苯羟化合成苯酚最佳反应条件的研究

在单因子实验基础上采用正交设计及极差分析方法,确定了以双氧水为氧化剂,以Ｆｅ３＋－７３２阳离子交换树脂为催化剂,苯直接羟化合成苯酚的最佳反应条件。     

Novel Fe‐based complex oxide catalysts for hydroxylation of phenol

Novel catalysts for the hydroxylation of phenol, Fe–Si–O, Fe–Mg–O and Fe–Mg–Si–O complex oxides, have been synthesized by a coprecipitation method. X‐ray diffraction studies show that MgFe₂O₄ crystallites with spinel structure are formed in Fe–Mg–Si–O and Fe–Mg–O complex oxides and the crystallite size of the metal oxide or complex oxide is reduced after addition of Si. In the hydroxylation of phenol with hydrogen peroxide, Fe‐based complex oxides exhibit high activities after a short induction period. The phenol conversion is improved when silicon is introduced into the Fe‐based complex oxides, and formation of MgFe₂O₄ crystals with spinel structure in the catalysts increases the diphenol selectivity. The addition of a little acetic acid to the reaction liquid can shorten the induction period effectively. Under the same reaction conditions, phenol conversion and diphenol selectivity over the Fe–Mg–Si–O catalyst are close to those over TS‐1, and furthermore, the reaction time is more than ten times shorter as compared to TS‐1. The reaction mechanism of the hydroxylation of phenol on the catalysts has been studied, and a free‐radical mechanism initiated by the formation of phenoxy free radicals is suggested. This revised version was published online in August 2006 with corrections to the Cover Date.     

The structural basis for the enhanced oxygenase activity of copper acetate dimers encapsulated in zeolites

Topics in Catalysis - The oxygenase mimicking activity of copper acetate dimers in the regioselective ortho-hydroxylation of L-tyrosine to L-dopa is enhanced on encapsulation in zeolite Y. The...     

Cloning and functional characterization of the SUR2/SYR2 gene encoding sphinganine hydroxylase in Pichia ciferrii

Saccharomyces cerevisiae sphinganine C4-hydroxylase encoded by the SUR2 gene catalyses the conversion of sphinganine to phytosphingosine. We isolated the SUR2 gene from Pichia ciferrii using nucleotide sequence homology to S. cerevisiae SUR2 to study hydroxylation of sphinganine in the sphingoid base overproducing yeast P. ciferrii. A positive clone was confirmed by nucleotide sequencing. A syringomycin-E resistance phenotype of a S. cerevisiae sur2-null mutant was complemented by expression of the cloned P. ciferrii SUR2 gene. Restoration of phytosphingosine production in the complemented strain was also confirmed, indicating that the cloned gene is a functional homologue of S. cerevisiae SUR2. .     

微生物甾体C11羟化反应的研究现状

羟化反应是甾体微生物转化反应中最重要的反应.介绍了甾体C11羟化的反应机理,并从增加底物溶解性,改善细胞通透性及新型转化系统等方面对微生物C11羟化的新工艺和新技术进行了综述,概述了近五年以来甾体C11羟化的研究现状.在甾体新型转化工艺方面,着重介绍了双液相体系、固定化技术、静息细胞法、多菌协同转化等技术.     

金龟子绿僵菌对甾体底物11-α羟化反应的工艺

研究了金龟子绿僵茵（Metarhizium anisopliae）对甾体底物16α、17α-环氧黄体酮（16α，17α—epoxy-4-pregnene-3，20-dione）的羟化反应工艺，考察了培养基组成、接种量、投料时间、转化时间、溶料方式、发酵级数等因素，探索了稀释发酵液以提高转化效率的新工艺。     

类水滑石CuNiAl的制备、表征及其催化性能的研究

采用水热法和尿素水解法首次合成了三元类水滑石CuNiAl(Cu+Ni/Al=3,Cu/Ni=5.0,3.0,1.0,0.33),将合成的类水滑石用于苯羟基化反应。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)和透射电镜(TEM)等手段对类水滑石进行表征,以CuNiAl31作为催化剂,考察了反应时间、反应温度、溶剂及溶剂用量、催化剂用量、n(benzene)/n(H_2O_2)对苯羟化反应的影响。结果表明:与CuNiAl11、CuNiAl21、CuNiAl13催化剂相比,CuNiAl31具有较高的反应活性,反应的最佳条件为:反应时间6h、反应温度65℃、15 ml吡啶作为溶剂、10mg催化剂、n(benzene)/n(H_2O_2)=3.0时,苯的转化率为7%,苯酚的选择性几乎为100%。     

金属改性的介孔硅材料FSM-16催化苯酚与H_2O_2合成苯二酚

研究了金属改性的介孔硅材料FSM-16在该反应中的催化性能。其中Fe和Cu改性的FSM-16表现出比较好的性能。在Fe-FSM-16的作用下,苯酚的转化率达到27.8%,对苯二酚和邻苯二酚选择性达到96.4%(邻/对=1.8)。FT-IR和XRD表征证明铜离子进入了FSM-16的骨架,并形成了Si—O—Cu键。     

环氧菜籽油的羟基化

以二异丙醇胺(DIPA)为羟基化试剂,将环氧菜籽油中的环氧基团转化为醇羟基,得到菜籽油生物基多元醇。考察了投料比例、反应温度、反应时间对产物的影响。通过红外表征(FTIR)环氧菜籽油和产物的结构,验证了羟基化反应的发生。