CN113999254B - 一种苯并噻二唑并咪唑类荧光染料及其合成方法 - Google Patents
一种苯并噻二唑并咪唑类荧光染料及其合成方法 Download PDFInfo
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- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title claims abstract description 14
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Abstract
本发明公开了一种新型的苯并噻二唑并咪唑类荧光染料及合成方法，其结构通式如式I所示。苯并噻二唑为缺电子基团，是设计有机荧光小分子的良好受体，然而其在水中溶解性差，在水中荧光差等限制了其使用范围。本发明中，合成的染料具有苯并噻二唑并咪唑结构，由于咪唑具有供电子的氨基，可以增强苯并噻二唑的荧光强度，同时咪唑环上修饰的烷基或取代烷基R的不同，增大了苯并噻二唑母核的溶解度，取代芳基Ar的不同也可调节该类化合物从绿光到红光的改变。光学测试显示出该染料具有量子产率高、吸收发射波长长、Stokes位移大等优点，在光电材料、荧光探针等领域有着广阔的应用前景。
Description
【技术领域】
本发明合成了一种苯并噻二唑并咪唑类荧光染料，属于新型荧光染料合成领域。
【背景技术】
近年来，小分子有机荧光材料在有机发光二极管、太阳能敏化电池、生命传感成像分析等领域取得了广泛的应用。常用传统荧光染料如香豆素、花菁、半花菁、BODIPY染料、罗丹明、荧光素、苯并噻二唑等，根据其结构特点和不同性能，已在各种领域被广泛研究并实现商用。然而其自身结构特点所导致的缺陷无法通过结构修饰来改善，如花菁类染料的光稳定性差，BODIPY类染料的斯托克斯位移较小，苯并噻二唑类染料的水溶性差等。因此，开发新型母核结构的染料，并根据其结构特点克服传统染料无法改变的结构缺陷仍具有重要的意义。
苯并噻二唑类染料通常依据苯并噻二唑母核的吸电子性，在苯环修饰以供电子的基团构成供体-受体的推拉电子结构，而平面性大，易堆积的结构特点导致其在水中溶解性差，荧光猝灭。通过对苯并噻二唑进行修饰，并入咪唑环，可以大大改善这一结构缺陷，增强水中荧光和溶解性。
【发明内容】
本发明鉴于对苯并噻二唑类染料的研究，设计合成了一种新型的苯并噻二唑并咪唑类荧光染料，通过核磁氢谱、核磁碳谱、高分辨质谱和单晶衍射等分析方法对其结构进行了表征，其结构通式如式I所示：
所述式I结构通式中，其结构特征为：Ar为取代的苯基，具体可为：苯基、1-萘基、4-(二苯基)氨-苯基；R为烷基，具体可为：甲基、叔丁基。
制备式I所示化合物的方法，具体包括如下步骤：
1)将4,7-二溴-5,6-二硝基苯并噻二唑(式II)与芳基硼酸进行Suzuki偶联得式III化合物；
2)将式III化合物用铁粉还原得式Ⅳ化合物；
3)将式Ⅳ化合物与不同酰氯得式Ⅴ化合物；
4)将式Ⅴ化合物与三氯氧磷反应关环，得到式Ⅰ所示目标产物；
其中，步骤1)其特征在于：溶剂具体为甲苯，4,7-二溴-5,6-二硝基苯并噻二唑与芳基硼酸摩尔比为1:2～4，反应时间为4～8小时，反应温度为80～120℃；
步骤2)其特征在于：式III化合物与铁粉摩尔比例为1:6～10，温度为60～120℃，反应时间2～8小时；
步骤3)其特征在于：式Ⅳ化合物、酰氯摩尔比例为1:2～10：2～10，温度为0～40℃，反应时间4～12小时；
步骤4)其特征在于：式Ⅴ化合物与三氯氧磷摩尔比例为1:1～5，溶剂为二氯甲烷、甲苯、四氢呋喃，温度为0～40℃，反应时间2～8小时。
本发明所提供的化合物具有苯并噻二唑并咪唑的结构，母核具有分子内的供体-受体结构，具有良好的光学性质；在苯环两侧修饰不同取代苯基，更加增强分子内的供体-受体的电子结构，光学测试表明，该染料具有良好的光稳定性，在水和有机溶剂中都具有较好的量子产率，斯托克斯位移大，达到了140nm。且该新型染料具有良好的水溶性，在水中也有很好的荧光性能，大大改善了苯并噻二唑结构的结构缺陷，同时保留了一个活泼氢，使其在光电材料领域及荧光探针设计方面有着广阔的应用前景。
【附图说明】
图1为实施例4所制备化合物式ⅨA1的核磁氢谱图。
图2为实施例5所制备化合物式ⅨB1的核磁氢谱图。
图3为实施例6所制备化合物式ⅨC1的核磁氢谱图。
图4为实施例7化合物式ⅨA1的紫外-可见吸收谱图。
图5为实施例7化合物式ⅨA1的荧光发射谱图。
图6为实施例7化合物式ⅨB1的紫外-可见吸收谱图。
图7为实施例7化合物式ⅨB1的荧光发射谱图。
图8为实施例7化合物式ⅨC1的紫外-可见吸收谱图。
图9为实施例7化合物式ⅨC1的荧光发射谱图。
【具体实施方式】
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。
下述实施例所述的实验方法，如无特殊说明，均属常规方法；所述药品和溶剂，均可从商业途径购买或已有文献合成。
反应式如下式Ⅷ所示，反应后产物如下式Ⅸ所示：
【实施例1】
制备式ⅢA化合物：称取3.81g(10mol)式Ⅱ化合物于250mL干燥的烧瓶，溶于40mL甲苯，加入苯硼酸2.8g(22mmol)，0.35g(3mmol)四三苯基膦钯，120℃氮气保护下搅拌6h，有橙黄固体析出，TLC检测反应至反应完全。加100mL水，用二氯甲烷50mL萃取，有机相旋干，得3.15g橙色固体，产率83％。
【实施例2】
制备式ⅥA化合物：称取1.89g(5mmol)式ⅢA化合物和1.89g(3.38mmol)铁粉于50mL烧瓶，加入10mL醋酸，80℃下搅拌3h，加入25mL水，二氯甲烷25mL萃取，旋蒸得1.52g黄褐色固体，产率75％。
【实施例3】
制备式ⅤA1化合物：称取0.80g(2mmol)式Ⅲ化合物于25mL烧瓶，加入1.2g(10mmol)特戊酰氯，1.0g(10mmol)三乙胺，0℃搅拌12h，加10mL水，25mL二氯甲烷萃取，柱层析提纯得0.93g淡黄色固体，产率96％。
【实施例4】
制备式ⅨA1化合物：称取0.20g(0.4mmol)式ⅤA1化合物于25mL烧瓶，加入1mL甲苯，0.1g(0.6mmol)三氯氧磷，搅拌2h，析出黄色固体，加水抽滤，柱层析提纯得0.12g黄色固体，产率78％。1H NMR(500MHz,DMSO-d6)δ＝12.04(s,1H),8.24(d,J＝7.6Hz,2H),7.81(d,J＝7.5Hz,2H),7.61(t,J＝7.5Hz,2H),7.53(dt,J＝15.3,7.5Hz,3H),7.42(t,J＝7.2Hz,1H),1.45(s,9H).
