CN110499161A - Liquid-crystal compounds, liquid-crystal composition and liquid crystal display device - Google Patents
Liquid-crystal compounds, liquid-crystal composition and liquid crystal display device Download PDFInfo
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- CN110499161A CN110499161A CN201810474164.6A CN201810474164A CN110499161A CN 110499161 A CN110499161 A CN 110499161A CN 201810474164 A CN201810474164 A CN 201810474164A CN 110499161 A CN110499161 A CN 110499161A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 170
- 150000001875 compounds Chemical class 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 abstract 2
- CAADOIDIOZIPES-UHFFFAOYSA-N pentalane Chemical compound C12C3C4C3CC1C4C1C2C1 CAADOIDIOZIPES-UHFFFAOYSA-N 0.000 abstract 2
- 150000001940 cyclopentanes Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 59
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000012044 organic layer Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- QDFKKJYEIFBEFC-UHFFFAOYSA-N 1-bromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1 QDFKKJYEIFBEFC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Substances CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- ZUVAACFIEPYYOP-UHFFFAOYSA-N methoxycyclopropane Chemical compound COC1CC1 ZUVAACFIEPYYOP-UHFFFAOYSA-N 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
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- 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
-
- 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
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
-
- 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
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a kind of liquid-crystal compounds, belong to technical field of liquid crystal display, and the general structure of the liquid-crystal compounds is shown in formula I,
Description
Technical Field
The invention relates to the technical field of liquid crystal materials. And more particularly, to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display device including the liquid crystal compound or the liquid crystal composition.
Background
Since the first synthesis of liquid crystal by leinztz in 1888, the actual development of the liquid crystal industry was over 30 years, since liquid crystal display materials have obvious advantages, such as low driving voltage, low power consumption, high reliability, large display information amount, color display, no flicker, flat panel display realization, etc., liquid crystal monomers and liquid crystal displays have undergone great development, and liquid crystal monomers have synthesized 1 ten thousand liquid crystal materials at present, wherein the common liquid crystal display materials are classified according to the characteristics of central bridge bonds and rings of liquid crystal molecules, and mainly include biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, acetylenes, difluoromethoxy bridges, ethanes, heterocycles, etc. The liquid crystal display is also developed from TN and STN of black and white small screen 30 years ago to TN-TFT, VA-TFT, IPS-TFT, PDLC and the like of the present color large screen.
The novel liquid crystal display modes mainly include an optically compensated bend mode (OCB), an in-plane switching liquid crystal display (IPS), a vertical alignment mode (VA), an axially symmetric microstructure liquid crystal display (ASM), a multi-domain twisted liquid crystal display, and the like.
The liquid crystal cells of various display modes have different designs and different driving modes, the directions of liquid crystal molecular director and glass substrate are different, the directions of optical compensation bending mode (OCB) liquid crystal molecular director and glass substrate of in-plane switching liquid crystal display (IPS) liquid crystal molecular director are parallel, and the directions of vertical alignment mode (VA) liquid crystal molecular director and glass substrate of axisymmetric microstructure liquid crystal display (ASM) are vertical in the state without electric field.
In the parallel alignment type IPS, the dielectric anisotropy (Δ ∈) of the liquid crystal may be positive or negative.
All liquid crystal molecules in a vertical alignment mode (VA) are perpendicular to the direction of the glass substrate in zero field and are parallel to a vertical incident light ray. When the polarizers are crossed, a good dark state is displayed, so that such devices have a good contrast ratio and the dielectric anisotropy (. DELTA.. di-elect cons.) for the liquid crystal must be negative. The optical anisotropy (Δ n) of the liquid crystal, the thickness (d) of the liquid crystal cell, and the wavelength (λ) of the incident light hardly affect the contrast. The response time of the vertical alignment mode (VA) is much shorter than that of the twisted device, about half or so. Under the influence of an external voltage, the VA device mainly generates bending deformation of liquid crystal molecules, the ECB generates splaying deformation of the liquid crystal molecules, the twist display generates twisting deformation of the liquid crystal molecules, the response time of the twisting deformation is inversely proportional to bending, splaying and twisting elastic constants respectively, and the reason that the response time of the VA device is faster is also because the bending elastic constant of most liquid crystals is larger than the splaying elastic constant and the splaying elastic constant is larger than the twisting elastic constant under the common condition.
The existing liquid crystal monomer has small dielectric, low clearing point and small dissolved fraction in a liquid crystal mixture, and is greatly limited in practical application.
