CN107663187B - Compound, liquid crystal composition and liquid crystal display - Google Patents
Compound, liquid crystal composition and liquid crystal display Download PDFInfo
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- CN107663187B CN107663187B CN201610607822.5A CN201610607822A CN107663187B CN 107663187 B CN107663187 B CN 107663187B CN 201610607822 A CN201610607822 A CN 201610607822A CN 107663187 B CN107663187 B CN 107663187B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 83
- 150000001875 compounds Chemical class 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MPZCNPVCHBVCCW-UHFFFAOYSA-N 4-propylcyclopentane-1,2-diol Chemical compound CCCC1CC(O)C(O)C1 MPZCNPVCHBVCCW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical class OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ASOFZHSTJHGQDT-UHFFFAOYSA-N 3,5-difluorobenzaldehyde Chemical compound FC1=CC(F)=CC(C=O)=C1 ASOFZHSTJHGQDT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
- C09K2019/0414—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a compound, a liquid crystal composition and a liquid crystal display. The compound according to the invention is represented by formula I:
wherein R is at least one selected from hydrogen, vinyl and C1-C10 alkyl;
each independently selected from at least one of the following groups:
X1，X2，X3，X4，X5，X6，X7，X8and X9Each independently selected from H, F, Cl, CH3、CF3、OCF3One of (1); m is selected from 0, 1, 2 or 3; n is selected from 0 or 1. The liquid crystal composition according to the invention comprises at least one compound according to the invention. The liquid crystal display according to the present invention contains the liquid crystal composition according to the present invention.
Description
Technical Field
The invention relates to the field of liquid crystal display, in particular to a compound, a liquid crystal composition and a liquid crystal display.
Background
Among flat panel Display devices, a Thin Film Transistor liquid crystal Display (TFT-LCD) has the characteristics of small volume, low power consumption, relatively low manufacturing cost, no radiation, and the like, and occupies a leading position in the current flat panel Display market.
Liquid crystal displays have been widely used in various aspects of social life, and liquid crystal display technologies have been developed so far, and various liquid crystal compounds have been put to practical use. Some common requirements for liquid crystal compounds, including phase transition temperature, optical anisotropy, dielectric anisotropy, viscosity, resistivity, etc., of the liquid crystal compounds, have a great influence on the final application of the liquid crystal material. The development of new liquid crystal compounds and compositions comprising the same are extremely important for improving various properties of liquid crystals and improving the application effects of liquid crystal displays. The liquid crystal composition is prepared by mixing a plurality of monomer liquid crystal compounds according to the technical requirements of electro-optic physical properties and the like of a liquid crystal display. To obtain a liquid crystal composition with excellent properties, it is necessary to use a monomer liquid crystal compound with excellent properties, and it is necessary to synthesize compounds having different liquid crystal structures to realize different electro-optical physical properties of a mixed liquid crystal.
LCDs are classified into a dynamic flash type, a twist Type (TN), a super twist type (STN), and a plane switching type (IPS) according to their display modes, and although the liquid crystal compositions used for these LCDs have different display characteristics, they have the following common characteristics: low driving voltage, wide liquid crystal working temperature range, proper optical anisotropy and good thermal stability, optical stability and chemical stability.
The existing liquid crystal composition can not meet the use requirement of a liquid crystal display in a high-temperature state due to a low clearing point, and has the problem of narrow use temperature range; in addition, the prior liquid crystal composition has the problems of low dielectric constant, high driving voltage and low response speed of a liquid crystal display.
Therefore, it is desirable to provide a compound capable of improving the clearing point and the dielectric constant of the liquid crystal composition.
Disclosure of Invention
The invention provides a compound, which solves the problems of low clearing point and low dielectric constant of a liquid crystal composition in the prior art; the invention also provides a liquid crystal composition and a liquid crystal display, which solve the problems that the liquid crystal display cannot be used in a high-temperature state, and has a narrow working temperature range and a slow response speed.
