CN113913194B - Fluorine-containing liquid crystal compound and application thereof - Google Patents
Fluorine-containing liquid crystal compound and application thereof Download PDFInfo
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- CN113913194B CN113913194B CN202111234670.6A CN202111234670A CN113913194B CN 113913194 B CN113913194 B CN 113913194B CN 202111234670 A CN202111234670 A CN 202111234670A CN 113913194 B CN113913194 B CN 113913194B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 95
- 150000001875 compounds Chemical class 0.000 title claims abstract description 73
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- -1 fluoro 1,4-phenylene Chemical group 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 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
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 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
- 125000004430 oxygen atom Chemical group O* 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
- 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 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 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
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052744 lithium Inorganic materials 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
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 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
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 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
- 238000004519 manufacturing process Methods 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
- 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 4
- 230000002194 synthesizing effect Effects 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
- 239000007787 solid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 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
- 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 5
- 239000000178 monomer Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 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
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 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
- 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
- 238000010992 reflux Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LLBWYUVAENYQDR-UHFFFAOYSA-N 2-bromo-6-(4-propylphenyl)phenol Chemical compound CCCC(C=C1)=CC=C1C1=CC=CC(Br)=C1O LLBWYUVAENYQDR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid 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
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
Hair brushThe 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 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 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 and brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream 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 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 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 fluorobenzofuran-containing 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 liquid crystal compound having a structure represented by general formula (I):
wherein R is 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 12 carbon atoms;
A 1 、A 2 and A 3 Independently of one another, 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or fluoro 1,4-phenylene;
Z 1 、Z 2 and Z 3 Independently of each other, represents a single bond, a double bond, an oxygen atom, -CF 2 O-、-CH 2 CH 2 -、-CH 2 O-、-OCH 2 -or-CH = CH-;
x represents an oxygen atom, a sulfur atom, -CH 2 -、-CF 2 -or-CHF-;
m, n, p represent, independently of each other, 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 mono-fluoro 1,4-phenylene or di-fluoro 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, said m, n, p represent independently of each other 0 or 1.
As a preferred embodiment of the present invention, said R 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 5 carbon atoms.
Further preferably, said R 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 2 to 5 carbon atoms.
More preferably, said R 1 And R 2 Independently of one another, from ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the present invention, Z is 1 、Z 2 And Z 3 All represent single bonds.
In a preferred embodiment of the present invention, the fluorine-containing liquid crystal compound is selected from the group consisting of structures represented by any one of the following general formulae I-1 to I-17:
wherein in the general formulas I-1 to I-17, R is 1 And R 2 Each independently of the other represents an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms.
Still more preferably, in the above general formulae I-1 to I-17, said R 1 And R 2 Each independently of the others, represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
More preferably, in the above general formulae I-1 to I-17, R is 1 And R 2 Are each independently of the others 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 any compound selected from the group consisting of compounds represented by the following structures:
in a second aspect, the invention provides a preparation method of the fluorine-containing 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, n and p in the formula (I) are all 0, the fluorine-containing liquid crystal compound has the formula:
the synthetic route is as follows:
the synthesis method comprises the following steps:
(1) To be provided with
And &>
Prepared by Suzuki reaction as raw material
(2) The above-mentioned
In 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 to (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 second method, when n is 0,m and p is not 0 at the same time in the general formula (I), the synthetic route is as follows:
the synthesis method comprises the following steps:
(1) To be provided with
And/or>
Prepared by Suzuki reaction as raw material
(2) 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/or>
The reaction molar ratio of (1) to (0.9-1.2) and reactingThe temperature is 60-120 ℃. />
Wherein, the
The molar ratio of the alkali to the alkali is 1 to (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, p is 0 at the same time, and Z is 2 Represents a single bond, A 2 When it represents 1,4-cyclohexylene, the structural formula is:
the synthetic route is as follows:
the synthesis method comprises the following steps:
(1) To be provided with
Reacting with an organolithium reagent and then combining with->
Reacted and then dehydrated to get->
(2) The above-mentioned
Hydrogenation reaction is carried out to obtain->
/>
Wherein the content of the first and second substances,
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.