Accordingly, the present invention provides a liquid crystal compound, a liquid crystal composition and a liquid crystal display device, which solve at least one of the above problems.
Disclosure of Invention
A first object of the present invention is to provide a liquid crystal compound.
A second object of the present invention is to provide a liquid crystal composition.
A third object of the present invention is to provide a liquid crystal display device.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a liquid crystal compound has a structural general formula shown in formula I,
in the formula I, W represents cyclopentyl, cyclobutyl or cyclopropyl;
to represent
Z1、Z2Each independently represents a single bond, -O-, -CH2-、-CH2CH2-or-CH2O-；
R1Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;
R0represents an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or hydrogen;
x, Y each independently represents F or H;
n represents 0 or 1.
Preferably, the structural formula of the liquid crystal compound with the structural formula I is specifically any one of compounds shown in formulas I1 to I20:
wherein R is1Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;
R0represents an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or hydrogen.
Preferably, the structural formula of the liquid crystal compound with the structural formula I is specifically any one of compounds shown in formulas I1-1 to I20-2:
the present invention encompasses 50 specific compounds of I1-1 to I20-2 described above, but is not limited to the specific forms listed.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a liquid crystal composition comprising one or more of the liquid crystal compounds described above.
Preferably, the liquid crystal composition further comprises one or more compounds of formula IV as a second component:
in the formula IV, R2And R3Each independently represents any one of the following groups (i) to (iii):
linear alkyl with 1-7 carbon atoms or linear alkoxy with 1-7 carbon atoms;
(ii) one or more-CH groups in any of the groups shown in (i)2-a group formed by substitution with-O-, -COO-, -OOC-or-CH ═ CH-;
(iii) one or more-H in any of the groups represented by (i) is-F, -Cl, -CH2or-CH ═ CH-CH3Substitution of the formed group;
each independently selected from one or more of the following groups:
the above-mentionedAt least one of them is selected from One or more of; m, n, o each independently represent 0 or 1; z1’、Z2’、Z3Each independently represents a single bond, -C2H4-、-CH＝CH-、-COO-、-OOC-、-CH2O-、-OCH2-、-CF2O-or-OCF2-, wherein any H atom may be replaced by F.
Preferably, the compound of formula IV is in particular one or more of the following compounds:
wherein R is2And R3The definition of (A) is the same as that described above;
each independently represents any one of the following groups:
preferably, the liquid crystal composition may further comprise one or more compounds having the structure of formula V as a third component:
in the formula V, R4And R5Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; in addition, R4And R5Is any of-CH2May be-CH2O-、-OCH2-, -C ═ C-, any H atom may be replaced by F;
each independently selected from one or more of the following groups:
p, q, r each independently represent 0 or 1;
Z4、Z5、Z6each independently represents a single bond, -C2H4-、-CH＝CH-、-COO-、-OOC-、-CH2O-、-OCH2-、-CF2O-or-OCF2-, wherein any H atom may be replaced by F.
Preferably, the compound of formula V is in particular one or more of the following compounds:
wherein R is4And R5The definition of (A) is the same as that described above;
(F) represents F or H.
Preferably, in the liquid crystal composition, the weight percentage of the one or more liquid crystal compounds with the structural formula I is 1-30%, the weight percentage of the one or more compounds with the structural formula IV is 1-70%, and the weight percentage of the one or more compounds with the structural formula V is 0-70%.
Preferably, in the liquid crystal composition, the weight percentage of the one or more liquid crystal compounds with the structural formula I is 1-25%, and the weight percentage of the one or more compounds with the structural formula IV is 25-65%.
Preferably, in the liquid crystal composition, the weight percentage of the one or more liquid crystal compounds with the structural formula I is 1-25%, and the weight percentage of the one or more compounds with the structural formula V is 25-55%.
To achieve the third object, the present invention provides a liquid crystal display device comprising one or more liquid crystal compounds according to the first object or one or more liquid crystal compositions according to the second object.
Preferably, the liquid crystal display device is an active matrix display device, or a passive matrix display device.
In addition, the application of the liquid crystal compound shown in the formula I in preparing a liquid crystal composition, a liquid crystal display device material or an electro-optical display device material, and the liquid crystal composition, the liquid crystal display device material or the electro-optical display device material containing the compound shown in the formula I also belong to the protection scope of the invention.
