CN115806466A - Negative liquid crystal compound and application thereof - Google Patents
Negative liquid crystal compound and application thereof Download PDFInfo
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- CN115806466A CN115806466A CN202211696363.4A CN202211696363A CN115806466A CN 115806466 A CN115806466 A CN 115806466A CN 202211696363 A CN202211696363 A CN 202211696363A CN 115806466 A CN115806466 A CN 115806466A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 120
- 150000001875 compounds Chemical class 0.000 title claims abstract description 109
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 14
- 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 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- -1 boric acid ester Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000001979 organolithium group Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006263 metalation reaction Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000006751 Mitsunobu reaction Methods 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000004044 response Effects 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000010626 work up procedure Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 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 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- NUPWGLKBGVNSJX-UHFFFAOYSA-N 1-bromo-4-propylbenzene Chemical compound CCCC1=CC=C(Br)C=C1 NUPWGLKBGVNSJX-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of liquid crystal compounds, in particular to a negative liquid crystal compound and application thereof. The liquid crystal compound provided by the invention has a structure shown in a general formula (I), has extremely high negative dielectric anisotropy and low rotational viscosity, can effectively reduce the driving voltage of a liquid crystal display device and improve the response speed of the liquid crystal display device, has the characteristics of moderate optical anisotropy value, high charge retention rate and the like, and can be applied to liquid crystal display devices such as TN, ADS, VA, PSVA, FFS and IPS mode liquid crystal displays.
Description
Technical Field
The invention relates to the technical field of liquid crystal compounds, in particular to a novel negative liquid crystal compound and application thereof.
Background
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. The liquid crystal material as a novel display material has many advantages, such as extremely low power consumption and low driving voltage, and compared with other materials, the liquid crystal material also has the advantages of small volume, light weight, long service life, large display information amount, no electromagnetic radiation and the like, can almost meet the requirements of various information displays, and is particularly suitable for TFT-LCD (thin film transistor technology) products.
In the TFT active matrix system, there are mainly a TN (Twisted Nematic) mode, an IPS (In-Plane Switching) mode, an FFS (Fringe Field Switching) mode, a VA (Vertical Alignment) mode, and the like. At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. Meanwhile, the requirements for display technologies are continuously increasing, for example, liquid crystal displays are required to achieve faster response, and to reduce driving voltage to reduce power consumption.
The liquid crystal material plays an important role in improving the performance of the liquid crystal display, and particularly, the liquid crystal display performance can be 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 provide a novel liquid crystal compound with negative dielectric anisotropy, which has the advantages of 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.
In a first aspect, the present invention provides a negative liquid crystal compound comprising a structure represented by general formula (I):
wherein:
R 1 、R 2 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, a cycloalkyl group or a cycloalkoxy group;
ring A represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-phenylene in which 1 to 4 hydrogen atoms are replaced by fluorine atoms;
ring B represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene in which 1 to 4 hydrogen atoms are replaced by fluorine atoms;
m, n independently of one another represent 0, 1 or 2;
Z 1 and Z 2 Each independently represents a single bond, a double bond, an oxygen atom, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -or-CH = CH-.
As a preferable embodiment of the present invention, in the general formula (I), R is 1 、R 2 Each independently represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms;
ring A represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by fluorine atoms;
ring B represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by fluorine atoms;
m, n independently of one another represent 0 or 1;
Z 1 and Z 2 Each independently represents a single bond, -CH 2 O-。
In a further preferred embodiment of the present invention, the negative liquid crystal compound has a structure represented by any one of general formula I-1 to general formula I-26:
in the above general formula I-1 to general formula I-26, R 1 、R 2 Each independently represents an alkyl or alkoxy group having 1 to 7 carbon atoms.
Preferably, in the above general formula I-1 to general formula I-26, R is 1 、R 2 Each independently represents an alkyl group having 2 to 5 carbon atoms.
As a further preferable embodiment of the present invention, the negative liquid crystal compound is selected from one or more of the following structures:
in a second aspect, the invention provides a preparation method of the negative liquid crystal compound, which is as follows.
