CN106986755B - 一种光催化制备对羟基苯甲醛的方法 - Google Patents
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Abstract
本发明公开一种光催化制备对羟基苯甲醛的方法。该方法是在石英反应容器中,加入一定量的对羟基卞醇、反应溶剂和介孔TMDs催化剂,通过可见光催化反应得到目标产物对羟基苯甲醛。本发明所用光催化工艺操作简便,后处理简单;另外由于介孔催化剂具有较大的表面积和孔容、可调的孔径、催化活性高。
Description
技术领域
本发明涉及医药技术领域,具体涉及一种对羟基苯甲醛的合成方法。
背景技术
对羟基苯甲醛是合成白藜芦醇系列产品的关键中间体。作为一类含有芪类结构的非黄酮类多酚化合物,白藜芦醇系列产品广泛天然存在于葡萄、桑葚、花生和虎杖等植物中。由于良好的抗氧化和抑制癌细胞作用被喻为继紫杉醇等药物之后的又一类新的抗肿瘤分子,市场需求量大。直接从植物中提取已经远远满足不了市场的需求,同时随着2007年高纯度的合成白藜芦醇、紫檀茋相继通过美国FDA认证,通过绿色合成方法来制备白藜芦醇系列产品也就越发迫切。通过对产品逆合成分析我们发现,对羟基苯甲醛是白藜芦醇系列产品研发工艺中的关键中间体。除此之外,对羟基苯甲醛还广泛应用于香料、医药和食品等精细化学品的研发,合成意义大。通过对文献和专利的调研,我们认为制备对羟基苯甲醛常用的工艺包括:苯酚的直接芳醛化,以及对羟基甲苯或者对羟基卞醇的氧化制得。苯酚的直接芳醛化可以通过Vilsmeier试剂(彭久合CN103787945A;刘鹏CN102992982A)、Reimer-Tiemann反应(裴文CN101270037A)制备,反应经典可行,但是过程中需要使用氯仿、三氯氧磷、类光气等有毒有害试剂;通过对羟基甲苯的金属催化、氧气氧化制得对羟基苯甲醛过程相对比较清洁(张大男,中国专利CN102115435A),但是该氧化反应受气液传质控制的影响明显,可通过设置反应流动床(刘有智CN101462933A)或者喷射反应器(张伟江CN102992973A)来改进氧化反应。近年来光催化技术在光催化选择性氧化中的应用得到了越来越多的关注,与传统有机氧化反应相比,光催化氧化反应具有得天独厚的优势:(1)反应条件温和,通常在常温常压下进行;(2)利用半导体吸收光子发生电子跃迁后在价带产生的空穴来提供强的氧化能力,无需高污染性强氧化剂作为反应原料,特别是避免了氧化剂投料过量后的复杂后处理过程;(3)光催化有可能激发常温下热力学不能自发进行的反应。(4)光化学激发有时可设计出更短的反应历程,从而将副反应减小到最小程度;(5)可以利用无限免费使用的太阳能。针对对羟基卞醇的光催化制备对羟基苯甲醛,最近也开始有科技论文报道(吴骊珠等,Angew.Chem.Int.Ed.2017,56,3020)。
发明内容
针对现有技术的不足,本发明提供一种过渡金属硫族化合物(TMDs:transitionmetal dichalcogenides)光催化制备对羟基苯甲醛的方法。该方法选用过渡金属硫族化合物(TMDs)作为催化剂,反应具有较高的反应活性和催化选择性,易于分离。
本发明所采用的技术方案如下:
在石英反应容器中,加入一定量的对羟基卞醇,然后加入介孔金属硫族化合物(TMDs)催化剂和一定量的溶剂,可见光照射下,20℃~80℃下反应2~12h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
所述的催化剂为介孔金属硫族化合物(TMDs),化学式为MX2,其中M为过渡金属,X为硫族元素。其中M主要包括Mo、W、V、中的一种或两种,X为S、Se、Te中的一种或两种。
催化剂与对羟基卞醇的重量比为:1%~5%:1。
所述的反应溶剂为乙腈、甲苯和环己烷中的一种,优选为乙腈。
所述的反应溶剂与对羟基卞醇的重量比为:5~15:1。
所述的介孔金属硫族化合物催化剂采用焙烧法制备,具体制备过程如下:
称取一定量的过渡金属化合物,溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钨酸、磷钼酸或乙酰丙酮氧钒@KIT-6前驱物。在二段式管式炉中,第一段放硫族化合物,第二段放磷钨酸、磷钼酸或乙酰丙酮氧钒@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为200~500℃,二段式管式炉中第二段的温度为400~800℃,H2的流量为50-1000mL/min;恒温2-12h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂。
所述的多孔硅KIT-6与过渡金属化合物的质量比为1:1~4;过渡金属化合物中金属离子与硫族化合物的摩尔比为1:3~20;多孔硅KIT-6与乙醇的质量体积比为1g:20mL。
