CN106519733B - One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application - Google Patents
One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application Download PDFInfo
- Publication number
- CN106519733B CN106519733B CN201610832268.0A CN201610832268A CN106519733B CN 106519733 B CN106519733 B CN 106519733B CN 201610832268 A CN201610832268 A CN 201610832268A CN 106519733 B CN106519733 B CN 106519733B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- liquid crystalline
- crystalline dyes
- benzanthrone
- crystal display
- 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.)
- Expired - Fee Related
Links
- 239000000975 dye Substances 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- -1 acetenyl Chemical group 0.000 claims abstract description 6
- 230000010415 tropism Effects 0.000 claims abstract description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 6
- ILLHQJIJCRNRCJ-UHFFFAOYSA-N dec-1-yne Chemical compound CCCCCCCCC#C ILLHQJIJCRNRCJ-UHFFFAOYSA-N 0.000 claims description 5
- KFSSLUMKUDMRLD-UHFFFAOYSA-N ethyl formate ethynylbenzene Chemical compound C(=O)OCC.C(#C)C1=CC=CC=C1 KFSSLUMKUDMRLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract description 6
- 238000010189 synthetic method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- ZKYWFKLLGNCXPJ-UHFFFAOYSA-N C1=CC=C2C=CC=C3C(=O)C4=CC=CC=C4C1=C23.[Br] Chemical class C1=CC=C2C=CC=C3C(=O)C4=CC=CC=C4C1=C23.[Br] ZKYWFKLLGNCXPJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 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 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-UHFFFAOYSA-N 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- WVECFEIAZAKUNF-UHFFFAOYSA-N O=C(c1ccccc1-1)c2cccc3c2c-1ccc3Br Chemical compound O=C(c1ccccc1-1)c2cccc3c2c-1ccc3Br WVECFEIAZAKUNF-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FFYDXIRYINVCCL-UHFFFAOYSA-N ethynylbenzene formic acid Chemical compound C(=O)O.C1(=CC=CC=C1)C#C FFYDXIRYINVCCL-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/02—Benzathrones
- C09B3/06—Preparation from starting materials already containing the benzanthrone nucleus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- 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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13725—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on guest-host interaction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of benzanthrone liquid crystalline dyes for containing 3 bit substituents, its preparation method and application.The present invention is introduced into solubility of the different acetenyl increase molecules in liquid crystal using 3 bromine benzanthrones as parent at 3, strengthens the linear structure of molecule and then improves the dichroism of liquid-crystal compounds；Big conjugated system is formed using the electronics of height delocalization on phenyl ring and parent.The present invention synthesizes a kind of tropism liquid crystalline dyes maximum absorption wavelength of benzanthrone class fluorescence two and concentrates on visible region, and launch wavelength concentrates on 500nm or so, and liquid crystalline dyes compound structure is novel, and raw material is easy to get, and synthetic method is simple；There is preferable dichroic ratio and order parameter in liquid crystal, available for liquid crystal display product is manufactured, especially there is high dichroism in guest-host type liquid crystal display.
Description
Technical field
The present invention relates to a kind of new benzanthrone class liquid crystalline dyes compounds containing 3 different substitutions and its application,
Belong to display material field.
Background technology
Information-based high speed development has driven the development of liquid crystal flat-panel technology and industry, traditional cathode-ray tube (CRT)
Technology is substituted by FPD, and flat-panel monitor brings revolutionary change to the life of people.
" guest-master " display is the new display pattern risen in the last few years." guest-master " (GH) pattern is to show color change
Mode of operation, almost put forward simultaneously by G.Heilmeier etc. and DS patterns.Adulterated in nematic liquid crystal main material
Some dichroic dyes form a pair of " guest-master " materials, apply electric field to it, and liquid crystal molecule occurs orientation and changed." guest-
Master " (GH) pattern is exactly to realize display using the dichroic dye light absorbs for changing molecularly oriented.