In the first case, when ring B is 1,4-phenylene or 1,4-phenylene in which the hydrogen atom is replaced by a fluorine atom, Z 2 When the compound is a single bond, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
metalating with organic lithium reagent, and reacting with boric acid ester to obtain
(2)
And
prepared by a Suzuki reaction
In the step (1), the step (c),
the feeding molar ratio of the organic lithium reagent to the boric acid ester is 1 to (1.0-2.0) to (1.0-3.0), and the reaction temperature is-50 to-100 ℃;
the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium, and the boric acid ester is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate or triisobutyl borate.
In the step (2), the step (c),
and
the feeding mol ratio is 1 to (0.9-1.5), and the reaction temperature is 60-140 ℃.
In the second case, when ring B is 1,4-cyclohexylene, Z 2 Is a sheetWhen the bond is formed, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
metallation with organolithium reagent, and reaction with
Reacting to obtain
(2) The above-mentioned
By reaction with boron trifluoride diethyl etherate and triethylsilane
In the step (1), the step (c),
organic lithium reagent and
the feeding molar ratio of (1.0-3.0): (1.0-3.0) to 1, and the reaction temperature is-50 to-100 ℃;
wherein, the organic lithium reagent is selected from one or more of sec-butyl lithium, tert-butyl lithium or n-butyl lithium, and n-butyl lithium is preferred.
In the step (2), the step (c),
the feeding molar ratio of boron trifluoride diethyl etherate to triethylsilane is 1: 1.0-3.0: (1.0E &3.0 The reaction temperature is-20 to-100 ℃.
In the third case, when ring B is 1,4-cyclohexenylene, Z 2 When the compound is a single bond, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
with an organolithium reagent, followed by a metalation reaction with
Reacting to obtain
(2) The above-mentioned
Dehydrating under the catalysis of acid to obtain
In the step (1), the step (c),
organic lithium reagent and
the feeding molar ratio of (1.0-3.0): (1.0-3.0) to 1, and the reaction temperature is-50 to-100 ℃;
wherein the organic lithium reagent is selected from one or more of sec-butyllithium, tert-butyllithium or n-butyllithium, and n-butyllithium is preferred.
In the step (2), the step (c),
the feeding molar ratio of the acid to the raw materials is 1 to (0.02-0.2), and the reaction temperature is 50-130 ℃;
wherein, the acid is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and potassium bisulfate, and is preferably p-toluenesulfonic acid.
In the fourth case, when Z 2 is-CH 2 O-, the liquid crystal compound is synthesized by adopting the following synthetic route:
the synthesis method comprises the following steps:
(1)
oxidation reaction to obtain
(2) The above-mentioned
And
by a Mitsunobu reaction to obtain
In the step (1), the step (c),
the feeding molar ratio of the oxidant to the oxidant is 1: (1.0-3.0), and the reaction temperature is 20-100 ℃;
wherein the oxidant is selected from one or more of hydrogen peroxide, peroxyacetic acid or peroxybenzoic acid, and hydrogen peroxide is preferred.
In the step (2), the step (c),
the feeding molar ratio of the phosphorus salt to the azodicarboxylic acid is 1: 0.9-1.2: 1-3: 1-2, and the reaction temperature is 0-60 ℃;
wherein the phosphorus salt is one or a mixture of two of triphenylphosphine and tri-tert-butylphosphine; the azodicarboxylic acid is selected from DIAD and DEAD, or their mixture.
The method of the invention, if necessary, involves conventional post-treatment, such as: extracting with dichloromethane, ethyl acetate or toluene, separating liquid, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
In each of the above preparation methods, the substituents mentioned above are as defined above.
In the above four synthetic schemes, the adopted raw materials
The synthetic route of (2) is as follows:
the specific synthesis comprises the following steps:
(1)
with an organolithium reagent in the presence of cuprous iodide
Reacting to obtain
(2)
Wittig reaction with bromoalkyl triphenylphosphine salt to obtain
(3)
Hydrogenation reaction to form
(4)
Alkaline hydrolysis to form
(5)
Reacting with thionyl chloride to give
(6)
Under the catalysis of Lewis acid, the catalyst is obtained by Friedel-crafts acylation
(7)
Reduction reaction with trifluoroacetic acid and triethylsilane to obtain
Wherein R in the compound related to each step is R in the obtained liquid crystal compound product 2 Alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy with one carbon element less.