所述的过渡金属化合物为磷钨酸、磷钼酸或乙酰丙酮氧钒的一种或两种。
所述的硫族化合物为S、Se、Te的一种或两种。
本发明具有的有益效果是:
1、自制的介孔TMDs催化剂具有较大的表面积和孔容、可调的孔径(2-50nm)、催化活性高。且TMDs类材料带隙宽度相对较窄(<2.4eV),可以在可见光照射下发生光催化反应。
2、本发明所用的固体催化剂可回收套用,具有反应条件温和,后处理简单,污染小的优点。
附图说明
图1为硒化钨的电镜图,其中(a)、(b)、(c)为SEM图,(d)、(e)为低分辨TEM图,(f)为高分辨TEM图。
具体实施方式
下面结合实施例对本发明做进一步的分析。
首先制备介孔复合金属氧化物催化剂,具体见如下实施例:
实施例1-1
称取4g磷钨酸,溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钨酸@KIT-6前驱物。在二段式管式炉中,第一段放4g Se粉,第二段放磷钨酸@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为400~450℃,二段式管式炉中第二段的温度为500~550℃,H2的流量为200mL/min;恒温3h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂WSe2。图1为硒化钨的电镜图,具有于具有较大的表面积和孔容、可调的孔径(2-50nm)。
实施例1-2
称取1g乙酰丙酮氧钒,溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到乙酰丙酮氧钒@KIT-6前驱物。在二段式管式炉中,第一段放2.4g S粉,第二段放乙酰丙酮氧钒@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为200~250℃,二段式管式炉中第二段的温度为400~450℃,H2的流量为100mL/min;恒温5h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂VS2。硫化钒电镜图显示其具有较大的表面积和孔容、可调的孔径(2-50nm)。
实施例1-3
称取2g磷钼酸,溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钼酸@KIT-6前驱物。在二段式管式炉中,第一段放5g Te粉(钼与Te的摩尔比为1:3),第二段放磷钼酸@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为450~500℃,二段式管式炉中第二段的温度为750~800℃,H2的流量为1000mL/min;恒温2h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂MoTe2。碲化钼电镜图显示其具有较大的表面积和孔容、可调的孔径(2-50nm)。
实施例1-4
称取0.2g磷钼酸、0.5g磷钨酸溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钼酸@KIT-6前驱物。在二段式管式炉中,第一段放2.2gTe粉(钼+钨与Te的摩尔比为1:5),第二段放磷钼酸@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为250~300℃,二段式管式炉中第二段的温度为550~600℃,H2的流量为50mL/min;恒温2h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂Mo3WTe8,电镜图显示其具有较大的表面积和孔容、可调的孔径(2-50nm)。
实施例1-5
称取0.2g磷钼酸、0.55g乙酰丙酮氧钒溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钼酸@KIT-6前驱物。在二段式管式炉中,第一段放2.2g Te粉(钼+钒与Te的摩尔比为1:5),第二段放磷钼酸@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为300~350℃,二段式管式炉中第二段的温度为500~550℃,H2的流量为500mL/min;恒温12h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂MoV3.5Te9,电镜图显示其具有较大的表面积和孔容、可调的孔径(2-50nm)。
实施例1-6
称取0.2g磷钨酸、0.55g乙酰丙酮氧钒溶于20mL乙醇中,完全溶解后,加入1g的KIT-6介孔模板,搅拌至乙醇挥发完全得到磷钼酸@KIT-6前驱物。在二段式管式炉中,第一段放2.7g Se粉(钨+钒与Se的摩尔比为1:10),第二段放磷钼酸@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为300~350℃,二段式管式炉中第二段的温度为500~550℃,H2的流量为500mL/min;恒温12h后,自然冷却至室温,除去模板,得到介孔金属硫族化合物(TMDs)催化剂WV2Te6,电镜图显示其具有较大的表面积和孔容、可调的孔径(2-50nm)。
然后利用上述实施例1-1~1-6制备得到的催化剂制备对羟基苯甲醛,具体见如下实施例:
实施例2-1
在石英反应容器中,加入1g对羟基卞醇,溶于10g乙腈中加入介孔金属硫族化合物(TMDs)催化剂WSe20.02g,可见光照射下,30℃下反应5h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
实施例2-2
在石英反应容器中,加入1g对羟基卞醇,溶于10g乙腈中加入介孔金属硫族化合物(TMDs)催化剂VS20.02g,可见光照射下,30℃下反应5h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
实施例2-3
在石英反应容器中,加入1g对羟基卞醇,溶于5g甲苯中加入介孔金属硫族化合物(TMDs)催化剂MoTe20.01g,可见光照射下,20℃下反应12h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
实施例2-4
在石英反应容器中,加入1g对羟基卞醇,溶于15g环己烷中加入介孔金属硫族化合物(TMDs)催化剂Mo3WTe8 0.05g,可见光照射下,80℃下反应2h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
实施例2-5
在石英反应容器中,加入1g对羟基卞醇,溶于10g乙腈中加入介孔金属硫族化合物(TMDs)催化剂MoV3.5Te90.02g,可见光照射下,30℃下反应5h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
实施例2-6
在石英反应容器中,加入1g对羟基卞醇,溶于10g乙腈中加入介孔金属硫族化合物(TMDs)催化剂WV2Te60.02g,可见光照射下,30℃下反应5h,反应结束后,过滤回收催化剂,滤液旋蒸回收反应溶剂,后处理得到目标产物对羟基苯甲醛。
上述固体催化剂均可回收套用。
上述实施例并非是对于本发明的限制,本发明并非仅限于上述实施例,只要符合本发明要求,均属于本发明的保护范围。
Claims (8)
2.如权利要求1所述的一种光催化制备对羟基苯甲醛的方法,其特征在于介孔TMDs催化剂与对羟基苄醇的重量比为0.01~0.05:1。
3.如权利要求1所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的反应溶剂为乙腈、甲苯和环己烷中的一种。
4.如权利要求3所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的反应溶剂为乙腈。
5.如权利要求1所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的反应溶剂与对羟基苄醇的重量比为5~15:1。
6.如权利要求1所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的介孔TMDs催化剂采用焙烧法制备,具体制备过程如下:
称取一定量的过渡金属化合物溶于乙醇中,完全溶解后,加入多孔硅KIT-6,搅拌至乙醇挥发完全得到过渡金属化合物@KIT-6前驱物;
在二段式管式炉中,第一段放硫族单质,第二段放上述得到的过渡金属化合物@KIT-6前驱物,二段式管式炉中通入H2;控制二段式管式炉中第一段的温度为200~500℃,二段式管式炉中第二段的温度为400~800℃,H2的流量为50~1000mL/min;恒温2~12h后,自然冷却至常温,除去KIT-6,得到介孔TMDs催化剂;
所述的过渡金属化合物为磷钨酸、磷钼酸或乙酰丙酮氧钒的一种或两种;
所述的硫族单质为S、Se或Te。
7.如权利要求6所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的多孔硅KIT-6与过渡金属化合物的质量比为1:1~4。
8.如权利要求6所述的一种光催化制备对羟基苯甲醛的方法,其特征在于所述的过渡金属化合物中金属离子与硫族单质的摩尔比为1:3~20。
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