WO2020143842A1 - 含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶化合物，其制备方法及其应用 - Google Patents

含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶化合物，其制备方法及其应用 Download PDF

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WO2020143842A1
WO2020143842A1 PCT/CN2020/073718 CN2020073718W WO2020143842A1 WO 2020143842 A1 WO2020143842 A1 WO 2020143842A1 CN 2020073718 W CN2020073718 W CN 2020073718W WO 2020143842 A1 WO2020143842 A1 WO 2020143842A1
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liquid crystal
dicyclohexyl
ethynyl
ester
methanol
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French (fr)
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李晓莲
潘柔辰
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大连理工大学
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    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
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    • C09K19/404—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing boron or phosphorus
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    • C09K2019/0433—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being a luminescent or electroluminescent unit
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    • C09K2323/031—Polarizer or dye

Definitions

  • the invention relates to a kind of fluoroboron pyrrole liquid crystal compound containing 8-(bisphenylethynyl)-ester group flexible multi-ring, its preparation method and application, and belongs to the field of display materials.
  • the liquid crystal display panel is at a high-end position, and it is also a key component in digital products such as computers and mobile communication terminals.
  • the innovation of display technology can drive the development of information technology. Therefore, it is particularly important to strengthen the in-depth research on liquid crystal display panels .
  • the "guest-host” display is a new display mode that has emerged in recent years.
  • the "Guest-Master” (GH) mode is a working mode that displays colored changes and was proposed by G. Heilmeier et al. and the DS mode almost simultaneously. Doping some dichroic dyes in the nematic liquid crystal host material constitutes a pair of “guest-host” materials, applying an electric field to them, the orientation of the liquid crystal molecules changes.
  • "Guest-host” (GH) mode is to use dichroic dye light absorption to change the molecular orientation to achieve display.
  • Fluorescent "guest-host” display is an improvement of the traditional “guest-host” display, it is the use of fluorescent dichroic dyes in liquid crystal displays, so that not only the intensity of light absorption, but also the intensity of the emitted light can also pass through the electric field To control, so as to integrate the advantages of the emissive display and the characteristics of the traditional liquid crystal display, making a more portable low-power electronic device.
  • a simple liquid crystal material can no longer satisfy various characteristics of liquid crystal display, such as low light source utilization, thick display panel, and slow response time. Therefore, it has become an obvious trend to use liquid crystal compounds and dyes to compound liquid crystal materials to obtain more superior liquid crystal materials.
  • the compounded liquid crystal dye can obtain higher and more stable liquid crystal phase temperature range, higher contrast and faster response time.
  • the present invention provides a green fluorescence, higher molar coefficient, better dichroic ratio and order in liquid crystal Parameters, fluorescent dichroic dyes suitable for liquid crystal display products and can improve response time.
  • One of the technical objectives of the present invention is to provide a new class of fluorescent dichroic dyes.
  • R is selected from propyl dicyclohexylmethyl, butyl dicyclohexylmethyl, pentyl dicyclohexylmethyl, propyl dicyclohexylethyl, butyl dicyclohexyl One of ethyl, pentyl dicyclohexylethyl, and cholesteryl.
  • R is preferably one of pentylbicyclohexylmethyl, propylbicyclohexylethyl and cholesteryl.
  • Another technical object of the present invention is to provide a method for preparing the above fluorescent dichroic dye, including the following steps:
  • the compound 4 is selected from 4-ethynylphenylpropyl dicyclohexyl methanol ester, 4-ethynyl phenylbutyl dicyclohexyl methanol ester, 4-ethynyl phenylpentyl dicyclohexyl methanol ester, 4-ethynyl phenylpropyl group One of dicyclohexyl methyl methanol ester, 4-ethynyl phenylbutyl dicyclohexyl methyl methanol ester, 4-ethynyl phenylpentyl dicyclohexyl methyl methanol ester, and 4-ethynyl benzene cholesteryl ester.
  • the compound 1 and trimethylsilylacetylene were reacted at a molar ratio of 1:1, and at the same time, a catalytic amount of bistriphenylphosphine palladium dichloride, triphenylphosphine, CuI and other catalysts were added, and dried three Ethylamine acts as an acid binding agent and solvent. It was heated to reflux under nitrogen protection, followed by TLC monitoring until the reaction was completely depressurized to remove excess solvent. The solid product was subjected to silica gel column chromatography to obtain a light yellow oil (Compound 2).