Fluorescence " guest-master " escope is the improvement of traditional " guest-master " escope, and it is should by the tropism dyestuff of fluorescence two
For in liquid crystal display, so not only light absorbing intensity, and the intensity for launching light can also be controlled by electric field, so as to
It will be integrated in one the advantages of emissive display and the characteristics of conventional liquid crystal, more portable low power dissipation electron device be made
Part.Pure liquid crystal material can not meet the various characteristics of liquid crystal material, such as light, electricity, heat.Then liquid-crystal compounds is utilized
Or dyestuff turns into an apparent trend to compound liquid crystal material so as to obtaining the more superior liquid crystal material of performance.Compounding
Liquid crystalline dyes can obtain higher more stable liquid crystal phase temperature range, higher clearing point and the function of adjusting refractive index.
The content of the invention
To solve the problems, such as to lack present in prior art fluorescence dichroic dye of good performance, the present invention provides
Liquid crystalline dyes, liquid crystal display product can be applied to as the tropism dyestuff of fluorescence two.
One of technical purpose of the present invention is to provide a kind of new liquid crystalline dyes.
Another technical purpose of the present invention is the preparation method for providing above-mentioned liquid crystalline dyes compound, including following step
Suddenly：
Respectively by 4 '-acetenyl -4- alkyl biphenyls, align the positive decine of butyl phenyl ether acetylene, 1-, to acetylenylbenzene formic acid second
Ester is coupled to obtain the liquid crystalline dyes compound with 3- bromine benzanthrones；
The preparation method of 4 '-acetenyl -4- alkyl biphenyls is：4 '-bromo- 4- alkyl biphenyls and 2- methyl -3- butine -
2- alcohol is coupled, and 4 '-acetenyl -4- alkyl biphenyls are obtained by alkali process；
Described 4 '-bromo- 4- alkyl biphenyls are selected from 4 ' the bromo- 4- n-pentyls biphenyl of-bromo- 4- ethyl biphenyls, 4 '-.
Specific synthetic line is as follows：
Further, the bromo- 4- ethyl biphenyls of-bromo- 4- n-pentyls biphenyl or 4 '-enter with 2- methyl -3- butyne-2-alcohols by 4 '
During row reaction, the optimal mixing mol ratio of the two is 1:1, using dry triethylamine as reaction dissolvent, add the triphen of catalytic amount
Base phosphine palladium bichloride, triphenylphosphine and cuprous iodide catalyst, magnetic agitation is heated to flowing back under nitrogen protective condition.React 8h
Excess of solvent is removed under reduced pressure in TLC tracking and monitorings to reaction completely afterwards, and solid product crosses silica gel column chromatography, obtains solid (compound 1).
Further, compound 1 is added into addition absolute ethyl alcohol magnetic agitation heating in bottle with two necks to be allowed to dissolve, added
The potassium hydroxide of amount, it is heated to flowing back, potassium hydroxide gradually dissolves, and the carry out degree of tracking and monitoring reaction, constantly adds KOH.
Persistently stop reaction after backflow a few hours, now reaction solution is brown.Room temperature is cooled to, reaction product is poured into water, is used
Hydrochloric acid solution adjusts pH value and separates out a large amount of yellow mercury oxides to neutrality, filters, be dry that white-yellowish solid, crude product cross silicon after washing
Plastic column chromatography, obtain solid 4 '-acetenyl -4- ethyl biphenyls, 4 '-acetenyl -4- n-pentyls biphenyl (compound 2)
Further, respectively by 4 '-acetenyl -4- ethyl biphenyls, 4 '-acetenyl -4- n-pentyls biphenyl, to n-butoxy
The positive decine of phenylacetylene, 1-, when reacting acetylenylbenzene Ethyl formate and 3- bromine benzanthrones, the optimal mixing mole of the two
Than for 1：1, using dry triethylamine as reaction dissolvent, the triphenylphosphine palladium chloride, triphenylphosphine and iodate for adding catalytic amount are sub-
Copper catalyst, magnetic agitation is heated to flowing back under nitrogen protective condition.TLC tracking and monitorings depressurize completely to reaction after reacting 8h
Excess of solvent is removed, solid product crosses silica gel column chromatography, obtains orange/yellow solid (F) liquid crystalline dyes.
