CN109336814B - 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 - Google Patents
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 Download PDFInfo
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Abstract
本发明公开了一类含有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,具有通式B结构,其中R1选自正丁基、苯基、对甲苯基和对乙苯基中的一种,R2选自乙基、正丙基、正丁基、正戊基、正己基中的一种。本发明染料不仅可以稳定向列相,而且可以增加向列相到各向同性的转变温度(TNI),从而增加液晶相的宽度。结构新颖,原料易得,合成绿色环保;在液晶E7中表现出较好的二向色比以及有序参数,最大吸收有序参数为0.71,最大荧光有序参数为0.65。具有在宾主型液晶显示器中的实用价值。
Description
技术领域
本发明涉及一类含有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,属于显示材料领域。
背景技术
人类信息的获取方式有很多种,但超过70%的信息都是通过视觉途径得到的,因此信息显示技术就充当了十分重要的角色。在众多显示模式中,“宾‐主”液晶显示(GH‐LCD)是光源利用率最高的显示模式,因为它在工作时只需要一片甚至不需要偏光片,这相比于其他必须用两片偏光片的显示模式来说,其大大提高了光源的利用率。除此之外,GH‐LCD还具有宽视角,色彩鲜艳,亮度高,能适用于特殊环境等特点。
GH‐LCD显示模式中,作为关键材料的二向色性染料,这类染料需要有足够高的二向色比;在主体液晶中有良好的溶解度,且不干扰主体液晶的性质;自身性能稳定等要求。但是由于荧光染料的结构限制,真正满足实际要求的荧光二向色性染料稀缺,对于萘酐的研究大多是停留在上个世纪末,本发明对萘酐做进一步的设计,制备出更多性能优异的荧光二向色性染料。
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黄绿色荧光、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、有较宽温度范围的液晶、有高的双折射值、易溶于主体液晶E7中、能降低液晶E7的响应时间、适用于液晶显示产品的荧光二向色性液晶染料。
本发明的技术目的之一在于提供一类新型的荧光二向性液晶染料:
一类含有4‐(烷基双环己基)取代的萘酰亚胺衍生物,具有以下的化学分子结构通式:
其中R1选自正丁基、苯基、对甲苯基和对乙苯基中的一种,R2选自乙基、正丙基、正丁基、正戊基、正己基中的一种。
进一步地,所述R1优选自正丁基、苯基和对甲苯基中的一种,R2选自乙基、正丙基、正丁基、正戊基、正己基中的一种。
本发明的另一技术目的在于提供上述一类含有4‐(烷基双环己基)取代的萘酰亚胺衍生物的制备方法,包括以下步骤:
以4‐溴‐1,8‐萘酐为原料,先与对应的烷基胺或苯基胺反应,生成4‐溴‐1,8 萘酰亚胺,再和哌嗪反应,生成4‐哌嗪‐1,8萘酰亚胺再分别与对应的烷基双环己烷甲酸反应,生成所述的荧光二色性液晶染料。
所述的烷基胺和苯基胺选自正丁胺、苯胺、甲苯胺和乙苯胺中的一种。所述的烷基双环己烷甲酸选自乙基双环己基甲酸、正丙基双环己基甲酸、正丁基双环己基甲酸、正戊基双环己基甲酸和正己基双环己基甲酸中的一种。
具体的合成线路如下:
进一步地,4‐溴‐1,8‐萘酐溶解在乙醇或乙二醇单甲醚溶液中,再加入等物质量的正丁胺或苯基胺,回流反应至反应完全,静置,抽滤得4‐溴‐1,8‐萘酰亚胺 (化合物2)。
进一步地,化合物2与过量哌嗪在乙二醇单甲醚溶剂中回流反应至反应完全,抽滤,洗涤,干燥得4‐哌嗪基‐1,8‐萘酰亚胺(化合物3)
进一步地,化合物3与烷基双环己基溶解在二氯甲烷溶剂中,化合物3和烷基双环己基得摩尔比为1:1,再加入适量的二环己基碳二亚胺(DCC)作催化剂,常温反应至反应完全,用乙酸乙酯和石油醚的混合物作展开剂,硅胶柱层析分离即得所述的一类含有4‐(烷基双环己基)取代的萘酰亚胺衍生物。
