New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

HgCl2/I2复合催化剂协同催化合成异丙醇钇的研究

以金属钇和异丙醇为原料，以HgCl2/I2为复合催化剂，通过对金属钇的机械加工以增加其比表面，并将异丙醇脱水使其含水量降低至0．05％，体系在82℃回流5h，经过滤、减压蒸馏，得到了白色海绵状异丙醇钇，其产率高达83％，合成时间比文献报道的缩短了19h，产率提高了8％。文章确定了催化剂的最佳用量为20gY加入60mg HgCl2/I2，研究了合成产率与HgCl2/I2催化剂和HgCl2催化剂的依赖关系及异丙醇中含水量对合成产率的影响，并对HgCl2/I2的催化作用机理进行了初步探讨。     

General strategy for a short and efficient synthesis of 3-hydroxy-4-methylprolines (HMP)

The non-proteinogenic amino acid 3-hydroxy-4-methylproline (HMP) is an active constituent of some potent antimicrobials including echinocandins, nostopeptins, pneumocandins, sporiofungin and mulundocandins. A synthesis has been achieved in 10 steps with 29% overall yield; the Evans’ aldol reaction using Crimmins’ modified method was pivotal to the success of the strategy.     

Synthesis of coumarins by Pt-catalyzed hydroarylation of propiolic acids with phenols

Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl₂/AgOTf, K₂PtCl₄/AgOTf, and K₂PtCl₄/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields.     

Asymmetric synthesis of homo-apioneplanocin A from d-ribose

Homo-apioneplanocin A was efficiently synthesized via stereoselective hydroxymethylation, regio- and chemoselective hydroboration, and chemoselective oxidation as key steps from d-ribose.     

Comparison of growth stress measurements with modelling in thin iron oxide films

High temperature oxidation of metals leads to residual stresses both in the metal and in the growing oxide. In this work, the evolution of this residual stresses is theoretically predicted in the growing oxide layers. The origin of these stresses is based on a microstructural model. Using experimental results providing from the oxidation kinetics, and an analysis proposed to describe the growth strain occurring in the thin layers, a set of equations is established allowing determining the stresses evolution with oxidation time. Then, the model is compared with experimental results obtained on both α-Fe and phosphated α-Fe, oxidised at different temperatures. Numerical data are extracted from experiments either with an asymptotic formulation or with an inverse method. These two methods give good agreement with experiments and allow extracting the model parameters.     

催化剂薄层内甲烷水蒸气重整反应强化管内对流换热的数值模拟

本文以竖直圆管内壁催化剂薄层内发生甲烷水蒸气重整反应强化对流换热作为研究对象,对其进行了数值模拟．结果发现,催化剂薄层内的吸热化学反应可以有效地强化对流换热,降低流体和壁面温度,从而对壁面起到保护作用;极限热流密度的大小与流体的入口温度有关,存在最佳入口温度使极限热流密度最大．     

纳米TiO_2用于甲基橙溶液的光催化氧化研究

本实验采用纳米级的二氧化钛,对甲基橙溶液进行了紫外光催化氧化处理,探讨了pH的影响和添加Fe3+的效果及反应动力学方程,结果表明,采用UV/O3/TiO2工艺对其进行处理,pH4-5时,10W紫外灯光照60min,CODcr去除率达84%,脱色率达96%以上。添加Fe3+,对溶液的催化降解速度提高不明显。动力学研究表明,CODcr降解速度对CODcr的浓度为一级反应。     

A solvent-free synthesis of coumarins using a Wells-Dawson heteropolyacid as catalyst

Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H₆P₂W₁₈O₆₂·24H₂O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples).