Reduction of Carboxylic Acids by Tetraalkyl Ammonium Borohydride

Tetraalkylammonium borohydride reduces carboxylic acids to the corresponding alcohols in good yields utilizing only stoichiometric quantities of hydride and also in the absence of any Lewis acids.     

Highly Efficient System for Reduction of Carboxylic Acids and Their Derivatives to Alcohols by HfCl4/KBH4

HfCl₄/KBH₄ was found to be a facile, efficient, convenient, and chemoselective system for the reduction of carboxylic acids and their derivatives to the corresponding alcohols under mild conditions. HfCl₄/NaBH₄ was also utilized to reduce the same carboxylic acids and their derivatives, and it was found that the reducing ability of HfCl₄/NaBH₄ was similar to that of HfCl₄/KBH₄. The action of HfCl₄/KBH₄ on other types of substrates, such as benzyl chloride, peracid, epoxide, ketone, amide, imine, pyridine-N-oxide, and nitrile, was investigated, too. In addition, some competitive reductions of styrene oxide in the presence of carboxylic acid, carboxylic ester, nitrile, and amide were achieved.     

Improved Procedure for the Reduction of Esters to Alcohols by Sodium Borohydride

An improved procedure for the employment of NaBH₄ in the reduction of ester function is described.     

脂肪族酯基选择性还原模型的建立

以不同烷基取代的酯作为模型, 对其进行NaBH4还原研究. 不同取代基酯的起始反应温度和半衰期显示出了明显的差别和一定的选择性; 用B3LYP/6-31++G(d,p)//HF/6-31G(d,p)方法计算得到的过渡态能量与实验得到的活化能变化趋势一致; 实验中观察到了奇偶碳效应; 对NaBH4还原酯基的溶剂影响进行了初步研究.     

One-Pot Facile Synthesis of Noble Metal Nanoparticles Supported on rGO with Enhanced Catalytic Performance for 4-Nitrophenol Reduction

In this study, reduced graphene oxide (rGO)-supported noble metal (gold, silver, and platinum) nanoparticle catalysts were prepared via the one-pot facile co-reduction technique. Various measurement techniques were used to investigate the structures and properties of the catalysts. The relative intensity ratios of I_D/I_G in rGO/Au, rGO/Ag, rGO/Pt, and GO were 1.106, 1.078, 1.047, and 0.863, respectively. The results showed the formation of rGO and that noble metal nanoparticles were decorated on rGO. Furthermore, the catalytic activities of the designed nanocomposites were investigated via 4-nitrophenol. The catalysts were used in 4-nitrophenol reduction. The catalytic performance of the catalysts was evaluated using the apparent rate constant k values. The k value of rGO/Au was 0.618 min⁻¹, which was higher than those of rGO/Ag (0.55 min⁻¹) and rGO/Pt (0.038 min⁻¹). The result proved that the rGO/Au catalyst exhibited a higher catalytic performance than the rGO/Ag catalyst and the rGO/Pt catalyst. The results provide a facile method for the synthesis of rGO-supported nanomaterials in catalysis.     

One-Pot Synthesis of Phenacyl Esters from Acetophenone, [Bmim]Br3, and Potassium Salts of Carboxylic Acids Under Solvent-Free Conditions

One-pot synthesis of phenacyl esters from acetophenone, [Bmim]Br₃, and potassium salts of carboxylic acids under solvent-free conditions gave the corresponding phenacyl esters with excellent yields.     

NaBH4/Charcoal: A New Synthetic Method for Mild and Convenient Reduction of Nitroarenes

NaBH₄ in the presence of charcoal (0.4–0.8 g) reduces varieties of nitroarenes to their corresponding amines. Reduction reactions were carried out in a mixture of H₂O‐THF (1:0.5 mL) at 50–60°C with high to excellent yields of products.     

A simple reduction of methyl aromatic esters to alcohols using sodium borohydride-methanol system

Several aromatic esters were reduced to the corresponding alcohol by using sodium borohydride-methanol system. The reduction was completed within 2.0-4.0 h after refluxing in THF. The alcohol products were isolated after aqueous workup in good yields (88-97%).     

Highly enantioselective reduction of achiral ketones with NaBH4/Me3SiCl catalyzed by (S)-α,α-diphenylpyrrolidinemethanol

The reducing agent prepared from sodium borohydride, trimethylsilyl chloride and a catalytic amount of (S)-α,α-diphenylpyrrolidinemethanol has been successfully applied to the enantioselective reduction of ketones. The optically active secondary alcohols were obtained in excellent enantiomeric excess and almost quantitative chemical yield.     

MoO3-C3N4复合光催化剂的可见光下高效催化降解甲基橙

以钼酸铵和C₃N₄为前驱体,利用浸渍法成功制备了高性能MoO₃-C₃N₄复合光催化剂,利用X射线衍射（XRD）、傅里叶红外（FT-IR）、高分辨电镜（HRTEM）及N₂吸附-脱附曲线等测试手段对所得MoO₃-C₃N₄光催化剂进行了结构和形貌表征。以可见光下光催化降解甲基橙反应表征MoO₃-C₃N₄的光催化活性。实验结果表明,MoO₃-C₃N₄光催化剂具有非常好的光催化降解性能,且MoO₃含量对反应活性产生显著影响。当MoO₃含量为1.6%（w/w）时光催化活性最好,其速率常数达到C₃N₄的50倍。通过研究发现该复合催化剂的高活性来自于其Z型光生载流子传输过程,抑制了光生电子空穴对的复合并延长了引入MoO₃产生的载流子的寿命。     

Selenium(IV) Oxide Catalyzed Oxidation of Aldehydes to Carboxylic Acids with Hydrogen Peroxide

A convenient method for oxidative transformation of aromatic, hetero-aromatic and aliphatic aldehydes into carboxylic acids is presented. It is based on the oxidation of aldehydes in THF using 30% hydrogen peroxide in the presence of 5 molar % of selenium(IV) oxide. The scope and limitation of the method are discussed.     

金属氯化物对硼氢化钠还原α-氯代苯乙酮的影响

用NaBH₄还原α-氯代苯乙酮制备相应的β-氯代-α-苯乙醇时, 在较高的反应温度下产生许多副产物, 钙、镧、镁、锰、锌等金属氯化物的存在能有效抑制副反应的发生, 高产率地得到产物.     

Reduction of Solid Benzophenones with Sodium Borohydride

The solvent-free reduction of benzophenone and five substituted benzophenones with sodium borohydride to the corresponding alcohols was studied by thermal analysis, X-ray powder diffractometry, NMR spectroscopy, and scanning electron microscopy. In most cases, the reaction occurs via liquid eutectic phases that are formed between the benzophenone and the resulting benzohydrol. Nevertheless, this reaction can be carried out without the need for a solvent, leading to pure alcohol without side products. In some cases, heating may be necessary to achieve a reasonably short reaction time. In conclusion, this reaction type appears to be feasible as a preparative organic reaction that avoids a solvent.This revised version was published online in November 2005 with corrections to the Cover Date.     

超声法制备Au/Fe3O4及其催化还原4-硝基苯酚性能

通过简易的超声法以及原位还原法成功制备出了负载型可再生Au/Fe₃O₄催化剂。利用3-氨丙基三乙氧基硅烷（APTES）作为有机桥键,将Au固定在Fe₃O₄的表面,得到单分散磁性Au/Fe₃O₄。Au⁰在氨基的作用下不会团聚,因此具有较高的催化活性及稳定性。XRD、HRTEM、EDS和XPS等测试结果表明Au/Fe₃O₄已被成功制备。将其用于催化还原4-硝基苯酚得到4-氨基苯酚,表现出较高的催化活性,速率常数可达0.225 6 min^-1。重复性实验表明该催化剂具有良好的稳定性,反应9个循环之后,催化还原反应的转化率仍可达到94%。     

超声法制备Au/Fe_3O_4及其催化还原4-硝基苯酚性能

通过简易的超声法以及原位还原法成功制备出了负载型可再生Au/Fe_3O_4催化剂。利用3-氨丙基三乙氧基硅烷(APTES)作为有机桥键,将Au固定在Fe_3O_4的表面,得到单分散磁性Au/Fe_3O_4。Au0在氨基的作用下不会团聚,因此具有较高的催化活性及稳定性。XRD、HRTEM、EDS和XPS等测试结果表明Au/Fe_3O_4已被成功制备。将其用于催化还原4-硝基苯酚得到4-氨基苯酚,表现出较高的催化活性,速率常数可达0.225 6 min~(-1)。重复性实验表明该催化剂具有良好的稳定性,反应9个循环之后,催化还原反应的转化率仍可达到94%。     

New Aspects of Cyclodextrin Chemistry Induced by Outside Type Complex Formation; Asymmetric Reduction of Indol-3-Pyruvic Acid with NaBH4 in Aqueous Solution

Asymmetric reduction of indol-3-pyruvic acid (IPA) with NaBH₄ in aqueous solution in the presence of various cyclodextrins (α-, β-, γ-, mono-6-amino-6-deoxy-β- and di-6^ABamino-6^AB-deoxy-β-cyclodextrin) was investigated. From the NMR and circular dichroism spectral studies, the conformation of the CyD–substrate complexes is suggested; the part of carboxylic group stay in the cavity of α-CyD, whole of IPA in β-CyD, two molecules in a γ-CyD cavity, and IPA(s) is/are on the rim of the cavity of mono-6-amino-6-deoxy-β- and di-6^ABamino-6^AB-deoxy-β-CyD (AβCyD, DAβCyD) with electrostatic interaction between amino group and carboxylic group. This conformational difference provides in the difference in the optical selectivity of reduction.     

Pt/Cu双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。     

Reductive Amination of Aldehydes and Ketones to Their Corresponding Amines with NaBH<Subscript>4</Subscript> in Micellar Media

Summary. A variety of aliphatic and aromatic aldehydes and ketones were efficiently reduced to their corresponding amines when treated with primary and secondary amines and NaBH₄ in micellar media at room temperature under neutral conditions.     

Metal Schiff-Base Complex Catalyzed Oxidation of p-Xylene and Methyl 4-Methylbenzoate to Carboxylic Acids

Oxidation of p-xylene and methyl 4-methylbenzoate were catalyzed by transition metal Schiff-base complexes having the general formula LMCl_1–2 (where M = manganese or ruthenium and L = salen, salicylaldehydeethylenediimine, saloph, salicylaldehyde-o-phenylenediimine and EDTA, ethylenediaminetetraacetate) at 150°C and 500 psig air and gave p-toluic acid (> 85 %) and monomethyl terephthalate (> 70%) as the major oxidation products, respectively.     

Isotopically Labelled Phosphorus Compounds: Some Deuterated Methyl and Ethyl Derivatives

The synthesis of fifteen phosphylated compounds having P─OCD₃, P─CD₃, or P─OCD₂CH₃ groups is described. Selective chemistry for the precise placement of the deuterated groups was devised, and the products were isolated in a high purity in generally good yields. The compounds were required to study their behavior after electrospray ionization in an ion trap mass spectrometer.