In the step (1) of the above method,
organic lithium reagent, cuprous iodide and
the feeding molar ratio of 1 to (1.0-2.0) and the reaction temperature of-60 to-90 ℃; wherein, the organic lithium reagent is selected from one or more of lithium dimethylamide, lithium amide or lithium diisopropylamide, and Lithium Diisopropylamide (LDA) is preferred;
in the step (2), the step (c),
the feeding molar ratio of the organic alkali to the bromoalkyl triphenylphosphine salt is 1: 1.0-2.0, the reaction temperature is-20 ℃, and the organic alkali is selected from one or the mixture of two of tert-butyl potassium alkoxide and tert-butyl sodium alkoxide.
In the step (3), the step (c),
the hydrogenation reaction temperature is 10-60 ℃, wherein the catalyst is one or the mixture of two of palladium carbon, ruthenium carbon and Raney nickel, and the adding proportion of the catalyst is 0.5-20%;
in the step (4), the step of (C),
the feeding mol ratio of the alkali and the alkali is 1: 1.0-2.0, the reaction temperature is 50-100 ℃, and the alkali is one or the mixture of two of potassium hydroxide, sodium hydroxide and lithium hydroxide.
In the step (5), the step (c),
the feeding molar ratio of the raw materials to the thionyl chloride is 1: 1-5, and the reaction temperature is 60-100 ℃;
in the step (6), the step (c),
the feeding molar ratio of the Lewis acid and the Lewis acid is 1 to (1.0-2.0), and the reaction temperature is 30-20 ℃; the Lewis acid is selected from one or more of aluminum trichloride, boron trifluoride or titanium tetrachloride, and is preferably aluminum trichloride;
in the step (7), the step (c),
the feeding molar ratio of the reaction product to trifluoroacetic acid and triethylsilane is 1 to (1.0-4.0), and the reaction temperature is 20-40 ℃.
The liquid crystal compound can be stably and efficiently obtained by the preparation method.
In a third aspect, the invention provides a liquid crystal material composition, wherein the liquid crystal material composition comprises the negative liquid crystal compound.
Preferably, the negative liquid crystal compound is contained in the composition in an amount of 0.1 to 60% by mass, more preferably 1 to 50% by mass, and still more preferably 3 to 30% by mass.
In a fourth aspect, the invention provides an application of the negative liquid crystal compound or the liquid crystal material composition in the liquid phase display field.
As a preferred embodiment, the present invention provides a use of the negative liquid crystal compound or the liquid crystal material composition of the present invention in a liquid phase display device.
Further preferably, the liquid crystal display device includes, but is not limited to, a liquid crystal display of TN, ADS, VA, PSVA, FFS, or IPS mode.
The invention provides a novel negative 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 liquid crystal composition containing the liquid crystal compound provided by the invention has extremely high negative dielectric anisotropy and low rotational viscosity, so that the driving voltage of a liquid crystal display device is effectively reduced, the response speed of the liquid crystal display device is improved, and the liquid crystal compound or the liquid crystal composition containing the liquid crystal compound has the advantages of moderate optical anisotropy value, high charge retention rate and the like, is a liquid crystal material with excellent performance, and can be applied to liquid crystal display devices such as TN, ADS, VA, PSVA, FFS and IPS mode liquid crystal displays.