本发明另一方面提供上述的衍生物作为荧光二向色性染料的应用。所述染料为具有液晶相的染料。
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。
此外,本发明的液晶染料还具有液晶相,有较大的液晶相温度范围。所述的液晶主要为近晶相液晶、向列相液晶或者胆甾相液晶。加入E7中缩短了混合液晶的响应时间;加入E7中降低了混合液晶的阈值电压,减少液晶显示器的功耗。
本发明的有益效果:本发明以1,8-萘酐为母体合成含4-(对烷基双环己基基)-1,8-萘酐类荧光二向色性染料,设计了荧光二向色性染料新结构;新结构化合物应用可以稳定向列相,而且可以增加向列相到各向同性的转变温度(TNI),从而增加液晶相的宽度,有较大的液晶相温度范围。该系列化合物的最大吸收波长均为390nm,最大荧光发射波长均为500nm,呈现黄绿色荧光。在二氯甲烷溶剂中的荧光量子产率为0.62‐0.69。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0.59‐0.71。
附图说明
图1为实施例中制备的液晶化合物B3差热扫描量热图。
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。
实施例1
荧光二向色性染料B1的合成
(1)4‐溴‐N‐正丁基‐1,8‐萘酰亚胺(化合物2)的合成
在100mL单口瓶中加入2771mg(10mmol)4‐溴‐1,8‐萘酐,30mL无水乙醇,在室温搅拌下加入1.48mL(12mmol)正丁胺,升温回流反应6h,静置析出浅棕色固体,过滤,用乙醇洗涤,干燥,得2412mg浅白色固体,产率73%。
(2)4‐哌嗪基‐N‐正丁基‐1,8‐萘酰亚胺(化合物3)的合成
在50ml两口烧瓶中加入化合物4‐溴‐N‐正丁基‐1,8‐萘酰亚胺1328mg (4mmol),加入15ml乙二醇单甲醚作为溶剂,加热直回流,将无水哌嗪1034mg (12mmol)滴加结束后,点板检测反应的完成情况,反应完成。将混合物冷却,静置过夜,此时析出黄色固体,抽滤、洗涤、干燥得到亮黄色固体1036mg,产率77%。
(3)目标化合物B1的合成与表征
在50mL两口瓶中加入4‐哌嗪‐N‐正丁基‐1,8‐萘酰亚胺672mg(2mmol),戊基双环己基甲酸421mg(1.5mmol),再向反应体系中加入二环己基碳二亚胺(DCC) 618mg(3mmol)和4‐二甲氨基吡啶DMAP 122mg(1mmol),常温反应24h,用硅胶柱层析法进行分离提纯,洗脱液为二氯甲烷:甲醇=30:1(V/V)。得橘黄色固体,熔点:222.2℃,清亮点:223.8℃。产率:51%。+ESI MS(M+H):C38H53N3O3,计算值:600.4120,实测值:600.4151。
1H NMR(400MHz,CDCl3)δ8.59(d,J=7.2Hz,1H),8.51(d,J=8.0Hz,1H),8.42 (d,J=8.4Hz,1H),7.72(t,J=7.9Hz,1H),7.21(d,J=8.0Hz,1H),4.19–4.13(t,2H), 3.88(d,J=43.1Hz,4H),3.23(d,J=14.2Hz,4H),2.47(m,J=11.8Hz,1H),1.83(d,J =11.2Hz,4H),1.79–1.62(m,8H),1.59(dd,J=23.5,12.0Hz,2H),1.50–1.38(m, 2H),1.35–1.19(m,7H),1.14(d,J=6.7Hz,4H),1.10–1.00(m,4H),0.97(t,J=7.3 Hz,3H),0.87(t,J=6.9Hz,3H).13C NMR(126MHz,CDCl3)δ174.87,164.25,163.80, 155.10,132.26,131.11,129.70,126.21,125.98,123.38,117.55,115.28,53.25,45.55, 43.32,42.53,41.69,40.73,40.07,37.86,37.41,33.55,32.20,30.23,29.96,29.63, 29.35,26.62,22.68,20.36,14.09,13.83.