The hydrogenation reaction in the second step adopts any one or more of palladium carbon, ruthenium carbon and nickel as catalyst, and the dosage of the catalyst is
0.1-10% of mole number.
In the above respective production methods, the R 1 And R 2 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, which comprises the fluorine-containing liquid crystal compound. The fluorine-containing liquid crystal compound is contained in the composition in an amount of 0.1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 3 to 25% by mass.
In a fourth aspect, the invention provides the application of the fluorine-containing liquid crystal compound or the liquid crystal material composition in the liquid phase display field.
As a preferred embodiment, the invention provides the application of the fluorine-containing liquid crystal compound or the liquid crystal 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, 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 is 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, 2,3,4-trifluoro-4-ethoxyphenylboronic acid 22g (0.1 mol), 50ml ethanol, toluene 100ml, water 50ml, sodium bicarbonate 13.4g (0.16 mol), 2-hydroxy-3-propylbromobenzene 21.4g (0.1 mol) were added into a reaction flask, the temperature was raised to 50 ℃, dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium 0.01g was added, and the temperature was further raised to 70 ℃ to 75 ℃ for refluxing for 2 hours. Work-up after the reaction gave 27.9g of a white solid in 90% yield. The white solid LC-01-1 obtained was analyzed by GC-MS to obtain the productM/z is 310 (M) + )。
(2) Synthesis of Compound LC-01: under the protection of nitrogen, 27.9g 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 bottle, and the temperature is raised to 110-120 ℃ for reaction for more than 4 hours. After-treatment of the reaction, 24g of a white solid was obtained in 92% yield. The white solid obtained, LC-01, was analyzed by GC-MS and the product had an M/z of 290 (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, 2,3,4-trifluoro-4-ethoxyphenylboronic acid 22g (0.1 mol), 60ml ethanol, toluene 120ml, water 60ml, potassium carbonate 22g (0.16 mol), trans-3-propylcyclohexyl-2-hydroxy bromobenzene 29.6g (0.1 mol) are added into a reaction bottle, the temperature is raised to 50 ℃, dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium 0.01g is added, and the temperature is raised to 70 ℃ to 75 ℃ continuously and refluxed for 2 hours. Work-up after the reaction gave 35.3g of a white solid in 90% yield. The white solid LC-02-1 obtained was analyzed by GC-MS, and the M/z of the product was 392 (M) + )。
(2) Synthesis of Compound LC-02: under the protection of nitrogen, 35.3g 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 bottle, and the temperature is raised to 110 ℃ to 120 ℃ for reaction for more than 4 hours. Work-up after the reaction gave 31.8g of a white solid in 95% yield. The white solid obtained, LC-02, was analyzed by GC-MS and the product had an M/z of 372 (M) + )。
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, 2,3,4-trifluoro-4-ethoxyphenylboronic acid 22g (0.1 mol), 60ml ethanol, toluene 120ml, water 60ml, potassium carbonate 22g (0.16 mol), 4-propylphenyl-2-hydroxy bromobenzene 29g (0.1 mol) were added into a reaction flask, the temperature was raised to 50 ℃, dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium 0.01g was added, and the temperature was further raised to 70 ℃ to 75 ℃ and refluxed for 2 hours. After-treatment of the reaction, 34.7g of a white solid was obtained in a yield of 90%. The white solid LC-03-1 obtained was analyzed by GC-MS and the product M/z was 386 (M) + )。
(2) Synthesis of Compound LC-03: under the protection of nitrogen, 34.7g 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 reaction for more than 4 hours. Work-up after the reaction gave 31.2g of a white solid in 95% yield. The white solid obtained, LC-03, was analyzed by GC-MS and the product had an M/z of 366 (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, 2,3-difluoro-9-ethyl-dibenzofuran 23.2 (0.10 mol) and 180ml 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, 14g 4-propyl cyclohexyl ketone (0.10 mol) is dripped at the temperature of-75 to-85 ℃, and then the temperature is naturally returned to-60 ℃ and kept 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 aftertreatment to obtain 24.8g of light yellow solid, namely a compound LC-04-1, GC:99.8% and a yield of 70.0%. The solid LC-04-1 obtained was analyzed by GC-MS and the product had an M/z of 354 (M) + )。
(2) Synthesis of Compound LC-04: under the protection of nitrogen, 24.8g of compound LC-04-1 (0.07 mol), 160ml of toluene, 40ml of ethanol, 2.5g 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 15g of a white solid in 60% yield. The white solid LC-04 obtained was analyzed by GC-MS and the product had an M/z of 356 (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 used for the mixed crystal test, which is 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:
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 by 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 following structural 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.