According to one aspect of the present invention, there is provided a compound of formula I:
wherein,
r is at least one selected from hydrogen, vinyl and C1-C10 alkyl;
X1，X2，X3，X4，X5，X6，X7，X8and X9Each independently selected from H, F, Cl, CH3、CF3、OCF3One of (1);
m is 0, 1, 2 or 3;
n is 0 or 1.
Alternatively, a compound according to the invention, said compound comprising:
according to another aspect of the present invention, there is provided a liquid crystal composition comprising at least one compound according to the present invention.
Optionally, the liquid crystal composition comprises 3-40% by mass of the compound according to the invention.
According to another aspect of the present invention, there is provided a liquid crystal display comprising the liquid crystal composition according to the present invention.
The invention has the following beneficial effects:
the compound has higher clearing point and proper optical anisotropy, and is suitable for liquid crystal displays. The application of the compound to the liquid crystal composition can improve the clearing point of the liquid crystal composition, thereby improving the working temperature range of the liquid crystal composition. In addition, the dielectric constant of the liquid crystal composition containing the compound is also improved, so that the driving voltage of a liquid crystal display containing the liquid crystal composition can be reduced, and the response speed of the liquid crystal display can be improved.
Detailed Description
The present invention will now be described with reference to the following detailed description, which is to be construed as illustrative only and not limiting in any way.
According to one aspect of the present invention, there is provided a compound of formula I:
wherein,
r is at least one selected from hydrogen, vinyl and C1-C10 alkyl;
X1，X2，X3，X4，X5，X6，X7，X8and X9Each independently selected from H, F, Cl, CH3、CF3、OCF3One of (1);
m is 0, 1, 2 or 3;
n is 0 or 1.
The compound has higher clearing point and proper optical anisotropy, and is suitable for liquid crystal displays. The application of the compound to the liquid crystal composition can improve the clearing point of the liquid crystal composition, thereby improving the working temperature range of the liquid crystal composition. In addition, the dielectric constant of the liquid crystal composition containing the compound is also improved, so that the driving voltage of a liquid crystal display containing the liquid crystal composition can be reduced, and the response speed of the liquid crystal display can be improved.
The compounds according to the invention are preferably the following compounds represented as P1-P28:
various synthetic routes may be selected depending on the substituents selected for the compounds of formula I, and applicants have synthesized and characterized a number of specific compounds in the present invention to illustrate and describe the present invention.
In the synthesis of the compounds described below, the materials used are commercially available unless otherwise specified. Wherein,
GC means gas chromatographic purity;
MS means mass spectrum;
CPindicating a clearing point;
△ ε indicates the dielectric anisotropy;
△ n represents optical anisotropy;
γ1represents rotational viscosity;
identifying the obtained compound by using a mass spectrum obtained by MS;
the GC-MS analysis measuring instrument is QP2010SE model of Shimadzu corporation;
the clearing points are tested by a conventional test method.
The method for measuring the physical properties of the compounds is carried out according to the specifications of the industry, and is published by the publication of "handbook of liquid crystal devices" for aviation industry.
Method for measuring physical properties of liquid crystal composition:
1. determination of phase Structure and clearing Point temperature (. degree. C.)
The type of phase was determined by observing the phase change with a polarization microscope while heating the compound on a hot plate equipped with a polarization microscope melting point apparatus (model FP-52 manufactured by Mettler corporation) at a rate of 3 ℃/min.
2. Optical anisotropy (refractive index anisotropy measured at 25 ℃ C. △ n)
Measurement △ n was measured at 25 ℃ with a light having a wavelength of 589nm using an Abbe refractometer.
The refractive index (n |) is a value measured when the polarization direction is parallel to the rubbing direction, the refractive index (n ⊥) is a value measured when the polarization direction is perpendicular to the rubbing direction, and the value of the optical anisotropy (△ n) is calculated from △ n ═ n | -n ⊥.
