CN118206999A - Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof - Google Patents
Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof Download PDFInfo
- Publication number
- CN118206999A CN118206999A CN202410619644.2A CN202410619644A CN118206999A CN 118206999 A CN118206999 A CN 118206999A CN 202410619644 A CN202410619644 A CN 202410619644A CN 118206999 A CN118206999 A CN 118206999A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- benzothiophene
- isothiocyanato
- monomer compound
- crystal monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 97
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 239000000178 monomer Substances 0.000 title claims abstract description 41
- 150000002240 furans Chemical class 0.000 title claims abstract description 32
- -1 isothiocyano Chemical group 0.000 title description 4
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 10
- 230000007704 transition Effects 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000012071 phase Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 2
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RAFNCPHFRHZCPS-UHFFFAOYSA-N di(imidazol-1-yl)methanethione Chemical compound C1=CN=CN1C(=S)N1C=CN=C1 RAFNCPHFRHZCPS-UHFFFAOYSA-N 0.000 description 2
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical group CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- BFQSQUAVMNHOEF-UHFFFAOYSA-N 4-bromo-2,6-difluoroaniline Chemical compound NC1=C(F)C=C(Br)C=C1F BFQSQUAVMNHOEF-UHFFFAOYSA-N 0.000 description 1
- UXIULWIJWDJDQD-UHFFFAOYSA-N 4-bromo-2-iodophenol Chemical compound OC1=CC=C(Br)C=C1I UXIULWIJWDJDQD-UHFFFAOYSA-N 0.000 description 1
- QGXKGXSOQYMBCK-UHFFFAOYSA-N 4-ethynyl-2,6-difluoroaniline Chemical compound NC1=C(F)C=C(C#C)C=C1F QGXKGXSOQYMBCK-UHFFFAOYSA-N 0.000 description 1
- RDSIMGKJEYNNLF-UHFFFAOYSA-N 5-bromo-1-benzothiophene Chemical compound BrC1=CC=C2SC=CC2=C1 RDSIMGKJEYNNLF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical group CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
-
- 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
- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
- C09K2219/11—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the High Frequency technical field
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to the technical field of liquid crystal materials, in particular to a benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato and application thereof, wherein the structural formula of the benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato is as follows: ; wherein R is selected from any one of alkyl or alkoxy; x is selected from S or O; z 1、Z2 is independently selected from any one of single bond, -C mH2m+1, -C≡C-, -CH=CH-, and m is an integer of 1-12; y 1、Y2、Y3、Y4、Y5、Y6、Y7、Y8 is independently selected from H, F, alkyl or alkoxy; n is 1 or 2. The benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato has higher clear point, better solubility, higher double refractive index and wider phase transition temperature range, and can effectively improve the performance of liquid crystal components.
Description
Technical Field
The invention relates to a benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato and application thereof, belonging to the technical field of liquid crystal materials.
Background
In recent years, with the development and progress of liquid crystal materials and related industries, the application of liquid crystal materials and liquid crystal compositions is not limited to the field of traditional liquid crystal displays, and research and application of liquid crystal materials and liquid crystal compositions in microwave components of high-frequency devices such as microwave phase shifters, microwave smart antenna arrays and the like are also attracting attention.
The liquid crystal and the liquid crystal composition can continuously change the dielectric constant (delta epsilon) and the birefringence (delta n) under the action of external fields such as electromagnetic fields, light fields and the like, and the microwave dielectric loss shows a decreasing trend along with the increase of frequency, so that the phase shifter has obvious advantages compared with the working rule of the traditional phase shifter; when the microwave propagates in the liquid crystal medium, the changing dielectric constant can change the phase of the microwave, thereby realizing the continuous tunable function of the phase of the microwave. The device manufactured by the liquid crystal has the advantages of low cost, easy industrialization and the like, so the liquid crystal is an excellent tuning medium material for the microwave phase shifter. The liquid crystal material has the characteristics of adjustable dielectric constant, low power consumption, electric control scanning and the like, and has wide application prospect in the field of high-directivity microwave intelligent antenna arrays.
Although the application potential of the liquid crystal material in the field of microwave components is huge, the liquid crystal material meeting the requirements of the microwave components is required to have high birefringence and low viscosity, large dielectric anisotropy and optical anisotropy, low dielectric loss and other performance parameters besides good physical and chemical stability and wide working temperature range, and the conventional liquid crystal material still cannot meet the requirements. At present, some documents have reported liquid crystal compounds useful in microwave technology devices. The use of liquid-crystalline media in microwave technology, in particular phase shifters, is described in German patent application DE102004029429A1, which discusses liquid-crystalline media based on mixtures of mostly aryl nitriles and isothiocyanates. The use of liquid-crystalline media in the microwave range and technical improvements relating to the use of liquid-crystalline media containing isothiocyanate compounds in the field of microwave devices are described in European patent applications EP4073205A1, EP4022007A1, EP4041846A 1. The liquid crystal compositions for microwave devices described in these documents have some drawbacks such as insufficient Δn (mostly between 0.2 and 0.4), insufficient phase range, poor solubility, poor stability in low-temperature storage, and the like.
In view of the several drawbacks of liquid crystalline compounds that are useful in microwaves, it is desirable to develop a composition having a mixture component for such liquid crystalline media that has better overall properties and a wider range of applications.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato and the application thereof, wherein the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato has higher clear point, better solubility, higher double refractive index and wider phase transition temperature range, and can effectively improve the performance of liquid crystal components.
The technical scheme for solving the technical problems is as follows: the structural formula of the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is as follows:
；
wherein R is selected from any one of alkyl or alkoxy;
x is selected from S or O;
Z 1、Z2 is independently selected from any one of single bond, -C mH2m+1, -C≡C-, -CH=CH-, and m is an integer of 1-12;
Y 1、Y2、Y3、Y4、Y5、Y6、Y7、Y8 is independently selected from H, F, alkyl or alkoxy;
n is 1 or 2.
Further, R is selected from any one of C1-C12 alkyl or alkoxy.
Further, Z 1、Z2 is independently selected from any one of single bond, -C mH2m+1, -C≡C-, -CH=CH-, and m is an integer of 1 to 5.
Further, Y 1、Y2、Y3、Y4、Y5、Y6、Y7、Y8 is independently selected from any one of H, F, C-C5 alkyl or C1-C5 alkoxy.
Further, R is selected from C1-C5 linear alkyl;
Said Z 1、Z2 is independently selected from the group consisting of a single bond, -C≡C-;
Y 1、Y2、Y3、Y4、Y5、Y7 is H, Y 6 and Y 8 are F.
Further, the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is selected from any one of the following structures:
。
The invention also discloses application of the benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato: the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is applied to a liquid crystal composition.
Application of benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato: the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is applied to a liquid crystal display.
Application of benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato: the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is applied to a microwave component of a high-frequency device.
Further, the microwave component of the high-frequency device is a microwave phase shifter, a tunable filter, a tunable metamaterial structure or a microwave intelligent antenna array.
The beneficial effects of the invention are as follows:
The benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato has better solubility and wider liquid crystal phase transition temperature range, and can not only improve the phase transition temperature of the liquid crystal composition, but also ensure that the liquid crystal composition can be stably stored for a long time when being added into the liquid crystal composition for use; in addition, the liquid crystal monomer compound has higher clearing point and higher double refraction index, is used in a mixed crystal formula, and can improve the clearing point and double refraction index of the liquid crystal component, improve the performance of the liquid crystal component, further reduce the thickness of a liquid crystal device and shorten the response time. The benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato can be applied to the field of liquid crystal display and can also be applied to a microwave component of a high-frequency device.
Drawings
FIG. 1 is a 1 H NMR chart of 3Bt-5-TPUNCS described in the examples;
FIG. 2 is a 1 H NMR chart of 3Bt-5-TPUNCS of FIG. 1 with a chemical shift of 0.3-3.5;
FIG. 3 is a 1 H NMR chart of 3Bt-5-TPUNCS of FIG. 1 with a chemical shift of 6.8-8.1;
FIG. 4 is a 1 H NMR chart of 5Bt-5-TPUNCS described in the examples;
FIG. 5 is a 1 H NMR chart of 5Bt-5-TPUNCS of FIG. 4 with a chemical shift of 6.8-8.0;
FIG. 6 is a 1 H NMR chart of 3BFPTUNCS described in the examples;
FIG. 7 is a 1 H NMR chart of 3BFPTUNCS with a chemical shift of 0-4.0 in FIG. 6;
FIG. 8 is a 1 H NMR chart of 3BFPTUNCS of FIG. 6 with a chemical shift of 5.5-8.0;
FIG. 9 is a 1 H NMR chart of 5BFPTUNCS described in the examples;
FIG. 10 is a 1 H NMR chart of 5BFPTUNCS of FIG. 9 with a chemical shift of 0-3.0;
FIG. 11 is a 1 H NMR chart of 5BFPTUNCS with a chemical shift of 6.0-8.0 in FIG. 9.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The starting materials used in the present invention are all known compounds and are commercially available.
Example 1
In the general formulaIn the method, R is-C 3H7, X is S, Z 1 is-C≡C-, Z 2 is a single bond, Y 1~Y4、Y5、Y7 is H, Y 6、Y8 is F, n=1 is an example (3 Bt-5-TPUNCS for short), and the method for synthesizing the benzothiophene or furan-series liquid crystal monomer compound 3Bt-5-TPUNCS containing isothiocyanato is as follows:
step 1: synthesis of intermediate A1
；
23.3G of diisopropylamine and 93.2g of tetrahydrofuran are put into a three-mouth bottle, nitrogen is replaced and cooled to-55 to-45 ℃, 88.0mL of n-hexane solution of n-butyllithium (2.5 mol/L) is added dropwise, and the reaction is carried out for 0.5h after the dropwise addition. 42.6 g of 5-bromobenzo [ b ] thiophene and 85.2g of tetrahydrofuran are added dropwise, and the reaction is carried out for 2h after the dropwise addition. 44.2g of 1-iodopropane is added dropwise, and the reaction is carried out at room temperature for 2h after the dropwise addition. Pouring the reaction solution into concentrated hydrochloric acid and ice water for hydrolysis for 0.5h, standing for layering, and extracting the aqueous phase with toluene. The organic phases were combined, washed with saturated brine to neutrality and the solvent was stripped off to give 46.8g of a reddish brown solid intermediate A1, yield: 91.8% and purity >80.0%.
Step 2: synthesis of intermediate A2
；
23.1G of intermediate A1, 11.7g of trimethylsilanethine and 92.4g of triethylamine are put into a three-necked flask, after the nitrogen is fully replaced, 0.190g of Pd (PPh 3)2Cl2 and 0.051g of CuI, the temperature of 80-90 ℃ C.) is added for reaction for 6 hours, the reaction liquid is filtered by suction, the filtrate is dehydrated, toluene and 10% hydrochloric acid aqueous solution are added, after acidification, water is washed until the mixture is neutral, the organic phase is passed through a silica gel column, and the solvent is dehydrated to obtain 20.9g of reddish brown solid intermediate A2, wherein the yield is 84.6%, and the purity is more than 85.0%.
Step 3: synthesis of intermediate A3
；
20.9G of intermediate A2, 41.8mL of methylene chloride and 41.8mL of methanol were charged into a 250mL three-necked flask, and the mixture was sufficiently replaced with nitrogen. 1.1g of potassium carbonate is added, and the reaction is carried out for 2 hours at 20-30 ℃. The reaction solution is filtered by suction, the filtrate is dehydrated, dichloromethane and water are added and stirred for 10min, the layers are separated, the organic phase is washed to be neutral, and 14.9g of yellow brown solid intermediate A3 is obtained after dehydration, the yield is: 96.8% and purity >85.0%.
Step 4: synthesis of intermediate A4
；
Putting 14.9g of intermediate A3, 21.0g of p-bromoiodobenzene and 74.5g of triethylamine into a three-necked flask, fully replacing nitrogen, adding 0.260g of Pd (PPh 3)2Cl2 and 0.070g of CuI), heating to 30-40 ℃, preserving heat for 9h, cooling to room temperature, carrying out suction filtration, drying filtrate, adding toluene and 5% hydrochloric acid aqueous solution, washing an organic phase to be neutral, removing a dry solvent, adding petroleum ether and toluene, and recrystallizing to obtain 17.2g of pale yellow solid intermediate A4, wherein the yield is 65.2%, and the purity is more than 99.0%.