Another aspect of the present invention provides above-mentioned liquid crystalline dyes compound as fluorescence dichroic dye in manufacture liquid crystal
Show the application in product.Described liquid crystal display product is guest-host type liquid crystal display.Specifically as the brilliant dye of guest's body fluid
Material, applied to preparing guest-host type liquid crystal display.
The present invention provides a kind of guest-host type liquid crystal display, and described liquid crystal display is with liquid crystalline dyes of the present invention
Compound is as guest's body liquid crystalline dyes.
In addition, the liquid-crystal compounds of the present invention also has liquid crystalline phase, described liquid crystal host is smectic liquid crystal, nematic phase
Liquid crystal or cholesteric liquid crystal.
The compound of the present invention has liquid crystalline phase, can be mixed with liquid crystal E7 and be applied to liquid crystal display.
Invention beneficial effect
Firstth, the present invention introduces different substituted acetenyls using benzanthrone as parent, in 3- positions, strengthens the linear of molecule
Structure and then the dichroism for improving dyestuff, liquid-crystal compounds structure is novel, and raw material is easy to get, and synthetic method is simple；
Secondth, 5 tropism liquid crystalline dyes maximum absorption wavelengths of benzanthrone class fluorescence two of present invention synthesis concentrate on visible
Light area, launch wavelength concentrate on 500nm or so, launch bright-coloured yellow-green fluorescence, are rubbed in dichloromethane and different solvents
That extinction coefficient is more than 104.Preferable dichroic ratio and order parameter are shown in liquid crystal E7, available for manufacturing liquid crystal
Product, especially guest-host type liquid crystal display are shown, as guest's body liquid crystalline dyes；
3rd, liquid-crystal compounds of the invention also has liquid crystalline phase, in addition, it is also used as liquid crystal addO-on therapy, adds
Add in liquid crystal host and improve the photoelectric properties of liquid crystal host.
Brief description of the drawings
Fig. 1 is F1 prepared by embodiment 1 differential scanning calorimetric figure.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Wherein, align the positive decine of butyl phenyl ether acetylene, 1-, to acetylenylbenzene Ethyl formate raw material be purchase gained.
Embodiment 1
Liquid crystalline dyes F1 synthesis
(1) synthesis of 2- methyl -4- (4 '-ethyl biphenyl) 3- crotonylenes-methanol (compound 1)
By 302mg (1mmol) 4 '-bromo- 4- ethyl biphenyls and 100 μ L (1mmol) 2- methyl -3- butyne-2-alcohols and 7mg
Two triphenylphosphine palladiums, 15mg triphenylphosphines, 8mgCuI are separately added into 50mL twoport round-bottomed flasks as catalyst, are used
15mL dry triethylamines are as acid binding agent and solvent.Stirred under nitrogen protective condition, be heated to backflow and be allowed to reaction completely.Decompression
Triethylamine is removed, crude product crosses silica gel column chromatography (eluant, eluent：Dichloromethane), removal of solvent under reduced pressure obtains 281.7mg white solids,
Yield 92%.Fusing point：48.4-49.7℃.
1H-NMR(400MHz,CDCl3):δ=7.54 (s, 4H), 7.50 (d, J=8.0Hz, 2H), 7.25 (d, J=
3.2Hz,2H),3.12(s,1H),2.68-2.61(m,2H),1.69-1.60(m,2H),1.38-1.31(m,4H),0.90(t,J
=6.8Hz, 3H)
Fusing point：113.4-114.7℃.TOF MS EI+：Calculated value：[C19H20]+(m/z)=248.1565, measured value：
[C19H20]+(m/z)=248.1574.
The synthesis of (2) 4 '-acetenyl -4- ethyl biphenyls (compound 2)
The obtained 281.7mg white solids of upper step reaction are added 20mL absolute ethyl alcohol magnetic force is added in 50mL bottle with two necks
Agitating and heating is allowed to dissolve, and adds excessive potassium hydroxide, is heated to flowing back, and potassium hydroxide gradually dissolves, tracking and monitoring reaction
Carry out degree, constantly add KOH.Persistently stop reaction after backflow a few hours, now reaction solution is brown.It is cooled to room
Temperature, reaction product is poured into 100mL water, separated out a large amount of yellow to neutral with hydrochloric acid solution regulation pH value and floatd wadding, suction filtration, washed
It is dry that 187.1mg white-yellowish solids, crude product cross silica gel column chromatography, eluant, eluent PE, yield 82% afterwards.
(3) target product F1 synthesis
1mmol 3- bromine benzanthrones 309mg is added in two mouthfuls of flasks, respectively by 14mg triphenylphosphine palladium chlorides, 52mg
Triphenylphosphine, 16mg cuprous iodides, 20mL dry triethylamines are added in two mouthfuls of flasks, and nitrogen protection is lower to add 206mg 4 '-second
Alkynyl -4- ethyl biphenyls, the reaction of back flow reaction 8h TLC tracking and monitorings is complete under magnetic agitation, and mixture is cooled into room temperature and subtracted
Pressure removes solvent, and silica gel column chromatography purification, eluant, eluent is dichloromethane and petroleum ether ratio is 1：1, collect orange-yellow fluorescence Spectra
Band, obtain orange/yellow solid 357.5mg, yield 82%.
1H NMR (500MHz, CDCl3) δ 8.83 (ddd, J=8.4,7.7,1.1Hz, 2H), 8.51 (dd, J=7.9,
1.2Hz, 1H), 8.42 (d, J=7.9Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.93 (d, J=7.8Hz, 1H), 7.90-
7.86 (m, 1H), 7.75 (dd, J=13.7,7.6Hz, 3H), 7.65 (d, J=8.3Hz, 2H), 7.60-7.54 (m, 3H), 7.31
(d, J=8.1Hz, 2H), 2.72 (q, J=7.6Hz, 2H), 1.30 (t, J=7.6Hz, 3H)
13C NMR (126MHz, CDCl3) δ 183.51 (d, J=45.0Hz), 144.14 (s), 141.64 (s), 137.54
(s), 135.74 (s), 135.59 (s), 134.26 (s), 133.64 (s), 133.56 (d, J=21.3Hz), 133.48 (s),
132.18 (s), 130.78-130.51 (m), 130.26 (s), 128.69 (s), 128.49 (s), 128.22 (d, J=3.0Hz),
127.73 (s), 127.01 (d, J=5.0Hz), 124.24 (s), 123.26 (s), 123.07 (s), 97.20 (s), 87.67 (s),
58.43(s),28.57(s),18.43(s).
Fusing point：253.5℃.TOF MS EI+(m/z)：Calculated value：[C33H22O]+(m/z)=434.5272, measured value：
[C33H22O]+(m/z)=434.1667.
Embodiment 2
Liquid crystalline dyes F2 synthesis
The same F1 of synthetic method, 4 ' in step (1)-bromo- 4- ethyl biphenyls are changed into 4 '-bromo- 4- n-pentyls biphenyl.Step
Suddenly solvent is DCM in (3)：PE=2：1, obtain end-product yellow solid 406.3mg, yield 85%.
1H NMR (500MHz, CDCl3) δ 8.84 (dd, J=19.2,7.7Hz, 2H), 8.51 (d, J=7.9Hz, 1H),
8.43 (d, J=7.8Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.96-7.84 (m, 2H), 7.75 (dd, J=15.9,
8.1Hz, 3H), 7.66 (d, J=8.3Hz, 2H), 7.57 (t, J=8.3Hz, 3H), 7.29 (d, J=8.1Hz, 2H), 2.70-
2.63(m,2H),1.72–1.62(m,2H),1.42–1.32(m,4H),0.95–0.88(m,3H).
13C NMR(126MHz,CDCl3)δ153.46(s),144.11(s),141.40–141.13(m),137.51(s),
137.03(s),136.10(s),132.44(s),132.26(s),131.43(s),130.23(s),129.71(s),129.61
(d, J=5.4Hz), 129.43 (d, J=4.1Hz), 128.76 (s), 128.47 (s), 128.13 (s), 128.13 (s),
126.96 (s), 125.10 (s), 123.67 (s), 122.52 (s), 122.30 (d, J=5.7Hz), 97.13 (s), 87.39 (s),
58.41(s),29.71(s),28.56(s),18.46(s),15.56(s).
