CN106883207B - 一种三聚茚基双香豆素荧光染料的制备方法 - Google Patents
一种三聚茚基双香豆素荧光染料的制备方法 Download PDFInfo
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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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Abstract
本发明公开了一种三聚茚基双香豆素荧光染料的结构及合成方法，通过如下方法实现：以双氯甲基三聚茚衍生物为原料，在甲苯中与三苯基膦反应得到双三苯基三聚茚双苄基氯化膦；再在无水无氧条件及在正丁基锂的作用下与香豆素醛发生wittig反应得到三聚茚共轭双香豆素化合物。本发明提供的方法操作简单、反应条件温和且收率较高，具有较大的实施价值。此外，该化合物具有较强的荧光发射，最大发射峰在518nm(激发波长425nm)，斯托克斯位移为78nm。
Description
技术领域
本发明属于有机合成技术领域，涉及一种三聚茚基双香豆素荧光染料的制备方法。
背景技术
香豆素类衍生物广泛存在于自然界植物界，具有抗HIV、抗肿瘤、抗菌等多方面的生物活性，在医药领域具有极大的实用价值。在香豆素母体结构的3，4和6，7位置分别引入吸电子基和推电子基，与香豆素的内酯结构形成“推-拉”共轭电子体系，使化合物具有强烈的荧光。由于香豆素衍生物的荧光量子产率高、光稳定性好、Stokes位移大等优异的理化性质，可以作为荧光染料、激光染料和荧光增白剂等，此外，与不同的阳离子受体结合可得到基于PET(光诱导电荷转移)或ICT(分子内电荷转移)等机理的荧光分子探针，香豆素分子结构的化学可调性在医药、环境和信息科学方面具有广阔的应用前景。
一些具有较好光电性能的香豆素衍生物还可以被应用到电致发光材料、染料敏化太阳能电池以及人工光合作用等方面。如今已经被报道的香豆素-卟啉、香豆素-BODIPY、香豆素-富勒烯等分子体系中，分子间可以在一定条件下实现能量转移，并体现了较高的转移效率，对于丰富和发展电荷转移理论和提高材料的光电转换效率具有重要的意义，在光学材料、人工光合作用、生物技术和化学传感器等领域具有潜在的应用价值。除了香豆素化合物，本发明中也涉及到了另一种共轭稠环芳烃三聚茚，三聚茚具有较大的刚性平面、分子结构高度对称，分子外围苯环上的2，7，12位容易被功能基团修饰，是近年来设计合成多元体系光功能材料的基本结构单元之一。对于三聚茚基共轭香豆素染料分子还没有相关报道，因此，开展此类荧光染料的合成研究具有重要的意义。
发明内容
发明目的：针对现有技术中存在的不足，本发明的目的是提供一种三聚茚基双香豆素荧光染料的制备方法。
技术方案：为了实现上述发明目的，本发明采用的技术方案为：
本发明涉及的三聚茚基双香豆素荧光染料的结构如下：
本发明涉及的三聚茚基双香豆素荧光染料的合成路线为：
本发明涉及的基于三聚茚双香豆素化合物的制备过程包括以下步骤：
(1)将双氯代三甲基三聚茚衍生物与三苯基膦加入干燥甲苯中，在氩气保护条件下升温至反应体系回流，继续搅拌4小时，反应结束后冷却至室温，静置待反应溶剂中析出白色固体，抽滤分离出固体并用甲苯洗涤固体，最终得到白色固体产物双三苯基三聚茚双苄基氯化膦；
(2)将原料双三苯基三聚茚双苄基氯化膦溶解在无水四氢呋喃中，在氩气保护条件下及在0℃条件下，向反应容器中滴加(1.6M)正丁基锂溶液，混合悬浮液颜色立即变黄，滴加完毕后，继续在0℃反应半小时，接着将香豆素醛溶于无水四氢呋喃后缓慢滴加入反应器中，加完后在0℃条件下搅拌半小时，升至室温搅拌反应，并通过TLC来监测反应进度直到反应结束(通常12-18h)。
(3)反应结束后，加入体积为溶剂1-2倍量蒸馏水淬灭，用二氯甲烷萃取分离，合并有机层，经水洗、无水硫酸钠干燥，除去有机溶剂，粗产物经硅胶层析柱分离提纯，洗脱剂为二氯甲烷-石油醚。
上述反应步骤(1)中，产物室温下能在甲苯中析出，过滤后固体产物直接用于下一步反应；
上述反应步骤(2)中，正丁基锂与双三苯基三聚茚双苄基氯化膦的摩尔比为1∶2，双三苯基三聚茚双苄基氯化膦与香豆素醛的摩尔比为1∶2.5；
上述反应步骤(2)中，反应条件为无水无氧环境，正丁基锂和香豆素醛的加料方式为逐滴滴加；
上述反应步骤(2)中，通过TLC来判断反应是否完成；
上述反应步骤(3)中，硅胶柱层析的洗脱剂为二氯甲烷和石油醚。
本发明的有益效果
与现有技术相比，本发明中以香豆素为端基的三聚茚衍生物的制备方法所具有的优点有：(1)本方法通过wittig反应在三聚茚的活性位置引入两个香豆素衍生物，分子间通过双键连接形成了大π共轭体系，拓宽了体系的吸收波长范围，使得体系具有独特的发光性质，并有利于分子间的电荷传递和能量转移；(2)具有反应操作简便、反应条件温和、能耗少、选择性好、产率较高等优点。
