General and efficient method for the synthesis of alkoxymethylsilanes

Although alkoxymethylsilanes serve as useful building blocks, various efforts to synthesize them by substitution reaction with an alkoxide ion at the carbon adjacent to the silicon failed. To solve this synthetic problem a new route which is very simple to perform was developed. Bromination of (methoxymethyl)trimethylsilane by using N‐bromosuccinimide/2,2′‐azobisisobutyronitrile (NBS/AIBN) was followed by a substitution by alcohols in the presence of triethylamine to give the corresponding [alkoxy‐­(methoxy)methyl]trimethylsilanes. These acetals can be used directly for the next reduction with di‐isobutylaluminium hydride (DIBAL‐H) or Et₃SiH/BF₃·OEt₂ to give alkoxymethylsilanes in good to moderate yields. The success of the substitution reaction with the alcohols suggests that the mechanism is of somewhat S_N1 by nature and formation of the cationic intermediate seems to release the steric hindrance around the carbon, allowing the attack of alcohols. Copyright © 1999 John Wiley & Sons, Ltd.     

类水滑石Mg3Al1-xFex负载Ir催化剂在肉桂醛加氢反应中的应用:Fe的促进作用

水滑石类化合物 (LDH) 的层板金属阳离子组成具有可调变性,通过将具有变价特性的过渡金属定量引入 LDH 层板,经热处理后可以得到具有高比表面积和层板金属原子级分散的混合金属氧化物,后者可广泛用作催化剂载体.如三元Mg-Al-Fe 类水滑石材料在光催化、H2S 选择性氧化和乙苯脱氢等反应中表现出较好的活性.Ir 催化剂在α,β-不饱和醛加氢反应中具有较好的活性,Fe 修饰 Ir 催化剂可提高不饱和醇选择性,但有关 Fe 的作用以及 Fe 与活性组分 Ir 间的相互作用本质还不是很清楚.本文以类水滑石材料 Mg3Al1–xFex为载体,采用等体积浸渍法制备了 Ir 催化剂,并用于肉桂醛加氢反应,通过考察 Fe的加入对 Ir 电子和几何结构的影响揭示了 Fe 的加入对活性和选择性的影响规律.结果表明,当 x 从 0 (Ir/Mg3Al) 增加到 1 (Ir/Mg3Fe) 时,肉桂醛加氢的反应速率在 x = 0.25 时达到最大值,肉桂醇选择性从 44.9% 增加到 80.3%,且不随肉桂醛转化率的增加而改变.透射电镜结果表明,Ir 纳米粒子的粒径随着 x 的增加未发生明显变化,均为 1.7±0.2 nm.H2程序升温还原结果发现 Ir 可以促进 Fe3+的还原且两者之间存在相互作用.X射线光电子能谱结果表明,Fe 的掺杂没有改变催化剂表面Ir0和 Ir4+含量的比值,但当 Fe 含量增加时,Fe2+2p3/2向高结合能方向偏移,且 Ir04f7/2向低结合能方向偏移,说明电子从 Fe2+转移到 Ir,形成了富电子的 Ir 物种和缺电子的 Fe 物种.富电子的 Ir 物种有利于肉桂醛分子中的 C=O 键在其表面吸附,并且和 Ir 相邻的 Fen+物种可以作为亲电位点吸附肉桂醛分子中氧,从而极化和活化 C=O 键,因而催化剂活性和选择性增大.采用吸附 CO 红外光谱表征了催化剂表面的几何结构,2058–2069 cm-1处出现了 CO 吸附峰,归属于 Ir0表面 CO 的线性吸附,高波数 2069 cm-1的吸附峰归属于 CO 在高配位 Ir 位点 (平台) 的吸附,低波数 2058 cm-1的吸附峰归属于 CO 在低配位Ir 位点 (台阶、角、楞) 的吸附.随着 Fe 含量的增加,CO 吸附峰蓝移 11 cm-1,表明 Fe 的加入改变了催化剂表面 Ir 的几何结构,低配位 Ir 位点减少,高配位 Ir 位点增多.高配位 Ir 位点 (平台) 有利于肉桂醛分子中 C=O 键的吸附,从而提高了肉桂醇的选择性.总之,Fe 的加入虽然没有明显改变 Ir 纳米粒子的粒径,但却改变了其电子和几何结构,从而提高了催化剂活性和选择性.     

High-speed separation system of randomly suspended single living cells by laser trap and dielectrophoresis

We developed a new system for random separation of a single microorganism, such as a living cell and a microbe, in the microfluidic device under the microscope by integrating the laser-trapping force and dielectrophoretic (DEP) force. An arbitrarily selected single microbe could be isolated in a microchannel, despite the presence of a large number of microbes in solution. Once the target microbe is trapped at the focal point of the laser, we can easily realize exclusion of excess microbes around the target by controlling the electric field, while keeping the target trapped by the laser at the focal point. To realize an efficient separation system, we proposed a new separation cell and produced it by microfabrication. Flow speed in the microchannel is adjusted and balanced to realize high-speed and high-purity extraction of the target. Some preliminary experiments are conducted to show the effectiveness. The target is trapped by the laser, transported, and is taken out from the extraction port. Total separation time is less than 20 s. Our method is extremely useful in the pure cultivation of the cell and will be a promising method for biologists in screening useful microbes.     

Control of methanol oxidation by ionic behavior in supercritical water

In supercritical water the rate of methanol oxidation was controlled by ionic behavior as follows: the oxidation rate of methanol decreased with increasing proton and hydroxide ion concentration, possibly due to stabilization of the reactant, while that of CO was suppressed by added protons and enhanced by added hydroxide ions.     

Hydrohalogenation of 1- and 2-vinylindazoles

The electronic absorption spectra of 1-vinyl- and 2-vinylindazoles and their protonated forms were analyzed. The spectra were subjected to quantum-chemical calculation within the Pariser-Parr-Pople (PPP) -electron approximation, and the thermodynamic parameters of the reaction of indazoles with phenol (K_as and H) were calculated. It is shown that 1-vinylindazole adds hydrogen halides to the nitrogen atom or the double bond of the vinyl group, depending on the reaction temperature. The formation of hydrohalides is characteristic for 2-vinylindazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 952–956, July, 1982.     

Fluorescence spectra and their temperature dependence of amorphous anthracene films doped with naphthacene

Fluorescence spectra and their temperature dependence of amorphous anthracene films doped with naphthacene were observed. An amorphous film was prepared by vacuum evaporation technique on a quartz plate cooled down to 30–40°K. The obtained results were discussed in relation to the structural change in the amorphous film.     

A convenient synthesis of 1-bromoolefins and acetylenes by a chain extension of aldehydes

Aldehydes are easily converted to 1-bromoolefins or terminal acetylenes by the use of Wittig reaction of bromomethylenetriphenylphosphorane which is prepared from bromomethyltriphenylphosphonium bromide with potassium tert-butoxide.