CN108892969A - 3,5-位非芳基取代R-azaBODIPY荧光染料及其制备方法 - Google Patents
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Abstract
3,5‑位非芳基取代R‑azaBODIPY荧光染料及其制备方法,涉及荧光染料及其制备方法,从经典传统的3,5‑位芳基取代azaBODIPY发展的新型3,5‑位非芳基取代的染料R‑azaBODIPY。R‑azaBODIPY染料为进一步应用于生物学、材料学研究的发展,提供新式染料,丰富染料家族的种类。作为新式的染料,在具备经典传统的azaBODIPY染料的光谱性能等优点之外,最大的特征是荧光量子产率高,抑制π‑π堆积,稳定性好。其通式如式Ⅰ所示。该R‑azaBODIPY荧光染料是具有3,5‑位非芳基取代结构,是对传统经典azaBODIPY结构的突破,兼有经典传统染料azaBODIPY光谱性能等优点,并且荧光量子产率更高,稳定性更好,亲水性更强。
Description
技术领域
本发明涉及一种荧光染料及其制备方法,特别是涉及一种3,5-位非芳基取代R-azaBODIPY荧光染料及其制备方法。
背景技术
众多染料中,氮杂氟硼二吡咯甲川(BF2-azadipyrrolemethene,简称azaBODIPY)染料是近年来受到广泛关注的一类新型近红外荧光染料,该类染料吸收和发射波长位于可见-近红外区域,易于调控而被广泛研究。其具有半峰宽窄、量子产率高、摩尔消光系数大等特点,在生物分析、材料等领域具有广阔的应用前景,已经成为近年来研究的热点。但有分子难修饰的不足,其分子结构单一。
近年来,氮杂氟硼二吡咯甲川得到广泛的发展,O’Shea研究小组,Carreira研究小组,Shen研究小组和Jiang研究小组等做了系统的报道(Chem. Soc. Rev., 2016, 45,3846-3864)。但其氮杂氟硼二吡咯甲川的母核结构中3,5-位都是芳基取代,至今为止并未有3,5-位非芳基取代的氮杂氟硼二吡咯甲川结构的报道。
发明内容
本发明的目的在于提供一种3,5-位非芳基取代R-azaBODIPY荧光染料及其制备方法,本发明引入新的战略设计,从经典传统的3,5-位芳基取代azaBODIPY发展的新型3,5-位非芳基取代的染料R-azaBODIPY。本发明R-azaBODIPY染料为进一步应用于生物学、材料学研究的发展,提供新式染料,丰富染料家族的种类。作为新式的染料,在具备经典传统的azaBODIPY染料的光谱性能等优点之外,最大的特征是荧光量子产率高,抑制π-π堆积,稳定性好。
本发明的目的是通过以下技术方案实现的:
3,5-位非芳基取代R-azaBODIPY荧光染料,其通式如式Ⅰ所示:
在式I中,其中R选自-t-Bu,-CF3等非芳基的基团;芳基Ar选自Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8等基团;
代表分子结构举例如下所示:
。
所述的3,5-位非芳基取代R-azaBODIPY荧光染料,其中R选自R1-R6等基团;Ar选自Ar1-Ar8等基团。
3,5-位非芳基取代R-azaBODIPY荧光染料制备方法,所述方法包括如下步骤:
(1)化合物M3:在圆底烧瓶中加入非芳基R取代基的乙酮M1和氢氧化钾,向体系中加入乙醇/水溶液,再加入芳基甲醛M2,室温搅拌24 h,在此反应过程中,产物从混合液中沉淀下来,反应结束后,过滤,得到的固体再用乙醇重结晶,得到黄色固体M3;
M1中R选自所述的R1-R6等基团;M2中Ar选自所述的Ar1-Ar8等基团;M3中R选自所述的R1-R6等基团,Ar选自所述的Ar1-Ar8等基团;
(2)化合物M4:将化合物M3加入反应瓶中,加入干燥的甲醇使其溶解,再向体系中加入硝基甲烷和二乙胺,加热回流6 h;反应完成后,将反应体系冷却静置至室温,用的盐酸酸化至弱酸性,用二氯甲烷/蒸馏水萃取,有机相用无水MgSO4 干燥,过滤滤去固体,滤液用旋转蒸发仪旋蒸除去溶剂后,得到粗产物;再用二氯甲烷、无水乙醚重结晶,抽滤,用冷乙醚冲洗,得白色固体M4;
M4中R选自R1-R6等基团;Ar选自Ar1-Ar8等基团;
(3)化合物M5:将化合物M4和醋酸铵加到反应瓶中,再加入乙醇使其溶解,加热回流48h,将体系冷却至室温,抽滤,用乙醇冲洗得到墨绿色固体M5;
M5中R选自所述的R1-R6等基团,Ar选自所述的Ar1-Ar8等基团;
