP:71℃；MS：m/z(％):436.13(100.0％),437.13(26.2％),438.13(3.4％)；Δn[589nm,20℃]：0.195；ε[1KHz,20℃]:18.9
Gc：99.97％；MP：250℃；CP:212℃；MS：m/z(％):m/z:446.17(100.0％),447.17(31.6％),448.17(4.7％)；Δn[589nm,20℃]：0.329；ε[1KHz,20℃]:21.5。
According to upper identical method, only the substituting group of reactant according to target product is replaced, obtains compound shown in following structural formula respectively
The liquid crystal property test of compound shown in above-mentioned formula with 1-e without substantive difference, no longer Ao Shu herein.
Compound 1C-9 shown in embodiment 2, preparation formula I
Step 1
69g (0.168mol) bromocyclopentane triphenylphosphine salt is added in 500ml there-necked flask, 600ml tetrahydrofuran (THF), in this solution, add potassium tert.-butoxide 18.8g (0.168mol) under stirring in-10 DEG C in batches, exothermic heat of reaction, obtain orange solution, after adding, stir lower reaction 1 hour again.At 0 DEG C, drip the solution that the 150ml methyl tertiary butyl ether of ketone 22g (0.14mol) protected by Isosorbide-5-Nitrae cyclohexanedione ethylene glycol list again, after adding, stir lower reaction 3 hours again.Poured into by reaction solution in 500ml water, dichloromethane extraction aqueous phase, organic phase concentrates, petroleum ether dissolution, crosses silicagel column, concentrates and obtains (2-a) 10.8g.
Step 2
10.8g (2-a) is added, 100ml toluene, 100ml ethanol, 2g Raney's nickel catalyst in 1L single port bottle, shake hydrogenation under normal pressure 6 hours, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steam neat solvent under filtrate decompression, obtain 10g (2-b)
Step 3
The 10g (2-b) that step 2 obtains, 50ml toluene, 20ml85% formic acid one to arise from 250ml bottle stirred at ambient temperature 20 hours, separatory is except formic acid removal layer, and washing removes acid remaining in organic phase, anhydrous sodium sulfate drying, concentrated, obtain (2-c) 6.5g.
Step 4
1g (0.042mol) magnesium chips is added in 250ml there-necked flask, 30ml tetrahydrofuran (THF), drip the solution of the 30ml tetrahydrofuran (THF) of 10.0g (0.04mol) 3 '-fluoro-4-bromo biphenyl under backflow, half an hour adds, reflux half an hour, obtain Grignard reagent.At room temperature drip the 20ml tetrahydrofuran solution of 6.5g (0.04mol) (2-c), add and reflux again 1.5 hours.Reaction solution is poured in dilute hydrochloric acid and is hydrolyzed, separatory methylbenzene extraction aqueous phase, merge organic layer, be washed to neutrality, concentrated.The product obtained adds toluene 50ml, tosic acid 0.5g, and reflux lower point water, until point water is complete, concentrated, adds petroleum ether dissolution, crosses silicagel column, obtain product sherwood oil recrystallization, obtain 6.3g (2-d) .Gc:98.2%
Step 5
6.2g (2-d) is added, 30ml toluene, 40ml ethanol, 1g Raney's nickel catalyst in 1L single port bottle, shake hydrogenation under normal pressure and temperature 6 hours, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steam neat solvent under filtrate decompression, obtain 5.9g (2-e), Gc:97.5%
Step 4
Add in 250mL there-necked flask 5.0g (0.015mol) (2-e), 20ml tetrahydrofuran (THF), inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-60 DEG C, drip 2.5M butyllithium aqueous solution 6.5ml (0.016mol), within one hour, add, after half an hour, the 100ml tetrahydrofuran solution of 4.5g (0.018mol) iodine is still dripped at-60 DEG C, half an hour adds, obtain clear solution, remove cryostat, naturally being warming up to-40 DEG C (2 hours used times) pours in the 500ml water of 27ml hydrochloric acid and is hydrolyzed, separatory, aqueous phase with 200ml Petroleum ether extraction once, merge organic layer, salt is washed to neutrality.Steam neat solvent under decompression, obtain yellow liquid, petroleum ether dissolution crosses silicagel column, and steaming desolventizes, and obtains 7.3g light yellow solid (2-f), Gc:71.3%
Step 5
Add in 100ml there-necked flask 6.9g (0.010mol) (2-f), 1.9g (0.011mol) 3,4,5-trifluoro-benzene boric acid, 3.2g (0.023mol) salt of wormwood, 50ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 100ml water, 20ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 150ml sherwood oil recrystallization 4 times, obtains white crystal (2-g) 3.7g.
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.95%; MP:245 DEG C; CP:214 DEG C; MS:m/z:452.21 (100.0%), 453.22 (31.7%), 454.22 (4.9%); Δ n [589nm, 20 DEG C]: 0.212; Δ ε [KHz, 20 DEG C]: 18.1.As from the foregoing, this product structure is correct, is the 2-g of compound shown in formula I.
Prepared by compound 2-g shown in gained formula I to this embodiment and carries out liquid crystal property test, concrete steps comprise: prepared by this embodiment compound 1-e shown in gained formula I with 10% ratio to be dissolved in clearing point CP be in the parent A of 80 DEG C, the clearing point CP of test gained liquid crystal compound, acquired results CP is 220 DEG C;
As from the foregoing, this embodiment is utilized to prepare the allotment of compound shown in gained formula I parent liquid crystalline cpd, compared with the liquid crystalline cpd of existing this area similar structures used, the clearing point CP of gained liquid crystal compound can be significantly improved, and Δ n, and demonstrate very high voltage retention, there is very outstanding thermostability, and in field of liquid crystal display, require that the clearing point of liquid crystal display device material used or electro-optical display part material is high as far as possible, high Δ n can have very large effect in fast response liquid crystal aspect more simultaneously, compound shown in visible formula I provided by the invention is preparing liquid crystal display device material or electro-optical display part Material Field has important using value.
Adopt the synthetic method of embodiment 2, use the raw material of different substituents instead, liquid crystalline cpd (physico-chemical property of product and structure confirmation data are listed in thereafter respectively) shown in the formula I obtaining following structural formula respectively:
Gc：99.95％；MP：273℃；CP：221℃；m/z(％):518.20(100.0％),519.21(32.8％),520.21(5.4％),Δn[589nm,20℃]：0.211；ε[1KHz,20℃]:.18.7；
According to upper identical method, only the substituting group of reactant according to target product is replaced, obtains compound shown in following structural formula respectively:
The liquid crystal property test of compound shown in above-mentioned formula with 2-g without substantive difference, no longer Ao Shu herein.
Compound 1F-1 shown in embodiment 3, preparation formula I
Step 1
48.3g (0.11mol) 2-cyclopentyl-1-bromotrifluoromethane triphenylphosphine salt is added in 500ml there-necked flask, 200ml tetrahydrofuran (THF), add 12.5g (0.11mol) potassium tert.-butoxide at-5 DEG C in batches, obtain orange solution, continue stirring reaction 30 minutes at this temperature, drip the solution of the 60ml tetrahydrofuran (THF) of 19.2g (0.1mol) 4-(3-fluorophenyl) pimelinketone at 0 DEG C, after adding, at room temperature react 3 hours.
Poured into by reaction solution in 400ml water, separatory, ethyl acetate is extracted, merge organic layer, be washed to neutrality, anhydrous sodium sulfate drying, steaming desolventizes, obtain solid product, with 100 × 3ml Petroleum ether extraction, silicagel column crossed by extracting solution, and steaming desolventizes, obtain solid product (3-a) 22.0g, Gc:97.2%.
