CN113816883A - Liquid crystal compound and preparation method and application thereof - Google Patents
Liquid crystal compound and preparation method and application thereof Download PDFInfo
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- CN113816883A CN113816883A CN202111129860.1A CN202111129860A CN113816883A CN 113816883 A CN113816883 A CN 113816883A CN 202111129860 A CN202111129860 A CN 202111129860A CN 113816883 A CN113816883 A CN 113816883A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000001033 ether group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006266 etherification reaction Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000004044 response Effects 0.000 abstract description 5
- 238000004904 shortening Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- FBDBWWLWTUPEHR-UHFFFAOYSA-N 1-[4-[4-(2,3-difluorophenyl)butoxy]butyl]-2,3-difluorobenzene Chemical compound C1=CC(=C(C(=C1)F)F)CCCCOCCCCC2=C(C(=CC=C2)F)F FBDBWWLWTUPEHR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- 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
- C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- 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
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- 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
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3087—Cyclohexane rings in which at least two rings are linked by a chain containing sulfur atoms
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- C07C2601/00—Systems containing only non-condensed rings
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- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/14—The ring being saturated
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- 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
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K2019/3096—Cyclobutane rings
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Abstract
The invention discloses a liquid crystal compound and a preparation method and application thereof. The structural formula of the liquid crystal compound is shown as formula I, wherein in the formula I, R1And R2The substituents are the same or different and each independently represent a linear or branched alkyl group having from C1 to C12, a cycloalkyl group having from C3 to C7, a linear or branched alkenyl group having from C2 to C12, a linear or branched alkynyl group having from C2 to C12, an ester group having from C2 to C12 or an ether group having from C2 to C12; l is1And L2The same or different, each independently represent-F, -Cl, -CN, -NO2Straight chain or branched chain alkyl of C1-C10, alkoxy of C1-C5, -COR1、‑COR2C1-C5 fluoroalkyl or C1-C5 fluoroalkoxy, Z1And Z2The same or different, each independently represents O or S, and is not simultaneously O. The liquid crystal compound has very low delta n, very low rotational viscosity gamma 1, larger negative dielectric anisotropy delta epsilon, good liquid crystal intersolubility and higher clearing point Cp, thereby effectively improving the clearing point of the liquid crystal composition, shortening the response time of a liquid crystal display device and improving the working temperature of the liquid crystal composition.
Description
Technical Field
The invention relates to a liquid crystal compound and a preparation method and application thereof, belonging to the technical field of liquid crystal materials.
Background
The liquid crystal material has great research value and good application prospect when being used as an environmental material in the fields of information display materials, organic optoelectronic materials and the like. Liquid crystal materials have many advantages as novel display materials, such as extremely low power consumption and low driving voltage. Compared with other materials, the 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. For a dynamic picture display application, in order to realize high quality display and eliminate afterimage and tailing of a display picture, a liquid crystal material is required to have a fast response speed, and thus the liquid crystal material is required to have a rotational viscosity γ 1 as low as possible. In addition, in order to reduce power consumption of the liquid crystal display device, it is necessary to reduce the driving voltage of the liquid crystal as low as possible, and therefore, it is required to increase the dielectric anisotropy Δ ∈ of the liquid crystal, reduce the rotational viscosity γ 1 of the liquid crystal material, and increase the clearing point Cp.
The liquid crystal material is used as a core functional material of a liquid crystal display device, and is required to have a wide variety of performance parameters, particularly to reduce the rotational viscosity gamma 1 of the liquid crystal material, improve the dielectric anisotropy delta epsilon of the liquid crystal material and higher clearing point Cp, in order to meet the requirements of various performance parameters of the liquid crystal display device and adapt to the process requirements of the liquid crystal display device. In order to improve the properties of materials and enable the materials to meet new requirements, the synthesis of novel structure liquid crystal compounds and the research of structure-property relationship become important work in the field of liquid crystal.
Disclosure of Invention
The invention aims to provide a liquid crystal compound which has low delta n, low rotational viscosity gamma 1, larger negative dielectric anisotropy delta epsilon, good liquid crystal intersolubility and higher clearing point Cp, thereby effectively improving the clearing point of a liquid crystal composition, shortening the response time of a liquid crystal display device and improving the working temperature of the liquid crystal composition.
The structural formula of the liquid crystal compound provided by the invention is shown as the formula I:
in the formula I, R1And R2The substituents are the same or different, and each independently represent a substituted or unsubstituted C1-C12 linear or branched alkyl group, C3-C7 cycloalkyl or cycloalkenyl group, C2-C12 linear or branched alkenyl group, C2-C7 linear or branched alkynyl group, C2-C12 ester group or C2-C12 ether group;
R1and R2The substituent in (1) is halogen, preferably fluorine;
preferably, R1And R2Independently represent a linear or branched alkyl group of C1-C7, a cycloalkyl group of C3-C6, a linear or branched alkenyl group of C2-C7, an ester group of C2-C7 or an ether group of C2-C7, more preferably a linear or branched alkyl group of C1-C7, a cycloalkyl group of C3-C6, a linear or branched alkenyl group of C2-C7 or an ether group of C2-C7;
L1and L2The same or different, each independently represent-F, -Cl, -CN, -NO2Straight chain or branched chain alkyl of C1-C10, alkoxy of C1-C5, -COR1、-COR2A fluoroalkyl group having 1-5 carbon atoms or a fluoroalkoxy group having 1-5 carbon atoms, wherein R is1Is C1-C5 alkyl, R2Is C1-C5 alkyl;
preferably, L1And L2Wherein the carbon atom number of the straight chain or branched chain alkyl is 1-5;
the carbon number of the alkoxy is 1-3;
R1is C1-C3 alkyl;
R2is C1-C3 alkyl;
the fluoroalkyl group has 1-3 carbon atoms and contains one or more fluorine atoms;
the carbon number of the fluoroalkoxy group is 1-3, and the fluoroalkoxy group contains one or more fluorine atoms;
more preferably, L1And L2Independently represent-F, -Cl, -CN, -CF3or-OCF3Further, L1And L2Both represent-F;
Z1and Z2The same or different, each independently represents O or S, and is not simultaneously O.
The liquid crystal compound provided by the invention is preferably one of the following structures:
the invention further provides a preparation method of the liquid crystal compound, and the reaction equation is as follows:
the reaction steps are as follows:
s1, reacting the compound shown as the formula II with X in the presence of tert-butyl lithium in an inert atmosphere12Obtaining a compound shown as a formula III through halogenation, wherein X1Represents Br or I;
s2, a compound of formula III and R2-Z2Carrying out etherification reaction on the-H to obtain the liquid crystal compound;
R1、R2、Z1、Z2、L1、L2the definition of (a) is the same as that of the liquid crystal compound shown in the formula I.
In the preparation method, in step S1, the n-hexane solution of the tert-butyl lithium is dripped into the system at the temperature of-70 to-80 ℃, the temperature is kept for 1 to 2 hours after dripping, and then X is continuously dripped12Controlling the temperature to be-70 to-80 ℃ for reaction for 1 hour, naturally returning the temperature to-30 to-10 ℃, and carrying out hydrolysis post-treatment;
a compound of formula II and X12In a molar ratio of 1: 1.0 to 1.5.
In the above preparation method, in step S2, the etherification reaction is performed under an inert atmosphere, and the solvent may be dioxane;
a compound of the formula III with R2-Z2-the molar ratio of H is 1: 1.0 to 1.5;
the etherification reaction is carried out in the presence of alkali, wherein the alkali can be sodium hydroxide, potassium hydroxide, anhydrous potassium carbonate or anhydrous sodium carbonate;
the temperature of the etherification reaction is 70-90 ℃, and the time is 3-8 hours.
The starting materials (formulae II and R) used in the process of the invention2-Z2-H) are commercially available.
The present invention still further provides a liquid crystal compound comprising the liquid crystal composition;
in the liquid crystal composition, the mass percent of the liquid crystal compound is 1-60%, preferably 1-50%, and more preferably 1-25%.
The application of the liquid crystal compound or the liquid crystal composition provided by the invention in the preparation of a liquid crystal display device also belongs to the protection range of the method;
the liquid crystal display device is a TN liquid crystal display, an ADS liquid crystal display, a VA liquid crystal display, a PSVA liquid crystal display, an FFS liquid crystal display or an IPS liquid crystal display.
The liquid crystal compound provided by the invention has very low delta n, very low rotational viscosity gamma 1, larger negative dielectric anisotropy delta epsilon, good liquid crystal intersolubility and higher clearing point Cp, thereby effectively improving the clearing point of the liquid crystal composition, shortening the response time of a liquid crystal display device and improving the working temperature of the liquid crystal composition.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The ethers used in the following examples are all available from Yongtai technologies, Zhejiang.
Example 1 preparation of liquid Crystal Compound BYLC-01
The liquid crystal compound BYLC-01 prepared in the embodiment has the structural formula:
the synthetic route for the preparation of compound BYLC-01 is shown below:
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-01-1:
under the protection of nitrogen, 50.0g of 2, 3-difluorophenylbutyl ether and 400ml of tetrahydrofuran are added into a reaction bottle, the temperature is controlled to be-70 to-80 ℃, 0.4mol of n-hexane solution of tert-butyllithium is dripped, the reaction is kept for 1 hour after dripping is finished, 64.5g of bromine is dripped at the temperature of-70 to-80 ℃ (the molar ratio of the 2, 3-difluorophenylbutyl ether to the bromine is 1: 1.5), and then the temperature is naturally returned to-30 ℃. 500ml of a saturated aqueous sodium sulfite solution was added for hydrolysis destruction, and conventional post-treatment was carried out, and distillation under reduced pressure was carried out to obtain 60.9g of a pale yellow liquid (compound BYLC-01-1), GC: 99.2% and yield 85.5%.
(2) Synthesis of Compound BYLC-01:
under the protection of nitrogen, 60.0g of compound BYLC-01-1, 18.2g of ethanethiol (the molar ratio of the compound BYLC-01-1 to the ethanethiol is 1: 1.29), 13.5g of sodium hydroxide and 200ml of dioxane are added into a reaction flask, and the temperature is controlled between 70 ℃ and 90 ℃ for reaction for 6 hours. Conventional work-up was carried out, purification by chromatography, elution with n-hexane and crystallization with ethanol gave 40.5g of a white solid (compound BYLC-01), GC: 99.7%, yield: 72.8 percent.
The obtained white solid BYLC-01 was analyzed by GC-MS and the M/z of the product was 246.3 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.95(m,10H)，2.51-2.95(m,2H)，3.53-4.75(m,2H)，6.55-7.75(m,2H)。
Example 2 preparation of liquid crystalline Compound BYLC-02
The liquid crystal compound prepared in this example has the structural formula:
the synthetic route for the preparation of compound BYLC-02 is shown below:
the method comprises the following specific steps:
synthesis of Compound BYLC-02:
under the protection of nitrogen, 33.0g of compound BYLC-01-1, 15.6g of butyl mercaptan (the molar ratio of compound BYLC-01-1 to butyl mercaptan is 1: 1.38), 7.5g of sodium hydroxide and 150ml of dioxane are added into a reaction flask, and the temperature is controlled at 70-90 ℃ for reaction for 6 hours. Conventional work-up was carried out, purification by chromatography, elution with n-hexane and crystallization with ethanol gave 25.7g of a white solid (compound BYLC-02), GC: 99.8%, yield: 75.6 percent.
The obtained white solid BYLC-02 was analyzed by GC-MS and the M/z of the product was 274.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.85(m,14H)，2.67-2.95(m,2H)，3.85-4.35(m,2H)，6.55-7.45(m,2H)。
According to the technical schemes of the embodiment 1 and the embodiment 2, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
examples 3,
The resulting white solid BYLC-03 was analyzed by GC-MS and the M/z of the product was 246.1(M +).
1H-NMR(300MHz,CDCl3):0.85-1.85(m,10H)，2.67-2.95(m,2H)，3.85-4.35(m,2H)，6.55-7.45(m,2H)。
Examples 4,
The obtained white solid BYLC-04 was analyzed by GC-MS and the M/z of the product was 260.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.85(m,12H)，2.67-2.95(m,2H)，3.85-4.35(m,2H)，6.55-7.45(m,2H)。
Examples 5,
The obtained white solid BYLC-05 was analyzed by GC-MS and the M/z of the product was 262.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.85(m,10H)，2.67-2.95(m,4H)，6.55-7.45(m,2H)。
Examples 6,
The obtained white solid BYLC-06 was analyzed by GC-MS and the M/z of the product was 290.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.85(m,14H)，2.67-2.95(m,4H)，6.55-7.45(m,2H)。
Example 7,
The obtained white solid BYLC-07 was analyzed by GC-MS and the M/z of the product was 248.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.85-1.85(m,8H)，2.67-2.95(m,4H)，6.55-7.45(m,2H)。
Example 8,
The obtained white solid BYLC-08 was analyzed by GC-MS and the M/z of the product was 298.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.15-0.85(m,5H)，1.15-1.95(m,9H)，2.67-2.95(m,2H)，3.85-4.25(m,2H)，6.55-7.45(m,2H)。
Examples 9,
The obtained white solid BYLC-09 was analyzed by GC-MS and the M/z of the product was 272.1 (M)+)。
1H-NMR(300MHz,CDCl3):1.15-1.85(m,10H)，1.95-2.95(m,3H)，3.85-4.25(m,2H)，6.55-7.45(m,2H)。
Examples 10,
The obtained white solid BYLC-10 was analyzed by GC-MS and the M/z of the product was 286.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.90-1.85(m,14H)，2.55-2.95(m,2H)，3.85-4.25(m,2H)，6.55-7.45(m,2H)。
Examples 11,
The resulting white solid BYLC-11 was analyzed by GC-MS and the M/z of the product was 316.1(M +).
1H-NMR(300MHz,CDCl3):0.90-1.85(m,16H)，2.55-2.95(m,4H)，6.55-7.45(m,2H)。
Examples 12,
The obtained white solid BYLC-12 was analyzed by GC-MS and the M/z of the product was 258.1 (M)+)。
1H-NMR(300MHz,CDCl3):1.05-1.85(m,11H)，2.25-2.75(m,1H)，3.85-4.25(m,2H)，6.55-7.45(m,2H)。
Examples 13,
The obtained white solid BYLC-13 was analyzed by GC-MS and the M/z of the product was 288.1 (M)+)。
1H-NMR(300MHz,CDCl3):0.90-1.95(m,13H)，2.25-2.95(m,3H)，6.55-7.45(m,2H)。
Comparative examples 1,
The structure of the compound of this comparative example is:
comparative examples 2,
The structure of the compound of this comparative example is:
the compounds prepared in the above examples of the invention and the compounds of the comparative examples were subjected to the relevant property measurements:
according to conventional detection methods in the art, for example, detection of Δ ε is measured using an INSTEC liquid crystal detection instrument, detection of γ 1 is measured using a viscometer, detection of Δ n is measured using an Abbe refractometer, and detection of Cp is measured using a differential thermal scanner.
And obtaining various performance parameters of the liquid crystal compound through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp stands for clearing point.
The data of the performance parameters of the compound prepared in the example and the liquid crystal compound of the comparative example are compared and the detection results are shown in table 1.
