CN114516790A - 双苯并菲并戊酮盘状液晶化合物的合成与发光性 - Google Patents
双苯并菲并戊酮盘状液晶化合物的合成与发光性 Download PDFInfo
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Abstract
本发明涉及双苯并菲并戊酮盘状液晶化合物合成与光线性质的研究。其特征在于具有通式（Ⅰ）。其中R1为C8~C16的烷基链，上述通式（Ⅰ）化合物在较宽的温度范围内能自组装成六方柱状液晶中间相，且通式（Ⅰ）化合物是多种极性/非极性有机溶剂的凝胶剂。通本发明还提供了一种双苯并菲并戊酮盘状液晶化合物制备方法，其合成路线简单快捷且条件温和，通式（Ⅰ）中化合物可通过通式（Ⅱ）中化合物在FeCl3分子内氧化关环获得。
Description
技术领域
本发明涉及双苯并菲并戊酮盘状液晶化合物的合成与发光性。
背景技术
目前，盘状液晶是一类独特的具有显著的电导和光电导性能的、能够通过自组装形成纳米微结构的材料。是一种具有π键共轭的平面盘状分子，由于其一维分子间柱状堆积，使其能够自组装成柱状结构，尤其是六方柱状相。这为一维电荷载体体系提供独特的可能性。因此，盘状液晶在分子电子学、光电学、光电导性、光伏和电致发光装置等领域的应用中，盘状液晶被认为是有前途的有机半导体。然而，高分子液晶中间相的柱状内堆积由于拓扑缺陷、热波动、和分子扩散等也会对电荷载子流动效率的参数造成一定的影响。这些属性的改进需要通过非常稳定的传感器材料、合适的温度以及理想的操作环境等各种方法达到想要的分子排序方式，使反应方便处理，从而可以提高了电荷迁移的性能。
发明内容
基于此设计合成了双苯并菲并戊酮盘状液晶化合物。该类化合物在合成上主要是通过Suzuki偶联得到的。主要通过4,4,5,5-四甲基-2-（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-1,3,2-二氧杂硼烷与2,7-二溴芴酮发生Suzuki偶联后进行关环。得到目标化合物，经研究表明该类化合物较宽的温度范围内形成稳定的柱状相且是一种性能优良的液晶。同时该类化合物具有一定的发光性能。
此外，还有必要提供双苯并菲并戊酮盘状液晶化合物的制备方法。
一种双苯并菲并戊酮盘状液晶化合物，其特征在于具有通式（Ⅰ）所示的结构：
(Ⅰ)
其中R为CnH2n+1，n表示碳原子数为8-16的整数。
一种权利要求2所述的通式（Ⅱ）2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮其特征在于包括如下步骤。
步骤一：中间体为b化合物的制备：
（a） （b）
以式a所示的化合物为原料，将其与溴单质以1:1的摩尔比在250ml圆底烧瓶中称取，加入150ml三氯甲烷，套上恒压滴液漏斗，往其中加入三氯甲烷（20ml）和溴单质，将圆底烧瓶放入室温的环境中，恒压滴液漏斗中的溶液控制在2秒每滴，每隔15分钟点板跟踪，反应完毕，加入亚硫酸氢钠终止反应，过滤，用旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用乙醇、乙酸乙酯重结晶，得产物b，其中R1为-CnH2n+1，n表示碳原子数为6-16的整数。
步骤二：中间体4,4,5,5-四甲基-2-（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-1,3,2-二氧杂硼烷(c)的合成：
（b） (c)
其中，R是CnH2n+1，n表示碳原子数为8-16。
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四（烷氧基）-1,1'-联苯（b）:双戊酰二硼: CH3COOK: PdCl2(dppf)= 1 : 1.5 : 0.05 : 3称取并加入1,4-二氧六环25 ml，在氩气保护下，在90 ℃下反应24h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和甲醇进行重结晶，得到白色固体 (c)。
步骤三：2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮的合成：
(c) （Ⅱ）
其中，R是CnH2n+1，n表示碳原子数为8-16。