Step 5: synthesis of intermediate A5
；
22.8G of 4-bromo-2, 6-difluoroaniline, 27.9g of bisboronic acid pinacol ester, 32.4g of potassium acetate and 68.4g of toluene are added into a reaction bottle, nitrogen is replaced, 0.22g of Pd (dppf) Cl 2 is added, and the mixture is reacted for 4 hours at 65-70 ℃. After the reaction is completed, suction filtration is carried out, the filtrate is washed to be neutral, then the solvent is removed, petroleum ether is added for recrystallization, and the off-white solid intermediate A5.7 g is obtained, the yield is 84.3%, and the purity is more than 97.0%.
Step 6: synthesis of intermediate A6
；
17.2G of intermediate A4, 12.6g of intermediate A5, 8.0g of potassium carbonate, 24.0g of water and 137.6g of THF are put into a three-necked flask, the mixture is fully replaced by nitrogen, 0.177g of Pd (dppf) Cl 2 is added, and the mixture is reacted for 8 hours under reflux and heat preservation. After the reaction, the layers are separated, the organic phase is washed to be neutral, and the solvent is removed to obtain 23.0g of light brown solid intermediate A6, the yield is 100%, and the purity is more than 97.0%.
Step 7: synthesis of 3Bt-5-TPUNCS
；
12.1G of intermediate A6, 8.0g of thiocarbonyldiimidazole and 121.0g of dichloroethane are put into a three-necked flask for reaction for 16h at 20-25 ℃. Washing the reaction solution to be neutral, removing the dry solvent, recrystallizing toluene, and performing silica gel column chromatography to obtain 4.1g of white solid 3Bt-5-TPUNCS, with a yield of 30.0% and a purity of >99.5%.
Phase transition point was measured by Differential Scanning Calorimeter (DSC) and microscopy: melting point 114.2 ℃. The characteristic ion M/Z is ：445.1H-NMR(400MHz,CDCl3)：δ＝7.844(d , 1H) ,δ＝7.715(d, 1H),δ＝7.596(m, 2H),δ＝7.486(m,2H),δ＝7.438(dd, 1H),δ＝7.171(m, 2H),δ＝6.982(s, 1H),δ＝2.858(m,2H),δ＝1.735(m, 2H),δ＝1.000(t ,3H); which is tested by a liquid phase mass spectrometer (HPLC-MS) and is particularly shown in figures 1-3.
Example 2
In the general formulaIn the method, R is-C 5H11, X is S, Z 1 is-C≡C-, Z 2 is a single bond, Y 1~Y4、Y5、Y7 is H, Y 6、Y8 is F, n=1 is an example (abbreviated as 5 Bt-5-TPUNCS), and the method for synthesizing the benzothiophene or furan-series liquid crystal monomer compound 5Bt-5-TPUNCS containing isothiocyanato is as follows:
5Bt-5-TPUNCS was prepared by the same method as in example 1, except that 1-iodopropane in step 1 of example 1 was replaced with 1-iodopentane.
1 H-NMR of 5Bt-5-TPUNCS is shown in FIGS. 4-5.
Example 3
In the general formulaIn the method, R is-C 3H7, X is O, Z 1 is a single bond, Z 2 is-C≡C-, Y 1~Y4、Y5、Y7 is H, Y 6、Y8 is F, n=1 is an example (3 BFPTUNCS for short), and the method for synthesizing the benzothiophene or furan-series liquid crystal monomer compound 3BFPTUNCS containing isothiocyanato is as follows:
Step 1: synthesis of intermediate B1
；
10.0G of 2-iodo-4-bromophenol, 2.5g of 1-pentyne and 80.0g of triethylamine are added into a three-necked flask, nitrogen is fully replaced, 0.024g of Pd (PPh 3)2Cl2 and 0.006g of CuI, heat preservation is carried out for 6 hours at 85-90 ℃), after the reaction is finished, the temperature is reduced to room temperature, suction filtration is carried out, the filtrate is subjected to solvent stripping, toluene and 10% of diluted hydrochloric acid are added for acidification, an organic phase is washed to be neutral, the solvent is stripped, n-hexane is added, a silica gel column is used, the solvent is stripped to obtain 6.7g of yellow liquid intermediate B, and the yield is 82.7%, and the purity is more than 99.0%.