  • One of cholesterol is fed in a molar ratio of 1:1, using dichloromethane as a solvent and adding 1.5 times the equivalent of dicyclohexylcarbodiimide (DCC) and catalytic amount of 4-dimethylaminopyridine (DMAP)
  • DCC dicyclohexylcarbodiimide
  • DMAP 4-dimethylaminopyridine
  • a molar ratio of p-iodobenzoyl chloride and 2,4-dimethylpyrrole at 1:2 is reacted at room temperature, after 6 hours, a catalytic amount of triethylamine is added, and after half an hour, an appropriate amount of boron trifluoride is added Diethyl ether, followed by TLC monitoring until the reaction was completely under reduced pressure to remove excess solvent.
  • the crude product of reddish brown solid was subjected to silica gel column chromatography to obtain a red solid (Compound 5).
  • compound 4 and compound 5 are mixed in a 1:1 molar ratio, while adding catalytic amounts of catalysts such as ditriphenylphosphine palladium dichloride, triphenylphosphine, CuI, etc., and using dry triethylamine as the acid binding agent And solvent.
  • the reaction was refluxed under nitrogen for 8-10 hours.
  • the invention provides an application of the above-mentioned compound as a fluorescent dichroic dye.
  • the dye compound of the present invention also has a liquid crystal phase and can also be added to the liquid crystal host as a liquid crystal component to increase the response time of the liquid crystal host.
  • the liquid crystal body is smectic liquid crystal, nematic liquid crystal or cholesteric liquid crystal.
  • the present invention provides an application of the above compound as a liquid crystal dye.
  • the liquid crystal display product is a guest-host type liquid crystal display. Specifically, it is used as a guest liquid crystal dye, and is used to prepare a guest-host liquid crystal display.
  • a further object of the present invention is to provide a class of guest-host liquid crystal displays that use the fluorescent dichroic dyes of the present invention as guest liquid crystal dyes.
  • the invention provides an application of the above compound as a liquid crystal material; the liquid crystal material is a color liquid crystal material.
  • the compound of the present invention is added as a guest dye to the host liquid crystal E7, and the flexible multi-element structure therein is beneficial to reduce the response time of the host liquid crystal;
  • the fluorescent dichroic dye of the present invention has a high dichroic ratio and order parameters in the liquid crystal, of which the dichroic ratio is 8.91 at the maximum and the order parameter is at most 0.725, which can be used to manufacture the guest-host liquid crystal display as the guest Liquid crystal dye.
  • Example 3 is a differential thermal scanning calorimetry diagram of the liquid crystal compound DC1 prepared in Example 1;
  • Example 4 is a differential thermal scanning calorimetry diagram of the liquid crystal compound DC2 prepared in Example 2;
  • FIG. 6 is a response time diagram of the liquid crystal compound guest dye DC1 prepared in Example 1 in the host liquid crystal E7;
  • FIG. 7 is a response time diagram of the liquid crystal compound guest dye DC2 prepared in Example 2 in the host liquid crystal E7;
  • FIG. 8 The response time graph of the liquid crystal compound guest dye DC3 prepared in Example 3 in the host liquid crystal E7.
  • pentyl dicyclohexyl methanol, propyl dicyclohexyl methyl methanol, and cholesterol raw materials are purchased.
  • step (4) propyl biscyclohexyl methyl methanol is used to replace pentyl biscyclohexyl methanol
  • step (6) 4-ethynyl phenylpropyl biscyclohexyl methyl methanol ester is used to replace 4-ethynyl phenylpentane
  • the other operation steps are the same as in Example 1, to obtain 427 mg of a red solid with a yield of 62%.
  • step (4) cholesterol is substituted for amylbiscyclohexyl methanol
  • step (6) 4-ethynylbenzenecholesterol is substituted for 4-ethynylbenzenepentylbicyclohexyl methanol ester.
  • step (6) 4-ethynylbenzenecholesterol is substituted for 4-ethynylbenzenepentylbicyclohexyl methanol ester.
  • Example 1 560 mg of a red solid was obtained with a yield of 67%.
  • Test concentration The concentration of the liquid crystal compound in different solvents is 1.0 ⁇ 10 -5 mol/L. Accurately weigh 1.0 ⁇ 10 -2 mmol of the prepared liquid crystal compound ( ⁇ 0.1mg), place it in a volumetric flask of 10mL and dilute with CH 2 Cl 2 to obtain a standby solution with a concentration of 1.0 ⁇ 10 -3 mol/L. Pipette 100 ⁇ L of the standby solution into a 10 mL volumetric flask. After the solvent has evaporated completely, dilute with other solvents to obtain a 1.0 ⁇ 10 -5 mol/L solution for UV absorption and fluorescence spectrum testing.
  • ⁇ (sample) and ⁇ (standard) represent the ⁇ F value of the sample and standard respectively
  • Abs (standard) and Abs (sample) represent the absorbance of the standard and sample at the excitation wavelength
  • Flu (sample) and Flu (standard) represents the fluorescence intensity of the sample and standard, respectively.
  • the synthesized target product DC1-DC3 emits green fluorescence at about 517nm, with a half-emission width of about 27nm, and high color recognition. It can be used for guest-host mode to achieve pure color display; the fluorescence quantum yield is about 0.32 -0.37; the molar extinction coefficient is 10 4.72 -10 4.93 .
  • Liquid crystal E7 has a wide and stable nematic phase range (-10-60°C), good chemical stability, and high positive dielectric anisotropy as the host liquid crystal.
  • Liquid crystal cell The orientation of the upper and lower substrates of the test liquid crystal cell is parallel to each other, and the cell thickness is 20 ⁇ m.
  • the liquid crystal compound DC is incorporated into the liquid crystal at a mass concentration of 0.5% (w/w), mixed uniformly at room temperature, and then the mixture is filled into a parallel liquid crystal cell, Seal the crystal gate.
  • the synthesized target compound DC series shows a good dichroic ratio and order parameters in the host liquid crystal E7.
  • the dichroic ratio of DC1 is as high as 8.16, and the maximum absorption order parameter is 0.73.
  • its fluorescence dichroic ratio and fluorescence order parameter are also the highest values, which are 8.16 and 0.70, respectively. Meet the actual requirements for the dichroic color ratio in the guest-host display mode.
  • the prepared liquid crystal dye DC series compounds were subjected to differential thermal scanning to obtain the differential thermal scanning calorimeter.
  • the mesophase appears during heating and cooling.
  • Compound DC1 exhibited a liquid crystal phase at 218-274.3°C during heating, a liquid crystal phase at 98-271°C during cooling, and a mesophase range of approximately 150°C; for compound DC2, liquid crystal appeared at 161-237°C during heating Phase, when cooling, a liquid crystal phase range as wide as 100°C appears at 156-266°C; while for compound DC3, the mesophase appears only during heating, in the range of 251-272°C.
  • the main liquid crystal is E7; the orientation of the upper and lower substrates of the test liquid crystal cell is parallel to each other, the cell thickness is 10 ⁇ m; the liquid crystal dye DC is incorporated into the main liquid crystal at a ratio of 0.5% (w/w) mass concentration In E7, the effect of the guest dye DC on the host liquid crystal E7 was tested separately.
  • Green light with a wavelength of 510 nm is used as the light source, and the transmission of the light source is collected by the detector.
  • the fluorescent dichroic liquid crystal dye DC can change the response time of the liquid crystal.
  • DC can shorten the response time of the host liquid crystal E7.
  • the fastest response time is the host liquid crystal E7 doped with DC1.

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  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一类含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶染料，其制备方法及应用。本发明以氟化硼络合二吡咯甲川为母体，通过Sonogashira偶联反应在8号位引入双苯乙炔刚性结构，将双环己烷、胆甾醇等柔性多元环利用酯化反应与双苯乙炔基连接，设计合成了一系列8-(双苯乙炔基)-酯基柔性多元环的BODIPY类二向色性染料。本发明化合物在二氯甲烷中最大发射波长均集中在525nm左右，呈现绿色荧光，在液晶E7中表现出良好的二向色比及有序参数；本发明的液晶化合物在100-280℃范围内存在液晶中间相，可用于制造液晶显示产品，尤其是作为宾体染料用于宾主模式液晶显示器；本发明化合物添加至E7液晶并用于宾主显示模式时可提高响应时间，达到快速响应的效果。

Description

含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶化合物，其制备方法及其应用 技术领域
本发明涉及一类含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶化合物，其制备方法及其应用，属于显示材料领域。
背景技术
在电子信息产业链中液晶显示面板处于高端地位，也是计算机以及移动通信终端等数字化产品中较为关键的部件，显示技术的推陈出新能够带动信息化的发展，因此加强对液晶显示面板的深化研究尤为重要。
“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一些二向色性染料构成一对“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。
单纯的液晶材料已经不能满足液晶显示的各种特性，如光源利用率低、显示面板厚、响应时间慢等。于是利用液晶化合物和染料来复配液晶材料借以获得性能更加优越的液晶材料成为一个很明显的趋势。复配的液晶染料可以获得 更高更稳定的液晶相温度范围、更高的对比度以及更快的响应时间。
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，本发明提供一种呈绿色荧光、摩尔系数较高、在液晶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且能提高响应时间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8-(双苯乙炔基)-酯基柔性多元环的BODIPY类荧光二向色性染料，所述染料具有以下化学分子通式B：
Figure PCTCN2020073718-appb-000001
进一步地，所述的荧光二向性液晶染料，R选自丙基双环己基甲基、丁基双环己基甲基、戊基双环已基甲基、丙基双环已基乙基、丁基双环己基乙基、戊基双环己基乙基、胆甾醇基中的一种。R优选戊基双环已基甲基、丙基双环已基乙基、胆甾醇基中的一种。
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2,4-二甲基吡咯和对碘苯甲酰氯为基本原料合成氟化硼络合二吡咯甲川类母体，再以对碘苯甲酸为原料与三甲基硅乙炔进行Sonogashira偶联合成对乙炔基苯甲酸。然后通过酯化将对乙炔基苯甲酸分别与丙基双环己基甲醇、丁基双环己基甲醇、戊基双环已基甲醇、丙基双环已基甲基甲醇、丁基双环己基甲基甲醇、戊基双环己基甲基甲醇、胆甾醇反应连接，再通过Sonogashira偶联反应将化合物4分别与氟化硼络合二吡咯甲川类母体连接形成双苯乙炔线性结构，生成所述荧光二向色性染料。
所述化合物4选自4-乙炔基苯丙基双环己基甲醇酯、4-乙炔基苯丁基双环己基甲醇酯、4-乙炔基苯戊基双环已基甲醇酯、4-乙炔基苯丙基双环已基甲基甲醇酯、4-乙炔基苯丁基双环己基甲基甲醇酯、4-乙炔基苯戊基双环己基甲基甲醇酯、4-乙炔基苯胆甾醇酯中的一种。
具体合成路径如下：
Figure PCTCN2020073718-appb-000002
进一步地，将对碘苯甲酸和乙醇二者按摩尔比1：3进行反应，同时加入催化量的浓硫酸，加热至回流反应4h后，TLC跟踪监测至反应完全，倒入水中用二氯甲烷萃取，减压除去多余溶剂，得淡黄色油状物(化合物1)。