在50 ml反应管中以摩尔比c : 2,6二溴芴酮: K2CO3 : Pd(PPh3)4 = 2.5 : 1 :30 : 0.2称取并加入混合溶剂水（3 ml）/THF(10 ml)，在氩气保护下，在70 ℃下反应48 h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和乙醇进行重结晶，得到黄色固体(Ⅱ)。
其中，R是CnH2n+1，n表示碳原子数为8-16。
双苯并菲并戊酮盘状液晶化合物（Ⅰ）的制备：
（Ⅱ） （Ⅰ）
其中，R是CnH2n+1，n表示碳原子数为8-16。
在100ml的圆底烧瓶中以化合物(Ⅱ) : FeCl3 = 1 : 6 的摩尔比称取，并加入三氯甲烷（60ml），硝基甲烷(5ml)、在室温下反应，每隔15min点板跟踪反应，反应完毕，加入甲醇终止反应，用三氯甲烷进行萃取， MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用乙酸乙酯和乙醇（甲苯和石油醚）进行重结晶，得到橙黄色固体（Ⅰ）。
上述双苯并菲并戊酮盘状液晶化合物的制备方法，其合成路线简单快捷且条件温和，该类化合物是以4,4,5,5-四甲基-2-（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-1,3,2-二氧杂硼烷与2,7-溴芴酮发生Suzuki偶联后进行关环，通过稠合的方式将多个芳基连在一起，在外围的多条烷氧基柔性链的调节作用下，其可以在较宽的温度范围内且在室温下自组装成稳定的六方柱状液晶中间相，在液晶材料方面有很好的应用价值。
附图说明
图1实施例1中所获R为C10H21的中间体b的核磁氢谱。
图2实施例2中所获R为C10H21的中间体c的核磁氢谱。
图3实施例3中所获R为C10H21时通式（Ⅱ）的核磁氢谱。
图4实施例4中所获R为C10H21时通式（Ⅰ）的核磁氢谱。
图5实施例4中所获R为C10H21时通式（Ⅰ）的DSC曲线图。
图6实施例4中所获R为C10H21时通式（Ⅰ）的偏光织构图。
图7是荧光发射光谱图，曲线C10是实施例4中所获R为C10H21时通式（Ⅰ）的荧光发射光谱图。
图8是紫外吸收光谱图，曲线C10是实施例4中所获R为C10H21时通式（Ⅰ）的紫外吸收光谱图。
图9是倒置的凝胶图片，是实施例4中所获R为C10H21时通式（Ⅰ）化合物依次在二氯甲烷、四氢呋喃 、己烷、环己烷、甲苯和三氯甲烷有机溶剂中形成的凝胶。
图10实施例4中所获R为C10H21时通式（Ⅰ）的XRD图。
具体实施方式
下面给出的实例是对本发明的具体描述，必须强调的是下面给出的实施例子只是对本发明的进一步阐述，而不是对本发明的保护范围的一种限制。本领域熟练技术人员根据上述发明内容在实际实施过程中，涉及到的改进或者调整若不是本质意义上的改变，仍然属于本发明的保护范围。
以下各个实施案例中所用到的合成方法均为现有技术：
T. Yasuda, T. Shimizu, F. Liu, G. Ungar, T. Kato, J. Am. Chem. Soc. 2011,133, 13437–13444.
实施例1。
] 本实施例提供的化合物是通式（Ⅱ）的化合物中间体b的制备，其中R为C10H21，其制备反应如下：
（a） （b）
其中，R是CnH2n+1，n表示碳原子数为8-16。
以3,3',4,4'-四（十烷氧基）-1,1'-联苯（a）(0.63 mg，0.80 mmol)为原料，将其与溴(0.11 g，0.80 mmol)单质以1:1摩尔比在250 ml圆底烧瓶中称取，加入150 ml三氯甲烷，套上恒压滴液漏斗，往其中加入三氯甲烷（20 ml）和溴单质，将圆底烧瓶放入室温的环境中，恒压滴液漏斗中的溶液控制在2秒每滴，每隔15分钟点板跟踪，反应完毕，加入亚硫酸氢钠终止反应，过滤，用旋干,过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用乙醇、乙酸乙酯重结晶，得产物b，（0.65 g，产率94 %）。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:7.10(s, 1H, ArH), 6.95(s, 1H, ArH), 6.89(d, J = 4 Hz, 2H, ArH),6.84(s, 1H,ArH), 4.02(t, J = 2.8 Hz, 8H, OCH2), 1.76-1.87(m, 8H, CH2), 1.27-1.57(m, 56H,CH2), 0.88(t, J = 2.8Hz, 12H, CH3).
