Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen source and solvent in the presence of NaOH. All complexes showed high catalytic activity as catalysts in the reduction of substituted acetophenones to corresponding secondary alcohols. The products of catalysis were obtained with conversion rates of between 80 and 99%. Among the seven new complexes investigated, the most efficient catalyst showed turnover frequencies in the range 255–291 h^?1 corresponding to 85 to 97% conversion, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Apparent Solubility of Ibuprofen in Dimethyl Dodecyl Ammonium-Propane Sulfonate, DDAPS, Micelles, DDAPS/Butanol Mixtures and in Oil-in-Water Microemulsions Stabilized by DDAPS

Solubility of drugs in aqueous media is a real issue for scientists and a lot of work is going on to resolve the issue. The same is the case for ibuprofen, which is a derivative of propionic acid, belongs to the NSAIDs family and has low solubility in pure water. Therefore, its solubility has been investigated in dimethyl dodecyl ammonium-propane sulfonate, DDAPS, micellar solution, DDAPS/butanol mixtures and in various (hexane, decane and tetradecane) oil-in-water microemulsions to find out a suitable vehicle. The aggregation number, size and flow ability of micelles and microemulsions were estimated using refractive index, viscosity and light scattering measurements. It has been observed that these microemulsions have a higher ability to solubilize ibuprofen than DDAPS/butanol mixtures or DDAPS micelles.     

Global stabilization in nonlinear discrete systems with time-delay

A class of scalar nonlinear difference equations with delay is considered. Sufficient conditions for the global asymptotic stability of a unique equilibrium are given. Applications in economics and other fields lead to consideration of associated optimal control problems. An optimal control problem of maximizing a consumption functional is stated. The existence of optimal solutions is established and their stability (the turnpike property) is proved.     

Effects of built-in electric field on donor binding energy in InGaN/ZnSnN2 quantum well structures

In_xGa${}_{1?x}$N/ZnSnN₂ quantum well structures are studied in terms of a binding energy of a donor atom. 1s and $2p_{\pm }$ impurity states are considered. The Schrödinger's and Poisson's equations are solved self-consistently. A hydrogenic type wave function to represent each impurity state is assumed. The calculations include band-bending in the potential energy profile introduced by the built-in electric field existing along the structures. The binding energy and the energy of the transition between the impurity states are represented as a function of the quantum well width, the donor position, and the indium concentration. An external magnetic field up to 10 T is included into the calculations to compute the Zeeman splitting. The maximum value of the transition energy is around 30 meV (nearly 7.3 THz) which occurs in a 15-Å In_0.3Ga_0.7N/ZnSnN₂ quantum well. Being strong, the built-in electric field makes the transition energy drop quickly with the decreasing well width. For the same reason, the energy curves are found to be highly asymmetric function of the donor position around the well center. Compared to the bulk value, the transition energy in the quantum well structures enhances nearly two-fold.     

New chiral ruthenium(II)–phosphinite complexes containing a ferrocenyl group in enantioselective transfer hydrogenations of aromatic ketones

A new and versatile class of unsymmetrical ferrocenyl-phosphinite ligands possessing a stereogenic center has been prepared from commercially available, inexpensive aminoacids such as, d-, l-phenylglycine and d-, l-phenylalanine, through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and display good enantioselectivities in the ruthenium-catalyzed asymmetric transfer hydrogenation of acetophenone derivatives, in which up to 91% ee was obtained. A comparison of the catalytic properties of amino alcohols and other analogues based on a ferrocenyl backbone is also discussed briefly. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.     

Synthesis and Reactivity of Hydrolysis Products of Cyclic Phosphites with Amino Substituents

Abstract

Hydrolysis of several cyclic aminophosphites are discussed and compared with that of cyclic chloro/ phenoxy phosphites. An X-ray structure of a hydrolysis product, (C₆H₁₁NH₃)⁺O^?P(O)(H)(2,2′-OC₆H₄-C₆H₄OH) has been determined.