Step 2: synthesis of intermediate B2
；
11.2G of intermediate B1, 11.9g of pinacol ester of bisboric acid, 13.8g of potassium acetate and 56.0g of toluene are added into a three-necked flask, the mixture is fully replaced by nitrogen, 0.034g of Pd (dppf) Cl 2 is added, and the mixture is reacted for 2 hours under reflux and heat preservation. Washing the reaction solution to be neutral, passing through a silica gel column, removing the solvent, adding petroleum ether, and recrystallizing to obtain a yellow oily liquid intermediate B2.7 g, wherein the yield is as follows: 79.3% and purity >99.0%.
Step 3: synthesis of intermediate B3
；
36.6G of 2, 6-difluoro-4-ethynylaniline, 67.6g of p-bromoiodobenzene, 36.3g of triethylamine and 74.5g of THF are put into a three-necked flask, nitrogen is fully replaced, 0.168g of Pd (PPh 3)2Cl2 and 0.046g of CuI) are added, the temperature is kept at 40-45 ℃ for 4h, the reaction solution is filtered by suction, the filtrate is dehydrated, 100.0g of toluene and 100% hydrochloric acid aqueous solution are added, the organic phase is washed to be neutral by water, a silica gel column is adopted, toluene and ethanol are added for recrystallization, and 51.5g of pale yellow solid intermediate B3 is obtained, wherein the yield is 70.0%, and the purity is more than 99.0%.
Step 4: synthesis of intermediate B4
；
9.9G of intermediate B2, 10.2g of intermediate B3, 9.1g of potassium carbonate, 79.6g of THF and 18.2g of water are added into a three-necked flask, the mixture is replaced by nitrogen, and 0.073g of Pd (dppf) Cl 2 is added for reaction for 3 hours at 60-70 ℃. Toluene and water are added, standing and layering are carried out, an organic phase is washed to be neutral by water, a silica gel column is adopted, a solvent is removed, petroleum ether is added for pulping, and 11.2g of yellow solid intermediate B4 is obtained, and the yield is: 87.5% and purity >99.0%.
Step 5: synthesis of 3BFPTUNCS
；
11.2G of intermediate B4, 7.2g of thiocarbonyldiimidazole, 4.2g of DMF and 33.6g of dichloromethane are put into a three-necked flask, replaced by nitrogen, and reacted at 30-40 ℃ for 6h. Washing the reaction solution with water to neutrality, removing the dry solvent, pulping with petroleum ether, subjecting the filtrate to silica gel column chromatography, removing the dry solvent, recrystallizing with petroleum ether and toluene to obtain 9.3g pale yellow solid 3BFPTUNCS, yield: 74.4% and purity >99.5%.
Phase transition point was measured by Differential Scanning Calorimeter (DSC) and microscopy: melting point 73.8 ℃. The characteristic ion M/Z is ：429.1H-NMR(400MHz,CDCl3)：δ＝7.677(s ,1H) ,δ＝7.565(dd ,4H) ,δ＝7.420(m ,2H), δ＝7.068(dt,2H),δ＝6.416(s ,1H),δ＝2.733(t,2H),δ＝1.757(m ,2H),δ＝0.861(t ,3H); as shown in FIGS. 6-8, as measured by liquid phase mass spectrometry (HPLC-MS).
Example 4
In the general formulaIn the method, R is-C 5H11, X is O, Z 1 is a single bond, Z 2 is-C≡C-, Y 1~Y4、Y5、Y7 is H, Y 6、Y8 is F, n=1 is an example (abbreviated as 5 BFPTUNCS), and the method for synthesizing the benzothiophene or furan-series liquid crystal monomer compound 5BFPTUNCS containing isothiocyanato is as follows:
5BFPTUNCS was prepared by the same procedure as in example 3 except that 1-pentyne in step 1 of example 3 was replaced with 1-heptyne.
1 H-NMR of 5BFPTUNCS is shown in FIGS. 9-11.
Application instance
M is a mother liquid crystal, and the formula is shown in Table 1 below.
TABLE 1 formulation of mother liquid Crystal M
The structure and physical properties of the single crystal compounds involved in the application examples are shown in Table 2 below.
TABLE 2 Single Crystal Compound Structure and physical Properties
The liquid crystal composition M-1 is obtained by mixing 90% of parent liquid crystal M and 10% of monocrystal 3 Bt-5-TPUNCS; the liquid crystal composition M-2 is obtained by mixing 90% of parent liquid crystal M by mass and 10% of single crystal 5Bt-5-TPUNCS by mass; the liquid crystal composition M-3 is obtained by mixing 90% by mass of mother liquid crystal M with 10% by mass of single crystal 3 BFPTUNCS; the liquid crystal composition M-4 was obtained by mixing 90% by mass of the mother liquid crystal M with 10% by mass of single crystal 5 BFPTUNCS. The relevant parameters of the liquid crystal composition are shown in table 3 below.
TABLE 3 liquid crystal composition property parameters
Patents CN115611833B and CN116515498a protect isothiocyanato compounds similar in structure to the present patent（3BTBfNCS）、(4 BTBfNCS)(F4 ONTPUNCS) the same was carried out by mixing 90% by mass of the mother liquid crystal M with 10% by mass of single crystals 3BTBfNCS or 4BTBfNCS or F4ONTPUNCS, and the property parameters of the liquid crystal composition were measured, and the data are shown in Table 4 below.
TABLE 4 liquid crystal composition-like Property parameters
As can be seen from a comparison of Table 3 and Table 4, the isothiocyanato liquid crystal compounds of the prior art disclosed in the patent CN115611833B and CN116515498A can only raise the birefringence of the mother liquid crystal (M) to 0.10-0.15%, while the isothiocyanato-containing benzothiophene or furan-series liquid crystal monomer compounds of the present invention can raise the birefringence of the mother liquid crystal (M) to 0.40-0.60%, which is significantly higher than the former. Therefore, the benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato has more remarkable effect on improving the birefringence of the liquid crystal component.
In combination with the data in the table, the isothiocyanato liquid crystal monomer containing benzothiophene or furan has higher melting point and clear point, has better miscibility with other liquid crystals, can obviously improve the double refractive index of the liquid crystal component and improve the performance of the liquid crystal component.
Conclusion: from the above data, it can be seen that the mixed liquid crystal added with the isothiocyanato liquid crystal monomer containing benzothiophene or furan has excellent physical properties.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. The benzothiophene or furan series liquid crystal monomer compound containing the isothiocyanato is characterized by comprising the following structural formula:
；
wherein R is selected from any one of alkyl or alkoxy;
x is selected from S or O;
Z 1、Z2 is independently selected from any one of single bond, -C mH2m+1, -C≡C-, -CH=CH-, and m is an integer of 1-12;
Y 1、Y2、Y3、Y4、Y5、Y6、Y7、Y8 is independently selected from H, F, alkyl or alkoxy;
n is 1 or 2.
2. The benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato according to claim 1, characterized in that R is selected from any one of alkyl groups or alkoxy groups of C1 to C12.
3. The isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound according to claim 1, characterized in that Z 1、Z2 is independently selected from any one of single bond, -C mH2m+1, -c≡c-, -ch=ch-, and m is an integer of 1 to 5.
4. The isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound according to claim 1, characterized in that Y 1、Y2、Y3、Y4、Y5、Y6、Y7、Y8 is independently selected from any one of H, F, C to C5 alkyl group or C1 to C5 alkoxy group.
5. The benzothiophene or furan series liquid crystal monomer compound containing isothiocyanato according to claim 1, characterized in that R is selected from C1 to C5 linear alkyl groups;
Said Z 1、Z2 is independently selected from the group consisting of a single bond, -C≡C-;
Y 1、Y2、Y3、Y4、Y5、Y7 is H, Y 6 and Y 8 are F.
6. The isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound according to claim 1, characterized in that the isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound is selected from any one of the following structures:
。
7. Use of a benzothiophene or furan series liquid crystal monomer compound containing an isothiocyanato group according to any one of claims 1 to 6, characterized in that the benzothiophene or furan series liquid crystal monomer compound containing an isothiocyanato group is applied to a liquid crystal composition.
8. Use of the isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound according to any one of claims 1 to 6, characterized in that the isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound is applied to a liquid crystal display.
9. Use of the isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound according to any one of claims 1 to 6, characterized in that the isothiocyanato-containing benzothiophene or furan series liquid crystal monomer compound is applied to a microwave component of a high frequency device.