Compared with the prior art, the liquid crystal compound shown in the formula I has the beneficial effects that due to the existence of an intramolecular rigid structure and lateral difluoro, the polyfluorinated dibenzocyclopentane liquid crystal of the naphthenic base shows a larger negative dielectric constant. When the cycloalkyl is introduced into the molecules of the polyfluoro dibenzocyclopentane liquid crystal, the obtained liquid crystal compound shows good intersolubility and large negative dielectric constant when being compared with the traditional polyfluoro dibenzocyclopentane liquid crystal taking a soft alkyl chain as an end group.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The production method of the present invention is a conventional method unless otherwise specified, and the starting materials used therefor are commercially available from public places unless otherwise specified.
The invention provides a method for preparing the compound shown in the formula I, and the following two synthetic routes can be selected according to different X and Y:
scheme 1 when X is-F-and Y is-F-, the synthesis can be carried out according to the following scheme:
scheme 2 when X is-H-and Y is-F-, the synthesis can be carried out according to the following scheme:
according to the synthetic routes shown in synthetic routes 1 and 2, formula II is a key intermediate for the synthesis of the target compounds.
A compound of formula II according toZ1、Z2And n are different, the preparation can be carried out by the following four methods:
wherein the first method is the preparation of the compound shown in the formula IIIs composed ofOne of (1), Z1And Z2A process for the preparation of a compound of formula ii, each independently being a single bond, and when n is 0 or 1, comprising the steps of:
the second method is that the compound shown in the formula II is preparedIs composed ofOne of (1), Z1And Z2A process for the preparation of a compound of formula ii, each independently being a single bond, and where n is 1, comprising the steps of:
the third method is to prepare the compound shown in the formula IIIs composed ofOne of (1), Z1And Z2Each independently is-O-or-CH2A process for the preparation of a compound of formula ii, wherein O-and n is 0 or 1, comprising the steps of:
the fourth method is to prepare the compound shown in the formula IIIs composed of One of (1), Z1And Z2Each independently is-CH2CH2A process for the preparation of a compound of formula ii, wherein n is 0 or 1, comprising the steps of:
the reactions of all the steps of all the above processes are carried out in a solvent; the solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water.
The preparation of the liquid-crystalline compounds according to the invention can be carried out by the person skilled in the art in the light of the above description of the routes. Wherein the reaction starting materials may be synthesized by methods known in the art or commercially available.
In the present invention, unless otherwise specified, the liquid crystal compounds having the structural formula I may be referred to as liquid crystal monomers.
In the specification of the present invention, the specific meanings and test conditions of each symbol are as follows:
GC means gas chromatographic purity;
MP represents the melting point;
MS means mass spectrum;
S-N represents the crystalline to nematic melting point (. degree. C.) of the liquid crystal;
cp denotes the clearing point (c) of the liquid crystal, and the test apparatus: a Mettler-Toledo-FP System micro thermal analyzer;
γ 1 is rotational viscosity (mPa · s) and the test conditions are: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
K11is a torsional elastic constant, K33For the splay spring constant, the test conditions were: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ ε represents dielectric anisotropy, and Δ ε ═ ε∥-ε⊥Wherein, epsilon∥Is a dielectric constant parallel to the molecular axis,. epsilon⊥For the dielectric constant perpendicular to the molecular axis, test conditions: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ n represents optical anisotropy, and Δ n ═ no-neWherein n isoRefractive index of ordinary light, neFor the refractive index of extraordinary rays, test conditions: 589nm, 25 + -0.2 deg.C.
In the present invention, the apparatus and equipment used for the preparation of the liquid crystal composition are:
(1) electronic precision balance (precision 0.1 mg);
(2) stainless steel beaker: for weighing the liquid crystal;
(3) spoon: for the addition of monomers;
(4) a magnetic rotor: is used for stirring;
(5) and (5) controlling the temperature of the electromagnetic stirrer.
The preparation method of the liquid crystal composition comprises the following steps:
(1) orderly placing the used liquid crystal monomers;
(2) placing the stainless steel beaker on a balance, and putting the liquid crystal monomer into the stainless steel beaker by using a small spoon;
(3) adding liquid crystal monomers according to the required weight in sequence;
(4) placing the stainless steel beaker added with the materials on a magnetic stirring instrument for heating and melting;
(5) and after most of the mixture in the stainless steel beaker is melted, adding a magnetic rotor into the stainless steel beaker, uniformly stirring the liquid crystal mixture, and cooling to room temperature to obtain the liquid crystal composition.
