CN114181712B - Fluorine-containing liquid crystal compound and application thereof - Google Patents
Fluorine-containing liquid crystal compound and application thereof Download PDFInfo
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- CN114181712B CN114181712B CN202111584588.6A CN202111584588A CN114181712B CN 114181712 B CN114181712 B CN 114181712B CN 202111584588 A CN202111584588 A CN 202111584588A CN 114181712 B CN114181712 B CN 114181712B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 87
- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 28
- 239000011737 fluorine Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 125000001979 organolithium group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002178 crystalline material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 238000007363 ring formation reaction Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- -1 fluoro-1, 4-phenylene Chemical group 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- CHFHJZQNRFZRNY-UHFFFAOYSA-N 4-[tert-butyl-(1,1-dichloro-2-methylpropan-2-yl)phosphanyl]-N,N-dimethylaniline Chemical compound ClC(C(C)(C)P(C1=CC=C(C=C1)N(C)C)C(C)(C)C)Cl CHFHJZQNRFZRNY-UHFFFAOYSA-N 0.000 description 3
- NEUHEAGBFGEQRX-UHFFFAOYSA-N CCOC(C(F)=C1F)=CC(B(O)O)=C1F Chemical compound CCOC(C(F)=C1F)=CC(B(O)O)=C1F NEUHEAGBFGEQRX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- 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
- C09K19/066—Non-steroidal liquid crystal compounds containing one heterocyclic ring having oxygen as heteroatom
-
- 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
-
- 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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- 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
- C09K19/06—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)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (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 relates to the technical field of liquid crystal compounds, in particular to a novel fluorine-containing liquid crystal compound and application thereof. The liquid crystal compound provided by the invention has a structure shown in a general formula (I), has higher negative dielectric anisotropy, good liquid crystal intersolubility and relatively low rotational viscosity, can improve the performance of liquid crystal materials, and has important application value.
Description
Technical Field
The invention relates to the technical field of liquid crystal compounds, in particular to a novel fluorine-containing liquid crystal compound and application thereof.
Background
In recent years, liquid crystal display devices have been developed more and more rapidly, and different types of liquid crystal display devices, such as a vehicle-mounted small-sized liquid crystal display device, a portable liquid crystal display device, an ultra-thin liquid crystal display device, and the like, have also appeared. The development in the field is proceeding, taking liquid crystal electricity as an example, and the liquid crystal display is characterized by light weight, small occupied space, convenient movement, notebook type personal computers, palm computers, mobile phones and the like.
The application of the liquid crystal material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. At present, the technology of TFT-LCD products is mature, the technical problems of visual angle, resolution, color saturation, brightness and the like are successfully solved, and large-size and medium-small-size TFT-LCD displays gradually occupy the mainstream position of flat panel displays in the respective fields. Meanwhile, the requirements on display technology are continuously increasing, for example, a liquid crystal display is required to realize faster response, drive voltage is reduced to reduce power consumption, and the like, and a liquid crystal material is required to have the performances of low-voltage drive, fast response, wide temperature range, good low-temperature stability and the like.
The liquid crystal material itself plays an important role in improving the performance of the liquid crystal display, and particularly, the performance of the liquid crystal display can be remarkably improved by reducing the rotational viscosity of the liquid crystal material and improving the dielectric anisotropy delta epsilon of the liquid crystal material. Therefore, in order to improve the performance of liquid crystal materials to adapt to new requirements, the synthesis of liquid crystal compounds with novel structures and the research on the structure-performance relationship have become an important task in the field of liquid crystals.
Disclosure of Invention
The invention aims to develop a novel fluorine-containing liquid crystal compound, in particular to a fluorine-containing benzofuran liquid crystal compound which has higher negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, can improve the performance of liquid crystal materials, and has important application value.
In a first aspect, the present invention provides a fluorine-containing liquid crystal compound having a structure as shown in general formula (I):
wherein R 1 and R 2 independently of each other represent an alkyl, alkoxy or alkenyl group having 1 to 12 carbon atoms;
A 1、A2 and A 3 independently of one another represent 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluorinated 1, 4-phenylene;
Z 1、Z2 and Z 3 independently of one another represent a single bond, a double bond, an oxygen atom, -CF 2O-、-CH2CH2-、-CH2O-、-OCH2 -or-CH=CH-;
x represents an oxygen atom, a sulfur atom, -CH 2-、-CF2 -, or-CHF-;
m, n, p independently of one another represent 0,1 or 2.