Step 2
22.0g (3-a) is added in 1L single port bottle, 100ml toluene, 100ml ethanol, 5g Raney's nickel catalyst, shakes hydrogenation 6 hours under normal pressure, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steams neat solvent under filtrate decompression, obtains 21g (3-b), Gc:98.2%, yield: 95.4%
Step 3
Add in 250ml there-necked flask 21g (0.075mol) (3-b), 100ml tetrahydrofuran (THF), inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-60 DEG C, drip 2.5M butyllithium aqueous solution 33ml (0.083mol), within one hour, add, after half an hour, the 20ml tetrahydrofuran solution of 22.7g (0.09mol) iodine is still dripped at-60 DEG C, half an hour adds, obtain clear solution, remove cryostat, naturally being warming up to-40 DEG C (2 hours used times) pours in the 200ml water of 7ml hydrochloric acid and is hydrolyzed, separatory, aqueous phase with 100ml Petroleum ether extraction once, merge organic layer, salt is washed to neutrality.Steam neat solvent under decompression, obtain yellow liquid, petroleum ether dissolution crosses silicagel column, and steaming desolventizes, and obtains 27.3g light yellow solid (3-c), Gc:55.6%
Step 4
25.2g (0.035mol) light yellow solid (3-c) is added in 250ml there-necked flask, 6.2g (0.042mol) 3,4,5-trifluoromethyl phenol, 11.3g (0.082mol) salt of wormwood, 150ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 300L water, 90ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 100ml sherwood oil recrystallization 5 times, obtains white crystal (3-d) 7.5g
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.95%; MP:278 DEG C; CP:231 DEG C; MS:m/z (%): 498.23 (100.0%), 499.24 (33.9%), 500.24 (5.6%); Δ n [589nm, 20 DEG C]: 0.203; Δ ε [KHz, 20 DEG C]: 16.3
As from the foregoing, this product structure is correct, is the 1F-1 of compound shown in formula I.
According to upper identical method, only the substituting group of reactant according to target product is replaced, compound shown in the formula I obtaining following structural formula respectively:
The test result of liquid crystal property test and previous embodiment 1 gained liquid crystalline cpd 3-d that this embodiment prepares compound shown in gained formula I, without substantive difference, repeats no more herein.
Compound 1D-5 shown in embodiment 4, preparation formula I
Step 1
0.12mol cyclopentyl-methyl bromine triphenylphosphine salt is added in 500ml there-necked flask, 200ml tetrahydrofuran (THF), potassium tert.-butoxide 0.12mol is added at-5 DEG C, become orange, stirring reaction 0.5 hour, be added dropwise to the 80ml tetrahydrofuran solution of 0.1mol4-(3-fluorophenyl) phenyl aldehyde, add and react 3 hours again.
Be poured into water, separate organic phase, ethyl acetate extracts aqueous phase, merges organic phase, salt is washed, and anhydrous sodium sulfate drying, steams neat solvent under decompression, Petroleum ether extraction solid, cross silicagel column removing by product, obtain (4-a) 22.0g (0.08mol), Gc:98.0%
Step 2
22.0g (4-a) is added in 1L single port bottle, 100ml toluene, 100ml ethanol, 5g Raney's nickel catalyst, shakes hydrogenation 6 hours under normal pressure, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steams neat solvent under filtrate decompression, obtains 21.5g white solid (4-b), Gc:98.0%, yield: 97.5%
Step 3
Add in 1L there-necked flask 20.6g (0.075mol) (4-b), 300ml tetrahydrofuran (THF), inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-60 DEG C, drip 2.5M butyllithium aqueous solution 33ml (0.082mol), within one hour, add, after half an hour, the 100ml tetrahydrofuran solution of 22.7g (0..09mol) iodine is still dripped at-60 DEG C, half an hour adds, obtain clear solution, remove cryostat, naturally being warming up to-40 DEG C (2 hours used times) pours in the 500ml water of 27ml hydrochloric acid and is hydrolyzed, separatory, aqueous phase with 200ml Petroleum ether extraction once, merge organic layer, salt is washed to neutrality.Steam neat solvent under decompression, obtain yellow liquid, petroleum ether dissolution crosses silicagel column, and steaming desolventizes, and obtains 24.8 light yellow solids (4-c), Gc:93.2%
Step 5
Add in 1L there-necked flask 21g (0.05mol) (4-c), 9.6g (0.055mol) 3,4,5-trifluoro-benzene boric acid, 14.0g (0.1mol) salt of wormwood, 200ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 1L water, 60ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 150ml sherwood oil recrystallization 4 times, obtains white crystal (4-d) 14.0g.