附图说明
图1为本发明实施例2的高分辨质谱
图2为本发明实施例2的紫外-可见吸收光谱；
图3为本发明实施例2的荧光光谱；
具体实施方式
下面结合具体实例对本发明作进一步地解释，具体实施事例并不对本发明做任何限定。
用1H-NMR、紫外-可见光谱及荧光光谱表征化合物的结构并研究化合物的光物理性质。检测所用仪器为：Bruker ARX500型核磁共振仪(TMS为内标，氘代氯仿为溶剂)，岛津UV-3100型紫外-可见分光光度计(扫描范围400～800nm，光路狭缝2nm)，PE LS-55型荧光分光光度计(波长范围：激发光200-800nm，发射光200-900nm；狭缝可变：激发光路2.5-15nm，发射光路2.5-20nm；步距：0.1nm)。
实施例1
取化合物双氯甲基三聚茚衍生物(0.92mmol，631.4mg)溶于甲苯中，再加入三苯基膦(2.208mmol，579.2mg)，升温至回流，待原料完全溶解后继续搅拌4小时，降至室温并停止搅拌，产物析出后过滤除去溶剂，并用甲苯多次洗涤产物，得到白色固体产物双三苯基-三聚茚双苄基氯化膦为1.02g(产率92.7％)。1H NMR(CDCl3，600MHz，ppm)δ8.13(t，J＝8.4，2H)，8.06(d，J＝8.4，1H)，7.94(t，J＝7.2，2H)，7.82(s，1H)，7.70-7.76(m，24H)，7.62(d，J＝7.8，1H)，7.25(d，J＝7.8，1H)，7.18(d，J＝7.8，1H)，7.25(d，J＝7.2，2H)，2.68-2.82(m，6H)，2.58(s，4H)，2.13-2.17(m，2H)，1.60-1.65(m，4H)，0.09(d，J＝7.2，6H)，-0.06(d，J＝2.4，12H).
实施例2
将双三苯基-三聚茚双苄基氯化膦(1mmol，1.197mg)溶解在干燥的四氢呋喃(50mL)中，向反应器中通入氩气，然后在0℃条件下逐滴滴加正丁基锂(2mmol，1.6M，1.25mL)，滴加结束后低温搅拌30分钟，再将原料香豆素醛(3mmol，735.84mg)溶解在四氢呋喃中滴加到反应器中，通过点板来监测反应进度，反应结束后用蒸馏水稀释，再用二氯甲烷萃取，合并有机层，水洗，再用无水硫酸钠干燥有机层；旋干溶剂后，残余物用硅胶层析柱分离提纯，洗脱剂用50％石油醚-二氯甲烷，得到产物为699.2mg(产率61.9％)。1H NMR(600MHz，CDCl3，ppm)δ8.31-8.33(m，1H)，8.27(d，J＝8.4Hz，1H)，8.22(d，J＝8.4Hz，1H)，7.76(s，2H)，7.62(d，J＝5.4Hz，2H)，7.60(s，1H)，7.58(s，2H)，7.51-7.56(m，3H)，7.33(d，J＝9.0Hz，2H)，7.41(d，J＝7.2Hz，2H)，7.34(d，J＝9.0Hz，2H)，7.28(s，1H)，7.25(s，1H)，6.62(d，J＝8.4Hz，2H)，6.55(s，2H)，6.02(s，2H)，3.04-3.07(m，8H)，2.59(s，6H)，2.21-2.27(m，6H)，1.52(s，6H)，1.22-1.25(m，12H)，0.26-0.32(m，18H).HR-Esi-MS：calcd forC69H71BrN2O4[M+H+]1071.4670，found：1071.4590，UV-vis(CH2Cl2)，λmax/nm[10-5ε/(L.mol- 1.cm-1)]：246(0.190002)，261(0.21445)，310(0.16286)，343(0.19300)，440(0.71187)(附图2)；Emission Wavelength：518nm(附图3)。
Claims (4)
1.一种结构如下所示的三聚茚基双香豆素荧光染料的合成方法，所述方法包括：双氯代三甲基三聚茚衍生物与三苯基膦溶解在干燥甲苯中，加热回流搅拌4小时，反应结束后析出的粗产物经甲苯洗涤得到双三苯基三聚茚双苄基氯化膦；然后在无水无氧条件及在正丁基锂作用下与溶解在新干燥四氢呋喃的香豆素醛反应，反应结束后通过硅胶柱层析分离提纯得到产物；
其中，三聚茚基双香豆素荧光染料的合成路线为：
2.根据权利要求1所述的方法，其特征在于所述双三苯基三聚茚双苄基氯化膦与正丁基锂的物质的量之比为1∶2，与香豆素醛的物质的量之比为1∶2.5。
3.根据权利要求1所述的方法，其特征在于所述双三苯基三聚茚双苄基氯化膦与与香豆素醛的物质的量之比为1∶2.5。
4.根据权利要求1所述的方法，其特征在于所述双三苯基三聚茚双苄基氯化膦与香豆素醛需在正丁基锂作用下在冰浴条件反应。
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