Fusing point：157.3-158.6℃.TOF MS EI+(m/z)：Calculated value：[C36H28O]+(m/z) it is=476.6069, real
Measured value：[C36H28O]+(m/z)=476.2149.
Embodiment 3
Liquid crystalline dyes F3 synthesis
With step in F1 (3), difference is synthetic method, and 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into
Align butyl phenyl ether acetylene.Solvent is DCM：PE=1：2, obtain orange-yellow end-product 313.6mg, yield 78%.
1H NMR (500MHz, CDCl3) δ 8.82 (dd, J=15.1,7.7Hz, 2H), 8.50 (d, J=7.9Hz, 1H),
8.41 (d, J=7.7Hz, 1H), 8.33 (d, J=8.1Hz, 1H), 7.88 (dd, J=16.2,8.0Hz, 2H), 7.75 (t, J=
7.6Hz, 1H), 7.64-7.52 (m, 3H), 6.94 (d, J=8.7Hz, 2H), 4.02 (t, J=6.5Hz, 2H), 1.84-1.76
(m, 2H), 1.57-1.48 (m, 2H), 1.00 (t, J=7.4Hz, 3H)
13C NMR(126MHz,CDCl3)δ183.61(s),159.79(s),135.75(s),133.47(s),133.35
(s),133.26(s),132.71(s),130.30(s),130.12(s),128.41(s),128.16(s),126.99(s),
126.56 (s), 123.86 (s), 123.52 (s), 123.15 (s), 114.70 (d, J=9.7Hz), 97.48 (s), 85.90 (s),
67.87(s),31.26(s),19.25(s),13.86(s).
Fusing point：150.1-151.2℃.TOF MS EI+(m/z)：Calculated value：[C29H22O2]+(m/z) it is=402.4838, real
Measured value：[C29H22O2]+(m/z)=402.1627.
Embodiment 4
Liquid crystalline dyes F4 synthesis
With step in F1 (3), difference is synthetic method, and 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into
The positive decine of 1-.Solvent is DCM：PE=1：1, obtain yellow solid end-product 263.5mg, yield 72%.
1H NMR (400MHz, CDCl3) δ 8.72 (dd, J=19.1,7.7Hz, 2H), 8.47 (d, J=7.1Hz, 1H),
8.28 (dd, J=21.7,8.0Hz, 2H), 7.80 (t, J=7.8Hz, 1H), 7.71 (dd, J=15.0,7.4Hz, 2H), 7.53
(t, J=7.4Hz, 1H), 2.60 (t, J=7.1Hz, 2H), 1.80-1.68 (m, 2H), 1.59-1.50 (m, 2H), 1.34 (d, J
=21.2Hz, 8H), 0.90 (t, J=6.7Hz, 3H)
13C NMR(126MHz,CDCl3)δ183.58(s),135.75(s),135.75(s),133.49(s),132.99
(s),130.77(s),130.34(s),129.96(s),128.58(s),128.26(s),128.04(s),127.64(s),
126.79(s),126.14(s),124.37(s),123.42(s),123.05(s),98.71(s),78.38(s),31.88(s),
29.27(s),29.17(s),29.12(s),28.82(s),22.70(s),19.91(s),14.14(s).
Fusing point：55.1-56.2℃.TOF MS EI+(m/z)：Calculated value：[C27H26O]+(m/z)=366.4947, survey
Value：[C27H26O]+(m/z)=366.1913.
Embodiment 5
Liquid crystalline dyes F5 synthesis
With step in F1 (3), difference is synthetic method, 4 '-acetenyl -4- ethyl biphenyls in step (3) are changed into
To acetylenylbenzene Ethyl formate.Solvent is DCM：PE=4：1, obtain yellow solid 345.7mg, yield 86%.
1H NMR (400MHz, CDCl3) δ 8.84-8.74 (m, 2H), 8.50 (dd, J=7.9,1.2Hz, 1H), 8.39 (d,
J=7.9Hz, 1H), 8.30 (d, J=8.1Hz, 1H), 8.12 (d, J=8.4Hz, 2H), 7.89 (dd, J=16.2,8.0Hz,
2H), 7.79-7.70 (m, 3H), 7.57 (dd, J=14.6,7.4Hz, 1H), 4.44 (q, J=7.1Hz, 2H), 1.46 (t, J=
7.1Hz,3H).