【实施例5】
制备式ⅨB1化合物：称取0.24g(0.4mmol)式ⅤB1化合物于25mL烧瓶，加入1mL甲苯，0.1g(0.6mmol)三氯氧磷，搅拌2h，析出黄色固体，加水抽滤，柱层析提纯得0.13g黄色固体，产率76％。1H NMR(500MHz,DMSO-d6)δ＝11.92(s,1H),8.14(td,J＝22.5,8.5Hz,4H),7.79(ddd,J＝17.6,13.9,7.6Hz,4H),7.57(ddd,J＝28.5,16.4,8.1Hz,3H),7.47–7.33(m,3H),1.30(s,J＝4.9Hz,9H)。
【实施例6】
制备式ⅨC1化合物：称取0.33g(0.4mmol)式ⅤB1化合物于25mL烧瓶，加入1mL甲苯，0.1g(0.6mmol)三氯氧磷，搅拌2h，析出紫红固体，加水抽滤，柱层析提纯得0.26g红色固体，产率85％。1H NMR(500MHz,DMSO-d6)δ＝11.92(s,1H),8.29(t,J＝10.4Hz,2H),7.76(d,J＝8.5Hz,2H),7.41–7.33(m,8H),7.18–7.07(m,16H),1.45(d,J＝9.3Hz,9H)。
【实施例7】
用不同溶剂配制浓度为10μmol/L的最终化合物ⅨA1、ⅨB1和ⅨC1溶液，测试其紫外-可见吸收光谱、荧光发射光谱图。其中，在四氢呋喃溶液中的光物理性质汇总为表1.
表1：光物理性质
表1结果显示，染料ⅨC1在四氢呋喃中的最大吸收波长是488nm，最大发射波长是628nm，有140nm的大斯托克斯位移。根据不同取代苯的供电子能力，可实现发射507nm到628nm的绿光到红光调节，在光电材料、生物成像等领域有着很好的应用前景。
Claims (7)
1.一种苯并噻二唑并咪唑类荧光染料，其特征在于：结构通式如式I所示，
Ar为萘基，R为叔丁基。
2.如权利要求1所述的一种苯并噻二唑并咪唑类荧光染料的合成方法，其特征在于，包括以下步骤：
(1)将如式Ⅱ所示4,7-二溴-5,6-二硝基苯并噻二唑化合物与芳基硼酸在甲苯中通过钯催化剂反应生成如式Ⅲ所示化合物；
(2)将如式Ⅲ所示化合物在醋酸溶剂中用铁粉还原为如式Ⅳ所示化合物；
(3)将如式Ⅳ所示化合物与特戊酰氯在二氯甲烷溶剂中，三乙胺存在下酰基化，得到如式Ⅴ所示化合物；
(4)将如式Ⅴ所示化合物在溶剂中与三氯氧磷反应，得到式Ⅰ所示目标产物；
3.如权利要求2所述的一种苯并噻二唑并咪唑类荧光染料的合成方法，其特征在于，步骤1)中，溶剂为甲苯，式Ⅱ化合物与芳基硼酸摩尔比为1:2～4，反应时间为4～8小时，反应温度为80～120℃，具体芳基硼酸如式Ⅵ所示，
4.如权利要求2所述的一种苯并噻二唑并咪唑类荧光染料的合成方法，其特征在于，步骤2)中，式Ⅲ化合物与铁粉摩尔比为1:6～10，温度为60～120℃，反应时间2～8小时。
5.如权利要求2所述的一种苯并噻二唑并咪唑类荧光染料的合成方法，其特征在于，步骤3)中，式Ⅳ化合物与三乙胺、特戊酰氯摩尔比为1:2～10:2～10，温度为0～40℃，反应时间4～12小时。
6.如权利要求2所述的一种苯并噻二唑并咪唑类荧光染料的合成方法，其特征在于，步骤4)中，式Ⅴ化合物与三氯氧磷摩尔比为1:1～5，溶剂为甲苯或四氢呋喃，温度为0～40℃，反应时间2～8小时。
7.权利要求1所述的一种苯并噻二唑并咪唑类荧光染料的应用，具体为，在制备有机发光材料、有机荧光染料、荧光探针及细胞成像类的荧光染料中的应用。
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