CN106433185B - 一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 - Google Patents
一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 Download PDFInfo
- Publication number
- CN106433185B CN106433185B CN201610802136.3A CN201610802136A CN106433185B CN 106433185 B CN106433185 B CN 106433185B CN 201610802136 A CN201610802136 A CN 201610802136A CN 106433185 B CN106433185 B CN 106433185B
- Authority
- CN
- China
- Prior art keywords
- acetenyl
- biphenyl
- fluorescence
- liquid crystal
- dichroic dye
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 31
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000004305 biphenyl Substances 0.000 title claims abstract description 20
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000000975 dye Substances 0.000 claims abstract description 52
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 35
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000010415 tropism Effects 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- -1 normal-butyl Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- VYMOHWBFGOUYGX-UHFFFAOYSA-N 1-ethynyl-4-(4-octylphenyl)benzene Chemical group C(#C)C1=CC=C(C=C1)C1=CC=C(C=C1)CCCCCCCC VYMOHWBFGOUYGX-UHFFFAOYSA-N 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000001268 conjugating effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 206010001497 Agitation Diseases 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- DLMYHUARHITGIJ-UHFFFAOYSA-N 1-ethyl-2-phenylbenzene Chemical group CCC1=CC=CC=C1C1=CC=CC=C1 DLMYHUARHITGIJ-UHFFFAOYSA-N 0.000 description 1
- IFUOTAQBVGAZPR-UHFFFAOYSA-N 1-pentyl-4-phenylbenzene Chemical group C1=CC(CCCCC)=CC=C1C1=CC=CC=C1 IFUOTAQBVGAZPR-UHFFFAOYSA-N 0.000 description 1
- 0 Brc(c1ccc2)ccc-3*1c2-c1n*(cccc2)c2nc-31 Chemical compound Brc(c1ccc2)ccc-3*1c2-c1n*(cccc2)c2nc-31 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- PHPQHHFMRUWUJG-UHFFFAOYSA-N O=C(c1c(c2ccc3Br)c3ccc1)C2=O Chemical compound O=C(c1c(c2ccc3Br)c3ccc1)C2=O PHPQHHFMRUWUJG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WSZKUEZEYFNPID-UHFFFAOYSA-N hydrogen sulfate;quinolin-1-ium Chemical compound OS(O)(=O)=O.N1=CC=CC2=CC=CC=C21 WSZKUEZEYFNPID-UHFFFAOYSA-N 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization 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
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization 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
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Liquid Crystal (AREA)
Abstract
本发明公开了一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用,丰富了荧光二向色性染料种类;在苊醌的双羰基上缩合邻苯二胺扩大了分子的共轭体系和刚性以及共平面性有利于在主体液晶中的取向。通过偶联反应连接上联苯乙炔基团,延长分子的共轭于线性,结构新颖,原料易得,合成方法简单;获得高荧光量子产率的荧光二向色性染料;在这类荧光二向色性染料中引入不同的烷基端链增加分子在液晶中的溶解度,增强分子的线性结构进而改善染料的二向色性。
Description
技术领域
本发明涉及一类含有3-(联苯乙炔基)代苊并[1,2-b]喹恶啉的荧光二向色性染料及其应用,属于显示材料领域。
背景技术
信息化的高速发展带动了液晶平板技术和产业的发展,传统的阴极射线管(CRT)技术已经被平板显示所取代,平板显示器给人们的生活带来了革命性的变化。
“宾-主”显示是近些年来兴起的新型显示模式。“宾-主”(GH)模式是显示有色变化的工作模式,是由G.Heilmeier等与DS模式几乎同时提出来的。在向列相液晶主材料中掺杂二向色性染料,这种染料因分子方向而改变吸收光谱,具有光吸收各向异性,构成一对“宾-主”材料,对其施加电场,液晶分子发生取向而变化。“宾-主”(GH)模式就是利用改变分子取向的二色性染料光吸收来实现显示。
荧光“宾-主”型显示器是传统“宾-主”型显示器的改进,它是将荧光二向性染料应用于液晶显示中,这样不仅能改变吸收光的强度,而且发射光的强度也可以通过电场来控制,从而将发射型显示器的优点和传统液晶显示器的特点集于一体,制成更加便携的低功耗电子器件。荧光“宾-主”显示模式具有色彩明亮、暗处可视化、视角更宽、能耗更低的优点。
发明内容
为解决现有技术中存在的缺少性能良好的荧光二向色性染料的问题,本发明提供一种呈现蓝色荧光、具有高荧光量子产率、在液晶E7中表现出较好的二向色比以及有序参数、适用于液晶显示产品的荧光二向色性染料。
本发明的技术目的之一在于提供一类新型的荧光二向性染料:
一类含有3-(联苯乙炔基)代苊并[1,2-b]喹恶啉的荧光二向色性染料,所述染料具有以下的化学分子结构通式:
其中R选自甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基和正辛基中的一种。
进一步地,所述R优选自甲基、乙基和正戊基中的一种。
本发明的另一技术目的在于提供上述荧光二向色性染料的制备方法,包括以下步骤:
以苊醌为原料,先与液溴反应生成4-溴苊醌,4-溴苊醌与邻苯二胺反应生成3-溴代苊并[1,2-b]喹恶啉,再与相应的4’-乙炔基-4-烷基联苯反应生成所述荧光二向色性染料;
所述4’-乙炔基-4-烷基联苯选自4’-乙炔基-4-甲基联苯、4’-乙炔基-4-乙基联苯、4’-乙炔基-4-正丙基联苯、4’-乙炔基-4-正丁基联苯、4’-乙炔基-4-正戊基联苯、4’-乙炔基-4-正己基联苯、4’-乙炔基-4-正庚基联苯和4’-乙炔基-4-正庚辛基联苯中的一种。
具体的合成线路如下:
进一步地,苊醌与液溴反应时,一般加入过量液溴,反应完成后以饱和Na2SO3溶液除去过量的溴和溴化氢,产品经抽滤、洗涤和干燥后,以冰乙酸重结晶,即得到4-溴苊醌(化合1)。
进一步地,把1.31g(5mmol)4-溴苊醌加入100mL两口烧瓶中,加入50mL乙醇磁力搅拌均匀,然后加入邻苯二胺648mg(6mmol)加热回流反应5h后TLC检测反应完全。停止反应待反应物冷却至室温后倒入冰水中静置,抽滤、洗1涤干燥,得到化合物3-溴代苊并[1,2-b]喹恶啉(化合物2)。
进一步地,将4’-溴-4-烷基联苯和2-甲基-3-丁炔-2-醇二者按摩尔比1:1进行反应,同时加入催化量的二三苯基膦二氯化钯、三苯基膦、CuI等催化剂,用干燥三乙胺作为缚酸剂和溶剂。氮气保护条件下搅拌,加热至回流使之反应完全。减压除去三乙胺,粗产物过硅胶层析柱(洗脱剂:二氯甲烷),减压除去溶剂得白色固体(化合物3)。
进一步地,将化合物3加入到适量的无水乙醇中磁力搅拌加热使之溶解,加入过量的氢氧化钾,加热至回流,氢氧化钾逐渐溶解,跟踪监测反应的进行程度,不断补加KOH。持续回流数小时后停止反应,此时反应溶液呈褐色。冷却至室温,将反应产物倒入水里,用盐酸溶液调节pH值到中性析出大量黄色飘絮,抽滤、洗涤后干燥得4’-乙炔基-4-正烷基联苯(化合物4)。