13C NMR(126MHz,CDCl3)δ183.61(s),166.01(s),135.61(s),133.25(s),132.75
(s),131.62(s),131.12(s),130.33(s),129.67(s),128.80(s),128.25(s),127.65(s),
127.39(s),123.44(s),123.33(s),122.71(s),96.10(s),89.80(s),65.34(s),61.30(s),
58.45(s),18.44(s).
Fusing point：185.5-186.8℃.TOF MS EI+(m/z)：Calculated value：[C28H18O3]+(m/z) it is=402.4407, real
Measured value：[C28H18O3]+(m/z)=402.1262.
The property measure of the liquid crystalline dyes compound of the present invention：
(1) spectral quality tests of the liquid crystalline dyes compound F in dichloromethane：
Test concentrations：Concentration of the liquid-crystal compounds in different solvents is 1.0 × 10-5mol/L.Accurately weigh respectively
1.0×10-2Liquid-crystal compounds (± 0.1mg) prepared by mmol, volume is put into use CH after 10mL volumetric flasks2Cl2Constant volume, obtain
Concentration is 1.0 × 10-3Mol/L stock solutions.The μ L of stock solution 100 are pipetted in 10mL volumetric flasks, after solvent volatilization completely
With other solvent constant volumes to be measured, 1.0 × 10 are obtained-5Mol/L solution, tested for UV absorption, fluorescence spectrum.
Liquid-crystal compounds fluorescence quantum yield ΦFThe measure of value：With concentration 1.0 × 10-5Mol/L, ΦFIt is worth the sulphur for 0.55
Sour quinoline is given repeated exhortations solution (5.0 × 10-2Mol/L aqueous sulfuric acids) on the basis of.To prevent liquid-crystal compounds fluorescence under a high concentration condition
Quenching, the absorbance of liquid-crystal compounds solution is controlled in the range of 0.02-0.05 during test.Required parameter is in same test condition
Under measure, substitute into formula (1) calculate：
In formula：Φ(sample)、Φ(standard)Representative sample, the Φ of reference material respectivelyFValue；Abs(standard)、Abs(sample)
The absorbance of reference material under excitation wavelength, sample is represented respectively；Flu (sample) and Flu (standard) difference representative sample,
The fluorescence spectrum integral area of reference material.
The test result of F series liquid crystal dyestuffs is as follows：
Spectral qualities of the liquid crystalline dyes F3 of table 1. in different solvents
Table 2.F series dyes spectral signature in methylene chloride
Conclusion：The maximum absorption wavelength of benzanthrone derivative series dyes concentrates on 400nm or so, the maximum of F series
Launch wavelength is in 500nm or so, and half-peak breadth is larger concentrates between 70-80 for the absorption half-peak breadth of F series and transmitting, and color is pure
Just, it is more beneficial for realizing that pure color is shown.
(2) polarization spectrum property tests of the liquid crystalline dyes F in liquid crystal E7：
Bulk liquid crystal：Nematic phase ranges (- 10-60 DEG C) of the liquid crystal E7 with wider stabilization, good chemical stability,
High positive dielectric anisotropy is as bulk liquid crystal.
Liquid crystal cell：Test is parallel to each other with the orientation of two substrates above and below liquid crystal cell, and box thickness is 15 μm.
Measure of the dichroic than, order parameter：Liquid crystalline dyes F is mixed according to the ratio that mass concentration is 0.5% (w/w)
Into liquid crystal, it is well mixed at room temperature, the mixture is then loaded into parallel liquid crystal cell, seals irrigation crystal mouth.Test fluid respectively
Crystallization compound and the absorbance A in liquid crystal cell alignment films parallel direction‖With the absorbance A in vertical direction⊥, in parallel direction
Fluorescence intensity F‖With the fluorescence intensity F in vertical direction⊥；And (2), (3), (4), (5) calculate liquid-crystalization according to the following formula
Absorption order parameter Ss of the compound F in liquid crystalA, dichroic compare DAWith fluorescence order parameter SF, dichroic compare DF：
Liquid crystalline dyes compound F polarization spectrum test results are as follows：
Polarized UVs and polarized fluorescence data of the liquid-crystal compounds F of table 3. in liquid crystal E7
The target product F of synthesis shows preferable dichroic ratio and order parameter in liquid crystal E7.F1 SAAnd SFIt is
Maximum, respectively reaching 0.66 and 0.55 has practical value.Dichroic ratio is 5.46.Meet that host and guest shows practical application
It is required that.
