CN107469828A - 一种核‑壳结构负载型钨复合催化剂及其制备方法和应用 - Google Patents
一种核‑壳结构负载型钨复合催化剂及其制备方法和应用 Download PDFInfo
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种核‑壳结构负载型钨复合催化剂及其制备方法和应用。现有喹诺酮类药物主环的合成大多存在着合成步骤长、操作繁琐、三废量大和成本较高等缺陷。本发明通过制备Fe3O4胶体、SiO2/Fe3O4复合纳米粒子制备磁分离核‑壳负载型钨复合催化剂WO3/SiO2/Fe3O4，此磁分离核‑壳负载型钨复合催化剂WO3/SiO2/Fe3O4用于催化合喹诺酮类化合物，提供了一种高效、催化剂可磁分离回收并循环利用的喹诺酮类化合物制备方法，本发明制备之催化剂能在喹诺酮类化合物的制备中重复利用，催化剂仍保有原来活性没有失活现象，不仅大大提高了生产效率，而且减少了环境的污染。
Description
技术领域
本发明是有关于催化剂、制备方法及其应用，特别是有关磁分离核-壳结构负载型钨复合催化剂、制备方法及其应用于喹诺酮类化合物合成的制备方法。
背景技术
喹诺酮类抗菌药是临床使用最广的抗感染药之一，由于喹诺酮类药物具有抗菌谱广、抗菌活性强、给药方便、不良反应小、与其他抗生素无交叉耐药性等优点而成为临床联合用药的首选，市场需求量大。
近年来研究发现，喹诺酮类药物在抗疟、抗艾滋病、抗肿瘤等多种疾病上有新的疗效，喹诺酮类化合物对原核II型拓扑异构酶、促旋酶和DNA拓扑异构酶IV也具有较好的活性，其活性谱和应用范围正在不断拓展。
然而，喹诺酮类药物主环的合成基本上都要经过三步反应才能得到其关键中间体，进而去进行水解和取代反应得到喹诺酮类药物，存在着合成步骤长、操作繁琐、三废量大和成本较高等缺陷。因此，寻找新的合成技术、探索新的催化剂制备方法，是目前研究工作的重点。式(Ⅰ)为喹诺酮分子结构。
发明内容
本发明的目的之一是提供一种磁分离核-壳结构负载型钨复合催化剂的制备方法，其制得的磁分离核-壳结构负载型钨复合催化剂用于合成喹诺酮类化合物时，降低生产成本，减少三废，提高产品质量。
为此，本发明采用的技术方案为：一种核-壳结构负载型钨复合催化剂的制备方法，其包含如下步骤：
步骤1)，在铁化合物水溶液中加入还原剂和碱，加温至50-80℃并搅拌，得到Fe3O4胶体；
步骤2)，在适量的分散溶剂中加入步骤1)得到的Fe3O4胶体、正硅酸乙酯和水解催化剂，反应4-8小时，得到SiO2/Fe3O4复合纳米粒子；
步骤3)，在偏钨酸铵水溶液中加入步骤2)得到的SiO2/Fe3O4复合纳米粒子，搅拌8-14小时，于90-150℃下干燥得第一固体，该第一固体经450-650℃焙烧1-6小时，得到磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4；
上述铁化合物：正硅酸乙酯：偏钨酸铵的摩尔数比＝1:1-10:0.1-1；
其中，所述的铁化合物为FeCl3、FeCl3·6H2O或三乙酰丙酮铁；所述的还原剂为Na2SO3、抗坏血酸或水合肼；所述的碱为氨水、氢氧化钠或醋酸钠。
作为上述技术方案的优选，所述的铁化合物为FeCl3。
作为上述技术方案的优选，所述的还原剂为Na2SO3。
作为上述技术方案的优选，所述的碱为氨水。
作为上述技术方案的优选，步骤1)加温后，加入作为表面活性剂的聚乙烯吡咯烷酮，持续搅拌，之后离心并用水洗涤，最后分散再去除水得到Fe3O4胶体。
作为上述技术方案的优选，步骤2)中，所述的分散溶剂为乙醇，所述的水解催化剂为氨水。
作为上述技术方案的优选，步骤3)中，所述的第一固体先经研磨过120目标准筛后再经450-650℃焙烧1-6小时。
本发明的另一目的是提供上述制备方法得到的磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4。
本发明的又一个目的是提供上述磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4在合成喹诺酮类化合物中的应用，反应步骤如下：
步骤1)，搅拌混合甲酰基乙酸乙酯钠盐、非极性有机溶剂和WO3/SiO2/Fe3O4催化剂，通入胺类化合物，加入2，4-二氯-5-氟苯甲酰氯，反应0.5-3小时；
步骤2)，接着步骤1)，滴加伯胺同时通入CO2，控制反应压力为1-5个大气压，反应0.5-3小时；
步骤3)，接着步骤2)，加入碱金属氢氧化物和非极性有机溶剂，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收非极性有机溶剂；
步骤4)，接着步骤3)，加适量水，升温至100℃，滴加盐酸调节酸碱度控制pH值范围在4.8-6.5，待晶体析出后，离心、烘干得喹诺酮类化合物；
其中，所述的非极性有机溶剂为甲苯、二甲苯或前两者的混合物，所述的胺类化合物为二甲胺、二乙胺或二环己胺，所述的伯胺为环丙胺或S-丙二醇胺，所述的碱金属氢氧化物为氢氧化钠、氢氧化锂或氢氧化钾。
本发明喹诺酮类药物关键中间体的合成方法，以甲酰基乙酸乙酯盐和环丙胺等为主要起始原料，在新型磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4催化下，与多卤代芳酰氯“一锅法”制备得喹诺酮主环化合物。
作为上述技术方案的优选，所述的非极性有机溶剂为甲苯，所述的胺类化合物为二甲胺，所述的伯胺为环丙胺，所述的碱金属氢氧化物为氢氧化钠。
喹诺酮类化合物的制备流程如下：
本发明具有的优点是：本发明制备了磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4，利用其催化合喹诺酮类化合物，并通过磁分离方式回收催化剂。与传统使用强碱催化剂相比，C-N偶联硫效率明显提高，反应时间缩短，工艺成本明显降低。同时，提供了一种高效、催化剂可磁分离回收并循环利用的喹诺酮类化合物制备方法，本发明制备之催化剂能在喹诺酮类化合物的制备中重复利用，催化剂仍保有原来活性没有失活现象，不仅大大提高了生产效率，而且减少了环境的污染。与传统工艺相比，本发明喹诺酮类化合物的制备方法具有操作简单，生产效率高，强碱用量少，生产成本低等优点，是一种高效、经济、环保的生产工艺。
附图说明
图1为本发明磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的结构示意图；
图2为本发明实施例5的核-壳催化剂的投射电镜(TEM)图；
从图2中可以看出制备的催化剂具有包裹均匀、粒径小、团聚少等特点，有助于高效催化环合反应。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
本发明磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的制备流程如下：
首先运用部分还原-共沉淀法制备Fe3O4纳米粒子，然后通过溶胶凝胶法制备得到SiO2/Fe3O4复合纳米粒子，最后通过浸渍焙烧法制备得到磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4。
实施例1-12
制备磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的制备方法，依次按以下步骤进行：
1)、制备Fe3O4纳米粒子
运用部分还原-共沉淀法制备Fe3O4纳米粒子。在室温下将16.3g FeCl3加入到250mL烧瓶中，并用水溶解。在氮气保护下，缓缓加入还原剂Na2SO3溶液(含2.7g Na2SO3)并搅拌，10分钟后迅速加入40.8mL质量分数为28％的氨水，即可观察到黑色粒子生成。将恒温水浴温度升到70℃，并加入2mL油胺作为表面活性剂，持续搅拌6小时，之后将产物离心并用去离子水洗涤数次，最后分散再去除离子水，得到稳定的Fe3O4胶体。
2)、制备SiO2/Fe3O4复合纳米粒子
在常温下，往100mL烧杯中依次加入10mL EtOH，1.16g Fe3O4胶体，8mL去离子水和12.5g TEOS(正硅酸乙酯)，持续搅拌30分钟，然后加入42mL质量分数为28％的氨水催化TEOS(正硅酸乙酯)水解、缩合，密封反应6小时后将产物离心分离，分别经EtOH，去离子水清洗数次，得到SiO2/Fe3O4复合纳米粒子。
3)、制备磁分离Core-Shell负载型钨复合催化剂WO3/SiO2/Fe3O4
在常温下，往50mL烧杯中依次加入17.7g偏钨酸铵，10mL去离子水，并持续搅拌至完全溶解后，加入步骤2)制备所得的SiO2/Fe3O4复合纳米粒子，并持续强烈搅拌12小时。之后置于在烘箱中于110℃下干燥12小时。接着用研钵研磨，并过120目标准筛。将得到的固体粉末置于马弗炉中，于550℃下焙烧3小时，得到磁分离Core-Shell负载型钨复合催化剂WO3/SiO2/Fe3O4，备用。
实施例1-12除了使用的偏钨酸铵：TEOS：FeCl3摩尔数比列于表1，其他实施步骤和实施条件均相同。
表1：实施例1-12使用的偏钨酸铵：TEOS：FeCl3摩尔数比
实施例a1-a12：喹诺酮类化合物的制备方法
向反应釜内投入24.6g甲酰基乙酸乙酯钠盐，100mL甲苯和4g WO3/SiO2/Fe3O4催化剂，在搅拌下通入8.7g二甲胺，加入10g 2，4-二氯-5-氟苯甲酰氯，保温反应1小时，在50℃下滴加环丙胺，同时通入CO2，控制反应压力为1.5-2个大气压。反应1小时后，在反应液中加入12g片碱和200mL甲苯，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收甲苯至干。加适量水，升温至100℃，体系澄清后滴加盐酸调节酸碱度，待晶体析出后，离心、烘干得式(Ⅴ)的有机胺化物。
实施例a1-a12使用催化剂WO3/SiO2/Fe3O4来源的列于表2，其他实施步骤和实施条件均相同。
表2.实施例a1-a12各实施例条件及收率
以实施例a12为例，催化剂实施例12在这个条件下可以产率79.5％，另外在此催化条件下，催化剂实施例12磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O回收、循环使用第5次，仍保有优异的式(Ⅴ)的有机胺化物收率，催化效果没有明显下降，具体见下表3：
表3.磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的循环套用实验
以上列举的仅是本发明的若干个具体实施例。显然，本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (10)
1.一种核-壳结构负载型钨复合催化剂的制备方法，其包含如下步骤：
步骤1)，在铁化合物水溶液中加入还原剂和碱，加温至50-80℃并搅拌，得到Fe3O4胶体；
步骤2)，在适量的分散溶剂中加入步骤1)得到的Fe3O4胶体、正硅酸乙酯和水解催化剂，反应4-8小时，得到SiO2/Fe3O4复合纳米粒子；
步骤3)，在偏钨酸铵水溶液中加入步骤2)得到的SiO2/Fe3O4复合纳米粒子，搅拌8-14小时，于90-150℃下干燥得第一固体，该第一固体经450-650℃焙烧1-6小时，得到磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4；
上述铁化合物：正硅酸乙酯：偏钨酸铵的摩尔数比＝1:1-10:0.1-1；
其中，所述的铁化合物为FeCl3、FeCl3·6H2O或三乙酰丙酮铁；所述的还原剂为Na2SO3、抗坏血酸或水合肼；所述的碱为氨水、氢氧化钠或醋酸钠。
2.根据权利要求1的制备方法，其特征在于，所述的铁化合物为FeCl3。
3.根据权利要求1的制备方法，其特征在于，所述的还原剂为Na2SO3。
4.根据权利要求1的制备方法，其特征在于，所述的碱为氨水。
5.根据权利要求1的制备方法，其特征在于，步骤1)加温后，加入作为表面活性剂的聚乙烯吡咯烷酮，持续搅拌，之后离心并用水洗涤，最后分散再去除水得到Fe3O4胶体。
6.根据权利要求1的制备方法，其特征在于，步骤2)中，所述的分散溶剂为乙醇，所述的水解催化剂为氨水。
7.根据权利要求1的制备方法，其特征在于，步骤3)中，所述的第一固体先经研磨过120目标准筛后再经450-650℃焙烧1-6小时。
8.由权利要求1-7任一项制备方法制备的磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4。
9.权利要求8所述磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4在合成喹诺酮类化合物中的应用，反应步骤如下：
步骤1)，搅拌混合甲酰基乙酸乙酯钠盐、非极性有机溶剂和WO3/SiO2/Fe3O4催化剂，通入胺类化合物，加入2，4-二氯-5-氟苯甲酰氯，反应0.5-3小时；
步骤2)，接着步骤1)，滴加伯胺同时通入CO2，控制反应压力为1-5个大气压，反应0.5-3小时；
步骤3)，接着步骤2)，加入碱金属氢氧化物和非极性有机溶剂，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收非极性有机溶剂；
步骤4)，接着步骤3)，加适量水，升温至100℃，滴加盐酸调节酸碱度控制pH值范围在4.8-6.5，待晶体析出后，离心、烘干得喹诺酮类化合物；
其中，所述的非极性有机溶剂为甲苯、二甲苯或前两者的混合物，所述的胺类化合物为二甲胺、二乙胺或二环己胺，所述的伯胺为环丙胺或S-丙二醇胺，所述的碱金属氢氧化物为氢氧化钠、氢氧化锂或氢氧化钾。
10.根据权利要求9所述的应用，其特征在于，所述的非极性有机溶剂为甲苯，所述的胺类化合物为二甲胺，所述的伯胺为环丙胺，所述的碱金属氢氧化物为氢氧化钠。
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