Detailed Description
The technical solution of the present invention will be explained in detail below. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
The liquid crystal compound prepared in this example has the structural formula:
the synthetic route is as follows:
the method comprises the following specific steps:
(1) Synthesis of Compound LC-01-1
114g of o-difluorobenzene (1.0 mol), 111g of diisopropylamine (1.1 mol) and 700ml of tetrahydrofuran are added into a three-necked flask, the temperature is reduced to-70 to-75 ℃ by stirring, 1.2mol of n-butyllithium is dropwise added at a controlled temperature, and the temperature is controlled to react for 2 hours after the dropwise addition. Controlling the temperature to be-70-75 ℃, slowly adding 190g of cuprous iodide (1.0 mol) and reacting for 1h. Controlling the temperature to be-70 to-75 ℃, dropwise adding 165g of chloroformyl ethyl acetate (1.1 mol), controlling the temperature to react for 2h after the dropwise adding is finished, and then naturally stirring overnight. Acidification was carried out by addition of 1000ml of 2M aqueous hydrochloric acid, conventional work-up, GC:75 percent, obtaining 256g by spin drying, distilling under reduced pressure, taking 98 percent of middle distillate GC, 165g, theoretical yield: 228g, yield: 72 percent;
(2) Synthesis of Compound LC-01-2
286g of ethyl triphenyl phosphonium bromide (0.77 mol) and 900ml of tetrahydrofuran are added into a three-mouth bottle, the temperature is reduced to minus 10 to minus 15 ℃, 94g of potassium tert-butyl alcoholate (0.84 mol) are added in batches, and the reaction is carried out for 2 hours at the temperature of minus 5 to minus 10 ℃. Slowly dripping a mixed solution of 160g of LC-01-1 (0.70 mol) and 200ml of tetrahydrofuran at the temperature of-5 to-10 ℃, and reacting for 2 hours at the temperature of-5 to-10 ℃. The reaction solution was added to 100g of water to terminate the reaction. After conventional work-up, petroleum ether was subjected to column recrystallization to give 151g of a pale yellow solid (Compound LC-01-2, 0.63mol), GC:99.6 percent and the yield is 90.0 percent;
(3) Synthesis of Compound LC-01-3
151g of LC-01-2 (0.0.63mol), 300ml of toluene, 100ml of ethanol, 7.5g of palladium carbon (with the water content of 50 percent) are added into a hydrogenation kettle to react for 5 hours at the temperature of between 30 and 40 ℃. Sampling to test no alkene, and filtering palladium carbon. After exsolution, petroleum ether was recrystallized to give 143g of a pale yellow solid (Compound LC-01-3, 0.59mol), GC:99.9 percent and the yield is 94.0 percent;
(4) Synthesis of Compound LC-01-4
143g of LC-01-3 (0.59 mol), 35g of sodium hydroxide (0.89 mol) and 400ml of ethanol are added into a three-neck flask, then the temperature is slowly raised to 65-68 ℃, and the reflux reaction is carried out for 4 hours. After distilling off the ethanol, the reaction mixture was poured into a beaker containing 100ml of hydrochloric acid (pH < 7) and subjected to conventional work-up, and petroleum ether was subjected to column desolventization to give 120g of a pale yellow solid (compound LC-01-4, 0.56mol): 99.5 percent and the yield is 95.0 percent;
(5) Synthesis of Compound LC-01-5
120g of LC-01-4 (0.56 mol) and 150g of thionyl chloride (1.26 mol) are added into a three-neck flask, and the temperature is raised to 70 ℃ with stirring to react for 5 hours. Conventional work-up was carried out to give 130g of a pale yellow liquid (Compound LC-01-5, 0.56mol), yield 100%;
(6) Synthesis of Compound LC-01-6
Adding 112g of aluminum trichloride (0.84 mol) and 300ml of dichloromethane into a three-neck flask, cooling to 0-10 ℃, dropwise adding a mixed solution of 130g of LC-01-5 (0.56 mol) and 400ml of dichloromethane at a controlled temperature, stirring for 2 hours at the controlled temperature of 0-10 ℃ after dropwise adding, and then heating to 30 ℃ and stirring for 3 hours. The reaction solution was poured into ice water containing 260ml hydrochloric acid for acidification, and conventional post-treatment was carried out to obtain 93g of crude product (compound LC-01-6, 0.48mol), theoretical yield: 110g, GC:99%, yield: 85 percent;