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.92%; MP:80 DEG C; CP:66 DEG C; MS:m/z (%): 398.17 (100.0%), 399.17 (27.3%), 400.17 (3.5%); Δ n [589nm, 20 DEG C]: 0.183; Δ ε [1KHz, 20 DEG C]: 17.2.As from the foregoing, this product structure is correct, is the 4-d of compound shown in formula I.
As from the foregoing, this product structure is correct, is the 4-d of compound shown in formula I (i.e. I D-5)
According to upper identical method, only the substituting group of reactant according to target product is replaced, compound shown in the formula I obtaining following structural formula respectively:
The liquid crystal property test of compound shown in above-mentioned formula with 4-d without substantive difference, no longer Ao Shu herein.
Chemical compounds I A-8 shown in embodiment 5, preparation formula I
Step 1
The 5-a of 100mmol is dissolved in the ether of 30ml, adds the hexahydroaniline of 100mmol and the salt of wormwood of 60mmol wherein, at room temperature by this mixture stirred overnight.Use G5 sand core funnel to coordinate diatomite to filter gained suspension, move to afterwards and revolve steaming instrument, concetrated under reduced pressure filtrate.Obtain 18g yellow oily shape liquid, by the 18g dissolving crude product that obtains in the ethyl propenoate of 250mmol, add wherein simultaneously 0.4g Resorcinol and at 105 DEG C reflux 10 hours.Be cooled to room temperature, add 300ml tetrahydrofuran (THF) wherein, and drip the saturated oxalic acid aqueous solution of 200ml, subsequently with the extracted with diethyl ether organic phase twice of 50ml, and with the water washing organic layer twice of 50ml, and with anhydrous magnesium sulfate drying, filtration drying agent, and move to and revolve steaming and carry out concentrating under reduced pressure.Column chromatography purification gained 19.5g brown residue thing, obtains the 5-b that 12.5g is yellow oily form, yield: 63.0%.
Step 2
Be dissolved in the Virahol of 120ml by the 5-b of the 63mmol obtained in a first step, add the sodium cyanoborohydride of 69mmol wherein, and at room temperature stir 3 hours, the hydrochloric acid soln adding 2M after reaction terminates is adjusted to pH=3.In reaction liquid, add the water of 100ml, extract three times with the toluene of 50ml, by the washing organic phase twice of 40ml, anhydrous sodium sulfate drying.Organic layer concentrating under reduced pressure.Carry out column chromatography purification gained orange liquid, obtain 6.6g yellow transparent liquid 5-c, yield: 68.0%.
Step 3
In the there-necked flask of 250m1, add 45mmol magnesium chips, the tetrahydrofuran (THF) of 30m1, the lower tetrahydrofuran solution dripping 30ml and contain 43mmo1 paradibromobenzene of backflow, adds, reflux half an hour, obtain Grignard reagent half an hour.At room temperature drip the tetrahydrofuran solution that 20ml contains the 5-c of 43mmo1, add and reflux again 1.5 hours.Reaction solution is poured in dilute hydrochloric acid and is hydrolyzed, separatory methylbenzene extraction aqueous phase, merge organic layer, be washed to neutrality, concentrated.The product obtained adds the toluene of 50m, the tosic acid of 0.5g, and reflux lower point water, until point water is complete, concentrated, adds petroleum ether dissolution, crosses silicagel column, obtain product sherwood oil recrystallization, obtain the 5-d of 11.7g, productive rate: 93.2%.