The invention is illustrated below with the following specific examples:
preparation of liquid crystal compound:
example 1
The structural formula of the liquid crystal compound is shown as the following formula I6-2:
the preparation method comprises the following steps:
step 1, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A2L three-necked flask is added with 10g (0.036mol) of 2-fluoro-4-bromobenzene cyclopentylmethyl ether, 11g (0.45mol) of magnesium chips, 1g (0.375mol) of iodine, 500mL of tetrahydrofuran, and nitrogen protection, stirred, heated to reflux, and reacted after initiation. 90g (0.324mol) of 2-fluoro-4-bromobenzocyclopentylmethyl ether were dissolved in 500ml of tetrahydrofuran and added dropwise to the above system. After the dropwise addition, the reaction was carried out under reflux for 1 hour, the temperature was reduced to-30 ℃ and 45.7g (0.439mol) of trimethyl borate was added dropwise, after the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and then 100ml of concentrated hydrochloric acid was added to adjust the pH to 2-4. Pouring into 500mL of deionized water, extracting twice with 500mL of ethyl acetate, separating, combining organic phases, washing once with 500mL of deionized water, drying an organic layer, and concentrating to obtain 75g of white solid (1-a), HPLC: 97.5% and yield 87%.
Step 2, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
75g (0.31mol) (1-a), 500mL toluene, 100g water, 68g (0.27mol) 2-fluoro-4-bromobenzene butyl ether, 64.2g (0.465mol) anhydrous potassium carbonate and 1g catalyst are added into a 1L three-necked bottle, stirring is started, nitrogen is filled for replacing air, the temperature is increased to reflux, the reaction is carried out for 1 hour, the temperature is reduced, liquid is separated, and an organic layer is washed to be neutral by water. The solvent was evaporated under reduced pressure, 150ml of petroleum ether and 200ml of ethanol were added and heated to boil, and after cooling, 80g of white crystals (1-b) were obtained by filtration, yield: 81 percent.
Step 3, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
30g (0.083mol) (1-b) and 200mL tetrahydrofuran are added into a 500mL three-necked flask and stirred to be completely dissolved, nitrogen is used for protection, 33mL butyl lithium is dropped into the flask after the temperature is reduced to-78 ℃, the mixture is stirred for 1 hour, 7.5g (0.083mol) dimethyl carbonate is dropped into the flask, the mixture is kept at the temperature of-78 ℃ for 1 hour, then the mixture is stirred to the room temperature, 100mL 10% hydrochloric acid aqueous solution is added into the flask, the reaction is stopped after the mixture is stirred for 30 minutes, the mixture is extracted by 500mL multiplied by 2 ethyl acetate, organic layers are combined, the mixture is washed twice by 50mL of mixed solution of ethanol and 100mL water, the solvent is removed by decompression after the mixture is dried by anhydrous sodium sulfate, and then 20g of light yellow.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 10g (0.026mol) (1-c) of dichloromethane (100 mL) into a 500L three-necked flask, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding DAST (4.3 g (0.026mol), and stirring to room temperature after dropwise adding; the reaction was stopped, extracted with 500ml of ethyl acetate × 2, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 5g of a white solid (1-d), GC: 99.2% and a yield of 47.6%.
Example 2
The structural formula of the liquid crystal compound is shown as the following formula I6-3:
the preparation method comprises the following steps:
the synthesis process and starting materials in step 1 to step 3 are the same as those in step 1 to step 3 of the compound shown in formula 16-2 in example 1, and are not described herein again.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A500L three-necked flask was charged with 10g (0.026mol) (1-c), 100ml (10:1 ═ V/V) THF/H2Stirring until the O is completely dissolved, cooling to 0 ℃, adding 1.48g (0.039mol) of sodium borohydride in batches, and stirring to room temperature after the addition is finished; the reaction was stopped, the system was poured into 100ml of water, adjusted to pH4-5 with 20ml of 0.1mol/L aqueous hydrochloric acid, extracted with 500ml of 2 ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 8g of a yellow solid (2-d), GC: 99.2% and yield 76.2%.
Step 5, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 8g (0.021mol) (2-d) of 50mL of dichloromethane into a 100mL three-necked bottle, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 5.0g (0.031mol) of DAST, and stirring to room temperature after the dropwise adding is finished; the reaction was stopped, extracted with 100ml × 2 ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 50g of ethanol at-20 ℃ to give 6.5g of a white solid (2-d), GC: 99.5% and a yield of 81.3%.
