4-甲基-3-硫代氨基脲型钌配合物的合成和性质研究

钌配合物由于其的高效、低毒的特点,可有效克服铂金属配合物副作用大、对癌细胞缺少选择性等缺点,而成为研究热点。本论文采用邻甲氧基苯甲醛和4-甲基-3-硫代氨基脲反应制备邻甲氧基苯甲醛缩4-甲基-3-硫代氨基脲,将邻甲氧基苯甲醛缩4-甲基-3-硫代氨基脲作为配体与[Ru(p-cymene)Cl_2]_2反应制备邻甲氧基苯甲醛缩4-甲基-3-硫代氨基脲配合物,并研究其性质。     

离子液体中Ru改性HAP催化氧化邻硝基苯甲醇合成邻硝基苯甲醛

在离子液体溴化1-丁基-3-甲基咪唑([bmim]Br)中,以Ru(Ⅲ)改性羟基磷灰石(HAP)为催化剂,用氧气常压氧化邻硝基苯甲醇合成了邻硝基苯甲醛,考察了不同反应介质、Ru质量分数和反应条件对氧化反应的影响.结果表明,在离子液体[bmim]Br中,Ru/HAP对氧化反应具有较高的催化活性和选择性,在邻硝基苯甲醇20...     

蒙脱土担载钴配合物催化剂制备及性能研究

制备了系列蒙脱土担载钴(Ⅱ)(Co(Ⅱ))配合物催化剂,并对其结构进行了X射线衍射和透射电镜等表征,初步研究了蒙脱土担载钴(Ⅱ)配合物催化剂对烯烃的催化氧化性能.结果表明:配体进入了蒙脱土的片层间与Co(Ⅱ)配位,形成蒙脱土担载的铜配合物复合催化材料;在催化剂催化H2O2氧化苯乙烯的反应中,对苯甲醛和环氧苯乙烷的选择性高达94.7%,转化率达到38.4%;在环己烯的氧化反应中,对环氧环己烷、环己醇、环己烯醇和环己烯酮的选择性共达到98.5%,转化率达到33.2%.     

水介质中糖基胺-酸对直接Aldol反应的协同催化研究

以Brnsted酸为催化剂,糖基对甲苯磺酰肼为助催化剂(胺),研究了芳香醛与酮在水介质中的直接Aldol反应。以对硝基苯甲醛和环己酮合成2-[羟基-(4-硝基苯基)]甲基环己酮为模型反应,考察了不同的酸、不同的糖基对甲苯磺酰肼、酸的用量、糖基对甲苯磺酰肼的用量、底物用量比r对模型反应的影响。在最佳反应条件(40 mol%乙酸为催化剂,30mol%葡萄糖基对甲苯磺酰肼为助催化剂(胺),水为溶剂,r=1∶5,于室温反应12 h)下,2-[羟基-(4-硝基苯基)]甲基环己酮的产率为93%。对反应底物进行扩展,结果表明,具有表面活性剂性质的葡萄糖基对甲苯磺酰肼与乙酸配合,能在水介质中有效地催化芳醛与环状酮的直接Aldol反应。     

新型含氟席夫碱配合物的合成与表征

目前抗肿瘤药物的需求依然非常急迫,有研究表明,含氟配合物具有良好的生物活性。本文选择了2-氨基-4-三氟甲基苯甲酸与2,4-二羟基苯甲醛进行缩合,并选择邻菲罗啉作为第二配体,合成了六种新型的含氟席夫碱配合物,为未来研究新型抗肿瘤药物提供可行性方向。     

固体碱碱性位对3-戊酮和碳酸二甲酯反应的影响

考察了固体碱碱性位对3-戊酮和碳酸二甲酯反应的影响,并推测了反应在不同碱性位上的反应机理.实验结果表明,由表面羟基引起的弱碱位有利于3-戊酮自身缩合反应(4-甲基-5-乙基-4-庚烯-3-酮)的进行;Lewis酸碱离子对有利于碳酸二甲酯的甲基化反应的发生,主产物为2-甲基-3-戊酮和3-甲氧基-2-戊烯;而由固体碱表面...     

甲氧基取代苯甲醛缩硫代氨基脲芳基钌配合物的合成

科研工作者围绕着芳基钌的配合物的合成、改性、作用靶点及作用机理等方面做了大量有意义的工作,有机金属钌氨基硫脲配合物的抗肿瘤性质成为研究热点。本论文采用邻甲氧基苯甲醛和3-硫代氨基脲反应制备邻甲氧基苯甲醛缩3-硫代氨基脲,将邻甲氧基苯甲醛缩3-硫代氨基脲作为配体与[Ru(p-cymene)Cl_2]_2反应制备配合物1,并研究其光谱特性。     

PEG6000-OSO3H催化下酮类的Baeyer-Villiger氧化反应

制备了PEG6000负载氯磺酸催化剂(PEG6000-OSO3H),利用FTIR、TG和元素分析方法对催化剂进行了表征。研究了以PEG6000-OSO3H为催化剂,质量分数30%的H2O2为氧化剂条件下,酮类的Baeyer-Villiger氧化反应,考察了溶剂、反应温度、反应时间、催化剂用量、氧化剂用量等因素对反应的影响,得到反应的最佳条件为:底物酮0.1 mmol,质量分数为30%的H2O20.3 mmol,催化剂用量10 mg,溶剂1,2-二氯乙烷3 mL,温度70℃,反应时间24 h。在该条件下,一些环酮类底物如2-金刚烷酮、环戊酮、环己酮、2-甲基环己酮、4-甲基环己酮和4-叔丁基环己酮等都可以在温和的条件下被氧化得到相应内酯,且反应具有89%~100%的底物转化率和80%~99%的内酯选择性。通过柱层析方法分离了产物,并进行了1HNMR和13CNMR波谱确证。     

六齿配位的8-羟基喹啉铁催化过氧化氢氧化环己烷的研究

合成了几种具六齿配位的8-羟基喹啉铁类配合物,考察了这些配合物在催化过氧化氢氧化环己烷的催化性能。结果表明,配体的卤素取代基对催化剂有稳定作用,能提高其催化活性。二卤代的催化剂具有稳定的六齿配位结构,其催化反应速率慢;采用混合配体配位的催化剂能够明显加快反应速率,提高催化活性。     

氨基磺酸催化的Mannich反应合成β-氨基酮

采用廉价的氨基磺酸作为催化剂,芳香酮以及环己酮、3-戊酮与芳香醛、芳香胺可直接发生Mannich反应,生成相应的Mannich碱,产率均在60%～95%.氨基磺酸作为催化剂表现出高效的催化活性,优良的稳定性及良好的利用效率.     

Baeyer–Villiger oxidation of ketones with hydrogen peroxide catalyzed by cellulose-supported dendritic Sn complexes

Cellulose supported dendritic Sn complexes were prepared by solid phase synthetic methodology. A series of cycloketones and acyclic ketones including 2-andamantanone, cyclohexanone, 4-methylcyclohexanone, 4-tert-butylcyclohexanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone and cyclopentanone were oxidized by hydrogen peroxide in a reaction catalyzed by cellulose-supported dendritic Sn complexes, affording the corresponding lactones or esters with the conversion of 70–99% and the product selectivity of 100%. The catalysts can be recycled for several times without any significant decline in catalytic activity.     

Dendrimer–Palladium Complex Catalyzed Oxidation of Terminal Alkenes to Methyl Ketones

Silica‐supported polyamidoamine (PAMAM) dendrimers with different spacer lengths were prepared. After the introduction of diphenylphosphino groups, complexation to dibenzylidenepalladium(0) gave the desired silica‐supported dendrimer–palladium catalyst complexes G0 to G4‐C2‐Pd. These catalysts showed activity towards the oxidation of terminal alkenes to methyl ketones. A dependence of catalytic activity on the spacer length of the diamine in PAMAM was observed.     

Recyclable Tridentate Stable Palladium(II) PCP‐Type Catalysts Supported on Silica for the Selective Synthesis of Lactones

Five‐ or seven‐membered ring lactones are synthesized, in good selectivity and high yields, by the cyclocarbonylation reaction of 2‐allylphenols, using a tridentate diphosphinoaryl ligand (PCP‐type) palladium(II) catalyst immobilized on silica ( A ) and silica supported dendrimers ( B, C and D ). These immobilized catalysts, which are highly active and can be recycled by simple filtration in air, and reused with only moderate loss of activity, combine the advantages of heterogeneous and homogeneous catalysts. These complexes are also stable towards oxygen and moisture.     

Chloromethyl polystyrene supported dendritic Sn complexes,preparation and catalytic Baeyer–Villiger oxidation

Dendritic Sn complexes were successfully incorporated to chloromethyl polystyrene through solid phase synthesis methodology and exhibited to be promising catalysts for the Baeyer–Villiger oxidation of ketones with hydrogen peroxide. Several cyclic and acyclic ketones were oxidized by hydrogen peroxide in a reaction catalyzed by these polymer-supported dendritic Sn complexes with high conversion and selectivity. The catalysts can be prepared in large scale in a simple manner without the utilization of any expensive materials and can be recycled as heterogeneous catalysts.     

Catalysis by Mesoporous Dendrimers

The present study reports the divergent synthesis, characterization and catalytic properties of different generation of triazine based aromatic amine dendritic mesoporous silicas derived via a stepwise functionalization of mesoporous silica substrates of different pore sizes with 2,4,6 tricholorotriazine and ethylene diamine. Mesoporous dendritic silicas up to second generation (2G) are grown in side the channels of mesoporous silica materials with 4 and 7 nm pore sizes. The catalytic properties of resulted dendritic materials in Knoevenagel condensation reaction were compared to the aliphatic polyamidoamine dendrimers that are also grown up to second generation (2G) inside the mesoporous channels. The reusability study of both aliphatic and aromatic dendritic mesoporous silica systems is also compared.     

Cu(II), Co(II) and Ni(II) Complexes Installed on Functionalized Silica Surface for Hydrogen Peroxide Assisted Cyclohexane Oxidation

In this work, Cu(II), Co(II) and Ni(II) complexes of the Schiff base ((S,E)-2-(3,4-dimethoxybenzylideneamino)-3-(1H-imidazol-4-yl)propionic acid) were synthesized and subsequently anchored onto amine functionalized silica. They were characterized by FT-IR, UV–vis., ²⁹Si NMR, TG-DTG, ESR, FE-SEM and AFM techniques, and employed as catalysts in cyclohexane oxidation using hydrogen peroxide oxidant. Silica supported Cu(II) catalyst was shown the highest catalytic activity (70%) than rest of the catalysts used. On the other hand, all the complexes were selective as they yield only cyclohexanol and cyclohexanone. Silica supported catalysts were maintained their catalytic activity over five successive catalytic run. As these catalysts are selective, reusable and functioning well with hydrogen peroxide, they could design the environment friendly catalytic system for effective cyclohexane oxidation.     

Synthesis of Silica-Supported Platinum(II) and Nickel(II) Complexes of Bis(Diphenylphosphinomethyl)Amino Ligand: Applications as Catalysts for the Synthesis of 2-Methyl-1,4-Naphthoquinone (Vitamin K3)

Pt(II) and Ni(II) complexes of N,N-bis(diphenylphosphinomethyl)aminopropyltriethoxysilane [(CH₃CH₂O)₃Si(CH₂)₃N(CH₂PPh₂)₂] (DIPAPTES) and silica supported [SiO₂–(DIPAPES)] ligands have been synthesized under nitrogen atmosphere using Schlenk method and characterized by using atomic absorption, FT-IR, NMR (¹H and ³¹P) and elemental analysis techniques. All the complexes were used as catalysts for the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone (vitamin K₃, menadione, 2MNQ) using hydrogen peroxide as a clean and cheap oxidant. [Pt–(DIPAPTES)Cl₂] and supported complex [SiO₂–(DIPAPES)–PtCl₂] showed medium catalytic activity whereas Ni(II) complexes did not show any catalytic activity for the selective oxidation of 2-methyl naphthalene to 2-methyl-1,4-naphthoquinone.     

Ring opening of epoxides catalysed by poly(amidoamine) dendrimer supported on crosslinked polystyrene

Three generations of polystyrene supported poly(amidoamine) dendrimer were synthesized and characterized. The supported dendrimers were found to be efficient organocatalysts in the nucleophilic ring opening of epoxides by anilines under mild conditions. Higher generation dendrimer showed increased catalytic activity. The polymer supported catalyst was reusable. The catalytic activity of supported dendrimer was compared with the unsupported one and found that the supported dendrimer was a much more active catalyst. The higher activity of the supported dendrimer is assumed to be due to the better hydrophobic/hydrophilic interaction existing between the polystyrene matrix and the polar dendritic chains.     

Oxidation of pinane over phthalocyanine complexes supported on activated carbon: Effect of the support surface treatment

The oxidation of cis-pinane with tert-butyl hydroperoxide, at room temperature and atmospheric pressure, was carried out in the presence of iron-phthalocyanines supported on activated carbons. The carbon supports were prepared from a NORIT activated carbon, which was modified by different chemical and thermal treatments (including oxidation in the gas and liquid phases). The carbon samples were characterized by nitrogen adsorption, mass titration and temperature programmed desorption (TPD). The TPD profiles were analysed by a simple deconvolution method, allowing for the determination of the amount of oxygen containing functional groups on the carbon surface. The main reaction product is 2-pinane hydroperoxide (77% selectivity at 91% conversion). Formation of 2-pinanol, pinocampheol and verbanol and the respective ketones was also observed. The influence of the surface chemistry of the carbon supports on catalytic activity and product selectivity is studied. The catalysts prepared from supports with very high or very low oxygen content exhibit low activity, whereas for supports with intermediate oxygen contents a good correlation between the amount of phenols and lactones and catalytic activity is obtained.