3. Dielectric anisotropy (△ ε, measured at 25 ℃ C.)
The measurement was performed by a Hewlett packard HP4284a precision LCR tester, the dielectric constant ε | of the liquid crystal molecules in the long axis direction was measured, the dielectric constant (ε ⊥) of the liquid crystal molecules in the short axis direction was measured, and the dielectric anisotropy △ ε was calculated by △ ε | - ε ⊥.
4. Viscosity (. gamma.1, measured at 20 ℃) using a Toyo6254 integrated tester.
Example 1
The synthesized specific compound is shown as a formula P1:
the synthetic route of P1 is as follows:
firstly, step 1 is carried out:
reacting a compound 3, 4-dihydroxy-1-propylcyclopentane and 3, 5-difluorobenzaldehyde in toluene to obtain a compound shown as a formula P1-1, and specifically comprising the following steps:
in a 250ml three-necked flask, 14.4 g of 3, 4-dihydroxy-1-propylcyclopentane (prepared by European journal of Medicinal Chemistry 46(2011)1263-,1HNMR(500MHz，CDCl3)，δ7.04(m，2H)，δ6.82(m，1H)，δ5.78(s，1H)，δ4.16(m，2H)，δ1.81～1.41(m，5H)，δ1.25(m，2H)，δ1.06～0.85(m，5H)。
then step 2 is carried out:
substituting butyl lithium for a compound shown as a formula P1-1, and then reacting with difluorodibromomethane to obtain a compound shown as a formula P1-2, wherein the method comprises the following specific steps:
adding 8g of compound P1-1 and 80ml of tetrahydrofuran into a reaction bottle, introducing nitrogen for protection, cooling to-60 ℃, dropwise adding 0.04mol of n-butyllithium, controlling the temperature in the dropwise adding process to be-55-60 ℃, and continuously stirring and reacting for 1 hour under controlled temperature after dropwise adding. Cooling to-70 ℃, dropwise adding 9.5g of difluorodibromomethane, controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuously controlling the temperature, stirring and reacting for 30 minutes, heating to room temperature, adding 10ml of concentrated hydrochloric acid and 50ml of water, separating liquid, extracting a water phase by 100ml of dichloromethane (solvent), washing an organic phase to neutrality by water, evaporating the solvent to dryness to obtain 8.3g of a light yellow solid compound P1-2, wherein the purity of a gas chromatography is 78.12%, and the purity yield is 54.63%.
Then, step 3 is carried out:
reacting a compound shown as a formula P1-2 with 3, 4, 5-trifluorophenol to obtain a compound shown as a formula P1, which comprises the following specific steps:
8g of the compound P1-2 having a purity of 78.12% by gas chromatography obtained in the previous step, 50ml of DMSO, 5.5g of anhydrous potassium carbonate and 3.5g of 3, 4, 5-trifluorophenol were added to a reaction flask, and the mixture was stirred and heated to 65 to 70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 30ml dichloromethane, adding 100ml water to the filtrate, stirring, separating, extracting the aqueous layer with 20ml dichloromethane (solvent), washing the organic phase to neutrality, and evaporating the solvent. The concentrate was dissolved in 50ml of toluene (solvent), and the resulting solution was passed through a silica gel column for decolorization, eluted with toluene (solvent), and the eluate was collected and evaporated to remove the solvent, and the resultant was recrystallized from anhydrous ethanol (solvent) 3 times to obtain 2.92 g of white needle-like crystal P1, yield 40%, and purity by gas chromatography 99.5%. Product mass spectrum (m/e): 464,1HNMR(500MHz，CDCl3))，δ7.10(m，2H)，δ6.80(m，2H)，δ5.70(s，1H)，δ4.26(m，2H)，δ1.75～1.36(m，5H)，δ1.25(m，2H)，δ1.08～0.87(m，5H)。