Example 3
The structural formula of the liquid crystal compound is shown as the following formula I17-1:
the preparation method comprises the following steps:
step 1, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A1L three-necked flask is charged with 20g (0.06mol) of Compound A, 1.73g (0.072mol) of magnesium turnings, 1g of iodine, 100mL of tetrahydrofuran, under nitrogen, stirred, heated to reflux, and the reaction is initiated. 80g (0.25mol) of Compound A were dissolved in 300ml of tetrahydrofuran and added dropwise to the above system. After the dropwise addition, the reaction was carried out under reflux for 1 hour, the temperature was lowered to-30 ℃ and 32.1g (0.46mol) of trimethyl borate was added dropwise, after the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and then 100ml of concentrated hydrochloric acid was added to adjust the pH to 2-4. Pouring into 500mL of deionized water, extracting twice with 500mL of ethyl acetate, separating, combining organic phases, washing once with 500mL of deionized water, drying an organic layer, and concentrating to obtain 70g of white solid (3-a), HPLC: 98.0% and yield 78.2%.
Step 2, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
70g (0.24mol) (3-a), 500mL toluene, 100g water, 52.3g (0.24mol) 2-fluoro-4-bromobenzene ethyl ether, 39.7g (0.36mol) anhydrous potassium carbonate and 1g catalyst are added into a 1L three-necked flask, stirring is started, nitrogen is filled for replacing air, the temperature is raised to reflux, the reaction is carried out for 1 hour, the temperature is reduced, liquid is separated, and an organic layer is washed by water to be neutral. The solvent was evaporated under reduced pressure, 150ml of petroleum ether and 200ml of ethanol were added and heated to boil, and after cooling, 85g of white crystals (3-b) were obtained by filtration, yield: 92.3 percent.
Step 3, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
20g (0.05mol) (3-b) and 100mL tetrahydrofuran are added into a 500mL three-necked flask and stirred to be completely dissolved, nitrogen is used for protection, 45mL butyl lithium is dropped into the flask after the temperature is reduced to-78 ℃, the mixture is stirred for 1 hour, 5.4g (0.06mol) dimethyl carbonate is dropped into the flask, the flask is kept at-78 ℃ for 1 hour, then the flask is stirred to the room temperature, 100mL 10% hydrochloric acid aqueous solution is added into the flask, the mixture is stirred for 30 minutes, the reaction is stopped, 500mL multiplied by 2 ethyl acetate is used for extraction, organic layers are combined, the organic layers are washed twice by a mixed solution of 50mL ethanol and 100mL water, the solvent is removed by decompression after the mixture is dried by anhydrous sodium sulfate, 15g of light yellow solid (3-c.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 15g (0.04mol) (3-c) of 100mL of dichloromethane into a 500L three-necked bottle, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 7.73g (0.05mol) of DAST, and stirring to room temperature after the dropwise adding is finished; the reaction was stopped, extracted with 500ml of ethyl acetate × 2, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 6.5g of a white solid (3-d), GC: 99.2% and a yield of 41.1%.
Example 4
The structure of the liquid crystal compound is shown as the following formula I1-1:
the preparation method comprises the following steps:
step 1, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A1L three-necked flask is charged with 20g (0.078mol) of Compound B, 2.8g (0.12mol) of magnesium turnings, 1g of iodine, 100mL of tetrahydrofuran, and under nitrogen, stirred, heated to reflux, and the reaction is initiated. 80g (0.31mol) of Compound A was dissolved in 300ml of tetrahydrofuran and added dropwise to the above system. After the dropwise addition, the reaction was carried out under reflux for 1 hour, the temperature was reduced to-30 ℃ and 60.9g (0.59mol) of trimethyl borate was added dropwise, after the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and then 100ml of concentrated hydrochloric acid was added to adjust the pH to 2-4. Pouring into 500mL of deionized water, extracting twice with 500mL of ethyl acetate, separating, combining organic phases, washing once with 500mL of deionized water, drying an organic layer, and concentrating to obtain 75g of white solid (4-a), HPLC: 98.0% and a yield of 75.1%.
Step 2, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
75g (0.34mol) (4-a), 500mL toluene, 100g water, 74.5g (0.34mol) 2-fluoro-4-bromobenzene propyl ether, 70g (0.50mol) anhydrous potassium carbonate and 1g catalyst are added into a 1L three-necked bottle, stirring is started, nitrogen is filled for replacing air, the temperature is increased to reflux, the reaction is carried out for 1 hour, the temperature is reduced, liquid is separated, and an organic layer is washed by water to be neutral. The solvent was evaporated under reduced pressure, 150ml of petroleum ether and 200ml of ethanol were added and heated to boil, and after cooling, 90g of white crystals (4-b) were obtained by filtration, yield: 84.3 percent.