Wherein the fluoro-1, 4-phenylene is monofluoro-1, 4-phenylene, difluoro-1, 4-phenylene, trifluoro-1, 4-phenylene or tetrafluoro-1, 4-phenylene; preferably, the fluoro-1, 4-phenylene is monofluoro-1, 4-phenylene or difluoro-1, 4-phenylene.
As a preferred embodiment of the present invention, said X represents an oxygen atom.
As a preferred embodiment of the present invention, m, n, p independently of each other represent 0 or 1.
As a preferred embodiment of the present invention, R 1 and R 2 independently of each other represent an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms.
Further preferably, the R 1 and R 2 independently of one another represent alkyl, alkoxy or alkenyl groups having 2 to 5 carbon atoms.
Still further preferably, the R 1 and R 2 are independently selected from ethyl, propyl, butyl, pentyl, ethoxy.
More preferably, R 1 and R 2 are independently selected from ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the invention, both Z 1、Z2 and Z 3 represent a single bond.
As a preferred embodiment of the present invention, the fluorine-containing liquid crystal compound is selected from the structures represented by any one of the following general formulae I-1 to I-17:
Wherein, in the above general formulae I-1 to I-17, R 1 and R 2 independently of each other represent an alkyl group, an alkoxy group or an alkenyl group having 1 to 5 carbon atoms;
Preferably, R 1 and R 2 represent, independently of each other, an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
Still further preferably, the R 1 and R 2 are independently selected from ethyl, propyl, butyl, pentyl, ethoxy.
More preferably, R 1 and R 2 are independently selected from ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the present invention, the fluorine-containing liquid crystal compound is optionally a compound represented by the following structure:
/>
in a second aspect, the present invention provides a method for preparing the fluorine-containing liquid crystal compound, which can be synthesized by the following methods according to the substituents in the general formula.
In the first method, when m, n and p are all 0 in the general formula (I), X represents an oxygen atom, namely the fluorine-containing liquid crystal compound has the general formula:
The synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for And/>Is used as raw material and prepared by Suzuki reactionSaid/>Ring closure under alkaline conditions to give/>
Wherein the saidAnd/>The reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the number of the groups of groups,
The saidThe mol ratio of the catalyst to the alkali is 1:1-4, and the reaction temperature is 70-150 ℃; wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, preferably potassium tert-butoxide and/or potassium carbonate.
In the second method, when n is 0, m and p are not 0 at the same time in the general formula (I), X represents an oxygen atom, the synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for And/>Is prepared by Suzuki reactionSaid/>Ring closure under alkaline conditions to give/>/>
Wherein,And/>The reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the number of the groups of groups,
The saidThe mol ratio of the catalyst to the alkali is 1:1-4, and the reaction temperature is 70-150 ℃; wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, preferably potassium tert-butoxide and/or potassium carbonate.
In the third method, when n is 1, m and p are simultaneously 0, X represents an oxygen atom, Z 2 represents a single bond, A 2 represents 1, 4-cyclohexylene in the general formula (I), namely, the structural formula is:
The synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for Reacts with an organolithium reagent and then with/>Reacted and then dehydrated to obtain/>Said/>Through hydrogenation reaction, obtain/>/>
Wherein,Organolithium reagent,/>The reaction molar ratio of 1:1.0-4.0:0.8-1.5, and the reaction temperature is-50 to-100 ℃; the organic lithium reagent is selected from any one or more of sec-butyllithium, tert-butyllithium and n-butyllithium; the dehydrating agent used in the dehydration is any one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate. The catalyst used in the hydrogenation reaction is any one or more of palladium carbon, ruthenium carbon and nickel. The catalyst is used in an amount of0.1% -10% Of mole number.
In each of the above preparation methods, the definitions of R 1 and R 2 are as described above.
The liquid crystal compound can be stably and efficiently obtained by adopting the preparation method.
In a third aspect, the present invention provides a liquid crystal material composition comprising a fluorine-containing liquid crystal compound according to the present invention. The mass percentage of the fluorine-containing liquid crystal compound in the composition is 0.1 to 60%, preferably 1 to 40%, and more preferably 3 to 25%.
In a fourth aspect, the present invention provides the use of a fluorine-containing liquid crystalline compound according to the present invention or of a liquid crystalline material composition according to the present invention in the field of liquid phase display.
As a preferred embodiment, the present invention provides the use of the fluorine-containing liquid crystalline compound of the present invention or the liquid crystalline material composition in a liquid phase display device.