the compounds shown in the above-mentioned P3, P4, P9, P11, P12, P17, P19, and P20 can be synthesized by referring to the synthesis method of example 1 except that 3, 4-dihydroxy-1-propylcyclopentane is replaced with the corresponding alkyl-substituted dihydroxycyclopentane, 3, 5-difluorobenzaldehyde is replaced with the corresponding aldehyde in step 1, and 3, 4, 5-trifluorophenol is replaced with the corresponding phenol in step 3 (one or two or three of dihydroxycyclopentane, aldehyde, and phenol are replaced depending on the structure of the synthesis product). The specific experimental data are tabulated below:
example 2
The synthesized specific compound is shown as a formula P7:
the synthetic route of P7 is as follows:
firstly, step 1 is carried out:
reacting a compound 3, 4-dihydroxy-1-propylcyclopentane and P-bromobenzaldehyde in toluene to obtain a compound shown as a formula P7-1, which comprises the following specific steps:
in a 250ml three-necked flask, 14.4 g of 3, 4-dihydroxy-1-propylcyclopentane (prepared by European journal of Medicinal Chemistry 46(2011)1263-,1HNMR(500MHz，CDCl3)δ7.78(m，2H)，δ7.30(m，2H)，δ5.79(s，1H)，δ4.14(m，2H)，δ1.65～1.35(m，5H)，δ1.28(m，2H)，δ1.02～0.83(m，5H)。
then step 2 is carried out:
reacting a compound P7-1 with n-butyllithium in THF, and then reacting with trimethyl borate to obtain a compound shown as a formula P7-2, wherein the method comprises the following specific steps:
adding 30g of compound P7-1 and 300ml of tetrahydrofuran into a reaction bottle, introducing nitrogen for protection, cooling to-70 ℃, dropwise adding 0.12mol of n-butyllithium within 1 hour, and stirring for reaction for 30 minutes at-70 ℃. Then cooling to-80 ℃, dropwise adding 70ml of tetrahydrofuran solution of 13g of trimethyl borate, continuing to perform stirring reaction for 1 hour under controlled temperature after adding, heating to room temperature, adding 0.2mol of dilute hydrochloric acid, stirring for 1 hour, adding water for washing, extracting and separating by 50ml of ethyl acetate, washing an organic phase to be neutral, and evaporating the solvent to dryness to obtain 22g of a compound P7-2, wherein the yield is 80.7%, and the purity of a liquid chromatogram is 95%.
Then, step 3 is carried out:
reacting a compound P7-2 with a compound shown as a formula P7-A to obtain a compound shown as a formula P7, which comprises the following specific steps:
27.6g of a compound P7-2, 38.9g of a compound shown as a formula P7-A (synthesized according to Angew. chem. int. Ed.2001.40.1480), 0.2g of palladium tetratriphenylphosphine, 15g of sodium carbonate, 500ml of toluene, 200ml of water and 300ml of ethanol are added into a reaction bottle, heated and refluxed for 4 hours, 100ml of water is added for liquid separation, an organic phase is evaporated to dryness, and products P7, 32.6g and the yield is 60.4 percent are obtained through column chromatography and recrystallization. Product mass spectrum (m/e) 540,1HNMR(500MHz，CDCl3)δ7.69(m，2H)，δ7.57(m，2H)，δ7.32(m，2H)，δ6.88(m，2H)，δ5.81(s，1H)，δ4.36(m，2H)，δ1.77～1.36(m，5H)，δ1.29(m，2H)，δ1.06～0.85(m，5H)。
referring to the synthesis method of example 2, compounds represented by the above-mentioned P5, P6, P8, P13, P14, P15, P16, P21, P22, P23, P24, P25, P26, P27, and P28 were synthesized by replacing 3, 4-dihydroxy-1-propylcyclopentane in step 1 with the corresponding alkyl-substituted dihydroxycyclopentane, the benzaldehyde in step 1 with the corresponding aldehyde, and the P7-A in step 3 with the corresponding bromide (one or two or three of the above-mentioned raw materials were replaced depending on the structure of the synthesized product). The specific experimental data are tabulated below:
according to another aspect of the present invention, there is provided a liquid crystal composition comprising at least one compound according to the present invention.