(7) Synthesis of Compound LC-01-7
80.4g of LC-01-6 (0.41 mol) are added into a three-necked flask, 96g of triethylsilane (0.82 mol) and 140g of trifluoroacetic acid (1.23 mol) are added under the temperature control of 40 ℃, and the mixture is stirred for 4 hours under the temperature control of 20 ℃. The reaction mixture was poured into a mixture of 370g of sodium carbonate (2.46 mol) and 500ml of water (pH > 7) and worked up conventionally, by spin-drying to give 52.2g of crude compound LC-01-7 (0.287 mol), GC:99%, theoretical yield: 74.6g, yield 70%;
(8) Synthesis of Compound LC-01-8
Under the protection of nitrogen, 52.2g of LC-01-7 (0.287 mol) and 150ml of tetrahydrofuran are added into a reaction bottle, 0.37mol of n-butyl lithium n-hexane solution is dripped at the temperature of-70 to-80 ℃, the temperature is kept for 1 hour after dripping, 46.6g of trimethyl borate (0.44 mol) is dripped at the temperature of-60 to-70 ℃, and then the temperature is naturally returned to-30 ℃. Acidification was carried out by adding 400ml of 2M aqueous hydrochloric acid solution, conventional work-up was carried out, and recrystallization from petroleum ether gave 59.7g of a pale yellow solid (Compound LC-01-8,0.264 mol), HPLC:99.6 percent and the yield is 92 percent;
(9) Synthesis of Compound LC-01
59.7g of the compound LC-01-8 (0.264 mol), 52.3g of the compound 4-propylbromobenzene (0.264 mol), 200ml of N, N-dimethylformamide, 100ml of deionized water, 72.8g of anhydrous potassium carbonate (0.53 mol) and 0.5g of palladium tetratriphenylphosphine were added to a reaction flask under a nitrogen atmosphere, and the mixture was heated to 70 ℃ to react for 3 hours. Conventional work-up was carried out, purification by chromatography, elution with n-hexane and recrystallization with ethanol gave 63.4g of a white solid (compound LC-01, 0.211mol), GC:99.9%, yield: 80 percent.
The white solid LC-01 obtained was analyzed by GC-MS and the M/z of the product was 300 (M +);
1 H-NMR(300MHz,CDCl 3 ):0.82-2.90(m,17H)，7.10-7.60(m,5H)。
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, adding 80g of LC-01-7 (0.44 mol) and 250ml of tetrahydrofuran into a reaction bottle, controlling the temperature to be-75 to-85 ℃, dropwise adding 0.48mol of n-butyl lithium n-hexane solution, keeping the temperature for 1 hour after dropwise adding, controlling the temperature to be-75 to-85 ℃, dropwise adding a solution consisting of 81.4g of propyl dicyclohexyl ketone (0.37 mol) and 100ml of tetrahydrofuran, and naturally returning the temperature to be-30 ℃. The reaction was quenched with 300ml of water and worked up conventionally to give a pale yellow solid (Compound LC-02-1,0.3 mol) 121.2g, GC:99 percent and yield of 81 percent;
(2) Synthesis of Compound LC-02
121.2g of LC-02-1 (0.3 mol), 5.6g of p-toluenesulfonic acid (0.03 mol), 0.1g of 2, 6-di-tert-butyl-p-cresol and 200ml of toluene were charged into a reaction flask, and the mixture was refluxed and dehydrated for 8 hours. Conventional work-up was carried out to give 98.4g of a white solid (Compound LC-02, 0.255mol) GC:99.9% and yield 85%.
The white solid LC-02 obtained was analyzed by GC-MS, and the product M/z was 386 (M +);
1 H-NMR(300MHz,CDCl 3 ):0.88-2.88(m,34H)，5.62-5.80(m,1H),6.80-7.00(m,1H)。
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
Under the protection of nitrogen, 72.7g of compound LC-02-1 (0.18 mol) and 150ml of dichloromethane are added into a reaction bottle, 41.8g of triethylsilane (0.36 mol) is dripped at the temperature of-70 to-80 ℃, the temperature is kept for reaction for 0.5 hour after dripping, 56.2g of boron trifluoride ethyl ether (0.39 mol) is dripped at the temperature of-70 to-80 ℃, and then the temperature is naturally returned to-10 ℃. The reaction was quenched with 300ml of water and worked up conventionally to give 52.5g of a white solid (Compound LC-03, 0.14mol), GC:99.9% and yield 78%.