进一步地,将化合物3和化合物4按摩尔比1:1进行反应,并加入催化量的二三苯基膦二氯化钯、三苯基膦和CuI等催化剂,无水三乙胺作溶剂,氮气保护条件下,磁力搅拌缓慢升温,回流温度下反应8h,TLC跟踪监测反应完全,减压除去溶剂,混合物过硅胶柱层析,洗脱剂是DCM,得到W。
本发明另一方面提供上述荧光二向色性染料在制造液晶显示产品中的应用。所述的液晶显示产品是宾主型液晶显示器。具体地,是用作宾体液晶染料,应用于制备宾主型液晶显示器。
本发明另一方面的目的在于提供一类宾主型液晶显示器,所述的液晶显示器以本发明所述的荧光二向性染料作为宾体液晶染料。
发明有益效果
(1)本发明以苊醌母体合成一类含有3-(联苯乙炔基)代苊并[1,2-b]喹恶啉的荧光二向色性染料,丰富了荧光二向色性染料种类;在苊醌的双羰基上缩合邻苯二胺扩大了分子的共轭体系和刚性以及共平面性有利于在主体液晶中的取向。通过偶联反应连接上联苯乙炔基团,延长分子的线性共轭长度,结构新颖,原料易得,合成方法简单;获得高荧光量子产率的荧光二向色性染料;在这类荧光二向色性染料中引入不同的烷基端链改善分子在液晶中的溶解度,增强分子的线性结构增加染料的二向色性。
(2)本发明所述染料最大发射波长为449nm,呈现蓝色荧光,在二氯甲烷中荧光量子产率为0.85-0.88。在液晶E7中表现出较好的二向色比以及有序参数。吸收有序参数为0.61-0.68,吸收二向色比为5.63-7.62,荧光有序参数为0.45-0.57,荧光二向色比为3.49-4.92,可用于宾主型液晶显示器。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
荧光二向色性染料W1的合成
(1)4-溴苊醌(化合物1)的合成
将10.02g(55mmol)苊醌加入250mL三口瓶中后用注射器量取12mL液溴加入其中,饱和NaOH溶液吸收尾气,缓慢加热到65℃,搅拌条件下反应两个小时。停止反应,将混合物冷却至室温,加入适量饱和Na2SO3溶液除去过量的溴和溴化氢至液体为无色。抽滤、洗涤至滤液显中性。粗产品干燥后用冰乙酸重结晶,得黄色固体12.34g,产率86%。熔点:236.0-236.8℃。
(2)3-溴代苊并[1,2-b]喹恶啉(化合物2)的合成
把1.31g(5mmol)4-溴苊醌加入100mL两口烧瓶中,加入50mL乙醇磁力搅拌均匀,然后加入邻苯二胺648mg(6mmol)加热回流反应5h后TLC检测反应完全。停止反应待反应物冷却至室温后倒入冰水中静置,抽滤、洗涤干燥,得到黄色固体1.53g,产率92%。
(3)2-甲基-4-(4’-乙基联苯)3-丁炔-2-甲醇(化合物3)的合成
将261.16mg(1mmol)4’-溴-4-乙基联苯和100μL(1mmol)2-甲基-3-丁炔-2-醇以及7mg二三苯基膦二氯化钯、15mg三苯基膦、8mgCuI作为催化剂分别加入50mL双口圆底烧瓶中,用15mL干燥三乙胺作为缚酸剂和溶剂。氮气保护条件下搅拌,加热至回流使之反应完全。减压除去三乙胺,粗产物过硅胶层析柱(洗脱剂:二氯甲烷),减压除去溶剂得白色固体,产率92%。
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).
熔点:103.4-104.4℃。TOF MS EI+:计算值:[C19H20]+(m/z)=206.1565,实测值:[C19H20]+(m/z)=206.1574。
(4)4’-乙炔基-4-乙基联苯(化合物4)的合成
将上步反应所制得的2-甲基-4-(4’-乙基联苯)3-丁炔-2-甲醇加入50mL双口瓶中加入20mL无水乙醇磁力搅拌加热使之溶解,加入过量的氢氧化钾,加热至回流,氢氧化钾逐渐溶解,跟踪监测反应的进行程度,不断补加KOH。持续回流数小时后停止反应,此时反应溶液呈褐色。冷却至室温,将反应产物倒入100mL水里,用盐酸溶液调节pH值到中性析出大量黄色飘絮,抽滤、洗涤后干燥得白色固体,粗产物过硅胶柱层析,洗脱剂PE,产率80%。
(5)荧光二向色性染料W1的合成及表征
在两口烧瓶中加入1mmol 3-溴代苊并[1,2-b]喹恶啉333mg,1mmol4’-乙炔基-4-乙基联苯206mg,加入7mg二三苯基膦二氯化钯、15mg三苯基膦、8mgCuI作为催化剂,无水三乙胺作溶剂,氮气保护条件下,磁力搅拌缓慢升温,回流温度下反应8h,TLC跟踪监测反应完全,减压除去溶剂,混合物过硅胶柱层析,洗脱剂是DCM,得到黄色固体300mg,产率60%。
1H NMR(400MHz,CDCl3)δ8.48(d,J=8.5Hz,1H),8.43(d,J=6.8Hz,1H),8.38(d,J=7.3Hz,1H),8.18(dd,J=6.3,2.3Hz,2H),8.04(dd,J=7.4,2.7Hz,1H),7.92–7.88(m,1H),7.78–7.69(m,4H),7.63(d,J=8.4Hz,2H),7.55(d,J=8.2Hz,2H),7.29(d,J=8.2Hz,2H),2.69(q,J=7.6Hz,2H),1.26(dd,J=15.6,8.0Hz,3H).