Step 3, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
30g (0.095mol) (4-b) and 100mL tetrahydrofuran are added into a 500mL three-necked flask and stirred to be completely dissolved, nitrogen is used for protection, 76mL butyl lithium is added dropwise when the temperature is reduced to-78 ℃, stirring is carried out for 1 hour, 8.6g (0.095mol) dimethyl carbonate is added dropwise, heat preservation is carried out for 1 hour at-78 ℃, then the mixture is stirred to room temperature, 50mL 10% hydrochloric acid aqueous solution is added, stirring is carried out for 30 minutes, reaction is stopped, 500mL multiplied by 2 ethyl acetate is used for extraction, organic layers are combined, after drying through anhydrous sodium sulfate, the solvent is removed through decompression, 18g of light yellow solid (4-c) is obtained, and the yield is 56.3%.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 18g (0.04mol) (4-c) of 100mL of dichloromethane into a 500L three-necked bottle, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 7.9g (0.05mol) of DAST, and stirring to room temperature after the dropwise adding is finished; the reaction was stopped, extracted with 500ml of ethyl acetate × 2, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 5g of a white solid (3-d), GC: 99.8% and a yield of 26.3%.
Example 5
The structure of the liquid crystal compound is shown as the following formula I15-4:
the preparation method comprises the following steps:
step 1, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A2L three-necked flask is added with 10g (0.041mol) of 2-fluoro-4-bromobenzene cyclopropyl methyl ether, 11g (0.45mol) of magnesium chips, 1g (0.375mol) of iodine, 500mL of tetrahydrofuran, and nitrogen protection, stirred and heated to reflux, and after the reaction is initiated. 90g (0.324mol) of 2-fluoro-4-bromobenzocyclopropylmethyl ether were dissolved in 500ml of tetrahydrofuran and added dropwise to the above system. After the dropwise addition, the reaction was carried out under reflux for 1 hour, the temperature was lowered to-30 ℃ and 46.7g (0.448mol) of trimethyl borate was added dropwise, after the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and then 100ml of concentrated hydrochloric acid was added to adjust the pH to 2-4. Pouring into 500mL of deionized water, extracting twice with 500mL of ethyl acetate, separating, combining organic phases, washing once with 500mL of deionized water, drying an organic layer, and concentrating to obtain 70g of white solid (1-a), HPLC: 98.0% and a yield of 82.3%.
Step 2, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
70g (0.33mol) (5-a), 500mL toluene, 100g water, 73g (0.0.33mol) 2-fluoro-4-bromobenzene ethyl ether, 69g (0.0.50mol) anhydrous potassium carbonate and 1g catalyst are added into a 1L three-necked flask, stirred, filled with nitrogen to replace air, heated to reflux, reacted for 1 hour, cooled and separated, and an organic layer is washed to be neutral. The solvent was evaporated under reduced pressure, 150ml of petroleum ether and 200ml of ethanol were added and heated to boil, and after cooling, 80g of white crystals (5-b) were obtained by filtration, yield: 81 percent.
Step 3, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
30g (0.098mol) (5-b) of tetrahydrofuran (200 mL) is added into a 500mL three-necked flask and stirred to be completely dissolved, nitrogen is used for protection, 98mL of butyl lithium is dropped into the flask after the temperature is reduced to-78 ℃, stirring is carried out for 1 hour, 10.5g (0.117mol) of dimethyl carbonate is dropped into the flask, heat preservation is carried out for 1 hour at-78 ℃, then the flask is stirred to the room temperature, 100mL of 10% hydrochloric acid aqueous solution is added into the flask, stirring is carried out for 30 minutes, reaction is stopped, 500mL of multiplied by 2 ethyl acetate is used for extraction, organic layers are combined, the organic layers are washed twice by a mixed solution of 50mL of ethanol and 100mL of water, the solvent is removed by decompression after drying by anhydrous sodium sulfate, and light yellow solid (1.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 22g (0.06mol) (5-c) of dichloromethane (100 mL) into a 500L three-necked bottle, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding DAST (13 g (0.08mol), and stirring to room temperature after dropwise adding; the reaction was stopped, extracted with 500ml of ethyl acetate × 2, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 4.5g of a white solid (5-d), GC: 99.8% and a yield of 19.5%.