Preferably, the liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS, IPS or the like liquid crystal display.
The invention provides a novel fluorine-containing liquid crystal compound, in particular a fluorine-containing benzofuran liquid crystal compound, which has higher negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, and has important application value required for improving liquid crystal materials.
The liquid crystal compound or the composition containing the liquid crystal compound has extremely high negative dielectric anisotropy and low rotational viscosity, thereby effectively reducing the driving voltage, improving the response speed of a liquid crystal display device, and simultaneously having the advantages of moderate optical anisotropy value, high charge retention rate and the like, and being a liquid crystal material with excellent performance.
Detailed Description
The technical scheme of the invention is described in detail below. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The starting materials are available from published commercial sources unless otherwise specified.
Example 1
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
The method comprises the following specific steps:
(1) Synthesis of Compound LC-01-1: to the reaction flask, 22g (0.1 mol) of 2,3, 4-trifluoro-5-ethoxyphenylboronic acid, 50ml of ethanol, 100ml of toluene, 50ml of water, 13.4g (0.16 mol) of sodium bicarbonate, 22.9g (0.1 mol) of 2-hydroxy-3-propyl-4-methylbenzene bromide, the temperature was raised to 50℃and 0.01g of dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphine palladium was added thereto, and the temperature was raised to 70℃to 75℃continuously for reflux for 2 hours. After the reaction, 28.7g of a solid was obtained in 88.6% yield. The resulting solid LC-01-1 was analyzed by GC-MS and the product had an M/z of 324 (M +).
(2) Synthesis of Compound LC-01: 29.2g of compound LC-01-1 (0.09 mol), 200ml of N-N-dimethylformamide and 20.7g (0.15 mol) of potassium carbonate are added into a reaction flask under the protection of nitrogen, and the temperature is raised to 110-120 ℃ for more than 4 hours. Work-up gave 23.2g of solid in 84.7% yield. The resulting solid LC-01 was analyzed by GC-MS and the product had an M/z of 304 (M +).
Example 2
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
The method comprises the following specific steps:
(1) Synthesis of Compound LC-02-1: to the reaction flask, 22g (0.1 mol) of 2,3, 4-trifluoro-5-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16 mol) of potassium carbonate, 31g (0.1 mol) of trans-3-propylcyclohexyl-4-methyl-2-hydroxybenzene were added under nitrogen protection, the temperature was raised to 50℃and 0.01g of dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphine palladium was added, and the temperature was further raised to 70℃to 75℃and the mixture was refluxed for 2 hours. After the reaction, 37.1g of a solid was obtained in a yield of 91.4%. The resulting solid LC-02-1 was analyzed by GC-MS and the product had an M/z of 406M +).
(2) Synthesis of Compound LC-02: under the protection of nitrogen, 36.6g of compound LC-02-1 (0.09 mol), 260ml of N-N-dimethylformamide and 12.3g (0.11 mol) of potassium tert-butoxide are added into a reaction flask, and the temperature is raised to 110 ℃ to 120 ℃ for more than 4 hours. After the reaction, 32.2g of a solid was obtained, and the yield was 92.5%. The resulting solid LC-02 was analyzed by GC-MS and the product had an M/z of 386 (M +).
Example 3
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
The method comprises the following specific steps:
(1) Synthesis of Compound LC-03-1: to the reaction flask, 22g (0.1 mol) of 2,3, 4-trifluoro-5-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16 mol) of potassium carbonate, 30.5g (0.1 mol) of 3-propylphenyl-2-hydroxy-4-methylbenzene bromide, the temperature was raised to 50℃and 0.01g of dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphine palladium was added thereto, and the temperature was raised to 70℃to 75℃continuously for reflux for 2 hours. Work-up gave 33.5g of solid in 83.7% yield. The resulting solid LC-03-1 was analyzed by GC-MS and the product had an M/z of 400 (M +).
(2) Synthesis of Compound LC-03: under the protection of nitrogen, 36g of compound LC-03-1 (0.09 mol), 260ml of N-N-dimethylformamide and 12.3g (0.11 mol) of potassium tert-butoxide are added into a reaction flask, and the temperature is raised to 110 ℃ to 120 ℃ for more than 4 hours. After the reaction, 30.1g of a white solid was obtained in 88.0% yield. The resulting solid LC-03 was analyzed by GC-MS and the product had an M/z of 380 (M +).