Step 4
The 5-d of 40mmol is added, the toluene of 60m1, the ethanol of 80m1, the Raney's nickel catalyst of 1g in 1L single port bottle, shake hydrogenation under normal pressure and temperature 6 hours, inhale hydrogen to theoretical amount, Filtration of catalyst carefully, steam neat solvent under filtrate decompression, obtain the 5-e of 11.6g, yield: 98.3%.
Step 5
The 5-e of 39mmol is added in the there-necked flask of 500ml, the 3-fluorobenzoic boric acid of 43mmol, the toluene of 40m1, the ethanol of 40m1, the water of 150m1, the sodium carbonate of 2.6g, inflated with nitrogen displaced air, add the four triphenyl phosphorus palladiums (catalyzer) of 0.4mmol, reflux carries out linked reaction 5 hours.Separate the organic phase in reaction solution, aqueous phase 100m1 methylbenzene extraction, merges organic phase, is washed to neutrality, neat solvent is steamed under decompression, 40m1 petroleum ether dissolution, overheated silicagel column, sherwood oil washes down, decompression is lower steams clean sherwood oil, with the ethyl alcohol recrystallization of 60m1, obtain the pale yellow crystals 5-f of 12.0g, yield: 92.5%.GC:93.2％
Step 6
36mmol 5-f is added in the there-necked flask of 250ml, the tetrahydrofuran (THF) of 50m1, inflated with nitrogen displaced air, be placed in cryostat, liquid nitrogen cooling, when being down to-60 DEG C, drip the hexane solution 57mmol of 2.5M n-Butyl Lithium, within one hour, add, after carrying out lithium hydrogen exchange reaction half an hour, still drip at-60 DEG C the tetrahydrofuran solution that 20m1 is dissolved with the difluorodibromomethane of 42mmol, add half an hour and carry out substitution reaction, obtain clear solution, remove cryostat, naturally the hydrochloric acid hydrolysis that-40 DEG C (2 hours used times) pour the 2M of 33ml into is warming up to, separatory, aqueous phase with 30m1 Petroleum ether extraction once, merge organic layer, salt is washed to neutrality.Steam neat solvent under decompression, obtain yellow liquid, petroleum ether dissolution crosses silicagel column, and steaming desolventizes, and obtains 13.2g light yellow solid 5-g, GC:62.4%.
0.019mol light yellow solid (5-g) is added, 3.4g (0.023mol) 3,4 in 250ml there-necked flask, 5-trifluoromethyl phenol, 7.8g (0.055mol) salt of wormwood, 150ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 300L water, 90ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 100ml sherwood oil recrystallization 5 times, obtains white crystal (5-h i.e. I A-8) 6.1g
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.91%; MP:292 DEG C; CP:253 DEG C; MS:m/z (%): 441.18 (29.5%), 442.18 (4.3%); Δ n [589nm, 20 DEG C]: 0.183; Δ ε [1KHz, 20 DEG C]: 23.2.。As from the foregoing, this product structure is correct, is Compound I A-8 shown in formula I.
According to upper identical method, only the substituting group of reactant according to target product is replaced, compound shown in the formula I obtaining following structural formula respectively:
The test result of liquid crystal property test and previous embodiment 1 gained liquid crystalline cpd 5-h that this embodiment prepares compound shown in gained formula I, without substantive difference, repeats no more herein.
