2-(α-芳氨基)苄基环已酮的合成新法

环已酮与苯甲醛和芳香胺在催化最浓盐酸或HCl-EtOH催化下能直接进行Mannich反应,用新方法——一步法合成了2-(α-芳氨基)苄基环己酮,共合成6个化合物,其中有一个是新的化合物.产率很高.对Mannich碱生成的条件进行了讨论.     

Catalysis of hydrosilylation: Part XXIV. H2PtCl6 in cyclohexanone as hydrosilylation catalyst—what is the active species in this catalytic system?

A cyclohexanone solution of H₂PtCl₆ was examined to find the catalytic species responsible for the hydrosilylation of the olefinic C=C bond. Similarly to other H₂PtCl₆–solvent systems (e.g. Speier's and Karstedt's catalysts), the real catalyst appeared to be colloidal platinum formed in situ by stepwise reduction [Pt(IV)→Pt(O)] and dechlorination of the platinum precursor. The role of cyclohexanone seems to be to form sufficiently stable platinum complexes to avoid rapid platinum precipitation and aggregation. The studies of H₂PtCl₆–solvent systems are of practical importance since these compounds are widely used catalyst precursors for hydrosilylation on an industrial scale.     

催化空气氧化环己烯制环己烯酮

由传统的浸渍法制备Al_2O_3担载的Co催化剂,以空气做氧源,催化氧化环己烯制环己烯酮。探讨了催化剂Co/Al_2O_3中Co含量、时间、温度等因素对该反应的影响。结果表明,以DMF做溶剂,用Co含量为7%的该催化剂在333 K反应6 h,可以得到转化率为34.3 mol%的环己烯和选择性为73.0%的环己烯酮,烯丙位氧化产物的总选择性可达到96.9%。     

含有螺环己烷结构的稠环斯德酮的合成

3-(3-芳基-3-羟基丙基)斯德酮在三氟化硼乙醚的催化作用下可以与环己酮发生类似于Oxa-Pictet-Spengler反应的成环反应,生成带有螺环己烷结构的稠环斯德酮.     

杂原子Sn-β分子筛的脱铝补位两步法制备、表征及其催化环己酮Baeyer-Villiger氧化性能

采用酸处理Al-β脱铝以产生T"空位",再高温焙烧插入Sn,即脱铝补位两步法制备了杂原子Sn-β分子筛.考察了β沸石中T"空位"数量、母体硅铝比和焙烧温度等因素对Sn-β分子筛形成与性能的影响,并利用X射线衍射、红外光谱、紫外-可见光谱、扫描电镜、X射线荧光光谱和电感耦合等离子体原子发射光谱等手段及环己酮Baeyer-Villiger(B-V)氧化反应,对催化剂进行了表征和评价.结果表明,脱铝补位两步法可以制备Sn-β分子筛,且Sn以四配位形式存在于分子筛骨架中,在对环己酮B-V氧化反应中表现出较高的催化活性.     

基于硝基甲烷与二烯酮的双Michael加成反应构建3,4,5-三取代环己酮的研究

在甲醇钠的催化下,过量的硝基甲烷能够顺利与双烯酮发生双Michael加成反应,以93~97%的产率专一性地构建一系列反式的多取代环己酮.反应表现出较好的底物适应性,富电子或贫电子的双烯酮、大位阻的邻位取代的双烯酮以及不对称的双烯酮都能够顺利发生反应.所有的产物结构都经~1H-NMR和~(13)C-NMR确认.     

Preparation and characterization of H3−2(x+y)MnxCoyPMo12O40 heteropolysalts. Application to adipic acid green synthesis from cyclohexanone oxidation with hydrogen peroxide

H_3−2(x+y)Mn_xCo_yPMo₁₂O₄₀ heteropolysalts (x + y ≤ 3/2 and x, y: 0–1.5) were prepared by a cationic exchange method based on barium sulfate precipitation. Structural and textural properties of salts were examined by several physicochemical techniques such as infrared, scanning electron microscopy-energy dispersive X-ray, and ³¹P nuclear magnetic resonance spectroscopies, X-ray diffraction diffraction, and thermogravimetric analysis, and their catalytic properties were evaluated in the cyclohexanone oxidation using hydrogen peroxide (30%). The reaction products, adipic, glutaric, succinic, hexanoic, 6-hydroxyhexanoic, 7,7-dimethoxy, and heptanoic acids and 1,1-dimethoxy octane were identified by gas chromatography–mass spectrometry analysis. Only adipic, glutaric, and succinic acids were quantified by chromatography (high-performance liquid chromatography), the other products were noted X. Adipic acid (AA) is the major product for all systems. The effects of molar ratios of catalyst/reactant and cyclohexanol/cyclohexanone, heteropolysalt composition, and reaction duration on AA yield were investigated. The stability of the catalytic system was also examined. H_3−2(x+y)Mn_xCo_yPMo₁₂O₄₀ catalysts were found to be efficient for the cyclohexanone oxidation with conversions >95%. Among them, H₁Mn_0.25Co_0.75 exhibits the highest AA yield (75%).     

氧气催化氧化环己烷

本文系统综述了O₂氧化剂用于环己烷催化氧化体系的研究进展,包括金属配合物催化、金属纳米粒子催化、金属氧化物粒子催化、分子筛催化、碳材料催化、光促进催化、杂多酸催化、金属-有机骨架材料催化等。本文认为研究、开发以O₂为氧化剂,高活性高选择性的非均相环己烷催化氧化体系将成为今后环己烷催化氧化研究的主要方向,尤其是多金属甚至多元素复合体系。本综述不仅对开发高催化活性高选择性的环己烷催化氧化体系,改进目前工业上的环己醇环己酮制备工艺具有重要的参考价值,而且还对其他烃类C-H键和C-C键高效催化氧化体系甚至其他氧化体系的研究与开发也具有重要的参考价值。     

一锅、二步法合成几种含环己基双酚化合物的研究

分别以环己酮、4-甲基环己酮、4-叔丁基环己酮为起始原料,经二氯亚砜氯化得到4,4-二氯环己酮及其衍生物中间体,不经分离,继而将其分别与苯酚及其衍生物进行取代反应,通过“一锅、二步法”制得了1,1-二(4-羟基苯基)环己烷、1,1-二(3-甲基-4-羟基苯基)环己烷、1,1-二(3,5-二甲基-4-羟基苯基)环己烷、1,1-二(4-羟基苯基)-4-甲基环己烷和1,1-二(4-羟基苯基)-4-叔丁基环己烷等5种含环己基的双酚化合物,产率为82.5;～86.0;.用FT-IR、NMR 和元素分析对其组成和结构进行了表征.该合成方法具有操作简单、反应条件温和、收率高等优点.     

钛硅分子筛TS-1上液相氨氧化制环己酮肟机理的原位红外研究

采用原位漫反射红外光谱法,对TS-1上环己酮和氨水、过氧化氢液相氧化反应体系进行了研究.结果表明,环己酮和氨水各自吸附,它们的混合物吸附均发生在表面-Si-OH,且二者相互作用生成亚胺中间物;过氧化氢与TS-1作用形成Ti的过氧化物-Ti-OOH,它与亚胺反应可形成肟.亚胺机理可以很好地解释一些高沸点有机物形成的原因.