实施例2
荧光二向色性染料B2的合成和表征
(4)4‐溴‐N‐对甲苯基‐1,8‐萘酰亚胺(化合物2)的合成
在100mL单口瓶中加入2771mg(10mmol)4‐溴‐1,8‐萘酐,30mL乙二醇单甲醚,在室温搅拌下加入1072mg(10mmol)对甲苯胺,升温回流反应2h,静置析出固体,过滤,用乙醇洗涤,干燥,得2628mg浅棕色固体,产率72%。
(5)4‐哌嗪基‐N‐对甲苯基‐1,8‐萘酰亚胺的合成
除用4‐溴‐N‐对甲苯基‐1,8‐萘酰亚胺替换4‐溴‐N‐正丁基‐1,8‐萘酰亚胺外,其合成步骤及提纯方法同步骤(2),得亮黄色固体,产率72%。
(6)目标化合物B2的合成与表征
除了用4‐哌嗪‐N‐对甲苯基‐1,8‐萘酰亚胺替换4‐哌嗪‐N‐正丁基‐1,8‐萘酰亚胺外,其余步骤同步骤(3),洗脱液为二氯甲烷:甲醇=10:1(V/V),得黄色固体,熔点:156.3℃,清亮点:300.0℃,产率:44%。+ESI MS(M+H):C41H51N3O3,计算值:634.3964,实测值:634.3995。
1H NMR(400MHz,CDCl3)δ8.64(d,J=6.9Hz,1H),8.56(d,J=8.0Hz,1H),8.47 (d,J=8.1Hz,1H),7.79–7.72(m,1H),7.34(d,J=8.1Hz,2H),7.23(s,1H),7.18(d,J =8.2Hz,2H),3.90(d,J=46.1Hz,4H),3.26(d,J=15.3Hz,4H),2.48(t,J=12.8Hz, 1H),2.43(s,3H),1.84(d,J=11.1Hz,4H),1.73(dd,J=21.2,11.3Hz,4H),1.65–1.54 (m,3H),1.33–1.19(m,7H),1.15(d,J=7.1Hz,4H),1.11–0.91(m,6H),0.88(t,J= 6.9Hz,3H).13C NMR(126MHz,CDCl3)δ174.92,164.60,164.12,155.48,138.48, 132.78,131.61,130.17,128.26,126.38,126.11,123.55,117.60,115.39,53.33,45.53, 43.36,42.78,42.47,41.68,40.95,40.54,38.03,37.75,37.46,33.91,33.25,32.24, 30.43,30.22,29.63,26.67,22.73,21.56,21.10,14.19,14.10.
实施例3
荧光二向色性染料B3的合成和表征
(7)4‐溴‐N‐苯基‐1,8‐萘酰亚胺的合成
在100mL单口瓶中加入2771mg(10mmol)4‐溴‐1,8‐萘酐,30mL乙二醇单甲醚,在室温搅拌下加入1.12mL(12mmol)苯胺,升温回流反应2h,静置析出固体,过滤,用乙醇洗涤,干燥,得2203mg浅棕色固体,产率63%。
(8)4‐哌嗪基‐N‐苯基‐1,8‐萘酰亚胺的合成
除用4‐溴‐N‐苯基‐1,8‐萘酰亚胺替换4‐溴‐N‐正丁基‐1,8‐萘酰亚胺外,其合成步骤及提纯方法同步骤(2),得亮黄色固体,产率69%。
(9)目标化合物B3的合成与表征
除了用4‐哌嗪‐N‐苯基‐1,8‐萘酰亚胺替换4‐哌嗪‐N‐正丁基‐1,8‐萘酰亚胺外,其余步骤同步骤(3),洗脱液为二氯甲烷:甲醇=10:1(V/V),得淡橘黄色固体,熔点:277.1℃,清亮点:278.3℃,产率:47%。+ESI MS(M+H):C40H49N3O3,计算值:620.3807,实测值:620.3842。