(4)将步骤(3)得到固体M5溶解在二氯甲烷中,然后加入三乙胺,反应半小时;最后,加入三氟化硼乙醚,反应3小时;混合物用冰淬灭;用二氯甲烷萃取,减压蒸馏,剩余物用硅胶柱提纯,展开剂为二氯甲烷/正己烷,得到固体I。
本发明的优点与效果是:
本发明荧光染料具有光稳定性好的特点,荧光量子产率高,可以应用于新型的材料中。同时这类染料具有有优异的水溶性,具有细胞透膜性,可以应用于生物染料,细胞成像方面的研究。
附图说明
图1 是本发明的新型荧光染料的结构通式I;
图2本发明的新型荧光染料I-1的氢谱;
图3 是发明的新型荧光染料I-1的碳谱;
图4是本发明的新型荧光染料I-1的吸收光谱(λ abs = 596 nm in CH2Cl2);
图5是本发明的新型荧光染料I-1的荧光光谱(λ em = 622 nm in CH2Cl2);
图6是本发明的荧光染料I-1的CH2Cl2溶液中的颜色;
图7是本发明的新型荧光染料I-1的对活细胞Hep-2细胞染色的荧光显微照片。
所用的仪器为共聚焦激光扫描显微镜;型号:ArrayScan® VTI HCS Reader。激光发光通道:590 nm。
具体实施方式
下面结合实施例对本发明进行详细说明。
除另有说明外,本文中使用的术语具有如下含义。
其中,在本发明通式Ⅰ中,R选自所述的R1-R6等基团,优先选用-t-Bu;Ar选自所述的Ar1-Ar8等基团,优先选用-Ph。
本发明提供一种制备所述的荧光染料的方法,即首先制备M3,其次制备M4,然后制备前驱体M5,最后络合三氟化硼乙醚,得到本发明所述的新型3,5-位非芳基取代的R-azaBODIPY。具体实施方案如下所述:
(1)化合物M3:在圆底烧瓶中加入非芳基R取代基的乙酮M1和氢氧化钾,向体系中加入乙醇/水溶液,再加入芳基甲醛M2,室温搅拌,过夜反应。在此反应过程中,产物从混合液中沉淀下来,反应结束后,过滤,过滤得到的固体再用乙醇重结晶,得到黄色固体M3。
反应时间3-24小时。相应的醛与相应的酮的投料摩尔比为1.2:1。
(2)化合物M4:将化合物M3加入反应瓶中,加入干燥的甲醇使其溶解,再向体系中加入硝基甲烷和二乙胺,加热回流6 h。反应完成后,将反应体系冷却静置至室温,用的盐酸酸化至弱酸性,用二氯甲烷/蒸馏水萃取混合液,有机相用无水MgSO4 干燥,过滤滤去固体,滤液用旋转蒸发仪旋蒸除去溶剂后得到粗产物,再用二氯甲烷、无水乙醚重结晶,抽滤,用冷乙醚冲洗,得白色固体M4。
在一个优选的实施方案中,反应温度80度。反应时间4-8小时。
(3)化合物M5:将化合物M4和醋酸铵加到反应瓶中,再加入乙醇使其溶解,加热回流24 h,将体系冷却至室温,抽滤,用乙醇冲洗得到墨绿色固体M5。
和醋酸铵的投料摩尔比为1:40。重点强调,醋酸铵必须过过量,不然没有反应。
(4)将步骤(3)得到固体M5溶解在二氯甲烷中,然后加入三乙胺,反应半小时。最后,加入三氟化硼乙醚,反应3小时。混合物用冰淬灭。用二氯甲烷萃取,减压蒸馏,剩余物用硅胶柱提纯展开剂为二氯甲烷/正己烷,得到固体I。
对本发明上述的化合物,采用核磁共振图谱包括1H,13C NMR核磁光谱,吸收光谱,荧光光谱,质谱等来确定其结构。
本发明所述新型R-azaBODIPY荧光染料具有如下特点:
所述的化合物最大特点是3,5-位非芳基取代的氮杂氟硼二吡咯甲川R-azaBODIPY荧光染料结构,是对传统经典的azaBODIPY结构的突破。
所述的化合物具有高的荧光量子产率。
所述的化合物,原料易得,结构新颖,易于制备,易产业化,经4步反应即可得到目标化合物。
本发明的这些特征和优点以及其他特征和优点,在参考以下附图和本发明的具体实施方式之后将变得显而易见。
实施例1
制备新型3,5-位非芳基取代的aza-BODIPY类荧光染料I-1
(1)新型3,5-位非芳基取代的R-azaBODIPY类荧光染料I-1的合成。
(2)化合物M3-1:在圆底烧瓶中加入频那酮(1.00 g,10 mmol)和氢氧化钾(8.4mg,0.15 mmol),向体系中加入乙醇/水溶液(85:15= v/v,100 mL),再加入苯甲醛(1.1 g,10 mmol),室温搅拌24 h,在此反应过程中,产物从混合液中沉淀下来,反应结束后,过滤混合液,过滤得到的固体再用乙醇重结晶,得到黄色固体M3-1(1.7 g,90%)。
(3)化合物M4-1:称取化合物M3-1(0.94 g,5 mmol)到反应瓶中,加入250 mL 干燥的甲醇使其溶解,再向体系中加入硝基甲烷(1.07 g,0.02 mol)和二乙胺(1.46 g,0.02mol),加热回流24 h。反应完成后,将反应体系冷却静置至室温,用1 mol/L 的盐酸酸化至弱酸性,用二氯甲烷/蒸馏水萃取混合液,有机相用无水MgSO4 干燥,过滤滤去固体,滤液用旋转蒸发仪旋蒸除去大部分溶剂后得到粗产物,再用二氯甲烷、无水乙醚重结晶,抽滤,用冷乙醚冲洗,得白色固体M4-1(1.6 g,64.3%)。
(4)称取化合物M4-1(1.2 g,5 mmol)和醋酸铵(15.4 g,200 mmol)到反应瓶中,加入60 mL 已蒸的乙醇使其溶解,加热回流48 h,待原料完全反应后,将体系冷却至室温,抽滤,用冷乙醇冲洗得到墨绿色固体M5-1 (0.83 g, 81%)。
(5)化合物I-1:化合物I-1:称取化合物M5-1(1.0 g,2.2mmol)到反应瓶中,抽真空,氮气置换,加入50 mL二氯甲烷作为溶剂,加入三乙胺(0.5 mL,3.5 mmol )搅拌30 min,加入三氟化硼乙醚溶剂(2 mL )搅拌12 h。用二氯甲烷/蒸馏水萃取混合液,有机相用无水MgSO4 干燥,过滤滤去固体,滤液用旋转蒸发仪旋蒸除去大部分溶剂后得到粗产物,再用二氯甲烷、无水乙醚重结晶,抽滤,用冷乙醚冲洗,得到金属光泽固体(0.71 g, 70%)。1H NMR(500 MHz, CDCl3): δ (ppm) 7.79 (d, 3 J = 8.0 Hz, 4H), 7.42 (t, 3 J = 8.0 Hz,4H), 7.38 (t, 3 J = 8.0 Hz, 2H), 6.81 (s, 2H), 1.57 (s, 18H). 13C-NMR (125 MHz,CDCl3): δ (ppm) 144.6, 143.8, 132.5, 130.5, 129.4, 129.1, 128.4, 116.9,113.7, 30.1. ESI-MS: m/z =457.2.
I-1荧光量子产率高达93%。
以上内容是结合具体的优化实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在本发明核心构思前提下,还可以做出若干简单演绎和替换,都应该视为属于本发明的保护范围。作为本发明所属技术领域的普通技术人员来说,在基于本发明下,还可以做出若干简单推理,得到本发明的化合物的其他领域应用,都应当视为属于本发明的保护范围。
Claims (3)
1.3,5-位非芳基取代R-azaBODIPY荧光染料,其特征在于,其通式如式Ⅰ所示:
在式I中,其中R选自-t-Bu,-CF3等非芳基的基团;芳基Ar选自Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8 等基团;
代表分子结构举例如下所示:
。
2.根据权利要求1所述的3,5-位非芳基取代R-azaBODIPY荧光染料,其特征在于,其中R选自R1-R6等基团;Ar选自Ar1-Ar8等基团。
3. 3,5-位非芳基取代R-azaBODIPY荧光染料制备方法,其特征在于,所述方法包括如下步骤:
(1)化合物M3:在圆底烧瓶中加入非芳基R取代基的乙酮M1和氢氧化钾,向体系中加入乙醇/水溶液,再加入芳基甲醛M2,室温搅拌24 h,在此反应过程中,产物从混合液中沉淀下来,反应结束后,过滤,得到的固体再用乙醇重结晶,得到黄色固体M3;
M1中R选自所述的R1-R6等基团;M2中Ar选自所述的Ar1-Ar8等基团;M3中R选自所述的R1-R6等基团,Ar选自所述的Ar1-Ar8等基团;
(2)化合物M4:将化合物M3加入反应瓶中,加入干燥的甲醇使其溶解,再向体系中加入硝基甲烷和二乙胺,加热回流6 h;反应完成后,将反应体系冷却静置至室温,用的盐酸酸化至弱酸性,用二氯甲烷/蒸馏水萃取,有机相用无水MgSO4 干燥,过滤滤去固体,滤液用旋转蒸发仪旋蒸除去溶剂后,得到粗产物;再用二氯甲烷、无水乙醚重结晶,抽滤,用冷乙醚冲洗,得白色固体M4;
M4中R选自R1-R6等基团;Ar选自Ar1-Ar8等基团;
(3)化合物M5:将化合物M4和醋酸铵加到反应瓶中,再加入乙醇使其溶解,加热回流48h,将体系冷却至室温,抽滤,用乙醇冲洗得到墨绿色固体M5;
M5中R选自所述的R1-R6等基团,Ar选自所述的Ar1-Ar8等基团;
(4)将步骤(3)得到固体M5溶解在二氯甲烷中,然后加入三乙胺,反应半小时;最后,加入三氟化硼乙醚,反应3小时;混合物用冰淬灭;用二氯甲烷萃取,减压蒸馏,剩余物用硅胶柱提纯,展开剂为二氯甲烷/正己烷,得到固体I。
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