CN112724374B - 一种基于含硼荧光染料的新型共轭微孔聚合物的制备及其光催化应用 - Google Patents
一种基于含硼荧光染料的新型共轭微孔聚合物的制备及其光催化应用 Download PDFInfo
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
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Abstract
本发明属于精细化工技术领域,公开了一种基于含硼荧光染料的新型共轭微孔聚合物的制备及其光催化应用。该聚合物通过Sonogashira–Hagihara反应进行制备,通过在1,3,5‑三(二氟硼氧基)‑2,4,6‑三((4‑溴苯基亚氨基)甲基)‑苯中引入含硼荧光染料结构增加光催化性能,将1,3,5‑三(二氟硼氧基)‑2,4,6‑三((4‑溴苯基亚氨基)甲基)‑苯与1,3,5‑三‑(4‑乙炔基苯基)苯加入到舒伦克管中在80℃氮气保护下反应48‑72h,得到基于含硼荧光染料的新型催化剂。本发明制备的催化剂具有良好的化学和热稳定性并且具有较高的催化性能,对苄胺衍生物催化产率可到99%以上。
Description
技术领域
本发明涉及精细化工技术领域,具体涉及一种基于含硼荧光染料的新型共轭微孔聚合物的制备及其光催化应用。
背景技术
能源危机和环境污染已成为世界性问题。主要原因之一是使用不可再生能源-化石燃料。太阳能作为一种清洁、可再生的能源,由于其具有储量丰富和无污染的优点,已成为研究的热点。其中,光催化是使用太阳能的相对成功和有效的例子,而传统的无机半导体是其中一种相对成熟的应用实例。但是在光催化领域,它们也因催化效率低以及结构性能单一而受到了限制。因此,开发具有高比表面积、结构可调、良好稳定性的新型材料作为高效光催化剂具有重要的意义,同时对科研人员来说也是一个巨大的挑战。
由于含硼染料本身具有具有较高的光和化学稳定性,较大的摩尔消光系数,较强的吸收和发射,较大的荧光量子产率等良好的发光特性,这些优良的性质使得这类配合物在有机功能材料领域的应用发展迅猛,但是作为均相催化剂,难以分离且重复使用性低,限制了其进一步的应用。而含硼共轭多孔聚合物因结合了多孔材料和含硼染料的优点的已经得到了一定的开发,因其具有可调几何结构,独特的路易斯酸硼中心和非常丰富的物理特性,例如高比表面,带电支架,强光致发光和分子内电荷转移等,已成为最有前途的功能材料之一。
目前合成的含硼聚合物主要是基于硼二吡咯亚甲基(BODIPY)衍生物的有机多孔聚合物,它表现出丰富的光物理性质,包括高吸收系数,良好的荧光量子产率,相对窄的吸收和发射谱带,因此,是一种重要的功能构建基,在有机太阳能电池,有机发光二极管,传感和成像等方面获得了不错的应用。但是另一种含硼染料苯胺及其相应的二氟化硼配合物(Boranil)的有机多孔聚合物还未见报道。研究发现Boranil中的杂环可以有效增加共轭区域,使得该系列配合物发射的荧光可以用肉眼观察到,同时化合物的紫外吸收和荧光强度也有大幅提高,使Boranil类化合物在荧光材料中的应用表现出巨大的潜力。因此,亟需设计合成一种基于Boranil的共轭微孔聚合物并用作高效光催化剂。
发明内容
为了克服现有技术的不足,本发明的目的提供一种基于含硼荧光染料的新型共轭微孔聚合物的制备及其光催化应用。本发明制备的聚合物催化剂具有良好的化学和热稳定性并且具有较高的催化性能,对苄胺衍生物催化产率可到99%以上。对非均相催化剂的设计提供了更为有效的处理方法和研究方向。
本发明的上述目的是通过以下技术方案实现的:
一种基于含硼荧光染料的新型共轭微孔聚合物,其结构如式I所示:
一种苄胺类化合物,其结构式如式II所示:
式中,R为H,或Me或OMe或F或Cl。
上述一种基于含硼荧光染料的新型共轭微孔聚合物的制备方法,聚合物通过Sonogashira–Hagihara反应进行制备,通过在1,3,5-三(二氟硼氧基)-2,4,6-三((4-溴苯基亚氨基)甲基)-苯中引入含硼荧光染料结构增加光催化性能,将1,3,5-三(二氟硼氧基)-2,4,6-三((4-溴苯基亚氨基)甲基)-苯与1,3,5-三-(4-乙炔基苯基)苯加入到舒伦克管中在80℃氮气保护下反应48-72h,得到基于含硼荧光染料的催化剂。
进一步的,一种基于含硼荧光染料的新型共轭微孔聚合物的制备方法,具体步骤如下所示:
(1)制备化合物A:
在氩气保护下依次将六亚甲基四胺和间苯三酚加入到250mL舒伦克瓶中。然后在冰水浴中加入30-50mL三氟乙酸,将反应混合物置于90-110℃油浴中恒温搅拌3-6小时,然后将60-80mL 3M的盐酸加入到舒伦克瓶中,继续加热搅拌2-4小时。反应结束后纯化得到单体结构化合物A,其结构式如式IV所示;
制备化合物A反应式如下所示:
(2)制备化合物B
在氩气保护下依次将对溴苯甲胺和单体化合物A加入到50mL舒伦克瓶中。然后加入有机溶剂,将反应混合物置于90-110℃油浴中恒温搅拌48-72小时。反应结束后纯化得到单体结构化合物B,其结构式如式V所示;
制备化合物B反应式如下所示:
(3)制备化合物C
在0℃氛围下将单体化合物B加入到的舒伦克瓶中。然后加入纯三氟化硼***。逐滴滴加二异丙基氨基锂。将混合物在氩气保护下于室温搅拌12-48小时。反应结束后纯化得到单体结构化合物C,其结构式如式VI所示;
制备化合物C反应式如下所示:
(4)制备化合物D
将4-溴苯乙酮和对甲苯磺酸放入研钵中充分研磨,将4-氨基苄腈加入到的舒伦克瓶中。然后逐滴加入三氟甲磺酸。将混合物移入100mL圆底烧瓶中并在130-150℃下搅拌24-48小时。反应结束后纯化得到单体结构化合物D,其结构式如式VII所示;
制备化合物D反应式如下所示:
(5)制备化合物E
在氩气氛围下依次将将单体化合物D,碘化铜,三苯基膦和双(三苯基膦)氯化钯加入到250mL的舒伦克瓶中。然后加入有机溶剂。将混合物在氩气保护下在40-60℃搅拌20-40分钟。然后再氩气保护下逐滴滴加三甲基硅基乙炔,在80-120℃搅拌24-48小时。反应结束后纯化得到单体结构化合物E,其结构式如式VIII所示;
制备化合物E反应式如下所示:
(6)制备化合物F
将单体化合物E加入到100mL圆底烧瓶中。然后加入体积比为1:1-4的二氯甲烷/甲醇溶液。然后加入固体碳酸钾。将混合物在室温下搅拌12-48小时。反应结束后纯化得到
单体结构化合物F,其结构式如式IX所示;
制备化合物F反应式如下所示:
(7)在氩气保护下依次将化合物C,化合物F,四(三苯基膦)钯和碘化铜加入到100mL舒伦克瓶中。然后加入为5-30mL体积比为2:1的N,N-二甲基甲酰胺/三乙胺,通过三次冷冻-解冻循环在舒伦克瓶中脱气。之后,将反应混合物在80-100℃油浴锅中恒温搅拌48-72小时。反应结束后纯化得到一种基于含硼荧光染料的新型催化剂;
步骤(1)所述的六亚甲基四胺和间苯三酚的摩尔比为:1-1.5:1。
步骤(2)所述的对溴苯甲胺和单体化合物A的摩尔比为3-4:1。所述的有机溶剂为乙醇。
步骤(3)所述的单体化合物B和二异丙基氨基锂的摩尔比为1:4-10。
步骤(4)所述的4-溴苯甲酮和对甲苯磺酸的摩尔比为8-10:1。
步骤(5)所述的单体化合物D,碘化铜,三苯基膦,双(三苯基膦)氯化钯和三甲基硅基乙炔的摩尔比为40:1:4:2:180。所述的有机溶剂为三乙胺。
步骤(6)所述的单体化合物E和固体碳酸钾的摩尔比为1:4-8。
步骤(7)所述的化合物C,化合物F,四(三苯基膦)钯和碘化铜的摩尔比为25:25:2:1。
进一步的,所述步骤(7)中反应结束后,将反应混合物过滤,将该固体用有机溶剂洗涤多次,最后,在索氏提取器中用有机溶剂萃取粗产物24小时,并在120℃下真空干燥过夜,得到红褐色固体粉末催化剂。将反应生成的固体用有机溶剂反复洗涤多次,具体为向反应生成的固体中分别加入丙酮,N,N-二甲基甲酰胺,四氢呋喃,水进行洗涤。索氏提取器中所用有机溶剂为四氢呋喃,甲醇。
上述制备方法制备得到的催化剂在催化氧化胺偶联反应和硫醚氧化反应的应用。
一种催化氧化胺偶联反应的测试方法:
将上述方法制备得到的催化剂和不同取代基的苄胺按照一定比例加入到有机溶剂,在室温及空气下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR,原料和产物以及副产物的积分峰之比用于计算产率和转化率。
所述的不同取代基苄胺为4-甲基苄胺、4-甲氧基苯胺、4-氟苄胺、4氯-苄胺。所述的有机溶剂为乙腈。所述的催化剂与苄胺的比例为0.5%:1。
本发明与现有技术相比的有益效果是:
本发明的优点和效果是利用Sonogashira–Hagihara偶联反应可以制备基于含硼荧光染料的新型共轭微孔聚合物,在结构中引入引入了硼荧光基团作为关键的光收集部分和吸电子体,有效地调控了能量和电子的转移,增加了催化剂的催化性能,催化氧化胺偶联反应的产率高达99%。而且催化反应的反应条件温和、绿色、简便、产率高、适用范围广。催化生成的化合物结构稳定,应用价值更高。
附图说明
下面结合附图和实施例对本发明进一步说明:
图1是实施例1制备得到的聚合物的红外光谱图。
图2是实施例1制备得到的聚合物的N2吸附-脱附图。
图3是实施例1制备得到的聚合物的孔径分布图。
图4是实施例1制备得到的聚合物的固体核磁图。
图5是实施例1制备得到的聚合物的热重图。
图6是实施例1制备得到的聚合物的XPS图。
图7是实施例1制备得到的聚合物的SEM图。
图8是实施例1制备得到的聚合物的固体紫外图。
具体实施方式
下面通过具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从商业途径获得。
实施例1
一种基于含硼荧光染料的新型催化剂的制备方法,步骤如下:
(1)制备化合物A:2,4,6-三羟基-1,3,5-苯三甲醛;
在氩气保护下依次将六亚甲基四胺(7.549g,54mmol)和间苯三酚(3.007g,24.5mmol)加入到250mL舒伦克瓶中。然后在冰水浴中加入45mL三氟乙酸,将反应混合物置于100℃油浴中恒温搅拌4小时,然后将75mL 3M的盐酸加入到舒伦克瓶中,继续加热搅拌3小时。反应结束后冷却至室温,过滤悬浮液。随后向滤液中加入二氯甲烷(3×50mL),分离两相,有机层用无水硫酸镁干燥,并过滤。通过旋转蒸发溶剂得到黄色固体。最后,用热乙醇洗涤得到的黄色固体,最终得到纯化的橘粉色固体产物化合物A。
(2)制备化合物B:2,4,6-三((4-溴苯基氨基)亚甲基)环己烷-1,3,5-三酮;
在氩气保护下依次将对溴苯甲胺(210mg,1mmol)和2,4,6-三羟基-1,3,5-苯三甲醛(860mg,5mmol)加入到50mL舒伦克瓶中。然后加入15mL无水乙醇溶液,将反应混合物置于90℃油浴中恒温搅拌48小时。反应结束后冷却至室温,过滤悬浮液,随后用热乙醇洗涤沉淀。所得固体产物在60℃下真空干燥12小时,得到亮黄色固体产物化合物B。
(3)制备化合物C:1,3,5-三(二氟硼氧基)-2,4,6-三((4-溴苯基亚氨基)甲基)-苯;