13C NMR(126MHz,CDCl3)δ154.05(s),153.49–153.23(m),144.06(s),141.53(s),141.22(t,J=11.9Hz),137.47(s),137.01(s),136.05(s),132.39(s),132.23(s),131.49(s),130.17(s),129.56(s),128.44(s),128.06(s),126.92(d,J=3.4Hz),123.61(s),122.22(s),121.33(s),97.08(s),87.38(s),58.39(s),15.54(s).
熔点:172.4-173.8℃。TOF MS EI+:计算值:[C34H22N2]+(m/z)=458.5519,实测值:[C34H22N2]+(m/z)=458.1785。
实施例2
荧光二向色性染料W2的合成
除了把步骤(3)中的4’-溴-4-乙基联苯换成4’-溴-4-正戊基联苯,步骤(4)中的2-甲基-4-(4’-乙基联苯)3-丁炔-2-甲醇换成2-甲基-4-(4’-正戊基联苯)3-丁炔-2-甲醇,步骤(5)中用4’-乙炔基-4-正戊基联苯和化合物2反应生成W2,其他操作步骤同实例1,得到目标产物W2为亮黄色固体,
产率71%。
1H NMR(400MHz,CDCl3)δ8.48(dd,J=15.8,7.6Hz,2H),8.40(d,J=7.3Hz,1H),8.26–8.18(m,2H),8.06(d,J=7.3Hz,1H),7.97–7.89(m,1H),7.82–7.72(m,4H),7.68(d,J=8.2Hz,2H),7.59(d,J=8.0Hz,2H),7.31(d,J=8.1Hz,2H),2.74–2.63(m,2H),1.68(dd,J=14.9,7.2Hz,2H),1.46–1.33(m,4H),0.94(t,J=6.7Hz,3H).
13C NMR(126MHz,CDCl3)δ154.12(s),153.43(s),142.81(s),141.57(s),141.33(s),141.17(s),137.43(s),136.13(s),132.43(s),132.25(s),132.01(s),131.57(s),130.24(s),129.60(s),129.24(s),129.21(s),129.11(s),128.99(s),128.11(s),126.89(d,J=6.8Hz),123.66(s),122.24(s),121.28(s),97.12(s),87.39(s),58.43(s),35.62(s),31.57(s),22.58(s),14.06(s).
熔点:195.1-196.6℃。TOF MS EI+:计算值:[C37H28N2]+(m/z)=500.6316,实测值:[C37H28N2]+(m/z)=500.2260。
本发明的荧光二向色性染料的性质测定:
(1)染料在二氯甲烷中的光谱性质测试:
染料测试浓度:无特别说明时染料在不同溶剂中的浓度均为1.0×10-5mol/L。分别精确称取1.0×10-2mmol(±0.1mg)实施例1~2制备的W系列染料,放入体积为10mL容量瓶后用CH2Cl2定容,得到浓度为1.0×10-3mol/L备用溶液。移取备用溶液100μL于10mL容量瓶中,待溶剂挥发完全后用其他待测的溶剂定容,得到1.0×10-5mol/L的溶液,用于紫外吸收、荧光光谱测试。本发明中以二氯甲烷定容。
染料荧光量子产率ΦF值的测定:以浓度1.0×10-5mol/L,ΦF值为0.55的硫酸喹咛溶液(5.0×10-2mol/L硫酸水溶液中)为基准。为防止染料在高浓度条件下荧光猝灭,测试时染料溶液的吸光度控制在0.02-0.05范围内。所需参数在同一测试条件下测得,代入式(1)计算:
式中:Φ(sample)、Φ(standard)分别代表样品、标准物的ΦF值;Abs(standard)、Abs(sample)分别代表激发波长下标准物、样品的吸光度;Flu(sample)和Flu(standard)分别代表样品、标准物的荧光光谱积分面积。
对化合物W1-W2的测试结果如下:
表1.染料W1-W2在二氯甲烷中的紫外和荧光数据
合成的目标产物W1-W2最大发射波长在449nm,呈现蓝色荧光,发射半峰宽较窄,为69nm左右,用于宾主显示器可实现纯色显示;荧光量子产率较高,在0.85-0.88之间,满足实际应用要求。
(2)染料在液晶中的偏振光谱性质测试:
主体液晶:液晶E7具有较宽的、稳定的向列相范围(-10-60℃),好的化学稳定性,高的正介电各向异性作为主体液晶。
液晶盒:测试用液晶盒上下两基板的取向相互平行,盒厚度为15μm。
二向色比、有序参数的测定:将染料W按照质量浓度为0.5%(w/w)的比例掺入到液晶中,在室温下混合均匀,然后将该混合物装入平行液晶盒,封住灌晶口。分别测试染料与液晶盒取向膜平行方向上的吸光度A‖和垂直方向上的吸光度A⊥、平行方向上的荧光强度F‖和垂直方向上的荧光强度F⊥;并按照下列公式(2)、(3)、(4)、(5)计算出染料在液晶中的吸收有序参数SA、二向色比DA和荧光有序参数SF、二向色比DF:
染料W1-W2偏振光谱测试结果如下:
表2.染料W1-W2在液晶E7中的偏振紫外和偏振荧光数据
合成的目标产物在液晶E7中表现出较好的二向色比以及有序参数。吸收有序参数为0.61-0.68,吸收二向色比为5.63-7.62,荧光有序参数为0.45-0.57,荧光二向色比为3.49-4.92,用于宾主型液晶显示器。
Claims (5)
1.一类含有3-(联苯乙炔基)代苊并[1,2-b]喹恶啉的荧光二向色性染料,其特征在于:所述染料具有以下的化学分子结构通式:
其中R选自甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基和正辛基中的一种。
2.如权利要求1所述的荧光二向色性染料的制备方法,包括以下步骤:
以苊醌为原料,先与液溴反应生成4-溴苊醌,4-溴苊醌与邻苯二胺加热回流反应生成3-溴代苊并[1,2-b]喹恶啉,再与相应的4’-乙炔基-4-烷基联苯反应生成所述荧光二向色性染料;
所述4’-乙炔基-4-烷基联苯选自4’-乙炔基-4-甲基联苯、4’-乙炔基-4-乙基联苯、4’-乙炔基-4-正丙基联苯、4’-乙炔基-4-正丁基联苯、4’-乙炔基-4-正戊基联苯、4’-乙炔基-4-正己基联苯、4’-乙炔基-4-正庚基联苯和4’-乙炔基-4-正辛基联苯中的一种。
3.如权利要求1所述的荧光二向色性染料在制造液晶显示产品中的应用。
4.根据权利要求3所述的应用,其特征在于所述的液晶显示产品是宾主型液晶显示器。
5.一类宾主型液晶显示器,其特征在于以权利要求1所述的荧光二向性染料作为宾体液晶二向性染料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610802136.3A CN106433185B (zh) | 2016-09-05 | 2016-09-05 | 一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610802136.3A CN106433185B (zh) | 2016-09-05 | 2016-09-05 | 一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106433185A CN106433185A (zh) | 2017-02-22 |
CN106433185B true CN106433185B (zh) | 2018-01-30 |
Family
ID=58163827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610802136.3A Expired - Fee Related CN106433185B (zh) | 2016-09-05 | 2016-09-05 | 一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106433185B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109096188B (zh) * | 2018-08-31 | 2021-06-22 | 大连理工大学 | 一类含有4‐(对联苯乙炔基)‐1,8‐萘酐的化合物,其制备方法及应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101514262A (zh) * | 2009-03-19 | 2009-08-26 | 大连理工大学 | 一类苊并吡嗪染料及其在染料敏化太阳能电池上的应用 |
US20100047485A1 (en) * | 2007-11-30 | 2010-02-25 | Nitto Denko Corporation | Polarizing film |
CN103435560A (zh) * | 2013-08-01 | 2013-12-11 | 大连理工大学 | 一类带柔性侧链的苊并[1,2-b]喹喔啉衍生物的合成及其应用 |
CN104293356A (zh) * | 2014-07-28 | 2015-01-21 | 大连理工大学 | 一种液晶化合物作为高双折射率液晶材料或在提高液晶主体双折射率中的应用 |
CN104357063A (zh) * | 2014-07-28 | 2015-02-18 | 大连理工大学 | 含有4-(联苯乙炔基)-1,8-萘二腈的液晶化合物,其制备方法及应用 |
-
2016
- 2016-09-05 CN CN201610802136.3A patent/CN106433185B/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100047485A1 (en) * | 2007-11-30 | 2010-02-25 | Nitto Denko Corporation | Polarizing film |