Example 6
The structure of the liquid crystal compound is shown as the following formula I15-3:
the preparation method comprises the following steps:
the synthesis process and starting materials in steps 1 to 3 are the same as those in steps 1 to 3 of the preparation of the compound shown in formula I15-4 in example 5, and are not described again.
Step 4, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
A500L three-necked flask was charged with 10g (0.03mol) (6-c), 100ml (10: 1. about. V/V) THF/H2Stirring until the O is completely dissolved, cooling to 0 ℃, adding 2.3g (0.06mol) of sodium borohydride in batches, and stirring to room temperature after the addition is finished; the reaction was stopped, the system was poured into 100ml of water, adjusted to pH4-5 with 20ml of 0.1mol/L aqueous hydrochloric acid, extracted with 500ml of 2 ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 100g of ethanol at-20 ℃ to give 7.5g of a yellow solid (6-d), GC: 98.0% and a yield of 76.2%.
Step 5, the preparation route is as follows:
the specific operation flow of the preparation is as follows:
adding 7.5g (0.023mol) (6-d) and 50mL of dichloromethane into a 100mL three-necked bottle, stirring until the dichloromethane is completely dissolved, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 4.4g (0.027mol) of DAST, and stirring to room temperature after the dropwise adding is finished; the reaction was stopped, extracted with 100ml of ethyl acetate × 2, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and recrystallized from 50g of ethanol at-20 ℃ to give 5.0g of a white solid (6-e), GC: 99.5% and yield 66.7%.
Example 7
The structure of the liquid crystal compound is shown as the following formula I3-1:
the preparation procedure is the same as in example 1, except that the raw materials in step 1 are mixedIs replaced by
Example 8
The structure of the liquid crystal compound is shown as the following formula I3-3:
the preparation procedure is the same as in example 2, except that the raw materials in step 1 are mixedIs replaced by
In summary, the liquid crystal compound provided by the embodiment of the invention shows a larger negative dielectric constant due to the existence of the rigid structure in the molecule and the lateral difluoro. When the cycloalkyl is introduced into a polyfluoro dibenzo cyclopentane liquid crystal molecule, the obtained liquid crystal compound shows good intersolubility and large negative dielectric constant when being compared with the traditional polyfluoro dibenzo cyclopentane liquid crystal compound taking a soft alkyl chain as an end group, and the liquid crystal compound shown in the formula I provided by the invention can improve the intersolubility of the liquid crystal compound and expand the application range of the liquid crystal composition.
Liquid crystal composition:
the parts referred to in the following examples are in weight percent, and the temperature unit is ℃:
examples 9 to 16 and comparative example 1
The formulations of examples 9 to 16 and comparative example 1 are shown below, and the liquid crystal compositions were prepared by weighing the liquid crystal compounds of the general formulas I, IV and V in percentage by weight. The various liquid crystal monomers used can be synthesized by methods known in the art or obtained commercially.
The resulting liquid crystal composition was filled in a test cell for parameter testing. The monomer structure, the dosage (weight percentage content) of the specific compound and the performance parameter test results of the obtained liquid crystal composition are all listed in tables 1-9.
Example 9
TABLE 1 structural formula, content and properties of the raw material compound for preparing the liquid crystal composition of example 9
Example 10
TABLE 2 EXAMPLE 10 structural formula, content and Properties of raw Material Compound for preparing liquid Crystal composition
Example 11
TABLE 3 formula, content and properties of the starting compounds for preparing liquid crystal compositions of example 11
Example 12
TABLE 4 EXAMPLE 12 structural formula, content and Properties of liquid Crystal composition of raw Material Compound for preparing liquid Crystal composition
Example 13
TABLE 5 examples 13 structural formulas and contents of raw material compounds for preparing liquid crystal compositions and properties of the liquid crystal compositions
Example 14
TABLE 6 EXAMPLE 14 structural formula, content and Properties of raw Material Compound for preparing liquid Crystal composition
Example 15
TABLE 7 examples 15 structural formulas and contents of raw material compounds for preparing liquid crystal compositions and properties of the liquid crystal compositions
Example 16
TABLE 8 EXAMPLE 16 structural formula, content and Properties of liquid Crystal composition of raw Material Compound for preparing liquid Crystal composition
Comparative example 1
TABLE 9 structural formula, content and properties of liquid crystal composition of raw material compound for preparing liquid crystal composition of comparative example 1
As is clear from the parameters of the liquid crystal compositions shown in examples 9 to 16, the liquid crystal compositions of the present invention have good mutual solubility and large negative dielectric constant. As can be seen from comparison between examples 9 to 16 and comparative example 1, the tetrafluorofluorene liquid crystal compound with a cycloalkyl group as an end group shows better intersolubility than the tetrafluorofluorene liquid crystal with a soft alkyl chain as an end group, and the dielectric constant (Δ ∈), clearing point (Cp) and low-temperature stability of the liquid crystal are improved accordingly, so that the compound shown in formula I provided by the invention can improve the intersolubility of the liquid crystal compound, expand the application range of the liquid crystal mixture, and has important application value.