进一步地，将化合物1和三甲基硅乙炔二者按摩尔比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。氮气保护下加热至回流，TLC跟踪监测至反应完全减压除去多余溶剂，固体产物过硅胶柱层析，得淡黄色油状物(化合物2)。
进一步地，用乙醇作溶剂，向所得化合物2中加入过量的氢氧化钾，持续回流数小时后停止反应，此时反应溶液呈黄色。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，抽滤、洗涤后干燥得白色固体，粗产物过硅胶层析柱得4-乙炔基-苯甲酸(化合物3)。
进一步地，将化合物3与丙基双环己基甲醇、丁基双环己基甲醇、戊基双环已基甲醇、丙基双环已基甲基甲醇、丁基双环己基甲基甲醇、戊基双环己基甲基甲醇、胆甾醇中的一种按照摩尔比1:1投料，以二氯甲烷为溶剂并加入1.5倍当量的二环己基碳二亚胺(DCC)和催化量的4-二甲氨基吡啶(DMAP)，常温反应24小时，减压除去多余溶剂，固体产物过硅胶柱层析，得纯白色固体(化合物4)。
进一步地，将对碘苯甲酰氯和2,4-二甲基吡咯按摩尔比1：2在常温下反应，6小时后加入催化量的三乙胺，再过半小时加入适量的三氟化硼乙醚，TLC跟踪监测至反应完全减压除去多余溶剂，红褐色固体粗产物过硅胶柱层析，得红色固体(化合物5)。
进一步地，化合物4与化合物5以1：1摩尔比进行混合，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。氮气保护下回流反应8-10小时，将混合物冷却至室温，减压旋干，过硅胶柱分离(洗脱剂为CH 2Cl 2：PE＝1：3)得固体化合物DC1-DC3即所述液晶染料。
本发明提供一种上述的化合物作为荧光二向色性染料的应用。
本发明的染料化合物还具有液晶相，并且还可作为液晶组分，添加至液晶主体中提高液晶主体的响应时间。所述的液晶主体为近晶相液晶、向列相液晶或者胆甾相液晶。
本发明提供一种上述化合物作为液晶染料的应用。
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。
本发明再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。
本发明提供一种上述的化合物作为液晶材料的应用；所述液晶材料为彩色液晶材料。
本发明的有益效果：
第一、以BODIPY为母体，合成同时含有双苯乙炔的刚性结构和酯基官能团的多元柔性环类液晶染料，结构新颖，丰富了荧光二向性染料的种类；
第二、通过修饰BODIPY的8号位，保留了BODIPY类荧光染料优异的光化学物理性能，如较高的摩尔消光系数、单色性良好的荧光和较高的光稳定性等；
第三、在含(双苯乙炔基)-酯基柔性多元环结构中引入含氟的BODIPY结构，有利于降低化合物的粘度、提高二向色比、有序参数和介电各向异性等；
第四、将本发明中的化合物作为宾体染料加入主体液晶E7，其中的柔性多元环结构有利于降低主体液晶的响应时间；
本发明的荧光二向性染料在液晶中具有较高的二向色比以及有序参数，其 中二向色比最大为8.91，有序参数最大为0.725，可用于制造宾主液晶显示器，作为宾体液晶染料。
附图说明
图1为实施例1-3制备的DC1-DC3在二氯甲烷中的紫外吸收图；
图2为实施例1-3制备的DC1-DC3在二氯甲烷中的荧光光谱图；
图3为实施例1制备的液晶化合物DC1的差热扫描量热图；
图4为实施例2制备的液晶化合物DC2的差热扫描量热图；
图5为实施例3制备的液晶化合物DC3的差热扫描量热图；
图6为实施例1制备的液晶化合物宾体染料DC1在主体液晶E7中的响应时间图；图7为实施例2制备的液晶化合物宾体染料DC2在主体液晶E7中的响应时间图；图8为实施例3制备的液晶化合物宾体染料DC3在主体液晶E7中的响应时间图。
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。
其中，戊基双环已基甲醇、丙基双环已基甲基甲醇、胆甾醇原料为购买所得。
实施例1
液晶染料DC1的合成
(1)对碘苯甲酸乙酯(化合物1)的合成
Figure PCTCN2020073718-appb-000003
将2.48g对碘苯甲酸和20ml乙醇加入到50ml双口圆底烧瓶中进行反应，同时加入催化量的浓硫酸，加热至回流，TLC跟踪监测至反应完全，倒入水中萃取用二氯甲烷，减压除去多余溶剂，得淡黄色油状物2.76g，产率85％。
(2)4-三甲基硅乙炔基-苯甲酸乙酯(化合物2)的合成
Figure PCTCN2020073718-appb-000004
将276mg(8.5mmol)对碘苯甲酸乙酯和2mL(10mmol)三甲基硅乙炔以及70mg二三苯基膦二氯化钯、150mg三苯基膦、80mgCuI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：DCM：PE＝1:5)，减压除去溶剂得1.88g白色固体4-三甲基硅乙炔基-苯甲酸乙酯，产率90％。
(3)4—乙炔基苯甲酸(化合物3)的合成
Figure PCTCN2020073718-appb-000005
用乙醇作溶剂，向所得化合物2中加入3倍当量的氢氧化钾，持续回流数小时后停止反应，此时反应溶液呈黄色。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，抽滤、洗涤后干燥得白色固体，粗产物过硅胶层析柱得4-乙炔基-苯甲酸1.06g，产率92％。
(4)4-乙炔基苯戊基双环已基甲醇酯(化合物4)的合成
Figure PCTCN2020073718-appb-000006