实施例2。
4,4,5,5-四甲基-2-（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-1,3,2-二氧杂硼烷（c）的制备，其中R为C10H21，其制备反应如下：
（b） （c）
其中，R是CnH2n+1，n表示碳原子数为8-16。
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四（烷氧基）-1,1'-联苯:双戊酰二硼（b）: CH3COOK: PdCl2(dppf)= 1（1.2 g） : 1.5（0.53 g） : 0.05（0.06 g） : 3（0.4 g）称取并加入1,4-二氧六环25 ml，在氩气保护下，在90 ℃下反应24h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和甲醇进行重结晶，得到白色固体 (c) （1.27 g，产率40 %）。
核磁氢谱核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400MHz), δ:7.21(s, 1H, ArH), 6.92(s, 1H, ArH), 6.85(s, 3H, ArH), 4.0-4.05(m, 8H,OCH2),1.80-1.85(m, 8H, CH2), 1.27-1.50(m, 56H, CH2), 1.19(s, 12H, CH3),0.88(t,J = 4Hz, 12H, CH3).
实施例3。
本实施例提供的化合物是通式（Ⅱ）化合物的制备，其中R为C10H21，其制备反应如下：
（c） （Ⅱ）
其中，R是CnH2n+1，n表示碳原子数为8-16。
在50 ml反应管中以摩尔比c : 2,7-二溴芴酮: K2CO3 : Pd(PPh3)4 = 2.5（0.36） : 1（0.05） : 30（0.61） : 0.2（0.03）称取并加入混合溶剂水（3 ml）/THF(10 ml)，在氩气保护下，在70 ℃下反应48 h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和乙醇进行重结晶，得到黄色固体(Ⅱ)。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:7.58 (s, 2H, ArH), 7.18 (d, J =8 Hz 2H, ArH), 7.06 (d, J = 8 Hz, 2H, ArH), 6.94 (s, 2H, ArH), 6.92 (s, 2H,ArH), 6.76 (d, J = 8 Hz, 2H, ArH), 6.70 (d, J = 8 Hz, 2H, ArH), 6.63 (s, 2H,ArH), 4.06 (t , J =8 Hz , 8H , OCH2), 3.95 (t, J = 4 Hz, 4H, OCH2), 3.75 (t, J = 4 Hz , 4H, OCH2), 1.79-1.87 (m, 12H, CH2), 1,63 (t, J = 8 Hz, 4H, CH2),1.22-1.49 (m, 112H, CH2), 0.87 (t, J = 8 Hz, 24H, CH3).