TABLE 1 results of examining the properties of the liquid-crystalline compounds
As is apparent from the detection results in table 1, compared with the conventional negative dielectric anisotropy compound with a similar chemical structure, the liquid crystal compound provided by the present invention has a very low Δ n, a very low rotational viscosity γ 1, a relatively large negative dielectric anisotropy Δ ∈ and a relatively high clearing point Cp, so that the clearing point of the liquid crystal composition is effectively increased, the response time of the liquid crystal display device is shortened, and the operating temperature of the liquid crystal composition is increased.
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 liquid crystal compound represented by the formula I,
in the formula I, R1And R2The substituents are the same or different, and each independently represent a substituted or unsubstituted C1-C12 linear or branched alkyl group, C3-C7 cycloalkyl or cycloalkenyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear or branched alkynyl group, C2-C12 ester group or C2-C12 ether group;
L1and L2The same or different, each independently represent-F, -Cl, -CN, -NO2Straight chain or branched chain alkyl of C1-C10, alkoxy of C1-C5, -COR1、-COR2A fluoroalkyl group having 1-5 carbon atoms or a fluoroalkoxy group having 1-5 carbon atoms, wherein R is1Is C1-C5 alkyl, R2Is C1-C5 alkyl;
Z1and Z2The same or different, each independently represents O or S, and is not simultaneously O.
2. The liquid crystal compound according to claim 1, characterized in that: in the formula I, R1And R2The substituent in (1) is halogen.
3. The liquid crystal compound according to claim 1 or 2, characterized in that: in the formula I, R1And R2Independently represent a linear or branched alkyl group of C1-C7, a cycloalkyl group of C3-C6, a linear or branched alkenyl group of C2-C7, an ester group of C2-C7 or an ether group of C2-C7.
4. The liquid crystal compound according to any one of claims 1 to 3, wherein: l in formula I1And L2Wherein the carbon atom number of the straight chain or branched chain alkyl is 1-5;
the carbon number of the alkoxy is 1-3;
R1is C1-C3 alkyl;
R2is C1-C3 alkyl;
the fluoroalkyl group has 1-3 carbon atoms and contains one or more fluorine atoms;
the fluoroalkoxy group has 1 to 3 carbon atoms and contains one or more fluorine atoms.
5. A method for producing a liquid crystal compound as described in any one of claims 1 to 4, comprising the steps of:
s1, reacting the compound shown as the formula II with X in the presence of tert-butyl lithium in an inert atmosphere12Obtaining a compound shown as a formula III through halogenation, wherein X1Represents Br or I;
s2, a compound of formula III and R2-Z2-H is subjected to etherification to obtain the liquid crystal compound of any one of claims 1 to 4;
R1、R2、Z1、Z2、L1、L2the definition of (a) is the same as that of the liquid crystal compound shown in the formula I.
6. The method of claim 5, wherein: in step S1, dropwise adding the n-hexane solution of tert-butyl lithium into the system at-70-80 ℃, reacting for 1-2 hours after dropwise adding, and then continuously dropwise adding X12Controlling the temperature to be-70 to-80 ℃ for reaction for 1 hour, naturally returning the temperature to be-30 to-10 ℃, and carrying out hydrolysis post-treatment.
7. The production method according to claim 5 or 6, characterized in that: in step S2, the etherification reaction is performed under an inert atmosphere;
the etherification reaction is carried out in the presence of alkali, wherein the alkali is sodium hydroxide, potassium hydroxide, anhydrous potassium carbonate or anhydrous sodium carbonate;
the temperature of the etherification reaction is 70-90 ℃, and the time is 3-8 hours.
8. A liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 4.
9. Use of the liquid crystal compound according to any one of claims 1 to 4 or the liquid crystal composition according to claim 8 for producing a liquid crystal display device.
10. Use according to claim 9, characterized in that: the liquid crystal display device is a TN liquid crystal display, an ADS liquid crystal display, a VA liquid crystal display, a PSVA liquid crystal display, an FFS liquid crystal display or an IPS liquid crystal display.
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