CN109232621A - 一种氨基取代氮杂氟硼荧近红外染料的制备方法 - Google Patents
一种氨基取代氮杂氟硼荧近红外染料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种氨基取代氮杂氟硼荧近红外染料的制备方法。本发明所述染料通过以下步骤制备获得:(1)醛和对氨基苯乙酮在二乙胺为添加剂、80 oC条件下进行羟醛缩合制备氨基取代查尔酮;(2)在氢氧化钠和二乙胺存在的条件下与硝基甲烷进行迈克加成反应;(3)在醋酸铵条件下进行成环‑偶合反应;(4)在得到(3)中的产物与三氟化硼‑乙醚进行络合反应得到目标产物氮杂氟硼荧近红外染料。本发明目标产物结构明确,合成工艺简单,易于纯化,产率较高。该目标产物紫外吸收和荧光发射强(在四氢呋喃溶液中紫外吸收光谱最大吸收波长达782 nm,荧光发射峰波长为838 nm)。这类染料在发光二极管、太阳能电池、生物成像、生物传感、肿瘤治疗等方面有着巨大的应用前景。
Description
技术领域
本发明属于近红外染料的制备技术领域,具体涉及一种氨基取代氮杂氟硼荧近红外染料的新型制备方法。
背景技术
近红外吸收染料是指吸收波长在750-2500nm范围内的电磁波,由于其显著的磁、光、电、热等响应性能,越来越受到国内外重视,近红外吸收染料在有机太阳能电池、发光二极管、生物检测、肿瘤诊疗、光学存储记录等领域有着巨大的研究价值。
近红外吸收染料可分为有机和无机近红外染料。常见的有机近红外染料有菁类染料,光稳定性差;酞菁染料,合成要求高,产率低,分子体积较大且溶解性差;金属络合物染料,溶解性较差,吸收强度不大;氟硼荧(BODIPY)染料等,而BODIPY类染料易于修饰且具有良好的光学性质,如摩尔消光系数高,荧光量子产率高,光稳定性好,紫外吸收和荧光发射较长,荧光光谱半峰宽窄等优点。
氮杂氟硼荧染料是以BODIPY为基本结构,将8-位的碳原子换成氮原子,HOMO-LUMO能级变窄,且吸收和发射波长发生红移。这类化合物是近年来受到人们广泛研究的一类新型近红外染料,由于这类染料具有较强的吸收和发射、半峰宽较窄、光稳定性良好、摩尔消光系数大等优点,在各个领域具有潜在的应用价值。已报道的氨基取代氮杂氟硼荧染料制备过程中,在制备查尔酮步骤中使用氢氧化钾为碱,乙醇/水为混合溶剂;在迈克加成步骤中,使用氢氧化钠为碱,甲醇为溶剂,这两个制备步骤中未添加二乙胺(DEA)作为反应添加剂,产率低、提纯复杂,且很难生成目标化合物。(参见:Yang.et al.Chem.Asian J.2018,13,989–995)。
因此本发明是一种氨基取代氮杂氟硼荧近红外染料及其新型制备方法,通过优化制备过程中的反应添加剂、温度、时间来简化制备工艺,提高产物收率。
发明内容
本发明所要解决的技术问题是:提供一种新型制备氨基取代氮杂氟硼荧近红外染料方法来简化制备工艺,提高产物收率。
为解决上述技术问题,本发明提供了一种新型制备氨基取代氮杂氟硼荧化合物的制备方法。该氨基取代氮杂氟硼荧化合物结构如下所示:
其制备反应路线如下:
反应条件为:
(1)将4-氨基苯乙酮和N,N-二烷基-4-氨基苯甲醛溶解在乙醇中,加入添加剂二乙胺,搅拌充分后,将氢氧化钾水溶液加入上述混合物中,加热回流,提纯后得到产物3;
(2)将产物3溶解于甲醇中,加入氢氧化钠、硝基甲烷和添加剂二乙胺加热回流,提纯后得到产物4;
(3)将产物4和醋酸铵溶解于正丁醇中,惰性气体保护下,加热回流,提纯后得到产物5;
(4)将产物5溶解于二氯甲烷中,惰性气体保护下加入DIPEA(N,N-二异丙基乙胺),避光,将三氟化硼-乙醚注射其中,室温反应,提纯后得到目标产物氨基取代氮杂氟硼荧。
作为优选,步骤(1)所述4-氨基苯乙酮和N,N-二烷基-4-氨基苯甲醛的摩尔比为1:1。
作为优选,步骤(1)所述的强碱氢氧化钾与原料4-氨基苯乙酮和N,N-二烷基-4-氨基苯甲醛的摩尔比为4:1,二乙胺与原料摩尔比为0.5:1。
作为优选,步骤(1)所述加热回流反应温度为60-90℃。
作为优选,步骤(1)所述加热回流反应时间为12-18小时。
作为优选,步骤(1)所述提纯步骤为水洗后二氯甲烷萃取,除去有机相后用硅胶色谱柱提纯。