（0.20 g，产率77 %）。
实施例4。
本实施例提供的化合物是通式（Ⅰ）的化合物，其中R1为C10H21，其制备反应如下：
（Ⅱ） （Ⅰ）
其中，R是CnH2n+1，n表示碳原子数为8-16。
在100ml的圆底烧瓶中以化合物(Ⅱ) : FeCl3 = 1（0.11） : 6（0.06） 的摩尔比称取，并加入三氯甲烷（60ml），硝基甲烷(5ml)、在室温下反应，每隔15min点板跟踪反应，反应完毕，加入甲醇终止反应，用三氯甲烷进行萃取， MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用乙酸乙酯和乙醇（甲苯和石油醚）进行重结晶，得到橙黄色固体（Ⅰ）。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), 1H NMR(CDCl3, TMS, 400 MHz), δ:8.35 (s, 2H, ArH), 8.18 (s, 2H, ArH), 7.91(s, 2H, ArH), 7.56 (s, 2H, ArH),7.43 (s, 2H, ArH), 7.41 (s, 2H, ArH), 4.36 (t, J = 8 Hz, 4H, OCH2), 4.10 (t, J = 4 Hz, 12H, OCH2), 1.92-2.07 (m ,16H, CH2), 1.62-1.72 (m, 10H, CH2), 1.25-1,48 (m, 102H, CH2), 0.90 (t, J = 8 Hz, 24H, CH3).（0.20 g，产率80 %）。
Claims (9)
1.一种双苯并菲并戊酮盘状液晶化合物，其特征在于具有通式（Ⅰ）所示的结构：
（Ⅰ）。
2.一种2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮，其特征在于具有通式（Ⅱ）所示的结构：
（Ⅱ）。
3. 根据权利要求1所示一种双苯并菲并芴酮盘状液晶化合物（Ⅰ）和权利要求2（Ⅱ）所示的2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮，所示其特征在于所述R为-CnH2n+1，n表示碳原子数为8-16的整数。
4.一种权利要求2所述的通式（Ⅱ）2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮，其制备方法为：
步骤一：中间体b(2-溴-3',4,4' ,5-四（烷氧基）-1,1'-联苯)的制备：
(a) (b)
以式3,3',4,4'-四（烷氧基）-1,1'-联苯(a)所示的化合物为原料，将其与溴单质以1:1摩尔比在250ml圆底烧瓶中称取，加入150ml三氯甲烷，套上恒压滴液漏斗，往其中加入三氯甲烷（20ml）和溴单质，将圆底烧瓶放入室温的环境中，恒压滴液漏斗中的溶液控制在2秒每滴，每隔15分钟点板跟踪，反应完毕，加入亚硫酸氢钠终止反应，过滤，用旋干，过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用乙醇、乙酸乙酯重结晶，得产物b，其中R1为-CnH2n+1，n表示碳原子数为8-16的整数；
步骤二：中间体4,4,5,5-四甲基-2-（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-1,3,2-二氧杂硼烷(c)的合成：
(b) （c）
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四（烷氧基）-1,1'-联苯:双戊酰二硼:CH3COOK: PdCl2(dppf)= 1 : 1.5 : 0.05 : 3称取并加入1,4-二氧六环25 ml，在氩气保护下，在90 ℃下反应24h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和甲醇进行重结晶，得到白色固体 (c)。
5.步骤三：2,7-双（3'，4,4'，5-四（烷氧基）-[1,1'-联苯] -2-基）-9H-芴酮的合成：
(c) (Ⅱ)
在50 ml反应管中以摩尔比c : 2,7-二溴芴酮: K2CO3 : Pd(PPh3)4 = 2.5 : 1 : 30 :0.2称取并加入混合溶剂水（3 ml）/THF(10 ml)，在氩气保护下，在70 ℃下反应48 h，冷至室温，用二氯甲烷进行萃取，有机相用无水MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:3），用乙酸乙酯和乙醇进行重结晶，得到黄色固体(Ⅱ)。
6.一种权利要求1所示的通式（Ⅰ）中双苯并菲并戊酮盘状液晶化合物，其制备方法为：
（Ⅱ） （Ⅰ）
在100ml的圆底烧瓶中以化合物(Ⅱ) : FeCl3 = 1 : 6 的摩尔比称取，并加入三氯甲烷（60ml），硝基甲烷(5ml)、在室温下反应，每隔15min点板跟踪反应，反应完毕，加入甲醇终止反应，用三氯甲烷进行萃取， MgSO4干燥，过滤，旋干，通过硅胶柱层析（洗脱剂：V二氯甲烷：V石油醚=1:2），用甲苯和石油醚进行重结晶，得到橙黄色固体（Ⅰ）。
7.一种权利要求1所述通式（Ⅰ）中双苯并菲并戊酮盘状液晶化合物作为有机液晶半导体材料的用途。
8.一种权利要求1所述通式（Ⅰ）中双苯并菲并戊酮盘状液晶化合物作为有机光致发光材料的用途。
9.一种权利要求1所述通式（Ⅰ）中双苯并菲并戊酮盘状液晶化合物作为有机凝胶剂的用途。
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