将146mg化合物3与252mg戊基双环已基甲醇投入到50ml双口圆底烧瓶，以二氯甲烷为溶剂并加入1.5倍当量的二环己基碳二亚胺(DCC)和催化量的4-二甲氨基吡啶(DMAP)，常温反应24小时，减压除去多余溶剂，固体产物过硅胶柱层析，得纯白色固体345mg，产率为91％。
(5)8-碘-BODIPY(化合物5)的合成
Figure PCTCN2020073718-appb-000007
将2.65g对碘苯甲酰氯和3ml的2,4-二甲基吡咯在常温下反应6小时后，加入4ml的三乙胺，再过半小时加入9ml的三氟化硼乙醚，TLC跟踪监测至反应完全减压除去多余溶剂，红褐色固体粗产物过硅胶柱层析，洗脱剂为DCM:PE＝1:6，减压除去溶剂得红色固体3.6g，产率80％。
(6)目标化合物DC1和合成与表征
Figure PCTCN2020073718-appb-000008
在50mL双口圆底烧瓶中加入450mg(1mmol)4-碘-BODIPY(化合物5)，380mg(1mmol)化合物4，18mg PdCl 2(PPh 3) 2，13mg PPh 3，10mg CuI，以20mL无水三乙胺作为溶剂，氮气保护下回流反应8小时，TLC检测反应完全，将混合物冷却至室温，旋干，过硅胶柱分离(洗脱剂为DCM：PE＝5：1)，得橙色固体393mg，产率：56％。
1H NMR(400MHz,CDCl 3)δ8.04(d,J＝8.3Hz,1H),7.68(d,J＝8.1Hz,1H),7.60(d,J＝8.3Hz,1H),7.31(d,J＝8.1Hz,1H),5.99(s,1H),4.97–4.81(m,1H),2.56(s,3H),2.13(d,J＝9.7Hz,1H),1.83(d,J＝11.9Hz,1H),1.75(t,J＝13.9Hz,2H),1.49(d,J＝11.7Hz,1H),1.43(s,3H),1.35–1.19(m,4H),1.17–1.08(m,3H),1.08–0.91(m,2H),0.88(t,J＝6.9Hz,2H).
13C NMR(101MHz,CDCl 3)δ165.49(s),155.85(s),142.96(s),140.64(s),135.46(s),132.46(s),131.34(d,J＝27.3Hz),129.58(s),128.35(s),127.19(s),123.64(s),121.43(s),91.25(s),90.09(s),74.68(s),42.77(s),42.30(s),37.85(s),37.44(s),33.56(s),32.25(s),32.03(s),30.23(s),27.97(s),26.68(s),22.73(s),14.61(s),14.14(s).
熔点：218℃,清亮点：274.3℃。TOF MS EI +：计算值：ESI+MS(M+H)：C 45H 53BF 2N 2O 2，计算值：702.4221，实测值：702.4158。
实施例2
液晶染料DC2的合成
除步骤(4)中用丙基双环已基甲基甲醇代替戊基双环已基甲醇，步骤(6)中用4-乙炔基苯丙基双环已基甲基甲醇酯代替4-乙炔基苯戊基双环已基甲醇酯外，其它操作步骤同实施例1，得到红色固体427mg，产率62％。
1H NMR(400MHz,CDCl 3)δ8.05(d,J＝8.3Hz,1H),7.69(d,J＝8.1Hz,1H),7.61(d,J＝8.3Hz,1H),7.32(d,J＝8.1Hz,1H),5.99(s,1H),4.14(d,J＝6.4Hz,1H),2.56(s,3H),1.88(s,1H),1.78(d,J＝8.8Hz,2H),1.71(d,J＝13.8Hz,2H),1.43(s,3H),1.29(dt,J＝15.3,7.7Hz,2H),1.18–1.11(m,2H),1.04(d,J＝15.1Hz,3H),1.01–0.91(m,1H),0.87(t,J＝7.3Hz,2H).
13C NMR(101MHz,CDCl 3)δ161.29(s),151.10(s),138.20(s),135.88(s),130.74(s),127.71(s),126.80(s),125.54(s),124.83(s),123.60(s),122.59(s),118.87(s),116.67(s),86.60(s),85.28(s),65.65(s),55.65(s),48.69(s),38.63(s),38.49(s),35.08(s),32.85(d,J＝7.3Hz),28.85(s),25.30(d,J＝6.6Hz),24.60(s),15.30(s),9.86(s),9.69(s).
熔点：161℃，清亮点：237℃。ESI+MS(M+H)：C 44H 51BF 2N 2O 2，计算值：688.4001，实测值：688.4014。
实施例3
液晶染料DC3的合成
除步骤(4)中用胆甾醇代替戊基双环已基甲醇，步骤(6)中用4-乙炔基苯胆甾醇酯代替4-乙炔基苯戊基双环已基甲醇酯外，其它操作步骤同实施例1，得到红色固体560mg，产率67％。
1H NMR(400MHz,CDCl 3)δ8.06(d,J＝8.5Hz,1H),7.70(d,J＝8.3Hz,1H),7.62(d,J＝8.5Hz,1H),7.33(d,J＝8.3Hz,1H),6.01(s,1H),5.44(d,J＝3.4Hz,1H),4.99–4.83(m,1H),2.58(s,3H),2.49(d,J＝7.6Hz,1H),2.13–1.96(m,2H),1.53(dd,J＝13.1,6.6Hz,2H),1.45(s,3H),1.36(d,J＝7.9Hz,1H),1.27(s,2H),1.09(s,2H),1.07–0.96(m,2H),0.94(d,J＝6.5Hz,2H),0.89(d,J＝1.8Hz,2H),0.88(d,J＝1.8Hz,2H),0.71(s,1H).