10. The use of a benzothiophene or furan based liquid crystal monomer compound containing isothiocyanato according to claim 9, characterized in that the microwave component of the high frequency device is a microwave phase shifter, a tunable filter, a tunable metamaterial structure or a microwave smart antenna array.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410619644.2A CN118206999B (en) | 2024-05-20 | 2024-05-20 | Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410619644.2A CN118206999B (en) | 2024-05-20 | 2024-05-20 | Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118206999A true CN118206999A (en) | 2024-06-18 |
| CN118206999B CN118206999B (en) | 2024-09-03 |
Family
ID=91447094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410619644.2A Active CN118206999B (en) | 2024-05-20 | 2024-05-20 | Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118206999B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466849A (en) * | 2023-12-27 | 2024-01-30 | 中节能万润股份有限公司 | Liquid crystal monomer compound containing isothiocyanato and preparation method thereof |
| WO2024024519A1 (en) * | 2022-07-28 | 2024-02-01 | Dic株式会社 | Compound, liquid crystal composition, and liquid crystal display element, sensor, liquid crystal lens, optical communication equipment, and antenna using same |
-
2024
- 2024-05-20 CN CN202410619644.2A patent/CN118206999B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024024519A1 (en) * | 2022-07-28 | 2024-02-01 | Dic株式会社 | Compound, liquid crystal composition, and liquid crystal display element, sensor, liquid crystal lens, optical communication equipment, and antenna using same |
| CN117466849A (en) * | 2023-12-27 | 2024-01-30 | 中节能万润股份有限公司 | Liquid crystal monomer compound containing isothiocyanato and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118206999B (en) | 2024-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2633578C2 (en) | Mesogenic compounds, liquid crystal compositions containing these compounds and devices for high-frequency equipment | |
| CN114213296B (en) | Naphthalene series liquid crystal monomer compound containing isothiocyanato and preparation method and application thereof | |
| CN110938438A (en) | Side ethyl fluorine-containing triphendiyne liquid crystal compound, preparation method, liquid crystal composition and application | |
| CN110776927B (en) | Isothiocyano fluorine-containing tetrabiphenyl liquid crystal compound, preparation method thereof, liquid crystal composition and application | |
| CN110746982B (en) | Achiral side methyl alkyl tetrabiphenyl liquid crystal compound, preparation method thereof, liquid crystal composition and microwave communication device | |
| CN110760311B (en) | Lateral methyl poly-biphenyl liquid crystal compound, liquid crystal composition and application thereof | |
| CN113234045A (en) | Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device | |
| CN105505406A (en) | Preparation method of blue-phase liquid crystal composite material containing bending molecule with branched chain structure | |
| KR100405930B1 (en) | Photo-crosslinkable naphthalene derivative | |
| KR101800036B1 (en) | Compounds for a liquid-crystalline medium, and the use thereof for high-frequency components | |
| EP4237507A1 (en) | Aromatic isothiocyanates | |
| CN113528148A (en) | Liquid crystal medium for high-frequency technology and assembly thereof | |
| US4212762A (en) | Liquid crystal materials having a formula containing a diphenylethane nucleus | |
| CN115960074A (en) | Fluorine-containing ferroelectric liquid crystal molecules containing heteroatom hexatomic alicyclic ring and synthesis method thereof | |
| Byron et al. | The synthesis and characterisation of a novel thiophene-based liquid crystal exhibiting ferro-, ferri-and antiferro-electric phase types | |
| CN117466849B (en) | Liquid crystal monomer compound containing isothiocyanato and preparation method thereof | |
| CN118206999B (en) | Benzothiophene or furan series liquid crystal monomer compound containing isothiocyano and application thereof | |
| WO2022090109A1 (en) | Aromatic isothiocyanates | |
| CN115611833B (en) | Benzofuran series liquid crystal monomer compound and preparation method and application thereof | |
| CN112759504A (en) | Liquid crystal compound containing diacetylene structure, liquid crystal composition and application thereof | |
| CN113528149B (en) | Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound | |
| CN115448861B (en) | Ethyl naphthalene series liquid crystal monomer compound, and preparation method and application thereof | |
| CN114015459B (en) | Liquid crystal containing dinaphthyl monomer, and preparation method and application thereof | |
| CN109054862B (en) | Benzo [ b ] thiophene liquid crystal compound with luminescent property and preparation method thereof | |
| KR20100030946A (en) | Novel pyran derivative, its preparation method, liquid crystal composition and liquid crystal display device comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |