CN114181711A - Fluorine-containing dibenzofuran liquid crystal compound and application thereof - Google Patents
Fluorine-containing dibenzofuran liquid crystal compound and application thereof Download PDFInfo
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- CN114181711A CN114181711A CN202111584568.9A CN202111584568A CN114181711A CN 114181711 A CN114181711 A CN 114181711A CN 202111584568 A CN202111584568 A CN 202111584568A CN 114181711 A CN114181711 A CN 114181711A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 85
- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 16
- 239000011737 fluorine Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 15
- 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 11
- 238000000034 method Methods 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
- 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
- -1 fluoro-1, 4-phenylene Chemical group 0.000 claims description 8
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 239000007789 gas Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 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 3
- 239000003054 catalyst Substances 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 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
- 239000012024 dehydrating agents Substances 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
- 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
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 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
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000052 comparative effect 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
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000010626 work up procedure Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OBKSFBWOZSQGGC-UHFFFAOYSA-N (4-ethoxy-2,3-difluorophenyl)boronic acid Chemical compound CCOC1=CC=C(B(O)O)C(F)=C1F OBKSFBWOZSQGGC-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
- 230000006872 improvement Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000005406 washing Methods 0.000 description 2
- ATEPEOFRDZUVAG-UHFFFAOYSA-N ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl Chemical compound ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl ATEPEOFRDZUVAG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FITHNTFYFCARSU-UHFFFAOYSA-N bis(4-propylcyclohexyl)methanone Chemical compound C(CC)C1CCC(CC1)C(=O)C1CCC(CC1)CCC FITHNTFYFCARSU-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005090 crystal field Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location 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
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group 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
Classifications
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- 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
- 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
- C09K19/42—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)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to the technical field of liquid crystal compounds, in particular to a novel fluorine-containing dibenzofuran liquid crystal compound and application thereof. The liquid crystal compound provided by the invention has a structure shown in a general formula (I), has high negative dielectric anisotropy, good liquid crystal intersolubility and relatively low rotational viscosity, can improve the performance of a liquid crystal material, 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 dibenzofuran liquid crystal compound and application thereof.
Background
In recent years, liquid crystal display devices have been developed more and more rapidly, and various types of liquid crystal display devices have appeared, such as small-sized liquid crystal display devices for vehicles, portable liquid crystal display devices, ultra-thin liquid crystal display devices, and the like. The development in the art is progressing, taking liquid crystal display as an example, which is characterized by light weight, small occupied space, and convenience in movement, as well as notebook-type personal computers, palm computers, mobile phones, and the like.
The liquid crystal material has great research value and good application prospect in the fields of information display materials, organic optoelectronic materials and the like. At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. Meanwhile, the requirements for display technologies are continuously increasing, for example, a liquid crystal display is required to achieve faster response, and a driving voltage is reduced to reduce power consumption, so that a liquid crystal material is required to have low-voltage driving, fast response, a wide temperature range, good low-temperature stability, and other properties.
The liquid crystal material plays an important role in improving the performance of the liquid crystal display, and particularly, the performance of the liquid crystal display can be obviously 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 properties of liquid crystal materials to meet new requirements, the synthesis of liquid crystal compounds with novel structures and the study of the structure-property relationship have become an important work in the liquid crystal field.
Disclosure of Invention
The invention aims to develop a novel fluorine-containing liquid crystal compound, in particular to a fluorine-containing dibenzofuran 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 a liquid crystal material, and has important application value.
In a first aspect, the present invention provides a fluorine-containing dibenzofuran liquid crystal compound having a structure represented by general formula (I):
wherein R represents an alkyl group, an alkoxy group or an alkenyl group having 1 to 12 carbon atoms;
A1、A2independently of one another, 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluoro-1, 4-phenylene;
Z1、Z2independently of each other, represents a single bond, a double bond, an oxygen atom, -CF2O-、-CH2CH2-、-CH2O-、-OCH2-or-CH ═ CH-;
m and n independently represent 0, 1 or 2.
Wherein the fluoro 1, 4-phenylene is mono-fluoro 1, 4-phenylene, difluoro 1, 4-phenylene, trifluoro 1, 4-phenylene or tetrafluoro 1, 4-phenylene; preferably, the fluoro 1, 4-phenylene is mono-fluoro 1, 4-phenylene or di-fluoro 1, 4-phenylene.
As a preferred embodiment of the present invention, in the general formula (I), m and n independently represent 0 or 1.
As a preferred embodiment of the present invention, R represents an alkyl group, an alkoxy group or an alkenyl group having 1 to 5 carbon atoms.
Further preferably, said R represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
More preferably, R is selected from any of ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the present invention, Z is1、Z2All represent single bonds.
In a preferred embodiment of the present invention, the fluorine-containing dibenzofuran liquid crystal compound is selected from the structures represented by any one of the following general formulae I-1 to I-11:
wherein, in the general formulas I-1 to I-11, R represents alkyl, alkoxy or alkenyl with 2-5 carbon atoms.
More preferably, R is selected from any of ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the invention, the fluorine-containing dibenzofuran liquid crystal compound is any compound selected from the compounds shown in the following structures:
in a second aspect, the invention provides a preparation method of the fluorine-containing dibenzofuran liquid crystal compound, which can be synthesized by the following methods according to different substituents in the general formula.
In the first method, when m and n are both 0 in formula (I), the compound has the formula:
the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
And
prepared by Suzuki reaction as raw material
The above-mentioned
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein, the
And
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃;
the above-mentioned
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxideOne or more, preferably potassium tert-butoxide and/or potassium carbonate.
In the second method, when n is 0 and m is 1 in the formula (I), the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
And
prepared by Suzuki reaction as raw material
The above-mentioned
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein the content of the first and second substances,
and
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the presence of a gas in the gas,
the above-mentioned
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate.
In the third method, when n is 1, m is 0, and Z is2Represents a single bond, A2When represents 1, 4-cyclohexylene, the structural formula is:
the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
With an organolithium reagent and then with
Reacting, then dehydrating to obtain
The above-mentioned
Through hydrogenation reaction, obtain
Wherein the content of the first and second substances,
an organic lithium reagent,
The reaction molar ratio of (1) to (1.0-4.0) to (0.8-1.5), and the reaction temperature of-50 to-100 ℃;
the organic lithium reagent is selected from any one or more of sec-butyl lithium, tert-butyl lithium and n-butyl lithium; dewatering miningThe dehydrating agent is one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate. The catalyst adopted in the hydrogenation reaction is any one or more of palladium carbon, ruthenium carbon and nickel. The preferred amount of catalyst is
0.1-10% of mole number.
In each of the above production methods, R is as defined above.
The liquid crystal compound can be stably and efficiently obtained by the preparation method.
In a third aspect, the invention provides a liquid crystal material composition, wherein the liquid crystal material composition comprises the fluorine-containing dibenzofuran liquid crystal compound. The fluorine-containing dibenzofuran liquid crystal compound is 0.1-60% by mass, preferably 1-40% by mass, and more preferably 2-25% by mass of the composition.
In a fourth aspect, the invention provides an application of the fluorine-containing dibenzofuran liquid crystal compound or the liquid crystal material composition in the liquid phase display field.
The invention provides application of the fluorine-containing dibenzofuran liquid crystal compound or the liquid crystal material composition in a liquid phase display device as a preferred embodiment.
Preferably, the liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS, IPS, and the like liquid crystal displays.
The invention provides a novel fluorine-containing liquid crystal compound, in particular to a fluorobenzofuran-containing liquid crystal compound which has higher negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, is required by liquid crystal material improvement and has important application value.
The liquid crystal compound or the composition containing the liquid crystal compound has extremely high negative dielectric anisotropy and low rotational viscosity, so that the driving voltage is effectively reduced, the response speed of a liquid crystal display device is improved, and the liquid crystal compound or the composition containing the liquid crystal compound has the advantages of moderate optical anisotropy value, high charge retention rate and the like, and is a liquid crystal material with excellent performance.
Detailed Description
The technical solution of the present invention will be explained in detail below. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
The liquid crystal compound prepared in this example has the structural formula:
the synthetic route is as follows:
the method comprises the following specific steps:
(1) synthesis of Compound LC-01-1: under the protection of nitrogen, 20.2g (0.1mol) of 2, 3-difluoro-4-ethoxyphenylboronic acid, 50ml of ethanol, 100ml of toluene, 50ml of water, 13.4g (0.16mol) of sodium bicarbonate and 25.9g (0.1mol) of 2-hydroxy-3-fluoro-4-cyclopentylmethyl-bromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is raised to 70-75 ℃ and the reflux is continued for 2 hours. Work-up after the reaction gave 29.1g of solid product in 86.6% yield. The product LC-01-1 was analyzed by GC-MS and had an M/z of 336 (M)+)。