1H NMR(400MHz,CDCl3)δ8.65(d,J=7.1Hz,1H),8.57(d,J=8.0Hz,1H),8.48 (d,J=8.1Hz,1H),7.79–7.74(m,1H),7.55(t,J=7.5Hz,2H),7.47(t,J=7.4Hz,1H), 7.30(d,J=7.3Hz,2H),7.25(d,J=5.6Hz,3H),3.90(d,J=44.1Hz,4H),3.27(d,J= 16.1Hz,4H),2.48(t,J=11.8Hz,1H),1.84(d,J=11.3Hz,4H),1.73(dd,J=21.6,11.1 Hz,4H),1.58(d,J=3.2Hz,3H),1.33–1.23(m,7H),1.16–1.12(m,3H),1.10–0.93 (m,6H),0.88(t,J=6.9Hz,3H).13C NMR(126MHz,CDCl3)δ174.93,164.50,164.03, 155.56,135.55,132.84,132.78,131.63,130.24,129.43,129.23,128.67,126.38, 123.49,117.49,115.47,115.37,53.32,43.40,42.66,42.41,42.41,41.56,40.93, 40.52,38.00,37.74,37.45,33.90,33.24,32.24,30.21,29.59,29.08,26.66,22.72, 14.19,14.10.
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:染料在不同溶剂中的浓度为1.0×10‐5mol/L。
染料荧光量子产率ΦF值的测定:以硫酸喹咛溶液为基准。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B1‐B3的测试结果如下:
表1.染料B1-B3在二氯甲烷中的紫外和荧光数据
(2)染料在液晶中的偏振光谱性质测试:
主体液晶为E7,液晶盒盒厚度为20μm。将染料B按照质量浓度为0.5%(w/w)的比例掺入到液晶中并装盒。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B1‐B3偏振光谱测试结果如下:
表2.染料B1-B3在液晶E7中的偏振紫外和偏振荧光数据
B1‐B3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 0.59‐0.71,吸收二向色比为5.28‐8.28,荧光有序参数为0.59‐0.65,荧光二向色比为5.33‐6.68,满足宾主显示实际应用要求。
(3)荧光二色性液晶染料B1‐B3的液晶行为
对制备的液晶化合物B进行差热扫描,得到其差热扫描量热图,如图1所示。
(4)荧光二色性液晶染料B对主体液晶E7响应时间的影响
得到如表3所示的液晶E7和E7+B(B的加入量为0.5wt%)的混合物的响应时间和阈值电压数据表。
表3液晶E7和E7+B的混合物的响应时间和阈值电压数据表
化合物B1、B2和B3的加入均降低了主体液晶的响应时间,化合物B1的加入,降低了主体液晶的阈值电压。
Claims (10)
2.权利要求1所述一类含有4‐(烷基双环己基)取代的萘酰亚胺衍生物的制备方法,包括以下步骤:
以4‐溴‐1,8‐萘酐为原料,先与对应的烷基胺或苯基胺反应,生成4‐溴‐1,8萘酰亚胺,再和哌嗪反应,生成4‐哌嗪‐1,8萘酰亚胺再分别与对应的烷基双环己烷甲酸反应,生成所述的荧光二色性液晶染料;
所述的烷基胺选自正丁胺,所述苯基胺选自苯胺、甲苯胺和乙苯胺中的一种;所述的烷基双环己烷甲酸选自乙基双环己基甲酸、正丙基双环己基甲酸、正丁基双环己基甲酸、正戊基双环己基甲酸和正己基双环己基甲酸中的一种。
3.权利要求1所述的衍生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.权利要求1所述的化合物作为液晶染料的应用。
6.权利要求1所述化合物作为液晶材料的应用。
7.权利要求1所述化合物在制造液晶显示产品中的应用。
8.根据权利要求7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。
9.一类宾主型液晶显示器,其特征在于以权利要求1所述化合物作为宾体液晶染料。
10.一种液晶材料,所述液晶材料为权利要求1所述衍生物与液晶E7的混合液晶。
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