在氩气保护下将2,4,6-三((4-溴苯基氨基)亚甲基)环己烷-1,3,5-三酮(335.5mg,0.5mmol)加入到50mL舒伦克瓶中,加入纯净的三氟化硼***(13mL)。将反应混合物搅拌5分钟并冷却至0℃。然后逐滴加入二异丙基氨基锂(10mmol,在1M THF溶液中)。将混合物在氩气保护下于室温搅拌24小时。之后,将反应冷却至0℃,并通过添加水(60mL)淬灭。通过过滤分离固体产物,用水和甲醇洗涤,并60℃真空干燥12小时。得到亮黄色固体产物化合物C。
(4)制备化合物D:1,3,5-三(4-溴苯基)苯;
将4-溴苯乙酮(1g,5.02mmol)和对甲苯磺酸(0.1g,0.58mmol)放入研钵中并充分研磨。然后转移至100mL圆底烧瓶中,并将混合物在140℃加热24小时。之后,将反应混合物用饱和碳酸钠溶液洗涤,并用二氯甲烷萃取。将有机相用无水硫酸镁干燥,旋转真空除去溶剂,并将粗产物用***洗涤,得到棕色固体产物化合物D。
(5)制备化合物E:1,3,5-三-(4-三甲基甲硅烷基乙炔基苯基)苯;
在氩气氛围下依次将1,3,5-三(4-溴苯基)苯(1g,1.83mmol),碘化铜(10.52mg,0.053mmol),三苯基膦(48.27mg,0.183mmol)和双(三苯基膦)氯化钯(64.6mg,0.09mmol)加入到250mL的舒伦克瓶中。然后加入三乙胺(80mL)。将混合物在氩气保护下在50℃搅拌30分钟。然后再氩气保护下逐滴滴加三甲基硅基乙炔(1.13mL,8.27mmol),在100℃搅拌36小时。反应结束后,旋转真空除去溶剂,并将粗产物通过柱色谱法纯化,使用石油醚(PE)作为洗脱剂。得到白色固体产物化合物E。
(6)制备化合物F:1,3,5-三-(4-乙炔基苯基)苯;
将1,3,5-三-(4-三甲基甲硅烷基乙炔基苯基)苯(2.0g,3.36mmol)加入到100mL圆底烧瓶中。然后加入体积比为1:1的二氯甲烷/甲醇溶液。然后加入固体碳酸钾(2.04g,14.76mmol)。将混合物在室温下搅拌24小时。反应结束后,向反应混合物中加入水(80ml),然后用二氯甲烷萃取三次。将有机相旋转真空除去溶剂,并将粗产物通过柱色谱法纯化,使用石油醚(PE)作为洗脱剂。得到白色固体产物化合物F。
步骤(1)、步骤(2)、步骤(3)、步骤(4)、步骤(5)、步骤(6)反应方程式如下所示:
(7)制备基于含硼荧光染料的新型共轭微孔聚合物;
在氩气保护下依次将化合物C(250mg,0.31mmol),化合物F(116mg,0.31mmol),四(三苯基膦)钯(60mg,0.05mmol)和碘化铜(24mg,0.126mmol)加入到100mL舒伦克瓶中。然后加入为35mL体积比为2:1的N,N-二甲基甲酰胺/三乙胺,通过三次冷冻-解冻循环在舒伦克瓶中脱气。之后,将反应混合物在80℃油浴锅中恒温搅拌72小时。反应结束后,将反应混合物过滤,将该固体用丙酮,N,N-二甲基甲酰胺,四氢呋喃,水等有机溶剂洗涤多次,最后,在索氏提取器中用四氢呋喃,甲醇分别萃取粗产物24小时,并在60℃下真空干燥过夜,得到红褐色固体粉末催化剂。反应结束后纯化得到基于含硼荧光染料的新型催化剂;该催化剂的红外、N2吸附-脱附、孔径分布、固体核磁、热重、XPS、SEM、固体紫外分析结果如图1、图2、图3、图4、图5、图6、图7、图8所示。从图1和图4、图6可知,成功合成了聚合物;如图2、图3所示说明合成的聚合物具有良好的孔道结构。从图5可以看出,合成的聚合物具有良好的热稳定性;从图7可以看出,合成的聚合物具有片状结构;从图8可以看出,引入含硼荧光染料的聚合物的吸收峰出现在可见光范围内的更高波长处。
上述方法制备得到的基于含硼荧光染料的新型催化剂催化氧化胺偶联反应的测试方法如下所示:
在空气中,将催化剂(2.5μmol,0.5mol%)和苄胺(0.5mmol)加入到石英管中,然后加入乙腈(5mL)将苄胺分散均匀,在室温下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR分析,原料、产物和副产物的积分峰之比用于计算产率、转化率。表征数据:1H NMR(500MHz,CDCl3)δ(ppm):4.86(s,2H),7.26~7.33(m,1H),7.33~7.41(m,4H),7.42~7.47(m,3H),7.77~7.85(m,2H),8.43(s,1H).产物为(E)-N-苄基-1-苯基甲亚胺。
结构式为:
应用例1
实施例1制备得到的基于含硼荧光染料的新型催化剂催化氧化胺偶联反应的测试方法如下所示:
在空气中,将实施例1制备的催化剂(2.5μmol,0.5mol%)和4-甲基苄胺(0.5mmol)加入到石英管中,然后加入乙腈(5mL)将苄胺分散均匀,在室温下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR分析,原料、产物和副产物的积分峰之比用于计算产率、转化率。表征数据:1H NMR(500MHz,CDCl3)δ(ppm):2.36(s,3H),2.41(s,3H),4.79(s,2H),7.17(d,J=8.0Hz,2H),7.25(d,J=4.0Hz,4H),7.69(d,J=8.0Hz,2H),8.37(s,1H).产物为(E)-N-(4-甲基苄基)-1-(对甲苯基)甲亚胺。
结构式为:
应用例2
实施例1制备得到的基于含硼荧光染料的新型催化剂催化氧化胺偶联反应的测试方法如下所示:
在空气中,将实施例1制备的催化剂(2.5μmol,0.5mol%)和4-甲氧基苄胺(0.5mmol)加入到石英管中,然后加入乙腈(5mL)将苄胺分散均匀,在室温下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR分析,原料、产物和副产物的积分峰之比用于计算产率、转化率。表征数据:1H NMR(500MHz,CDCl3)δ(ppm):3.82(s,3H),3.86(s,3H),4.75(s,2H),6.93(m,4H),7.27(d,J=8.0Hz,2H),7.74(d,J=8.0Hz,2H),8.32(s,1H).产物为(E)-N-(4-甲氧基苄基)-1-(4-甲氧基苯基)甲亚胺。
结构式为:
应用例3
实施例1制备得到的基于含硼荧光染料的新型催化剂催化氧化胺偶联反应的测试方法如下所示:
在空气中,将实施例1制备的催化剂(2.5μmol,0.5mol%)和4-氟苄胺(0.5mmol)加入到石英管中,然后加入乙腈(5mL)将苄胺分散均匀,在室温下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR分析,原料、产物和副产物的积分峰之比用于计算产率、转化率。表征数据:1H NMR(500MHz,CDCl3)δ(ppm):4.7(s,2H),7.05(t,J=8.0Hz,2H),7.13(t,J=8.0Hz,2H),7.31(dd,J1=12.0Hz,J2=8.0Hz,2H),7.80(dd,J1=8.0Hz,J2=4.1Hz,2H),8.37(s,1H).产物为(E)-N-(4-氟苄基)-1-(4-氟苯基)甲亚胺。
结构式为:
应用例4
实施例1制备得到的基于含硼荧光染料的新型催化剂催化氧化胺偶联反应的测试方法如下所示:
在空气中,将实施例1制备的催化剂(2.5μmol,0.5mol%)和4-氯苄胺(0.5mmol)加入到石英管中,然后加入乙腈(5mL)将苄胺分散均匀,在室温下用26W蓝色LED灯照射,搅拌。通过TLC和1H NMR监测反应进程,在原料消失后停止反应。然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物。粗产物采用1H NMR分析,原料、产物和副产物的积分峰之比用于计算产率、转化率。表征数据:1H NMR(500MHz,CDCl3)δ(ppm):4.80(s,2H),7.25~7.32(m,2H),7.32~7.38(m,2H),7.42(d,J=12.0Hz,2H),7.74(d,J=8.0Hz,2H),8.37(s,1H).产物为(E)-N-(4-氯苄基)-1-(4-氯苯基)甲亚胺。
结构式为:
实施例1制备的催化剂催化剂的氧化胺偶联的催化反应式如下所示:
实施例1和应用例1-4中由实施例1制备的催化剂催化剂的氧化胺偶联的催化性能表如下表表1所示:
表1催化剂催化剂的氧化胺偶联的催化性能
以上所述实施方式仅为本发明的优选实施例,而并非本发明可行实施的全部实施例。对于本领域一般技术人员而言,在不背离本发明原理和精神的前提下对其所作出的任何显而易见的改动,都应当被认为包含在本发明的权利要求保护范围之内。
Claims (6)
2.如权利要求1所述的一种基于含硼荧光染料的共轭微孔聚合物的制备方法,其特征是,具体步骤如下所示:
(1)制备化合物A:
在氩气保护下依次将六亚甲基四胺和间苯三酚加入到250mL舒伦克瓶中;然后在冰水浴中加入30-50mL三氟乙酸,将反应混合物置于90-110℃油浴中恒温搅拌3-6小时,然后将60-80mL 3M的盐酸加入到舒伦克瓶中,继续加热搅拌2-4小时;反应结束后纯化得到单体结构化合物A,其结构式如式所示;
制备化合物A反应式如下所示:
( 2 ) 制备化合物B
在氩气保护下依次将对溴苯甲胺和单体化合物A加入到50mL舒伦克瓶中;然后加入有机溶剂,将反应混合物置于90-110℃油浴中恒温搅拌48-72小时;反应结束后纯化得到单体结构化合物B,其结构式如式所示;
制备化合物B反应式如下所示:
(3)制备化合物C
制备化合物C反应式如下所示:
(4)制备化合物D
制备化合物D反应式如下所示:
(5)制备化合物E
在氩气氛围下依次将单体化合物D,碘化亚铜,双(三苯基膦)氯化钯加入到250mL的舒伦克瓶中;然后加入有机溶剂;将混合物在氩气保护下在40-60℃搅拌20-40分钟;然后再氩气保护下逐滴滴加三甲基硅基乙炔,在80-120℃搅拌24-48小时;反应结束后纯化得到单体结构化合物E,其结构式如式所示;
制备化合物E反应式如下所示:
(6)制备化合物F
将单体化合物E加入到100mL圆底烧瓶中;然后加入体积比为1:1-4的二氯甲烷/甲醇溶液;然后加入固体碳酸钾;将混合物在室温下搅拌12-48小时;反应结束后纯化得到单体结构化合物F,其结构式如式所示;
制备化合物F反应式如下所示:
(7)在氩气保护下依次将化合物C,化合物F,四(三苯基膦)钯和碘化亚铜加入到100mL舒伦克瓶中;然后加入为5-30mL体积比为2:1的N,N-二甲基甲酰胺/三乙胺,通过三次冷冻-解冻循环在舒伦克瓶中脱气;之后,将反应混合物在80-100℃油浴锅中恒温搅拌48-72小时;反应结束后纯化得到基于含硼荧光染料的催化剂。
3.如权利要求2所述的一种基于含硼荧光染料的共轭微孔聚合物的制备方法,其特征是,步骤(1)所述的六亚甲基四胺和间苯三酚的摩尔比为:1-1.5:1;
步骤(2)所述的对溴苯甲胺和单体化合物A的摩尔比为3-4:1;所述的有机溶剂为乙醇;
步骤(3)所述的单体化合物B和二异丙基氨基锂的摩尔比为1:4-10;
步骤(4)所述的4-溴苯乙酮和对甲苯磺酸的摩尔比为8-10:1;
步骤(5)所述的单体化合物D,碘化亚铜,双(三苯基膦)氯化钯和三甲基硅基乙炔的摩尔比为40:1:4:2:180;所述的有机溶剂为四氢呋喃;
步骤(6)所述的单体化合物E和固体碳酸钾的摩尔比为1:4-8;
步骤(7)所述的化合物C,化合物F,四(三苯基膦)钯和碘化亚铜的摩尔比为25:25:2:1。
4.如权利要求1所述的一种基于含硼荧光染料的共轭微孔聚合物在催化氧化胺偶联反应的应用。
5.如权利要求1所述的基于含硼荧光染料的共轭微孔聚合物作为催化剂在催化氧化胺偶联反应时的测试方法,其特征是,催化剂和不同取代基的苄胺按照一定比例加入到有机溶剂,在室温及空气下用26W蓝色LED灯照射,搅拌;通过TLC和1H NMR监测反应进程,在原料消失后停止反应;然后通过离心,过滤除去催化剂,并将滤液浓缩、蒸发后获得粗产物;粗产物采用1H NMR,原料,产物和副产物的积分峰之比用于计算产率、转化率。
6.如权利要求5所述的测试方法,其特征是,所述的不同取代基苄胺为4-甲基苄胺、4-甲氧基苄胺、4-氟苄胺、4-氯苄胺;所述的有机溶剂为乙腈;所述的催化剂与苄胺的比例为0.5%:1。
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Non-Patent Citations (4)
Title |
---|
"Conjugated porous polymer based on BOPHY dyes as photocatalyst under visible light";Lopez-Calixto Carmen G et al.;《Applied Catalysis B: Environmental》;20191205;第258卷;第117933页 * |
"Deprotection strategy of BODIPY conjugated porous polymer to obtain heterogeneous (dipyrrin)(bipyridine)ruthenium(II) visible light photocatalyst";Liras Marta et al.;《Journal of Materials Chemistry A: Materials for Energy and Sustainability》;20161010;第4卷(第44期);第17274-17278页 * |
"Hybrids Based on BOPHY-Conjugated Porous Polymers as Photocatalysts for Hydrogen Production: Insight into the Charge Transfer Pathway";Lopez-Calixto, Carmen G. et al.;《ACS Catalysis》;20200729;第10卷(第17期);第9804-9812页 * |
Justin A. Riddle et al.."Schiff Base Route to Stackable Pseudo-Triphenylenes: Stereoelectronic Control of Assembly and Luminescence".《Journal of the American Chemical Society》.2006,第128卷(第34期),第10986-10987页. * |
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