(3) F series is in negative liquid crystal BHR28000-300 polarization spectrums and optical-electronic property
Liquid crystalline dyes F1, F2 and F3 the additional different voltages of negative liquid crystal BHR28000-300 tests (2,4,6,8,10V)
Ultraviolet polarization spectrum, spectrum test data are as shown in table 4..
Polarization spectrum properties of the liquid crystalline dyes F of table 4. in negative liquid crystal BHR28000-300
(4) liquid crystalline dyes compound F liquid crystal behavior
Differential scanning is carried out to the liquid crystalline dyes compound F1 of preparation, obtains its differential scanning calorimetric figure, as shown in Figure 1.
Claims (6)
1. the benzanthrone class liquid crystalline dyes containing 3 alkynyl substituted bases, it is characterised in that：The dyestuff has following chemistry
General formula of molecular structure：
2. the preparation method of the benzanthrone class liquid crystalline dyes described in claim 1, comprises the following steps：
Respectively by 4 '-acetenyl -4- alkyl biphenyls, align the positive decine of butyl phenyl ether acetylene, 1-, to acetylenylbenzene Ethyl formate with
3- bromine benzanthrones are coupled to obtain the liquid crystalline dyes compound；
The preparation method of 4 '-acetenyl -4- alkyl biphenyls is：4 '-bromo- 4- alkyl biphenyls and 2- methyl -3- butyne-2-alcohols
Coupling, 4 '-acetenyl -4- alkyl biphenyls are obtained by alkali process；
Described 4 '-bromo- 4- alkyl biphenyls are selected from 4 ' the bromo- 4- n-pentyls biphenyl of-bromo- 4- ethyl biphenyls, 4 '-.
3. the benzanthrone class liquid crystalline dyes described in claim 1 are as the tropism liquid crystalline dyes of fluorescence two in manufacture liquid crystal display production
Application in product.
4. application according to claim 3, it is characterised in that liquid crystal display is guest-host type liquid crystal display.
5. a kind of guest-host type liquid crystal display, it is characterised in that using the benzanthrone class liquid crystalline dyes described in claim 1 as
Guest's body liquid crystalline dyes.
6. the benzanthrone class liquid crystalline dyes described in claim 1 mix application in a liquid crystal display with liquid crystal E7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610832268.0A CN106519733B (en) | 2016-09-18 | 2016-09-18 | One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610832268.0A CN106519733B (en) | 2016-09-18 | 2016-09-18 | One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519733A CN106519733A (en) | 2017-03-22 |
| CN106519733B true CN106519733B (en) | 2018-01-09 |
Family
ID=58344289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610832268.0A Expired - Fee Related CN106519733B (en) | 2016-09-18 | 2016-09-18 | One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519733B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489961A (en) * | 2006-07-11 | 2009-07-22 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| WO2013187749A1 (en) * | 2012-06-11 | 2013-12-19 | Даугавпилсский Университет | Method for producing a novel luminescent polymer material |
| WO2016126423A2 (en) * | 2015-02-03 | 2016-08-11 | E I Du Pont De Nemours And Company | Electroactive materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1769049A2 (en) * | 2004-07-16 | 2007-04-04 | Ciba Specialty Chemicals Holding Inc. | Luminescent silicon oxide flakes |
-
2016
- 2016-09-18 CN CN201610832268.0A patent/CN106519733B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489961A (en) * | 2006-07-11 | 2009-07-22 | 默克专利有限公司 | Electroluminescent polymers and use thereof |
| WO2013187749A1 (en) * | 2012-06-11 | 2013-12-19 | Даугавпилсский Университет | Method for producing a novel luminescent polymer material |
| WO2016126423A2 (en) * | 2015-02-03 | 2016-08-11 | E I Du Pont De Nemours And Company | Electroactive materials |
Non-Patent Citations (2)
| Title |
|---|
