CN114920908B - 含芴酮的有机共轭聚合物及其在α-酮酯合成中的应用 - Google Patents
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Abstract
本发明公开了一种含芴酮的有机共轭聚合物及其在催化烯胺酮氧化酯化合成α‑酮酯中的应用,属于光催化技术领域。该有机共轭聚合物是以2,7‑二溴‑9‑芴酮和1,3,5‑三乙炔苯作为单体,通过过渡金属Pd一步催化聚合制得的。本发明制备的有机共轭聚合物可以良好的分散在乙醇中并保持稳定,且其具有较强的可见光响应能力,在绿色可见光照射下可展示出良好的光催化烯胺酮氧化酯化生成α‑酮酯的活性。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种含芴酮的有机共轭聚合物及其在光催化烯胺酮氧化酯化合成α-酮酯中的应用。
背景技术
α-酮酯作为合成砌块和生物学相关的前体是一种具有广泛应用价值的化合物。目前,α-酮酯可以通过几种不同的方法合成,例如,钯催化的芳基卤化物的双羰基化(J. Org.Chem. 1987, 52, 5733-5740),铜催化的α-酮醛的C-H键酯化(Org. Chem. Front. 2014,1, 109-112),铑催化的芳基硼酸和氰基酸酯的偶联以及串联的C-H键氧化/甲基酮的酯化(Chem. Commun. 2007, 2855-2857)。由于已知方法中通常需要复杂的底物、过渡金属催化或苛刻的反应条件,因而开发一种新型催化剂并通过使用容易获得的底物来合成α-酮酯的方法显得尤为重要。
2018年,Hwang等人开发了一种简单的可见光诱导铜催化末端炔和醇之间的反应,其中碳碳叁键被裂解与醇反应形成α-酮酯(Chem. Sci. 2018, 9, 7318)。2019年,Wan等人又报道了以玫瑰红作为光催化剂剪断碳碳双键合成α-酮酯的方法(Green Chem, 2019,21, 3436–3441)。这些工作都是采用均相光催化剂来进行,催化剂的回收利用存在很大问题,目前还没有异相催化形成α-酮酯的报道。
近年来,有机共轭聚合物材料作为一种不含金属元素的光催化剂,由于其化学结构可调、合成方法简单、具有良好的物理化学稳定性,受到科研工作者的广泛关注(Nat.Comm. 2018, 9, 4968-4970)。有机共轭聚合物材料在光催化分解水产氢(Polymer 2017,126, 283-290)、光催化降解污染物(New J. Chem. 2014, 38, 5695-5699)和光催化有机合成(Angew. Chem. Int. Ed. 2018, 57, 8316-8320)方面有着广泛的应用前景。本发明采用含芴酮小分子化合物和1,3,5-三乙炔基苯作为单体,通过过渡金属Pd催化一步聚合反应得到含芴酮的有机共轭聚合物,其在室温条件下可以实现烯胺酮和醇类反应合成α-酮酯。
发明内容
本发明的目的在于提供一种含芴酮的有机共轭聚合物及其制备与在室温可见光条件下催化烯胺酮和醇类反应高效生成α-酮酯类化合物中的应用。
为实现上述目的,本发明采用如下技术方案:
一种含芴酮的有机共轭聚合物,其是使用2,7-二溴-9-芴酮和1,3,5-三乙炔苯作为单体,通过过渡金属Pd催化一步聚合反应制得的,其反应式如下;该有机共轭聚合物在可见光照射下展示出良好的光催化烯胺酮氧化酯化生成α-酮酯的活性。
。
所述含芴酮的有机共轭聚合物的制备方法包括以下步骤:
(1)在氮气保护下,将2,7-二溴-9-芴酮和1,3,5-三乙炔苯、四三苯基膦钯、碘化亚铜溶于N,N-二甲基甲酰胺与三乙醇胺的混合溶剂中,加热至90 ℃,搅拌反应24小时,冷却至室温后,过滤收集固体样品,依次用水、无水乙醇、四氢呋喃各洗涤三次;
(2)将步骤(1)洗涤后的固体样品用水-乙醇-四氢呋喃的混合溶液索氏提取48小时,收集所得固体物质;
(3)将步骤(2)所得固体物质进行干燥,得到所述含芴酮的有机共轭聚合物。
步骤(1)所用2,7-二溴-9-芴酮、1,3,5-三乙炔苯、四三苯基膦钯和碘化亚铜的摩尔比为1.5:1:0.04:0.1;所用N,N-二甲基甲酰胺与三乙醇胺的混合溶剂中两者的体积比为1:1。
步骤(2)所用水-乙醇-四氢呋喃的混合溶液中三者的体积比为1:1:1;其所用体积为固体样品质量的1000倍。
步骤(3)中所述干燥的温度为75℃,时间为24小时。
上述含芴酮的有机共轭聚合物可用于可见光条件下高效催化烯胺酮氧化酯化生成α-酮酯类化合物,其具体是以烯胺酮和无水乙醇为反应原料,分子筛为干燥剂,无水乙酸为反应溶剂,利用所述含芴酮的有机共轭聚合物为光催化剂,在50W绿色LED灯照射下反应6小时,以生成α-酮酸酯。
本发明的显著优点在于:
(1)本发明所制备的含芴酮的有机共轭聚合物具有良好的可见光响应,同时具有较高的烯胺酮氧化酯化生成α-酮酯的反应活性和选择性,是一种具有实用价值的新型非均相光催化剂,可实现利用廉价易得、安全稳定的烯胺酮为反应原料制备α-酮酯。
(2)本发明所制备的含芴酮的有机共轭聚合物可以回收循环使用多次,并能保持良好的催化活性。
(3)本发明整个生产工艺过程简单易于控制,且能耗低,成本低,符合实际生产需要,有利于大规模的推广。
附图说明
图1为实施例1所得含芴酮的有机共轭聚合物的X射线粉末衍射图。
图2为实施例1所得含芴酮的有机共轭聚合物的傅里叶变换红外光谱图。
图3为实施例1所得含芴酮的有机共轭聚合物的扫描电镜图。
图4为实施例1所得含芴酮的有机共轭聚合物的紫外可见漫反射图。
图5为实施例2利用含芴酮的有机共轭聚合物光催化烯胺酮氧化酯化所得反应产物的核磁共振氢谱图。
图6为实施例2利用含芴酮的有机共轭聚合物光催化烯胺酮氧化酯化所得反应产物的核磁共振碳谱图。
图7为实施例3中催化剂多次循环利用的反应活性图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
在氮气保护条件下,在100毫升三颈瓶中加入2,7-二溴-9-芴酮(1.5 mmol,507 毫克)和1,3,5-三乙炔苯(1 mmol,150 毫克),四三苯基膦钯(0.04 mmol,46.8毫克)、碘化亚铜(0.1mmol,20毫克)和混合溶剂40毫升(N,N-二甲基甲酰胺:三乙醇胺=1:1,v/v),加热至90 ℃,搅拌24小时,冷却至室温,过滤得固体。所得固体用水、无水乙醇和四氢呋喃各洗涤三次(每次50毫升),然后于300毫升水-乙醇-四氢呋喃的混合溶液(1:1:1,v/v/v)中索氏提取48小时,所得固体样品在75 ℃烘箱中干燥24小时,得含芴酮的有机共轭聚合物固体粉末。
图1为所得含芴酮的有机共轭聚合物固体粉末的XRD图。从图中可以发现含芴酮的有机共轭聚合物固体粉末在21.5°处出现一个宽峰,表明合成的有机共轭聚合物是非晶态的,具有部分堆叠结构。
图2为所得含芴酮的有机共轭聚合物固体粉末的FT-IR图。图中可见,在1581 cm-1附近的信号归属于样品中芳香环的特征吸收;在1175 cm-1的信号归属于样品中羰基的特征吸收;在2183 cm-1处的信号归属于碳碳叁键的特征吸收;在3228 cm-1处的信号归属于炔氢基的特征吸收,表明含芴酮有机共轭聚合物光催化剂的顺利合成。
图3为所得的含芴酮的有机共轭聚合物的扫描电镜图。从图中可以看出聚合物样品呈堆叠状。
图4为所得的含芴酮的有机共轭聚合物的紫外可见漫反射图。从图中可以看出含芴酮的有机轭聚合物有较好的可见光吸收。
实施例2
取5毫克实施例1制备的含芴酮的有机共轭聚合物分散在2毫升无水乙醇中,然后加入烯胺酮(0.1 mmol,17.5毫克),4Å分子筛10毫克,乙酸(11.4 μL,0.2 mmol),在50W绿色LED灯照射下反应6小时,得到α-酮酸酯,其反应式如下,产品得率为55%,
。
图5、6分别为所得的α-酮酯产物的核磁共振氢谱和碳谱。由图中可见,氢谱中在低场的三组多重峰为苯环上的三种氢,在4.4 ppm左右的四重峰归属于亚甲基上的氢,在1.4ppm左右的三重峰归属于甲基上的氢。碳谱显示有8种不同化学结构的碳,与产物结构一致,证明了光催化反应的顺利发生。
实施例3
将实施例2反应后的反应液在10000转下离心5分钟,收集催化剂固体并用乙醇洗涤三次(每次5毫升),在75 ℃烘箱中烘干12小时后重复进行实施例2的反应。
图7为催化剂循环使用的活性情况图。从图中可见,该催化剂循环使用五次,收率基本保持稳定,充分说明了该异相催化剂稳定性较好,具有可重复利用的优点。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种含芴酮的有机共轭聚合物在光催化烯胺酮氧化酯化生成α-酮酯中的应用,其特征在于:使用2,7-二溴-9-芴酮和1,3,5-三乙炔苯作为反应单体,通过过渡金属Pd催化一步聚合反应制得所述含芴酮有机共轭聚合物;
应用时,以烯胺酮和无水乙醇为反应原料,无水乙酸为反应溶剂,利用所述含芴酮的有机共轭聚合物为光催化剂,在50W绿色LED灯照射下反应6小时,以生成α-酮酸酯。
2.根据权利要求1所述的应用,其特征在于:所述含芴酮的有机共轭聚合物的制备具体包括以下步骤:
(1)在氮气保护下,将2,7-二溴-9-芴酮和1,3,5-三乙炔苯、四三苯基膦钯、碘化亚铜溶于N,N-二甲基甲酰胺与三乙醇胺的混合溶剂中,加热至90 ℃,搅拌反应24小时,冷却至室温后,过滤收集固体样品,依次用水、无水乙醇、四氢呋喃各洗涤三次;
(2)将步骤(1)洗涤后的固体样品用水-乙醇-四氢呋喃的混合溶液索氏提取48小时,收集所得固体物质;
(3)将步骤(2)所得固体物质进行干燥,得到所述含芴酮的有机共轭聚合物。
3.根据权利要求2所述的应用,其特征在于:步骤(1)所用2,7-二溴-9-芴酮、1,3,5-三乙炔苯、四三苯基膦钯和碘化亚铜的摩尔比为1.5:1:0.04:0.1;
所用N,N-二甲基甲酰胺与三乙醇胺的混合溶剂中两者的体积比为1:1。
4.根据权利要求2所述的应用,其特征在于:步骤(2)所用水-乙醇-四氢呋喃的混合溶液中三者的体积比为1:1:1;其所用体积为固体样品质量的1000倍。
5.根据权利要求2所述的应用,其特征在于:步骤(3)中所述干燥的温度为75℃,时间为24小时。
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