13C NMR(101MHz,CDCl 3)δ165.36(s),155.87(s),142.96(s),140.64(s),139.57(s),135.48(s),132.42(d,J＝5.8Hz),131.50(s),129.59(s),128.36(s),127.26(s),122.92(s),121.42(s),91.31(s),90.08(s),74.93(s),56.72(s),56.17(s),50.08(s),42.35(s),39.77(s),39.54(s),38.24(s),37.05(s),36.68(s),36.22(s),35.82(s),31.94(d,J＝5.1Hz),28.25(s),27.97(d,J＝12.4Hz),24.32(s),23.86(s),22.84(s),22.59(s),21.09(s),19.39(s),18.75(s),14.61(s),11.89(s).
熔点：251℃，清亮点：272℃。ESI+MS(M+H)：C 55H 67BF 2N 2O 2，计算值：836.5321，实测值：836.5248。
本发明的液晶化合物的性质测定
(1)液晶化合物DC在二氯甲烷中的光谱性质测试：
测试浓度：液晶化合物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制备的液晶化合物(±0.1mg)，放入体积为10mL容量瓶后用CH 2Cl 2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。
液晶化合物荧光量子产率Φ F值的测定：以浓度1.0×10 -5mol/L，Φ F值为0.49的罗丹明b为基准。所需参数在同一测试条件下测得，代入式(1)计算：
Figure PCTCN2020073718-appb-000009
式中：Φ (sample)、Φ (standard)分别代表样品、标准物的Φ F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、标准物的荧光强度。
对液晶染料DC1-DC3的测试结果如下：
表1.化合物DC1-DC3在二氯甲烷中的紫外和荧光数据
Figure PCTCN2020073718-appb-000010
合成的目标产物DC1-DC3的发射波长在517nm左右处，呈绿色荧光，发射半峰宽窄，大约为27nm左右，颜色辨识度高，用于宾主模式可实现纯色显示；荧光量子产率大约在0.32-0.37之间；摩尔消光系数在10 4.72-10 4.93。
(2)化合物DC1-DC3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℃)，良好的化学稳定性，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20μm。
二向色比、有序参数的测定：将液晶化合物DC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。分别测试液晶化合物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)计算出液晶化合物DC系列在液晶中的吸收有序参数S A、二向色比D A和荧光有序参数S F、二向色比D F：
Figure PCTCN2020073718-appb-000011
液晶染料DC的偏振光谱测试结果如下：
表2.液晶染料DC在液晶E7中的偏振紫外和偏振荧光数据
Figure PCTCN2020073718-appb-000012
可见，合成的目标化合物DC系列在主体液晶E7中表现出较好的二向色比以及有序参数。DC1的二向色比高达8.16，吸收有序参数最大为0.73，同样其荧光二向色比和荧光有序参数亦为最高值，分别为8.16和0.70。满足宾主显示模式中对于二向色比的实际要求。
(3)二向性染料DC系列的液晶行为
对制备的液晶染料DC系列化合物进行差热扫描，得到其差热扫描量热图。如图3-5所示，在加热和冷却的过程中均出现中间相。化合物DC1在升温过程中的218-274.3℃呈现液晶相，冷却时在98-271℃出现液晶相，中间相的范围大约为150℃左右；对于化合物DC2，加热时在161-237℃时出现液晶相，冷却时在156-266℃出现宽达100℃的液晶相相范围；而对于化合物DC3，只在加热过程中出现中间相，范围在251-272℃。