作为优选,步骤(2)所述氢氧化钠与步骤(1)所得产物3的摩尔比为10:1;二乙胺与产物3的摩尔比为5:1;硝基甲烷与产物3的摩尔比为15:1。
作为优选,步骤(2)所述加热回流反应温度为50-70℃。
作为优选,步骤(2)所述加热回流反应时间为36-48小时。
作为优选,步骤(2)所述提纯步骤为加入正丁醇搅拌后,抽滤提纯。
作为优选,步骤(3)所述加热回流反应时间为3-4小时。
本发明的进步效果在于:与现有制备技术相比,本发明提供了一种新型制备氨基取代氮杂氟硼荧近红外染料的方法,通过优化制备过程中的反应试剂、温度、时间来简化制备工艺,优化提纯方法,提高产物收率。通过核磁共振氢谱(1H NMR),碳谱(13C NMR)以及基质辅助激光解析时间飞行质谱(MALDI-TOF Mass)证明了目标化合物氨基取代氮杂氟硼荧近红外染料的结构准确性。通过紫外分光光度计、荧光光谱仪表明该化合物的紫外吸收和荧光发射均在近红外区域。
附图说明
图1为氨基取代氮杂氟硼荧的1H-NMR谱图。
图2为氨基取代氮杂氟硼荧的13C-NMR谱图。
图3为氨基取代氮杂氟硼荧的MALDI-TOF-Mass谱图。
图4为氨基取代氮杂氟硼荧在四氢呋喃溶液中的紫外吸收光谱图。
图5为氨基取代氮杂氟硼荧在四氢呋喃溶液中的荧光发射光谱图。
具体实施方式
以下通过实施例进一步说明本发明,但这些实例技术方案并不限制本发明。
室温:是指25-30℃;
实施例1采用本发明所述方法制备氨基取代氮杂氟硼荧
(1)选取两口烧瓶(500mL),将4-氨基苯乙酮(5.40g,40mmol)和N,N-二乙基-4-氨基苯甲醛(7.08g,40mmol)溶解在乙醇(40mL)中,加入二乙胺(2mL,20mmol),搅拌5分钟,氢氧化钾(8.97g,160mmol)溶解于水中(40mL),并将氢氧化钾水溶液缓慢滴加到两口烧瓶中,80℃下加热回流12小时后,冷却至室温,水洗,用二氯甲烷萃取,除去有机相得到粗产品,用硅胶色谱柱提纯(二氯甲烷:石油醚:乙酸乙酯=1:1:0.1)得到深黄色固体,即产物3(10.36g,产率88%),其化学结构式如下所示:
(2)选取两口烧瓶(500mL),将上述产物3(7.36g,25.00mmol),溶解于甲醇(150mL)中,加入氢氧化钠(10.00g,250mmol),二乙胺(9.14g,125mmol)和硝基甲烷(22.89g,375mmol)70℃下加热回流48小时后,冷却至室温,得到深黄色粘稠粗产品,加入正丁醇搅拌10分钟,抽滤得到黄色固体产物4(7.99g,产率90%),其化学结构式如下所示:
(3)选取两口烧瓶(250mL),将产物4(3.39g,10.1mmol)和醋酸铵(27.25g,353.5mmol)溶解于正丁醇(40mL)中,氮气保护下,130℃加热回流3小时后,冷却至室温,抽滤,用甲醇洗,得到蓝色粉末,即产物5(2.20g,产率70%),其化学结构式如下所示:
(4)选取两口烧瓶(250mL),将产物5(0.62g,1.00mmol)溶解于二氯甲烷中(25mL),加入N,N-二异丙基乙胺(1.57mL,9.00mmol),抽换氮气三次后,避光,将三氟化硼-乙醚(1.89mL,15.00mmol)注射入烧瓶中,室温下反应10小时后,水洗,除去有机相,硅胶色谱柱提纯(二氯甲烷:乙酸乙酯=1:1)得到最终目标产物即氨基取代氮杂氟硼荧(0.48g,产率72%)。1HNMR(400MHz,CDCl3):δppm 8.08(d,J=8.8Hz,4H),7.98(d,J=8.8Hz,4H),6.83(s,2H),6.76-6.72(m,8H),4.00(s,4H),3.51-3.44(m,8H),1.30-1.24(m,12H).13C NMR(100MHz,CDCl3):δppm156.41,148.49,148.10,144.94,142.06,131.23,130.94,122.47,120.68,114.61,114.18,111.23,77.32,77.00,76.68,44.55,12.70.MALDI-TOF-MS(m/z):Calcd for:C40H42BF2N7([M]+):669.3563,found:669.2170.
实施例2采用现有技术所述方法制备氨基取代氮杂氟硼荧
选取两口烧瓶(500mL),将4-氨基苯乙酮(2.70g,20mmol)和N,N-二乙基-4-氨基苯甲醛(3.54g,20mmol)溶解在乙醇(20mL)中,搅拌5分钟,氢氧化钾(1.00g,25mmol)溶解于水中(10mL),并将此氢氧化钾水溶液缓慢滴加到两口烧瓶中,室温反应15小时后,除去乙醇,用二氯甲烷萃取,除去有机相得到粗产品,用硅胶色谱柱提纯(二氯甲烷:石油醚:乙酸乙酯=1:1:0.1)得到深黄色固体,即产物3(2g,产率34%)。
选取两口烧瓶(500mL),将产物3(1.19g,4mmol),溶解于乙醇(10mL)中,加入氢氧化钠(0.032g,0.8mmol)和硝基甲烷(4.88g,80mmol)于60℃下加热回流12-48小时后,全程通过薄层色谱法(TLC)监测反应,发现无产物4生成。
实施例3采用本发明制备的氨基取代氮杂氟硼荧性能测试
如图1、图2和图3所示通过核磁共振氢谱(1H NMR),碳谱(13C NMR)以及基质辅助激光解析时间飞行质谱(MALDI-TOF Mass)证明了目标化合物氨基取代氮杂氟硼荧近红外染料的结构准确性。于紫外测试的石英比色皿中加入2.5mL四氢呋喃溶液,加入少量氨基取代氮杂氟硼荧溶解于石英比色皿溶剂中,测试其紫外吸收光谱。结果如附图4所示,氨基取代氮杂氟硼荧染料的最大紫外吸收波长在近红外吸收范围内,为782nm;于荧光测试的石英比色皿中加入2.5mL四氢呋喃溶液,加入少量氨基取代氮杂氟硼荧溶解于石英比色皿溶剂中,测试其荧光发射光谱。如附图5所示,氨基取代氮杂氟硼荧染料的最大荧光发射波长在近红外吸收范围内,为838nm。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (4)
1.一种氨基取代氮杂氟硼荧近红外染料制备方法,其反应路线如下所示:
具体制备步骤如下所示:
步骤1:在氢氧化钾、二乙胺为添加剂及乙醇为溶剂的条件下,4-氨基苯乙酮与N,N-二烷基-4-氨基苯甲醛进行羟醛缩合反应,获得产物3;
步骤2:产物3在氢氧化钠、二乙胺为添加剂及甲醇为溶剂的条件下,与硝基甲烷进行迈克加成反应,获得产物4;
步骤3:产物4在醋酸铵和正丁醇的条件下进行成环及偶合反应,获得产物5;
步骤4:产物5在二异丙基乙基胺和二氯甲烷的条件下与三氟化硼-乙醚进行络合反应,最后合成氨基取代氮杂氟硼荧的近红外染料。
2.根据权利要求1所述的氨基取代氮杂氟硼荧近红外染料制备方法,其特征在于所述步骤(1)中4-氨基苯乙酮和N,N-二烷基-4-氨基苯甲醛的摩尔比为(1-1.5):1;氢氧化钾与原料摩尔比为(4-8):1,添加剂二乙胺与原料摩尔比为(0.5-2):1;反应温度为60-90℃;反应时间为12-18小时。
3.根据权利要求1所述的氨基取代氮杂氟硼荧近红外染料制备方法,其特征在于所述步骤(2)中氢氧化钠与步骤(1)所得产物3的摩尔比为(8-15):1;添加剂二乙胺与产物3的摩尔比为(3-8):1;硝基甲烷与产物3的摩尔比为(10-20):1;反应温度为50-70℃;反应时间为36-48小时;反应得到深黄色粘稠粗产品后,抽滤,正丁醇洗涤得到黄色固体产物4。
4.根据权利要求1所述的氨基取代氮杂氟硼荧近红外染料制备方法,其特征在于步骤(3)所述应时间为3-12小时。
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