| 4,10-Dibromoanthanthrone as a New Building Block for p-Type, n-Type, and Ambipolar p-Conjugated Materials;Giguere, Jean-Benoit et al;《Chemistry - A European Journal》;372-381;20121120;第19卷(第1期);372-381 * |
| Selective introducing of aryl and amino groups: reaction of benzanthrone and organometallic reagents;Rui Umeda et al;《Tetrahedron》;20121212;第69卷(第5期);1526-1531 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519733A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106520139B (en) | Containing -1,8 naphthalimide liquid-crystal compounds of 4- (biphenyl acetenyl), preparation method and application | |
| CN106433186B (en) | Fluorescence dichroic dye of the one kind containing the 4 biphenyl acetylene acenaphthenes simultaneously dintrile of [1,2 b] pyrazine 8,9, its preparation method and application | |
| US11629157B2 (en) | Fluoro-boron pyrrole liquid crystal compounds containing 8-(bisphenylethynyl)-ester group flexible multiple ring, preparation method and use thereof | |
| JP6792899B1 (en) | Phenylethynylborone dipyrromethene-based fluorescent dichroic liquid crystal compound and its use | |
| CN106336350B (en) | Fluorine-containing dinaphthyl ethine liquid crystal compound and its preparation method and application | |
| Kong et al. | Development of dimeric triarylmethine derivatives with improved thermal and photo stability for color filters | |
| CN106478599B (en) | One kind contains the fluorescence dichroic dye of 4- piperazinyl -1,8- naphthalimide, preparation method and application | |
| CN109336814B (en) | 4- (alkyl dicyclohexyl) -substituted naphthalimide derivative, and preparation method and application thereof | |
| CN104357063B (en) | Liquid crystalline cpd, its preparation method and application containing 4-(biphenyl ethynyl)-1,8-naphthalene dintrile | |
| CN106519733B (en) | One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application | |
| JP5286704B2 (en) | Dichroic dye, and liquid crystal composition and liquid crystal element using the same | |
| CN104293356B (en) | A kind of liquid crystalline cpd is as high birefringence rate liquid crystal material or improving the application in liquid crystal host degree of birefringence | |
| CN109096188B (en) | Compound containing 4- (p-phenylethynyl) -1, 8-naphthalic anhydride, preparation method and application thereof | |
| CN106433185B (en) | Fluorescence dichroic dye of the one kind containing 3 (biphenyl acetenyls) for acenaphthene simultaneously [1,2 b] quinoxaline, its preparation method and application | |
| CN112321619B (en) | 8- (diphenylethynyl) -ester group-containing boron-fluorine pyrrole compound and synthesis and application thereof | |
| JPS6362553B2 (en) | ||
| CN109180654B (en) | Compound containing N-normal alkyl-4-phenylethynyl-1, 8-naphthalimide and preparation method and application thereof | |
| CN109097028A (en) | Ester type compound of one kind phenylacetylene base containing 4- and its preparation method and application | |
| CN109180639B (en) | Substituted naphthalimide derivative, preparation method and application thereof | |
| CN102816454B (en) | Ester group containing 1,8-naphthalimide fluorescent dichroic dye, preparation method and application thereof | |
| CN109134370B (en) | Substituted 4-phenylethynyl-1, 8-naphthalimide compound, preparation method and application thereof | |
| CN106366689A (en) | Liquid crystal property anthraquinone type bidirectional dye, film containing liquid crystal property anthraquinone type bidirectional dye, and display device containing liquid crystal property anthraquinone type bidirectional dye | |
| CN105131973B (en) | A kind of liquid-crystal compounds contained to Trifluoromethoxyphen-l, composition and its preparation method and application | |
| JP6582716B2 (en) | Dichroic dye, liquid crystal composition, and liquid crystal element | |
| JPS58157883A (en) | Dichroic dyestuff for liquid crystal and improving method for dichroism of dyestuff |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180109 Termination date: 20200918 |