一价铜催化Ullmann 反应合成联苯醚和芳基烷基醚的研究

联苯醚和芳基烷基醚类化合物是天然产物和聚合物材料中的重要的片段结构，研究其合成具有重要意义。近年来，过渡金属催化形成碳-氧键已成为制备联苯醚和芳基烷基醚类化合物的重要方法。钯体系虽然成功，但由于其属于贵金属，价格昂贵，而且反应所必须的有机膦配体，毒性较大，对环境危害较大，所以其应用受到了限制。 本论文通过利用空气稳定的Cu(bpy)2BF4 配合物，使得苯酚和烷基醇有效地进行偶合得到联苯醚产物。该方法可以在不使用昂贵弱碱Cs2CO3 的情况下，取得很好的产率，并且在较低的催化剂载入量的情况下，可以很好地适应各种官能团取代的底物。 本论文通过配体的扫描筛选，使得溴代苯和烷基醇的偶合反应得到了发展。更重要的是，使用该体系时分子间和分子内的碳-氧键都可以形成。通过该方法合成了一系列苯并环醚类化合物，这也是一价铜体系催化制备该类化合物的首次报道。

An Efficient Ullmann-Type C-O Bond Formation Catalyzed by an Air-Stable Copper(I)-Bipyridyl Complex

An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Cu-Based Nanoalloys in the Base-Free Ullmann Heterocyle-Aryl Ether Synthesis

We report the first liquid-liquid Ullmann etherification process mediated not only by oxidatively stable Cu but also by CuZn and CuSn nanoparticle catalysts in conjunction with microwave heating that also avoids the use of solid and expensive bases. Conditions have led to improved turnovers and excellent yields in heteroaromatic Ullmann-type coupling reactions. Further enhancement is achieved upon the addition of 18-crown-6 as a kinetic promoter.

Microwave-assisted Cu-catalyzed Ullmann ether synthesis in a continuous-flow milli-plant

The combination of milli-scale processing and microwave heating has been investigated for the Cu-catalyzed Ullmann etherification in fine-chemical synthesis, providing improved catalytic activity and selective catalyst heating. Wall-coated and fixed-bed milli-reactors were designed and applied in the Cu-catalyzed Ullmann-type CO coupling of phenol and 4-chloropyridine. In a batch reactor the results show clearly increased yields for the microwave heated process at low microwave powers, whereas high powers and catalyst loadings reduced the benefits of microwave heating. Slightly higher yields were found in the Cu/ZnO wall-coated as compared to the Cu/TiO fixed-bed flow-reactor. The benefit here is that the reaction occurs at the surface of the metal nanoparticles confined within a support film making the nano-copper equally accessible. Catalyst deactivation was mainly caused by Cu oxidation and coke formation; however, at longer process times leaching played a significant role. Catalyst activity could partially be recovered by removal of deposited by-product by means of calcination. After 6h on-stream the reactor productivities were 28.3 and 55.1kgprod/(mR3h) for the fresh Cu/ZnO wall-coated and Cu/TiO fixed-bed reactor, respectively. Comparison of single- and multimode microwaves showed a threefold yield increase for single-mode microwaves. Control of nanoparticles size and loading allows to avoid high temperatures in a single-mode microwave field and provides a novel solution to a major problem for combining metal catalysis and microwave heating. Catalyst stability appeared to be more important and provided twofold yield increase for the CuZn/TiO catalyst as compared to the Cu/TiO catalyst due to stabilized copper by preferential oxidation of the zinc. For this catalyst a threefold yield increase was observed in single-mode microwaves which, to the best of our knowledge, led to a not yet reported productivity of 172kgprod/(mR3h) for the microwave and flow Ullmann CO coupling. © 2012 Elsevier B.V.

La nationalité dans la science sociale et dans le droit contemporain / par MM. B. Akzin, M. Ancel, Mlle S. Basdevant, MM. M. Caleb, Drouillat, M. Gégout, E. Gordon, R. Kiefé, P. de La Pradelle, Martin, R. Maunier, B. Mirkine-Guetzévitch, J. Ray ; préface de MM. Lévy-Ullmann et Gidel

Collection : Série de monographies de droit public ; 3

Crefeld: Nachträgliches zum Nekrolog des Dr. Ullmann

D.

Rosa Ullmann

E. Brader

Abraham Ullmann an Salomo Rosenthal [Illustration] : (Autograph)

Abraham Ullmann

Alexander Ullmann, Brustbild

Signatur des Originals: S 36/G02412

Jesus und Judas : ein historisch-kritischer Versuch, nebst einem Sendschreiben an den Professor Dr. Ullmann /

Includes bibliographic references.

Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles

Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald–Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.