Example 4
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
The method comprises the following specific steps:
(1) Synthesis of Compound LC-04-1: under the protection of nitrogen, 24.6g (0.10 mol) of 2, 3-difluoro-8-methyl-9-ethyl-dibenzofuran and 180ml of tetrahydrofuran are added into a reaction bottle, 0.12mol of n-hexane solution of n-butyllithium is dropwise added at the temperature of-75 to-85 ℃, the dropwise addition is carried out for 2 hours after the dropwise addition, 14g (0.10 mol) of 4-propyl cyclohexyl ketone is dropwise added at the temperature of-75 to-85 ℃, and then the temperature is naturally returned to-60 ℃ for 2 hours. Adding 200ml of water for quenching reaction, adding 160ml of toluene, washing and separating liquid, adding 5g of p-toluenesulfonic acid, refluxing and separating water for 6 hours, and performing conventional post-treatment to obtain 26.9g of solid, namely a compound LC-04-1, GC:99.7% and 73.1% yield. The resulting solid LC-04-1 was analyzed by GC-MS and the product had an M/z of 368 (M +).
(2) Synthesis of Compound LC-04: under the protection of nitrogen, 25.8g of compound LC-04-1 (0.07 mol), 160ml of toluene, 40ml of ethanol and 2.5g of 5% palladium on carbon are added into a hydrogenation kettle, the hydrogen pressure is 0.5MPa, the temperature is raised to 40-60 ℃ and the reaction is carried out for more than 4 hours. After the reaction, 17.6g of a solid was obtained, and the yield was 67.9%. The resulting solid LC-04 was analyzed by GC-MS and the product had an M/z of 370 (M +).
In the above preparation process, conventional post-treatments such as specifically: extracting with dichloromethane, ethyl acetate or toluene, separating, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
The liquid crystal compounds prepared in examples 1 to 4 of the present invention were used for mixed crystal test, and the details are described below. According to a conventional detection method in the field, each performance parameter of the liquid crystal compound is obtained through linear fitting, wherein the specific meaning of each performance parameter is as follows:
S-N represents the crystalline to nematic melting point (. Degree. C.) of the liquid crystal;
CP represents a clearing point of the liquid crystal;
Δn represents optical anisotropy (25 ℃);
Delta epsilon represents dielectric anisotropy (25 ℃,1000 Hz);
γ1 represents the rotational viscosity (mPas, 25 ℃).
The various liquid crystal monomers in the following mixed crystal examples can be synthesized by a known method or commercially available.
Mixed Crystal example 1
The liquid crystal compound provided in the embodiment 1 of the invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the proportions of the components and the detection results are shown in the following table 1.
The liquid crystal compound of example 1 in table 1 was replaced with the comparative compound 1, and the structural formula is as follows:
The comparative examples were obtained, and the proportions and the detection results of the components of the comparative examples are shown in Table 2.
TABLE 1
TABLE 2
Mixed crystal example 2
The liquid crystal compound provided in the embodiment 3 of the invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the proportion of the components and the detection results are shown in the following table 3.
The liquid crystal compound of example 3 in table 3 was replaced with the contrast compound 2, and the structural formula is as follows:
the comparative examples were obtained, and the proportions and the detection results of the components of the comparative examples are shown in Table 4.
TABLE 3 Table 3
TABLE 4 Table 4
Mixed crystal example 3
The liquid crystal compound provided in example 4 of the present invention and other liquid crystal monomers were prepared into a mixed crystal composition, and the proportions of the components and the detection results are shown in table 5 below.
The liquid crystal compound of example 4 in table 5 was replaced with the contrast compound 3, and the structural formula is as follows:
/>
The comparative examples were obtained, and the proportions and the detection results of the components of the comparative examples are shown in Table 6.
TABLE 5
TABLE 6
As is apparent from the test results of tables 1 to 6, it was found that the compound of the present invention, when specifically applied to a liquid crystal composition of a conventional system, can improve dielectric anisotropy Deltaε of the liquid crystal composition while maintaining a low rotational viscosity γ1 and a proper refractive index anisotropy Deltan, and the obtained liquid crystal composition has remarkable rapid response characteristics and low-voltage driving characteristics.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (14)
1. A fluorine-containing liquid crystal compound is characterized by having a structure represented by the general formula (I):
Wherein R 1 and R 2 independently of each other represent an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms;
A 1、A2 and A 3 independently of one another represent 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluorinated 1, 4-phenylene;
Z 1、Z2 and Z 3 independently of one another represent a single bond, a double bond, an oxygen atom, -CF 2O-、-CH2CH2-、-CH2O-、-OCH2 -or-CH=CH-;
X represents an oxygen atom;
m, n, p independently of one another represent 0 or 1.
2. A compound according to claim 1, wherein Z 1、Z2 and Z 3 represent a single bond.
3. The compound according to claim 1, wherein the fluorine-containing liquid crystal compound is selected from the structures represented by any one of the following general formulae I-1 to I-17:
Wherein, in the above general formula, R 1 and R 2 each independently represent an alkyl group, an alkoxy group or an alkenyl group having 1 to 5 carbon atoms.
4. A compound according to claim 3, wherein R 1 and R 2 each independently represent an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
5. A compound according to claim 1 or 3, wherein the fluorine-containing liquid crystal compound is selected from compounds of the formula:
6. a method for preparing the fluorine-containing liquid crystal compound according to claim 1, which is synthesized by the following method:
When m, n and p are all 0 in the general formula (I), namely the general formula of the fluorine-containing liquid crystal compound is as follows:
The synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for And/>Is used as raw material and prepared by Suzuki reactionSaid/>Ring closure under alkaline conditions to give/>
Wherein the saidAnd/>The reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or,/>
The saidThe mol ratio of the catalyst to the alkali is 1:1-4, and the reaction temperature is 70-150 ℃; wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide;
When n is 0, m and p are not 0 in the general formula (I), the synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for And/>As a raw material, through a Suzuki reaction,
Is prepared intoSaid/>Under alkaline conditions
Ring closure reaction to obtain
Wherein,And/>The reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the number of the groups of groups,
The saidThe mol ratio of the catalyst to the alkali is 1: (1-4), and the reaction temperature is 70-to-over
150 ℃; Wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide;
When n is 1, m, p are simultaneously 0 in the general formula (I), Z 2 represents a single bond, A 2 represents 1, 4-cyclohexylene, namely the structural formula is:
The synthetic route is as follows:
The synthesis method comprises the following steps:
To be used for Reacts with an organolithium reagent and then with/>Reacting and then dehydrating to obtainSaid/>Through hydrogenation reaction, obtain/>
Wherein,Organolithium reagent,/>The reaction molar ratio of 1:1.0-4.0:0.8-1.5, and the reaction temperature is-50 to-100 ℃; the organic lithium reagent is selected from any one or more of sec-butyllithium, tert-butyllithium and n-butyllithium; the dehydrating agent used in the dehydration is any one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate.
7. The process according to claim 6, wherein the base used is potassium tert-butoxide and/or potassium carbonate.
8. The preparation method according to claim 6, wherein the catalyst used in the hydrogenation reaction is any one or more of palladium carbon, ruthenium carbon and nickel.
9. A liquid crystal material composition comprising the fluorine-containing liquid crystal compound according to any one of claims 1 to 5; the mass percentage of the fluorine-containing liquid crystal compound in the composition is 0.1-60%.
10. The composition according to claim 9, wherein the fluorine-containing liquid crystal compound is present in an amount of 1 to 40% by mass of the composition.
11. The composition according to claim 9, wherein the fluorine-containing liquid crystal compound is present in an amount of 3 to 25% by mass of the composition.
12. Use of a fluorine-containing liquid-crystalline compound according to any one of claims 1 to 5 or a liquid-crystalline material composition according to any one of claims 9 to 11 in the field of liquid-crystal displays.
13. Use of a fluorine-containing liquid crystal compound according to any one of claims 1 to 5 or a liquid crystal material composition according to any one of claims 9 to 11 in a liquid crystal display device.
14. The use of claim 13, wherein the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS, IPS liquid crystal display.
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| CN106811209A (en) * | 2015-11-30 | 2017-06-09 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds, composition and its application |
| WO2021121022A1 (en) * | 2019-12-16 | 2021-06-24 | 北京八亿时空液晶科技股份有限公司 | Negative dielectric liquid crystal compound, preparation therefor, and application thereof |
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| CN106479514A (en) * | 2016-08-30 | 2017-03-08 | 北京云基科技有限公司 | A kind of 7,8 difluoro, 5 methyl 1,2,3,4- tetrahydronaphthalene liquid-crystal compoundss and preparation method and application |
| WO2021121022A1 (en) * | 2019-12-16 | 2021-06-24 | 北京八亿时空液晶科技股份有限公司 | Negative dielectric liquid crystal compound, preparation therefor, and application thereof |
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