(4)液晶染料DC对主体液晶E7的影响
液晶响应时间的测量：主体液晶为E7；测试用液晶盒上下两基板的取向相互平行，盒厚度为10μm；将液晶染料DC按照质量浓度为0.5％(w/w)的比例掺入到主体液晶E7中，分别测试宾体染料DC对主体液晶E7的影响。
用波长为510nm的绿光作为光源，通过检测器收集光源的透过情况。测试时样品的驱动电压为0-10V，相对亮度从10％到90％的时间为上升时间t r，从90％到10％为下降时间t f，响应时间为t r与t f之和，即t r+t f＝t。
如图6-8所示，为宾体染料DC系列在主体液晶E7中的响应时间图
表3.宾体染料DC系列化合物在主体液晶E7中的响应时间数据
Figure PCTCN2020073718-appb-000013
荧光二向性液晶染料DC能够改变液晶的响应时间，DC可以缩短主体液晶E7的响应时间，响应时间最快为DC1掺杂的主体液晶E7。

Claims (10)

  1. 一类含有8-(双苯乙炔基)-酯基柔性多元环的化合物，其特征在于所述化合物具有以下的化学分子结构通式B：
    Figure PCTCN2020073718-appb-100001
    其中，R选自丙基双环己基甲基、丁基双环己基甲基、戊基双环已基甲基、丙基双环已基乙基、丁基双环己基乙基、戊基双环己基乙基、胆甾醇基中的一种。
  2. 权利要求1所述的化合物的制备方法，包括以下步骤：将对碘苯甲酰氯和2,4-二甲基吡咯作为原料，以二氯甲烷为溶剂并加入三乙胺，反应一段时间后再加入三氟化硼乙醚进行配位，合成氟化硼络合二吡咯甲川类母体，所述氟化硼络合二吡咯甲川类母体分别与4-乙炔基苯丙基双环己基甲醇酯、4-乙炔基苯丁基双环己基甲醇酯、4-乙炔基苯戊基双环已基甲醇酯、4-乙炔基苯丙基双环已基甲基甲醇酯、4-乙炔基苯丁基双环己基甲基甲醇酯、4-乙炔基苯戊基双环己基甲基甲醇酯、4-乙炔基苯胆甾醇酯通过Sonogashira偶联反应后连接，得到所述液晶染料化合物；
    所述4-乙炔基苯甲酸的制法为：以对碘苯甲酸为原料合成的对碘苯甲酸乙酯，通过Sonogashira偶联反应与三甲基硅乙炔连接，再以甲醇为溶剂并加入3倍当量的碳酸钾，进行脱硅反应得到；
    所述4-乙炔基苯丙基双环己基甲醇酯、4-乙炔基苯丁基双环己基甲醇酯、4-乙炔基苯戊基双环已基甲醇酯的制备方法分别为：丙基双环己基甲醇、丁基双环己基甲醇、戊基双环已基甲醇分别与4-炔基苯甲酸以二氯甲烷为溶剂并加入二环己基碳二亚胺和催化量的4-二甲氨基吡啶，进行酯化反应得到；
    所述4-乙炔基苯丙基双环已基甲基甲醇酯、4-乙炔基苯丁基双环己基甲基甲醇酯、4-乙炔基苯戊基双环己基甲基甲醇酯的制备方法分别为：丙基双环已基甲基甲醇、丁基双环己基甲基甲醇、戊基双环己基甲基甲醇分别与4-乙炔基苯甲酸以二氯甲烷为溶剂，加入1.5倍当量的二环己基碳二亚胺和催化量的4-二甲氨基吡啶，进行酯化反应得到；
    所述4-乙炔基苯胆甾醇酯的制备方法为：胆甾醇与4-乙炔基苯甲酸以二氯甲烷为溶剂并加入1.5倍当量的二环己基碳二亚胺和催化量的4-二甲氨基吡啶，进行酯化反应得到。
  3. 权利要求1所述的化合物作为荧光二向色性染料的应用。
  4. 根据权利要求3所述的应用，其特征在于，所述染料为具有液晶相的染料。
  5. 根据权利要求1所述的化合物作为液晶材料的应用。
  6. 根据权利要求5所述的应用，其特征在于，所述液晶材料为彩色液晶材料。
  7. 根据权利要求3～6任意一项所述的应用，其特征在于，所述化合物作为缩短响应时间的液晶组分添加至液晶E7中成为混合液晶材料。
  8. 权利要求1所述的化合物作为荧光二向性液晶染料在制造液晶显示产品中的应用。
  9. 根据权利要求8所述的应用，其特征在于所述的液晶显示器为宾主型液晶显示器。
  10. 一类宾主型液晶显示器，其特征在于以权利要求1所述的化合物作为宾体液晶染料。
PCT/CN2020/073718 2019-01-11 2020-01-22 含有8-(双苯乙炔基)-酯基柔性多元环的氟硼吡咯类液晶化合物，其制备方法及其应用 WO2020143842A1 (zh)

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