A liquid crystal composition according to an embodiment of the present invention comprises 3 to 40% by mass of the compound according to the present invention.
According to another aspect of the present invention, there is provided a liquid crystal display comprising the liquid crystal composition according to the present invention.
To better illustrate the improvement of the properties of the compounds of the present invention in liquid crystal compositions containing the compounds of the present invention, the following will be illustrated by specific test examples.
Test example
Firstly, 12 monomers shown in the following table 1 are selected to form a composition according to the weight ratio shown in the following table 1, and the composition is subjected to a performance parameter test, wherein the specific test result is shown in the following table 2.
TABLE 1
TABLE 2
| Performance parameter | Test results |
| Cp | 75℃ |
| Δn | 0.105 |
| Δε | 5.6 |
| γ1 | 75 |
Comparative test example 1
The P1 compound in an amount of 10 wt% is added to the composition of the above test example to form a new liquid crystal composition, and the new liquid crystal composition is subjected to the performance parameter test, and the specific test results are shown in table 3 below.
TABLE 3
| Performance parameter | Test results |
| Cp | 78℃ |
| Δn | 0.109 |
| Δε | 6.7 |
| γ1 | 63 |
As can be seen from the test results in table 3: the compound of the present invention was added to the composition of test example 1, which significantly improved clearing points (Cp) and Δ ∈ and decreased value of γ 1, compared to the composition of test example to which the compound of the present invention was not added, thereby improving the operating temperature range of the liquid crystal composition, decreasing the driving voltage of the device, and improving the response speed.
Comparative test example 2
The P7 compound in an amount of 10 wt% was added to the composition of the above test examples to form a new liquid crystal composition, and the new liquid crystal composition was subjected to the performance parameter test, and the specific test results are shown in table 4 below.
TABLE 4
| Performance parameter | Test results |
| Cp | 74℃ |
| Δn | 0.109 |
| Δε | 7.5 |
| γ1 | 61 |
As can be seen from the test results of table 4: the compound of the present invention was added to the composition of test example 1, which also significantly improved the clearing points (Cp) and Δ ∈ and decreased the value of γ 1, compared to the composition of test example without the compound of the present invention, thereby improving the operating temperature range of the liquid crystal composition, decreasing the driving voltage of the device, and increasing the response speed.
In conclusion, the liquid crystal compositions with high bright points and high dielectric constants are obtained according to the embodiments of the present invention. The liquid crystal displays using the liquid crystal composition have higher clearing points, can work at high temperature and have wider working range; in addition, the response speed is improved.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A compound of formula I, wherein the compound is represented by formula I:
wherein,
r is at least one selected from hydrogen, vinyl and C1-C10 alkyl;
X1，X2，X3，X4，X5，X6，X7，X8and X9Each independently selected from H, F, Cl, CH3、CF3、OCF3One of (1);
m is 0 or 1;
n is 0.
2. The compound of claim 1, wherein the compound comprises:
3. a liquid crystal composition comprising at least one compound of claim 1 or 2.
4. The liquid crystal composition according to claim 3, wherein the liquid crystal composition comprises 3 to 40 mass% of the compound according to claim 1 or 2.
5. A liquid crystal display comprising the liquid crystal composition according to claim 3 or 4.
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| CN103254908A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal mixture containing (3,3,0) bicycle-octane monomer |
| CN103254909A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition containing bicycle-octane |
| CN103534335B (en) * | 2011-11-24 | 2015-04-29 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound |
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| CN103534335B (en) * | 2011-11-24 | 2015-04-29 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound |
| CN103254908A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Positive dielectric liquid crystal mixture containing (3,3,0) bicycle-octane monomer |
| CN103254909A (en) * | 2013-05-07 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition containing bicycle-octane |
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