CN110357927A - 一种双核钯催化剂的制备方法及用途 - Google Patents
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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Abstract
本发明公开了一种双核钯催化剂的制备方法及用途,该种方法将Pd(OAc)2、N‑甲基咪唑、磷钼酸,二甲基亚砜置于烧杯中反应,反应完毕后滤液缓慢挥发,得到双核钯催化剂的晶体。本发明方法具有反应速度快、反应过程简单,得到的产品纯度高,后处理简单等特点。并且在芳香醇的选择性氧化中,转化率高达99%,选择性高达99%。
Description
技术领域
本申请属于催化剂材料制备技术领域,其中涉及到一种新型双核钯催化剂的制备方法。本发明中的新型双核钯催化剂在醇分子氧氧化反应中具有较好的催化活性。
技术背景
钯催化剂在有机合成反应中一直是科学家们研究的热点领域,广泛地应用于C-C键、C-N键偶联反应、氧化反应以及还原反应等,在很多化学领域都具有潜在的应用前景。然而,钯催化剂的结构对于不同的催化反应影响较大,因而扩展不同结构的钯催化剂也尤其重要。
醇类化合物氧化为相应的羰基化合物是有机合成及工业生产的重要反应,尤其是由芳香醇制备芳香醛,是一个非常重要的有机反应。因为芳香醛其主要用作制造染料、医药、香料、调味品、农药等重要中间体的原料。制备芳香醛的方法较多,如早期用MnO2等氧化剂氧化甲苯制得苯甲醛以及采用苄基氯氧化法来制备苯甲醛等。近年来,合成苯甲醛的方法不断被改进,最近报道的有用铬化合物和在相转移催化剂存在下次氯酸盐催化氧化苄基氯和在介质及配体存在下使用CrO3氧化苯甲醇等,这些方法虽然不同程度地提高了反应物的转化率和苯甲醛的选择性,但是使用卤化物和高价态金属氧化物带来严重的环境问题,不符合绿色化学发展的理念。从原子经济反应和环境友好的角度来看,用空气(或分子氧)代替化学计量的氧化剂是解决问题的最好途径。以分子氧为氧化剂,在环境压力下实现醇类分子的选择性氧化是人们长期以来追寻的目标,因此选择合适的催化剂体系成为解决这一问题的关键。
近年来,文献报道中报道使用[(Ar2NacNac)Pd(k2-OAc)](Ar=2,6-dibenzhydryl-4-methylphenyl)钯催化剂氧化芳香醇(P.Saxena,et al,Journal of OrganometallicChemistry,868(2018)76-85)利用叔丁基过氧化氢,以及过氧化氢异丙苯为氧化剂、Pd-STO催化剂(L.Saputra,et al,Molecular Catalysis 453(2018)132–138)氧化1-苯基乙醇,但是在以上反应中存在着贵金属用量大、反应压力大,反应条件不温和、氧化剂不够绿色、催化活性并不理想等问题。基于以上文献的基础上,根据绿色化学的发展理念,设计一个芳香醇氧化生成芳香醛的环境友好的钯催化剂高效催化体系是十分必要的。
通过检索,尚未发现与本发明申请相关的公开专利文献。
发明内容
本项发明的目的是解决某些钯催化剂在芳香醇的选择性氧化过程中催化活性有待提高和环境保护的问题。提供一种合成双核钯催化剂的制备方法,以期在芳香醇的选择性氧化中起到催化的作用。
这类催化剂的晶体结构信息通过如下方法获得的:
通过常规的溶液反应合成得到钯化合物的晶体,具体的描述实验方法如下:
在一个洁净的烧杯中依次加入醋酸钯(5~30mmol),N-甲基咪唑(30~180mmol),二甲基亚砜30~60mL,磷钼酸(1~5mmol)以及三氟乙酸(15~40mmol),强烈搅拌10~36h,反应完毕后过滤,静置,滤液缓慢挥发,7~9天后得到红色块状单晶。产率约45~71%。
产品通过单晶X衍射,粉末X射线衍射进行表征,得到关于晶体结构的准确信息。具体的结果如下:晶体的分子式为Pd2O(CF3O2)2(DMSO)4(H2O)4,中心钯原子采取六配位如图所示,亚砜基团采取了单齿配位模式与钯离子配位,同时钯离子还与三氟乙酸C-O键上和水分子上的氧原子配位,形成八面体稳定结构。进一步研究发现该催化剂对于芳香醇的催化氧化具有较高活性,并且在该反应中催化剂可回收利用。
这项发明主要是合成了一种双核钯催化剂,已经将其应用于芳香醇类化合物的选择性氧化。这项发明涉及了钯催化剂的制备方法。这类催化剂可以实现多种芳香醇的选择性氧化,转化率高达99%,选择性高达99%。该类催化剂的制备方法反应过程简单。
本发明的目的是通过如下技术方案实现的:
其分子结构为:
分子式分别为:
化合物1分子式为Pd2O(CF3O2)2(DMSO)4(H2O)4
上述芳香醇为苯甲醇、对硝基苯甲醇、对氯苯甲醇、邻溴苯甲醇等,溶剂选用乙腈等,转化率,选择性通过气相色谱检测。
本发明提供双核钯催化剂具有以下特点:
1.制备方法简单、并且催化剂都具有明确的分子结构,利于研究反应机理。
2.催化剂具有过渡金属、便于容易分离,经处理后可以多次使用,并且仍能保持良好的催化活性,有利于工业化生产。
附图说明
图1.化合物1Pd2O(CF3O2)2(DMSO)4(H2O)4的晶体结构(为了结构图清晰,氢原子已经省去);
图2.化合物1的RXRD表征。
具体实施方式
实施例1:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(5mmol),N-甲基咪唑(30mmol),二甲基亚砜30mL,磷钼酸(1mmol)以及三氟乙酸(15mmol),强烈搅拌12h,反应完毕后过滤,静置,滤液缓慢挥发,7天后得到红色块状单晶。产率约48%。
实施例2:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(10mmol),N-甲基咪唑(100mmol),二甲基亚砜40mL,磷钼酸(3mmol)以及三氟乙酸(20mmol),强烈搅拌16h,反应完毕后过滤,静置,滤液缓慢挥发,9天后得到红色块状单晶。产率约51%。
实施例3:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(15mmol),N-甲基咪唑(150mmol),二甲基亚砜50mL,磷钼酸(3mmol)以及三氟乙酸(30mmol),强烈搅拌30h,反应完毕后过滤,静置,滤液缓慢挥发,9天后得到红色块状单晶。产率约64%。
实施例4:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(25mmol),N-甲基咪唑(180mmol),二甲基亚砜60mL,磷钼酸(4mmol)以及三氟乙酸(40mmol),强烈搅拌36h,反应完毕后过滤,静置,滤液缓慢挥发,9天后得到红色块状单晶。产率约58%。
实施例5:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(25mmol),N-甲基咪唑(160mmol),二甲基亚砜50mL,磷钼酸(5mmol)以及三氟乙酸(40mmol),强烈搅拌24h,反应完毕后过滤,静置,滤液缓慢挥发,7天后得到红色块状单晶。产率约54%。
实施例6:化合物Pd2O(CF3O2)2(DMSO)4(H2O)4的制备
在一个洁净的烧杯中依次加入醋酸钯(30mmol),N-甲基咪唑(180mmol),二甲基亚砜30mL,磷钼酸(2mmol)以及三氟乙酸(20mmol),强烈搅拌12h,反应完毕后过滤,静置,滤液缓慢挥发,9天后得到红色块状单晶。产率约69%。
表1.化合物1的晶体学数据
试验例:芳香醇的催化氧化应用
取0.2mmol芳香醇溶于1~2ml溶剂中,并加入催化剂8~15mg,通入0.6MPa氧气,加热搅拌并维持温度在100~130摄氏度,反应12~24h后,用气相色谱检测,具体芳香醇氧化的数据见表2;
表2.化合物1对芳香醇选择性氧化结果列表
由表2可知,所合成的双核钯催化剂对于芳香醇均具有良好的催化活性,转化率大于90%,选择性高达99%。,实现了分子氧条件下钯催化剂对芳香醇的催化氧化。
Claims (7)
1.一种双核钯催化剂的制备方法,其特征在于:其合成步骤为:
在一个洁净的烧杯中依次加入醋酸钯,N-甲基咪唑,二甲基亚砜,磷钼酸以及三氟乙酸,强烈搅拌,反应完毕后过滤,静置,滤液缓慢挥发,7~9天后得到红色块状单晶。
2.根据权利要求1所述的双核钯催化剂的制备方法,其特征在于:所述双核钯催化剂的分子式:Pd2O(CF3O2)2(DMSO)4(H2O)4。
3.根据权利要求1所述的一种双核钯催化剂的制备方法,其特征在于:所述醋酸钯:N-甲基咪唑:磷钼酸:三氟乙酸物质的量之比为5~30:30~180:1~5:15~40,反应时间为10~36h。
4.根据权利要求1所述的一种双核钯催化剂的制备方法,其特征在于:所述溶剂为二甲基亚砜,其体积与醋酸钯的物质的量之比为30~60:5~30(ml:mmol)。
5.根据权利要求1所述的一种双核钯催化剂的制备方法,其特征在于:强烈搅拌时间为10-36h(优选30h)。
6.一种权利要求1-5任一项所述制备方法制备得到的双核钯催化剂。
7.一种权利要求1-5任一项所述制备方法制得的双核钯催化剂在芳香醇催化氧化中的应用。
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