Example 4 in table 5 was replaced with comparative compound 3, of the 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 modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (15)
1. A fluorine-containing liquid crystal compound characterized by having a structure represented by the general formula (I):
wherein R is 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 12 carbon atoms;
A 1 、A 2 and A 3 Independently of one another, 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or fluoro 1,4-phenylene;
Z 1 、Z 2 and Z 3 Independently of one another, a single bond, a double bond, an oxygen atom, -CF 2 O-、-CH 2 CH 2 -、-CH 2 O-、-OCH 2 -or-CH = CH-;
x represents an oxygen atom, a sulfur atom, -CH 2 -、-CF 2 -or-CHF-;
m, n, p represent, independently of each other, 0,1 or 2.
2. A compound according to claim 1, wherein X represents an oxygen atom.
3. A compound according to claim 1 or 2, characterized in that m, n, p represent, independently of each other, 0 or 1; and/or the presence of a gas in the gas,
the R is 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 5 carbon atoms.
4. The method of claim 1 or 2Compound, characterized in that Z is 1 、Z 2 And Z 3 Represents a single bond.
5. A compound according to claim 3, wherein Z is 1 、Z 2 And Z 3 Represents a single bond.
6. The compound of 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 of the other represents an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms.
7. A compound of claim 6, wherein R is 1 And R 2 Each independently of the other represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
8. The compound of claim 1 or 6, wherein the fluorine-containing liquid crystal compound is selected from the compounds represented by the following structural formulas:
9. a method for producing a fluorine-containing liquid crystal compound according to claim 1, characterized by synthesizing by:
when m, n and p in the general formula (I) are all 0, 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 provided with
And/or>
Prepared by Suzuki reaction as raw material
Said +>
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein, the
And/or>
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 to (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;
when n is 0,m and p is not 0 at the same time in the general formula (I), the synthetic route is as follows:
wherein R is 1 And R 2 Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 12 carbon atoms;
ring A represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or fluoro 1,4-phenylene;
the synthesis method comprises the following steps:
to be provided with
And/or>
Prepared by Suzuki reaction as raw material
Is/are>
Under alkaline conditions, a ring closure reaction is carried out to obtain
Wherein the content of the first and second substances,
and/or>
The reaction molar ratio of 1 to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or, is->
The above-mentioned
The molar ratio of the alkali to the alkali is 1 to (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;
when n is 1,m, p is 0 at the same time, and Z is 2 Represents a single bond, A 2 When it 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
Reacting with an organolithium reagent and then combining with->
Reacting, then dehydrating to obtain
Is/are>
Hydrogenation reaction is carried out to obtain->
Wherein it is present>
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.
10. A liquid crystal material composition, characterized in that the liquid crystal material composition comprises the fluorine-containing liquid crystal compound according to any one of claims 1 to 8, and the fluorine-containing liquid crystal compound accounts for 0.1 to 60 percent of the composition by mass.
11. The liquid crystal material composition of claim 10, wherein the fluorine-containing liquid crystal compound is present in the composition in an amount of 1 to 40% by mass.
12. The liquid crystal material composition according to claim 11, wherein the fluorine-containing liquid crystal compound is present in an amount of 3 to 25% by mass of the composition.
13. Use of the fluorine-containing liquid crystal compound according to any one of claims 1 to 8 or the liquid crystal material composition according to any one of claims 10 to 12 in the field of liquid phase display.
14. Use of the fluorine-containing liquid crystal compound according to any one of claims 1 to 8 or the liquid crystal material composition according to any one of claims 10 to 12 in a liquid crystal display device.
15. Use according to claim 14, wherein the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS, IPS liquid crystal display.
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