The white solid LC-03 obtained was analyzed by GC-MS and the product had an M/z of 388 (M +);
1 H-NMR(300MHz,CDCl 3 ):0.88-2.88(m,39H)，6.80-7.00(m,1H)。
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
67.8g of LC-01-8 (0.3 mol) and 300ml of dichloromethane are added into a reaction bottle, 30 percent hydrogen peroxide (0.45 mol) is dripped at the temperature of 20-30 ℃, and reflux reaction is carried out for 5 hours. Conventional work-up was carried out to give 53.4g of a white solid (Compound LC-04-1, 0.27mol), GC:99.9 percent and the yield is 90 percent;
(2) Synthesis of Compound LC-04
53.4g of LC-04-1 (0.27 mol), 71.4 trans-propyldicyclohexylmethanol (0.3 mol), 288g of triphenylphosphine (0.33 mol) and 800ml of DMF were added to a reaction flask, and 72.7g of diisopropyl azodicarboxylate (0.36 mol) was added dropwise at 10 to 20 ℃ and reacted at 30 to 40 ℃ for 4 hours. Conventional work-up was carried out to give 106.6g of a white solid (Compound LC-04, 0.225mol) as a white solid, GC:99.9 percent and yield 83 percent;
the white solid LC-04 obtained was analyzed by GC-MS and the M/z of the product was 418 (M +);
1 H-NMR(300MHz,CDCl 3 ):0.88-2.88(m,37H)，4.00-4.50(m,2H)，6.80-7.00(m,1H)。
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.
Referring to the above synthetic schemes of examples 1-4, other specific liquid crystal compounds of the present invention can be synthesized by simply replacing the corresponding raw materials without any substantial manipulation.
The liquid crystal compounds prepared in examples 1 to 4 of the present invention were subjected to the performance test, which is specifically 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:
cp represents the clearing point (. Degree. C.) 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 ℃).
Experimental example 1
The data of the performance parameters of the compound LC-01 prepared in example 1 and the liquid crystal compound in comparative example 1 are compared and the detection results are shown in Table 1:
table 1: results of Property measurement of liquid Crystal Compound
The detection results in table 1 clearly show that the liquid crystal compound provided by the invention has higher negative dielectric anisotropy, moderate rotational viscosity gamma 1, good low-temperature intersolubility and higher clearing point performance compared with the traditional negative dielectric anisotropy compound with similar chemical structure, which are needed by improving liquid crystal materials, can effectively improve the dielectric anisotropy delta epsilon of the liquid crystal composition, reduce the driving voltage and obtain the liquid crystal composition with higher response speed.
Experimental example 2
The data of the performance parameters of the compound LC-02 prepared in example 2 and the liquid crystal compound of comparative example 2 are compared and the detection results are shown in Table 2:
table 2: results of Property measurement of liquid Crystal Compound
The detection results in table 2 clearly show that the liquid crystal compound provided by the invention has higher negative dielectric anisotropy, moderate rotational viscosity gamma 1, good low-temperature intersolubility and higher clearing point performance compared with the traditional negative dielectric anisotropy compound with similar chemical structure, which are needed by improving liquid crystal materials, can effectively improve the dielectric anisotropy delta epsilon of the liquid crystal composition, reduce the driving voltage and obtain the liquid crystal composition with higher response speed.
Experimental example 3
The data of the performance parameters of the compound LC-03 prepared in example 3 and the liquid crystal compound in comparative example 3 were compared and the results are shown in Table 3:
table 3: results of Property measurement of liquid Crystal Compound
The detection results in table 3 clearly show that the liquid crystal compound provided by the invention has higher negative dielectric anisotropy, moderate rotational viscosity gamma 1, good low-temperature intersolubility and higher clearing point performance compared with the traditional negative dielectric anisotropy compound with similar chemical structure, which are needed by improving liquid crystal materials, can effectively improve the dielectric anisotropy delta epsilon of the liquid crystal composition, reduce the driving voltage and obtain the liquid crystal composition with higher response speed.
Experimental example 4
The data of the performance parameters of the compound LC-04 prepared in example 4 and the liquid crystal compound of comparative example 4 were compared and the results are shown in Table 4:
table 4: results of Property measurement of liquid Crystal Compound
As is apparent from the detection results in Table 4, the liquid crystal compound provided by the invention has higher negative dielectric anisotropy, moderate rotational viscosity gamma 1, good low-temperature intersolubility and higher clearing point performance compared with the traditional negative dielectric anisotropy compound with similar chemical structure, which are needed by improving liquid crystal materials, can effectively improve the dielectric anisotropy delta epsilon of the liquid crystal composition, reduce the driving voltage and obtain the liquid crystal composition with higher response speed.
