Synthesis and conversions of metallocycles. 8. Regioselective β-hydrovinylation of α-olefins with the participation of metallocomplex catalysts

A new method is proposed for the synthesis of 2-vinylalkanes by the reactions of aluminocyclopentanes with allyl halides or ethers in presence of catalytic amounts of nickel or cobalt complexes.For previous communication, see [1].Institute of Chemistry, Bashkir Scientific Center, Ural Branch, Russian Academy of Sciences, 450054 Ufa. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 382–385, February, 1992.     

钯催化反应中的β-氢消除反应

总结了作者小组发展的Pd(II)催化的反应, 在卤离子或含氮配体(吡啶、联吡啶、菲咯啉等)存在下淬灭碳—钯键以再生二价钯物种. 卤离子和含氮配体是完成反应的催化循环和高得率所必需的, 它们的主要作用是抑制β-氢消除反应. 对于Pd(0)催化的反应, 控制β-氢消除也是使偶联反应多样化的一个关键, 已发现有许多配体适用于脂肪族化合物的偶联反应. 最近, 又报道了应用卤离子和菲咯啉衍生物为配体应用于这一目的.     

A Convenient One-Pot Completely Stereoselective Synthesis of trans-4-Hydroxystilbenes and Its Derivatives and X-Ray Structure of Its Precursor

Abstract

The synthesis of E-isomer of 4-Hydroxystilbene and its derivatives 3 by reductive elimination of the carbonyl function in 2-phenyl-1-(4-hydroxyphenyl)ethan-1-one and its derivatives 2 and the X-ray structure of 2a are described.     

Chemically modified polymeric filtration membranes for the selective elimination of active pharmaceutical ingredients from water

Poly(ether sulfone) (PES) filtration membranes were chemically modified by ultraviolet‐assisted graft polymerization radical reactions using two monomers, namely acrylic acid (AA) and N‐vinyl‐2‐pyrrolidone (NVP). The reaction kinetics was assessed by applying increasing irradiation durations keeping the monomer concentration constant, and the degree of substitution of the produced materials was monitored by attenuated total reflection‐Fourier transform infrared spectroscopy. The selective binding properties of the produced chemically modified membranes of a series of active pharmaceutical ingredients (APIs), namely 4‐acetamidophenol (APAP), ofloxacin (OFX), ciprofloxacin (CFX), tetracycline (TC), chloramphenicol (CHPH), (±)‐propranolol (PRO) and diclofenac (DF) were evaluated by means of high‐performance liquid chromatography. It was observed that native PES membranes showed specific elimination of some of the selected pharmaceuticals (i.e. PRO, OFX, CFX and DF), and this elimination was improved after chemical modification with AA (except for DF). After chemical modification by NVP, the binding properties were partially improved for several pharmaceuticals, namely TC, CHPH and PRO, and partially reduced for OFX and CFX. The selective elimination of PRO was significantly improved with both AA‐ and NVP‐modified membranes. The reported results demonstrated that the chemical modification of PES filtration membranes allowed improving significantly their API retention properties. Copyright © 2013 John Wiley & Sons, Ltd.     

Study on the formation mechanism of isoniazid crystal defects and defect elimination strategy based on ultrasound

In crystallization, crystal growth defects may reduce the strength and purity of crystals, which are not welcomed in the industry. Herein, isoniazid (INH) crystals were chosen as an example to investigate the formation of crystal defects at the molecular scale by combining experiments and molecular dynamics simulations. It was found that the strong interaction between the solvent and the crystal surface, high temperature, small stirring rate, and low supersaturation can lead to more pronounced crystal defects. The bulk severity of INH crystal defects was reflected by N₂ adsorption–desorption measurement. Besides, the single-crystal growth experiments manifested the rough growth mechanism for the (1 1 0) surface in the axial direction and the stepwise growth mechanism for the (0 0 2) surface in the radial direction. For the (1 1 0) surface, cavities occurred under the condition where the growth rate of the crystal edges and corners was greater than that of the surface center due to the starvation phenomenon of diffusion. While for the (0 0 2) surface, when the solvent removal rate was lower than the solute insertion rate, liquid inclusions were formed, which was verified by Raman microscopy. Furthermore, the ultrasonic strategy was successfully proposed to eliminate INH crystal defects and prepare perfect INH crystals. Moreover, the mechanism of ultrasound to reduce the crystal defect was proposed. We believe this work can provide insights into the design and preparation of defect-free crystals in crystallization.     

Superior selectivity of high-frequency ultrasound toward chorine containing-pharmaceuticals elimination in urine: A comparative study with other oxidation processes through the elucidation of the degradation pathways

This work considered the sonochemical degradation (using a bath-type reactor, at 375 kHz and 106.3 W L^-1, 250 mL of sample) of three representative halogenated pharmaceuticals (cloxacillin, diclofenac, and losartan) in urine matrices. The action route of the process was initially established. Then, the selectivity of the sonochemical system, to degrade the target pharmaceuticals in simulated fresh urine was compared with electrochemical oxidation (using a BDD anode, at 1.88 mA cm⁻²), and UVC/H₂O₂ (at 60 W of light and 500 mol L^-1 of H₂O₂). Also, the treatment of cloxacillin in an actual urine sample by ultrasound and UVC/H₂O₂ was evaluated. More than 90% of the target compounds concentration, in the simulated matrix, was removed after 60 min of sonication. However, the sono-treatment of cloxacillin in the real sample was less efficient than in the synthetic urine. The ultrasonic process achieved 43% of degradation after 90 min of treatment in the actual matrix. In the sonochemical system, hydroxyl radicals in the interfacial zone were the main degrading agents. Meanwhile, in the electrochemical process, electrogenerated HOCl was responsible for the elimination of pharmaceuticals. In turn, in UVC/H₂O₂ both direct photolysis and hydroxyl radicals degraded the target pollutants. Interestingly, the degradation by ultrasound of the pharmaceuticals in synthetic fresh urine was very close to the observed in distilled water. Indeed, the sonodegradation had a higher selectivity than the other two processes. Despite the sono-treatment of cloxacillin was affected by the actual matrix components, this contrasts with the UVC/H₂O₂, which was completely inhibited in the real urine. The sonochemical process led to 100% of antimicrobial activity (AA) elimination after 75 min sonication in the synthetic urine, and ∼ 20% of AA was diminished after 90 min of treatment in the real matrix. The AA decreasing was linked to the transformations of the penicillin nucleus on cloxacillin, the region most prone to electrophilic attacks by radicals according to a density theory functional analysis. Finally, predictions of biological activity confirmed that the sono-treatment decreased the activity associated with cloxacillin, diclofenac, and losartan, highlighting the positive environmental impact of degradation of chlorinated pharmaceuticals in urine.     

A Key Intermediate in Copper‐Mediated Arene Trifluoromethylation, [nBu4N][Cu(Ar)(CF3)3]: Synthesis,Characterization, and C(sp2)−CF3 Reductive Elimination

The synthesis, characterization, and C(sp²)?CF₃ reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu₄N][Cu(Ar)(CF₃)₃] are described. Mechanistic investigations, including kinetic studies, studies of the effect of temperature, solvent, and the para substituent of the aryl group, as well as DFT calculations, suggest that the C(sp²)?CF₃ reductive elimination proceeds through a concerted carbon–carbon bond‐forming pathway.