(2) Synthesis of Compound LC-01: under the protection of nitrogen, 26.9g of compound LC-01-1(0.08mol), 200ml of N-N-dimethylformamide and 20.7g (0.15mol) of potassium carbonate are added into a reaction bottle, the temperature is raised to 110-120 ℃, and the reaction is carried out for more than 4 hours. Work-up after the reaction gave 21.7g of solid product in 85.8% yield. The product LC-01 was analyzed by GC-MS and had an M/z of 316 (M)+)。
Example 2
The liquid crystal compound prepared in this example has the structural formula:
the synthetic route is as follows:
the method comprises the following specific steps:
(1) synthesis of Compound LC-02-1: under the protection of nitrogen, 20.2g (0.1mol) of 2, 3-difluoro-4-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16mol) of potassium carbonate and 34.1g (0.1mol) of trans-2-hydroxy-3-fluoro-4-p-cyclopentylpolyclohexylidene-bromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is raised to 70-75 ℃ and the reflux is carried out for 2 hours. Work-up after the reaction gave 38.6g of solid product in 92.3% yield. The solid product LC-02-1 was analyzed by GC-MS and the M/z of the product was 418 (M)+)。
(2) Synthesis of Compound LC-02: 37.6g of compound LC-02-1(0.09mol), 260ml of N-N-dimethylformamide and 12.3g (0.11mol) of potassium tert-butoxide are added into a reaction flask under the protection of nitrogen, and the reaction is carried out for more than 4 hours at the temperature of 110-120 ℃. Work-up after the reaction gave 32.9g of solid product in 91.7% yield. The obtained solid product LC-02 was analyzed by GC-MS and the M/z of the product was 398M+)。
Example 3
The liquid crystal compound prepared in this example has the structural formula:
the synthetic route is as follows:
the method comprises the following specific steps:
(1) synthesis of Compound LC-03-1: under the protection of nitrogen, 20.2g (0.1mol) of 2, 3-difluoro-4-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16mol) of potassium carbonate and 33.5g (0.1mol) of 3-fluoro-4-p-cyclopentylphenylene-2-hydroxybromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is raised to 70-75 ℃ and the reflux is continued for 2 hours. Work-up after the reaction gave 36.2g of solid product in 87.9% yield. The solid LC-03-1 obtained was analyzed by GC-MS and the product had an M/z of 412 (M)+)。
(2) Synthesis of Compound LC-03: 41.2g of compound LC-03-1(0.1mol), 260ml of N-N-dimethylformamide and 12.3g (0.11mol) of potassium tert-butoxide are added into a reaction flask under the protection of nitrogen, and the reaction is carried out for more than 4 hours at the temperature of 110 ℃ to 120 ℃. After-treatment of the reaction, 35.4g of a solid product was obtained in a yield of 90.3%. The solid LC-03 obtained was analyzed by GC-MS and the M/z of the product was 392 (M)+)。
Example 4
The liquid crystal compound prepared in this example has the structural formula:
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, 27.2g (0.1mol) of 2,2 '-difluoro-3' -cyclopentylmethyl-dibenzofuran and 180ml of tetrahydrofuran are added into a reaction bottle, 0.12mol of n-hexane solution of n-butyllithium is dripped at the temperature of-75 to-85 ℃, the reaction is kept for 2 hours after dripping, and 14g of 4-propylcyclohexyl ketone (0.10 mo) is dripped at the temperature of-75 to-85 DEGl), then naturally returning to-60 ℃ and preserving the temperature for 2 hours. Adding 200ml of water for quenching reaction, adding 160ml of toluene, washing with water, separating liquid, adding 5g of p-toluenesulfonic acid, refluxing, separating water for 6 hours, and performing conventional post-treatment to obtain 30.0g of a solid product, namely a compound LC-04-1, GC: 99.3% and a yield of 76.1%. The solid LC-04-1 obtained was analyzed by GC-MS and the M/z of the product was 394 (M)+)。
(2) Synthesis of Compound LC-04: under the protection of nitrogen, 39.4g of compound LC-04-1(0.10mol), 180ml of toluene, 50ml of ethanol, 3.0g of 5% palladium carbon and 0.5MPa of hydrogen pressure are added into a hydrogenation kettle, the temperature is raised to 40-60 ℃, and the reaction is carried out for more than 4 hours. Work-up after the reaction gave 25.2g of solid product in 63.6% yield. The solid LC-04 obtained was analyzed by GC-MS and the product had an M/z of 396 (M)+)。
In the preparation process, the conventional post-treatment is involved if necessary, and the conventional post-treatment specifically comprises the following steps: extracting with dichloromethane, ethyl acetate or toluene, separating, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the 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 subjected to a mixed crystal test as described below. According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
S-N represents the crystalline to nematic melting point (. degree. C.) of the liquid crystal;
CP represents the clearing point of the liquid crystal;
Δ n represents optical anisotropy (25 ℃);
Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz);
γ 1 represents the rotational viscosity (mPa.s, 25 ℃).
The 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 embodiment 1 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 1 below.
The liquid crystal compound of example 1 in table 1 was replaced with comparative compound 1, of the formula:
thus obtaining a comparative example, and the proportion and the detection result of the components of the comparative example are shown in the table 2.
TABLE 1
TABLE 2
Mixed crystal example 2
The liquid crystal compound provided by embodiment 3 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 3 below.