Although the present invention has been described with reference to the specific compounds and their ratios (weight percentage) of the above 8 examples, and has been tested, the liquid crystal composition of the present invention can be further extended and modified based on the above examples by using the liquid crystal compounds represented by the general formulas I, IV, and V and the liquid crystal compounds with the preferred specific structures of the general formulas I, IV, and V, and the purpose of the present invention can be achieved by properly adjusting the ratios and amounts.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A liquid crystal compound is characterized in that the structural general formula of the liquid crystal compound is shown as formula I:
in the formula I, W represents cyclopentyl, cyclobutyl or cyclopropyl;
to represent
Z1、Z2Each independently represents a single bond, -O-, -CH2-、-CH2CH2-or-CH2O-；
R1Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;
R0represents an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or hydrogen;
x, Y each independently represents F or H;
n represents 0 or 1.
2. The liquid crystal compound of claim 1, wherein the liquid crystal compound of formula I has a formula of any one of compounds represented by formulae I1 to I20:
3. the liquid crystal compound of claim 1, wherein the structural formula of the liquid crystal compound is specifically any one of compounds represented by formulas I1-1 to I20-2:
4. a liquid crystal composition comprising one or more liquid crystal compounds according to any one of claims 1 to 3.
5. The liquid crystal composition of claim 4, further comprising one or more compounds of formula IV:
wherein R is2And R3Each independently represents any one of the following groups (i) to (iii):
linear alkyl with 1-7 carbon atoms or linear alkoxy with 1-7 carbon atoms;
(ii) one or more-CH groups in any of the groups shown in (i)2-a group formed by substitution with-O-, -COO-, -OOC-or-CH ═ CH-;
(iii) one or more-H in any of the groups represented by (i) is-F, -Cl, -CH2or-CH ═ CH-CH3Substitution of the formed group;
each independently selected from one or more of the following groups:
preferably, theAt least one of them is selected fromOne or more of;
m、n、oeach independently represents 0 or 1;
Z1’、Z2’、Z3each independently represents a single bond, -C2H4-、-CH＝CH-、-≡-、-COO-、-OOC-、-CH2O-、-OCH2-、-CF2O-or-OCF2-, wherein any H atom may be replaced by F.
6. The liquid crystal composition of claim 5, wherein the compound of formula IV is one or more of the following compounds:
wherein,each independently represents any one of the following groups:
7. the liquid crystal composition of any one of claims 4 to 6, further comprising one or more compounds having the structure of formula V:
in the formula V, R4And R5Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; r4And R5Is any of-CH2May be-CH2O-、-OCH2-, -C ═ C-, any H atom may be replaced by F;
each independently selected from one or more of the following groups:
p, q, r each independently represent 0 or 1;
Z4、Z5、Z6each independently represents a single bond, -C2H4-、-CH＝CH-、-≡-、-COO-、-OOC-、-CH2O-、-OCH2-、-CF2O-or-OCF2-, wherein any H atom may be replaced by F.
8. The liquid crystal composition of claim 7, wherein the compound of formula V is one or more of the following compounds:
wherein, (F) represents F or H.
9. The liquid crystal composition of claim 7, wherein the liquid crystal compound of formula I is present in an amount of 1 to 30 wt%, the compound of formula IV is present in an amount of 1 to 70 wt%, and the compound of formula V is present in an amount of 0 to 70 wt%.
10. A liquid crystal display device comprising the liquid crystal compound according to any one of claims 1 to 3, or comprising the liquid crystal composition according to any one of claims 4 to 9; preferably, the liquid crystal display device is an active matrix display device, or a passive matrix display device.
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|---|---|---|---|---|
| WO2020244396A1 (en) * | 2019-06-06 | 2020-12-10 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device |
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| CN110499161B (en) | 2022-07-08 |
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