CN101514262A (zh) * | 2009-03-19 | 2009-08-26 | 大连理工大学 | 一类苊并吡嗪染料及其在染料敏化太阳能电池上的应用 |
CN103435560A (zh) * | 2013-08-01 | 2013-12-11 | 大连理工大学 | 一类带柔性侧链的苊并[1,2-b]喹喔啉衍生物的合成及其应用 |
CN104293356A (zh) * | 2014-07-28 | 2015-01-21 | 大连理工大学 | 一种液晶化合物作为高双折射率液晶材料或在提高液晶主体双折射率中的应用 |
CN104357063A (zh) * | 2014-07-28 | 2015-02-18 | 大连理工大学 | 含有4-(联苯乙炔基)-1,8-萘二腈的液晶化合物,其制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106433185A (zh) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106433186B (zh) | 一类含有4‑联苯乙炔苊并[1,2‑b]吡嗪‑8,9‑二腈的荧光二向色性染料,其制备方法及应用 | |
CN106520139B (zh) | 含有4-(联苯乙炔基)-1,8萘酰亚胺类液晶化合物,其制备方法及应用 | |
US11629157B2 (en) | Fluoro-boron pyrrole liquid crystal compounds containing 8-(bisphenylethynyl)-ester group flexible multiple ring, preparation method and use thereof | |
CN104449669A (zh) | 一种多芳基取代咪唑荧光探针及其制备方法和在检测g-四链体结构中的应用 | |
JP6792899B1 (ja) | フェニルエチニルボロンジピロメテン系蛍光二色性液晶化合物及びその使用 | |
CN106336350B (zh) | 含氟二萘乙炔液晶化合物及其制备方法和应用 | |
CN106433185B (zh) | 一类含有3‑(联苯乙炔基)代苊并[1,2‑b]喹恶啉的荧光二向色性染料,其制备方法及应用 | |
CN109336814B (zh) | 一类含有4‐(烷基双环己基)取代的萘酰亚胺衍生物,其制备方法及应用 | |
CN106478599B (zh) | 一类含有4-哌嗪基-1,8-萘酰亚胺的荧光二向色性染料,其制备方法及应用 | |
CN104357063B (zh) | 含有4-(联苯乙炔基)-1,8-萘二腈的液晶化合物,其制备方法及应用 | |
CN102719111B (zh) | 一类含酰胺键的1,8-萘二腈类荧光二向性染料、其制备方法及应用 | |
CN102757662B (zh) | 一类含酰肼键的1,8-萘酰亚胺类荧光二向性染料,其制备方法及应用 | |
CN104293356B (zh) | 一种液晶化合物作为高双折射率液晶材料或在提高液晶主体双折射率中的应用 | |
CN108277019A (zh) | 一种反式环己基类液晶化合物的制备方法 | |
CN109096188B (zh) | 一类含有4‐(对联苯乙炔基)‐1,8‐萘酐的化合物,其制备方法及应用 | |
CN112321619B (zh) | 一类含有8-(双苯乙炔基)-酯基的氟硼吡咯化合物及其合成和应用 | |
CN106519733B (zh) | 一类含3位取代基的苯绕蒽酮液晶染料,其制备方法及应用 | |
CN104212461A (zh) | 对称的***类棒状液晶化合物及其制备方法 | |
CN109097028A (zh) | 一类含4-苯乙炔基的酯类化合物及其制备方法和应用 | |
JPS6362553B2 (zh) | ||
CN102816454B (zh) | 一类含酯基的1,8-萘酰亚胺类荧光二向性染料、其制备方法及应用 | |
CN109180639B (zh) | 一类取代的萘酰亚胺衍生物,其制备方法及应用 | |
CN109180654B (zh) | 一类含有n‐正烷基‐4‐苯乙炔基‐1,8‐萘酰亚胺的化合物及其制备方法和应用 | |
CN109134370B (zh) | 一类含有取代的4-苯乙炔基-1,8-萘酰亚胺化合物,其制备方法及应用 | |
CN107652705B (zh) | 糖分子偶联二酮吡咯并吡咯化合物在塑料用红颜料制备中的应用、塑料用红颜料及制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into 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: 20180130 Termination date: 20200905 |