The liquid crystal compound of example 3 in table 3 was substituted for comparative compound 2, the structural formula is as follows:
thus, comparative examples were obtained, and the proportions of the components and the test results of the comparative examples are shown in Table 4.
TABLE 3
TABLE 4
Mixed crystal example 3
The liquid crystal compound provided in embodiment 4 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 5 below.
The liquid crystal compound of example 4 in table 5 was replaced with comparative compound 3, of the following structural formula:
thus, comparative examples were obtained, and the proportions of the components and the test results of the comparative examples are shown in Table 6.
TABLE 5
TABLE 6
As is apparent from the detection results in tables 1 to 6, when the compound of the present invention is specifically applied to a liquid crystal composition of a conventional system, it is found that the compound can improve the dielectric anisotropy Δ ∈ of the liquid crystal composition, while maintaining a low rotational viscosity γ 1 and a suitable refractive index anisotropy Δ n, and the obtained liquid crystal composition has a significant fast response characteristic and a low voltage driving characteristic.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A fluorine-containing dibenzofuran liquid crystal compound is characterized by having a structure shown in a general formula (I):
wherein R represents an alkyl group, an alkoxy group or an alkenyl group having 1 to 12 carbon atoms;
A1、A2independently of one another, 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluoro-1, 4-phenylene;
Z1、Z2independently of each other, represents a single bond, a double bond, an oxygen atom, -CF2O-、-CH2CH2-、-CH2O-、-OCH2-or-CH ═ CH-;
m and n independently represent 0, 1 or 2.
2. A compound according to claim 1, wherein m, n independently of each other represent 0 or 1.
3. A compound according to claim 1 or 2, wherein R represents an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms.
4. A compound according to any one of claims 1 to 3, wherein Z is1、Z2All represent single bonds.
5. The compound of claim 1, wherein the compound is selected from the structures represented by any one of the following general formulae I-1 to I-11:
wherein, in the general formula, the R represents alkyl, alkoxy or alkenyl with 1-5 carbon atoms;
preferably, said R's each represent an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
6. The compound of claim 1 or 5, wherein the compound is selected from the group consisting of compounds represented by the following structural formulae:
7. a process for the preparation of a compound according to claim 1, characterised in that it is synthesized by:
when m and n in the general formula (I) are both 0, the compound is shown as the general formula:
the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
And
prepared by Suzuki reaction as raw material
The above-mentioned
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein, the
And
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃;
the above-mentioned
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate;
when n is 0 and m is 1 in the general formula (I), the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
And
prepared by Suzuki reaction as raw material
The above-mentioned
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein the content of the first and second substances,
and
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the presence of a gas in the gas,
the above-mentioned
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate;
when n is 1, m is 0, and Z is2Represents a single bond, A2When represents 1, 4-cyclohexylene, the structural formula is:
the synthetic route is as follows:
the synthesis method comprises the following steps:
to be provided with
With an organolithium reagent and then with
Reacting, then dehydrating to obtain
The above-mentioned
Through hydrogenation reaction, obtain
Wherein the content of the first and second substances,
an organic lithium reagent,
The reaction molar ratio of (1) to (1.0-4.0) to (0.8-1.5), and the reaction temperature of-50 to-100 ℃; the organic lithium reagent is selected from any one or more of sec-butyl lithium, tert-butyl lithium and n-butyl lithium; the dehydrating agent used for dehydration is any one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate; and/or the catalyst adopted in the hydrogenation reaction is any one or more of palladium carbon, ruthenium carbon and nickel.
8. A liquid crystal material composition, comprising the compound according to any one of claims 1 to 6; the mass percentage content of the compound in the liquid crystal material composition is 0.1-60%, preferably 1-40%, and more preferably 2-25%.
9. Use of the compound of any one of claims 1 to 6 or the liquid crystal material composition of claim 8 in the field of liquid crystal display.
10. Use of a compound according to any one of claims 1 to 6 or a liquid crystal material composition according to claim 8 in a liquid crystal display device; preferably, the liquid crystal display device comprises TN, ADS, VA, PSVA, FFS and IPS liquid crystal displays.
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| CN109207160A (en) * | 2017-07-03 | 2019-01-15 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
| CN110300746A (en) * | 2017-02-27 | 2019-10-01 | 捷恩智株式会社 | Compound, liquid-crystal composition and liquid crystal display element with dibenzofurans ring |
| 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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| CN106883861A (en) * | 2015-12-16 | 2017-06-23 | 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 |
| CN110300746A (en) * | 2017-02-27 | 2019-10-01 | 捷恩智株式会社 | Compound, liquid-crystal composition and liquid crystal display element with dibenzofurans ring |
| CN109207160A (en) * | 2017-07-03 | 2019-01-15 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
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