Embodiment 6
Compound shown in preparation formula I (I C-13)
Step 1
The toluene of 300m1 is added, the 2-cyclopentyl-1 of the 6-a of 250mmol, 1mol in the there-necked flask of 1L, ammediol, the tosic acid of 8mmol, reflux water-dividing carries out dehydration reaction 4 hours, no longer includes moisture and goes out, neat solvent is steamed under decompression, with petroleum ether dissolution, excessively preheated silicagel column, sherwood oil washes down, concentrated chromatographic solution obtains the light yellow liquid 6-b of 63.4g
Step 2
The 6-b of 200mmo1 is dissolved in the tetrahydrofuran (THF) of 500m1, neutralization is cooled to-70 DEG C, first drips the hexane solution of the n-Butyl Lithium of 15% of 200mmo1, drips the tetrahydrofuran solution being dissolved with the boric acid trimethylammonium ester of 200mmo1 of 150m1 subsequently.Mixture rises to-30 DEG C, and the hydrochloric acid being 2M by interpolation concentration is adjusted to pH=2, then carries out water aftertreatment.Crude product is placed in hot sherwood oil and dissolves and crystallization at 0 DEG C, obtains the white solid 6-c of 41.2g, yield: 74.6%.
Step 3
Add 149mmol white solid (6-c) in 250ml there-necked flask, 29.7g (170m mol) 3-bromofluorobenzene, 48.5g (0.35mol) salt of wormwood, 600ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 300mL water, 200ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 100ml sherwood oil recrystallization 1 time, obtains white crystal (6-d) 45.2g GC:98.2%
Step 4
The 6-d of 100mmo1 is dissolved in the tetrahydrofuran (THF) of 250m1, neutralization is cooled to-70 DEG C, first drips the hexane solution of the n-Butyl Lithium of 15% of 100mmo1, drips the tetrahydrofuran solution being dissolved with the boric acid trimethylammonium ester of 100mmo1 of 80m1 subsequently.Mixture rises to-30 DEG C, and the hydrochloric acid being 2M by interpolation concentration is adjusted to pH=2, then carries out water aftertreatment.Crude product is placed in hot sherwood oil and dissolves and crystallization at 0 DEG C, obtains the white solid 6-f of 31.7g, GC:96.3%.
Step 5
30.7 (0.080mol) white (6-f) is added, 18.9g (0.090mol) 3,4 in 250ml there-necked flask, 5-trifluorobromobenzene, 27.8g (0.2mol) salt of wormwood, 150ml dimethyl sulfoxide (DMSO), is placed in 60 DEG C of water-bath stirring reactions 3 hours.Pour in 80mL water, 50ml × 2 Petroleum ether extraction, washing extract phase, crosses silicagel column once, with 100ml sherwood oil recrystallization 5 times, obtains white crystal (6-g) 36.3g
Physico-chemical property and the structure confirmation data of this product are as follows: Gc:99.91%; MP:243 DEG C; CP:211 DEG C; MS:m/z (%): 456.17 (100.0%), 457.17 (29.2%), 458.18 (4.6%); Δ n [589nm, 20 DEG C]: 0.223; Δ ε [1KHz, 20 DEG C]: 25.2.。As from the foregoing, this product structure is correct, is the C-13 of chemical compounds I shown in formula I.
Adopt the synthetic method of embodiment 6, use the raw material of different substituents instead, liquid crystalline cpd (physico-chemical property of product and structure confirmation data are listed in thereafter respectively) shown in the formula I obtaining following structural formula respectively:
Gc：99.92％；MP：267℃；CP：233℃；m/z(％):522.16(100.0％),523.17(30.7％),524.17(5.2％)Δn[589nm,20℃]：0.223；ε[1KHz,20℃]:.27.1；
According to upper identical method, only the substituting group of reactant according to target product is replaced, compound shown in the formula I obtaining following structural formula respectively:
The test result of liquid crystal property test and previous embodiment 1 gained liquid crystalline cpd (6-g) that this embodiment prepares compound shown in gained formula I, without substantive difference, repeats no more herein.
Claims (16)
1. liquid crystalline cpd shown in formula I
Wherein, Cycloalkyl representative ring butyl, cyclopentyl or suberyl;
Z
1, Z
2represent singly-bound ,-CH independently of one another
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
Y
1, Y
2, Y
3, Y
4, Y
5, Y
6represent H or F independently of one another;
X
0represent alkyl that F, Cl, carbonatoms are 1-6, halogenated alkoxy that haloolefin that haloalkyl that carbonatoms is 1-6, carbonatoms are 2-6, carbonatoms are 1-6 or carbonatoms are arbitrary group in the haloalkene oxygen base of 2-6;
M represents 0,1 or 2, m when representing 2,
may be the same or different;
represent
and/or
in one or more groups.
2. liquid crystalline cpd according to claim 1, is characterized in that, described m represents 0 or 1, described Z
1, Z
2represent singly-bound.
3. liquid crystalline cpd according to claim 1, is characterized in that, described Y
3, Y
4represent F.
4. liquid crystalline cpd according to claim 1, is characterized in that, described Y
2, Y
3, Y
4represent F.
5. liquid crystalline cpd shown in formula I A
Wherein, Z
1represent singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
represent
(F) H or F is represented;
X
0represent F or OCF
3.
6. liquid crystalline cpd according to claim 5, is characterized in that, liquid crystalline cpd shown in described formula I A is any one compound in compound shown in formula I A-1 to formula I A-17:
7. liquid crystalline cpd shown in formula I B
Wherein, Z
1represent singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
H (F) represents H or F;
X
0represent F or OCF
3.
8. liquid crystalline cpd according to claim 7, is characterized in that, liquid crystalline cpd shown in described formula I B is any one compound in compound shown in formula I B-1 to formula I B-8:
9. liquid crystalline cpd shown in formula I C
Wherein, Z
1represent singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
represent
(F) H or F is represented;
X
0represent F or OCF
3.
10. liquid crystalline cpd according to claim 9, is characterized in that, liquid crystalline cpd shown in described formula I C is any one compound in compound shown in formula I C-1 to formula I C-17:
Liquid crystalline cpd shown in 11. formula I D
Wherein, Z
1represent singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
H (F) represents H or F;
X
0represent F or OCF
3.
12. liquid crystalline cpds according to claim 11, is characterized in that, liquid crystalline cpd shown in described formula I D is any one in compound shown in formula I D-1 to formula I D-8:
Liquid crystalline cpd shown in 13. formula I E
Wherein, Z
1represent singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-or-CF=CF-;
H (F) represents H or F;
X
0represent F or OCF
3;
M represents 0,1 or 2, m when representing 2,
may be the same or different;
represent
and/or
in one or more groups.
14. liquid crystalline cpds according to claim 13, is characterized in that, liquid crystalline cpd shown in described formula I E is any one compound in compound shown in formula I E-1 to formula I E-25:
Liquid crystalline cpd shown in 15. formula I F-1
16. 1 kinds of liquid crystal display device, is characterized in that, described liquid crystal display device comprises the arbitrary described liquid crystalline cpd of one or more claims 1 to 15.
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| CN107099304A (en) * | 2017-05-09 | 2017-08-29 | 晶美晟光电材料（南京）有限公司 | Liquid crystal compound and its application |
| CN107723001A (en) * | 2017-10-31 | 2018-02-23 | 晶美晟光电材料（南京）有限公司 | A kind of liquid crystal compound and its application |
| CN107779205A (en) * | 2017-10-31 | 2018-03-09 | 晶美晟光电材料（南京）有限公司 | A kind of liquid crystal compound with high positive dielectric anisotropy and its application |
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| CN107779205A (en) * | 2017-10-31 | 2018-03-09 | 晶美晟光电材料（南京）有限公司 | A kind of liquid crystal compound with high positive dielectric anisotropy and its application |
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