In addition, after the liquid crystal compound provided by the invention is specifically applied to a liquid crystal composition of a conventional system, the dielectric anisotropy delta epsilon of the liquid crystal composition can be improved, meanwhile, the lower rotational viscosity gamma 1 and the proper refractive index anisotropy delta n are kept, and the obtained liquid crystal composition has a remarkable quick response characteristic and a low-voltage driving characteristic.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A negative liquid crystal compound comprising a structure represented by general formula (I):
wherein:
R 1 、R 2 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, a cycloalkyl group or a cycloalkoxy group;
ring A represents 1,4-phenylene, 1,4-cyclohexylene, or 1,4-phenylene in which 1 to 4 hydrogen atoms are replaced by fluorine atoms;
ring B represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene in which 1 to 4 hydrogen atoms are replaced by fluorine atoms;
m, n independently of one another represent 0, 1 or 2;
Z 1 and Z 2 Each independently represents a single bond, a double bond, an oxygen atom, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -or-CH = CH-.
2. The liquid crystal compound according to claim 1, wherein R is 1 、R 2 Each independently represents an alkyl group or an alkoxy group having 1 to 7 carbon atoms;
ring A represents 1,4-phenylene, 1,4-cyclohexylene, or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by fluorine atoms;
ring B represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by fluorine atoms;
m, n independently of one another represent 0 or 1;
Z 1 and Z 2 Each independently represents a single bond, -CH 2 O-。
3. The liquid crystal compound according to claim 1 or 2, wherein the negative liquid crystal compound has a structure represented by any one of general formula I-1 to general formula I-26:
in the general formula I-1 to the general formula I-26, R 1 、R 2 Each independently represents an alkyl or alkoxy group having 1 to 7 carbon atoms; preferably said R 1 、R 2 Each independently represents an alkyl group having 2 to 5 carbon atoms.
4. A liquid crystal compound according to any one of claims 1 to 3, characterized in that the negative liquid crystal compound is selected from one or several of the following structures:
5. a process for producing a negative liquid crystal compound according to any one of claims 1 to 4, wherein when ring B is 1,4-phenylene or 1,4-phenylene in which a hydrogen atom is substituted with a fluorine atom, Z is 2 When the compound is a single bond, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
metalating with organic lithium reagent, and reacting with boric acid ester to obtain
(2)
And
prepared by a Suzuki reaction
6. A process for preparing the negative liquid crystal compound of any one of claims 1 to 4, wherein when ring B is 1,4-cyclohexylene, Z is 2 When the compound is a single bond, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
metallation with organolithium reagent, and reaction with
Reacting to obtain
(2) The above-mentioned
By reaction with boron trifluoride diethyl etherate and triethylsilane
7. A process for preparing the negative liquid crystal compound of any one of claims 1 to 4, wherein when ring B is 1,4-cyclohexenylene, Z is 2 When the compound is a single bond, the synthesis route adopted by the synthesis of the liquid crystal compound is as follows:
the synthesis method comprises the following steps:
(1)
metallation with organolithium reagent, and reaction with
The reaction is carried out in the presence of a catalyst,to obtain
(2) The above-mentioned
Dehydrating under the catalysis of acid to obtain
8. A process for preparing the negative liquid-crystal compound according to any one of claims 1 to 4, wherein Z is a number of Z 2 is-CH 2 O-, the liquid crystal compound is synthesized by adopting the following synthetic route:
the synthesis method comprises the following steps:
(1)
oxidation reaction to obtain
(2) The above-mentioned
And
by a Mitsunobu reaction to obtain
9. A liquid crystal material composition, characterized in that the liquid crystal material composition comprises the negative liquid crystal compound of any one of claims 1 to 4; the negative liquid crystal compound is contained in the composition in an amount of 0.1 to 60% by mass, preferably 1 to 50% by mass, and more preferably 3 to 30% by mass.
10. Use of the negative liquid crystal compound of any one of claims 1 to 4 or the liquid crystal material composition of claim 9 in the field of liquid crystal display; the liquid crystal display device is preferably used in a liquid crystal display device, and more preferably used in a TN, ADS, VA, PSVA, FFS or IPS mode liquid crystal display.
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| CN117510298A (en) * | 2023-11-08 | 2024-02-06 | 武汉轻工大学 | Indane ring biphenyl liquid crystal composition and application thereof |
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