A Quantum Chemical Study of the Abnormal Reactivity of 2‐Methoxyfuran

The gas‐phase pyrolytic and oxidative chemistry of furans has received much attention recently because of their potential as platform chemicals and biofuels. Typically these compounds exhibit very strong ring carbon to H or CH₃ bonds. 2‐Methoxyfuran had been reported to be exceptionally unstable in comparison to related substituted heterocycles in pyrolytic experiments. The origins of its reactivity are shown to be due to the very weak O–CH₃, which at 189.5 ± 1.9 kJ mol^?1 is some 200 kJ mol^?1 weaker than C–H bonds in the molecule. We show that the reported reactivity is somewhat overestimated but that does not alter the fact that 2‐methoxyfuran is exceptionally unstable. It may prove to be a useful alternative to azomethane as a thermal source of methyl radicals.     

Large Eddy Simulation of a Free-Burning Arc Discharge in Argon with a Turbulent Cross Flow and External Field

In most of the numerical approaches proposed for modeling high-intensity plasma-arcs, the effects of turbulence on the arc structure are often excluded because of the intricate physics originating from the interaction of turbulent scales, high-temperature gas dynamics, magnetohydrodynamics (MHD) and chemical kinetics. The goal of this study is threefold: to develop a generic turbulent MHD model to simulate free-burning arc discharges, to validate the code with available experimental data, and to investigate the effect of an external field and turbulent cross flow on the free-burning arc configuration. The governing equations are solved in conservative form using a hybrid scheme that combines a high-order monotonic upwind scheme with a second-order central scheme. The fluid and MHD turbulence are resolved using a large eddy simulation (LES) approach with a recently developed sub-grid closure model. An implicit scheme is used to compute the magnetic diffusion term appearing in the magnetic induction equation to alleviate the severe time-step constraint. The comparison of the model prediction with experimental data for Argon arcs at different current intensities shows generally good agreement. When an external field is applied, the overall shape of the free-burning arc drastically changes. The straightening of the arc indicates the potential for stabilization of a free-burning arc by magnetic forces. Even though the turbulence is significantly attenuated as a result of the thermal expansion near the cathode, it adds an unsteady characteristic to the arc and, in general, has a negative impact on the stabilization of the electrical discharge.     

Formal (4+1) Cycloaddition and Enantioselective Michael–Henry Cascade Reactions To Synthesize Spiro[4,5]decanes and Spirooxindole Polycycles

Spiro[4,5]decanes and polycyclic compounds bearing spiro[4,5]decane systems are important biofunctional molecules. Described are diastereoselective formal (4+1) cycloaddition reactions to afford oxindole-functionalized spiro[4,5]decanes and organocatalytic enantioselective Michael–Henry cascade reactions of the (4+1) cycloaddition products to generate spirooxindole polycyclic derivatives bearing the spiro[4,5]decane system. Spiro[4,5]decanes bearing oxindoles containing three stereogenic centers and spirooxindole polycycles having seven stereogenic centers, including two all-carbon chiral quaternary centers and one tetrasubstituted chiral carbon center, were obtained with high diastereo- and enantioselectivities.     

Effect of ammonium groups on the properties and alkaline stability of poly(arylene ether)‐based anion exchange membranes

Five kinds of ammonium groups functionalized partially fluorinated poly(arylene ether) block copolymer membranes were prepared for investigating the structure–property relationship as anion exchange membranes (AEMs). Consequently, the pyridine (PYR)‐modified membrane showed the highest alkaline and hydrazine stability in terms of the conductivity, water uptake, and dry weight. The chloromethylated precursor block copolymers were reacted with amines, such as trimethylamine, N‐butyldimethylamine, 1‐methylimidazole, 1,2‐dimethylimidazole, and PYR to provide the target quaternized poly(arylene ether)s. The structures of the polymers, as well as model compounds and oligomers were well characterized by ¹H NMR spectra. The obtained AEMs were subjected to water uptake and hydroxide ion conductivity measurements and stabilities in aqueous alkaline and hydrazine media. The pyridinium‐functionalized quaternized polymers membrane showed the highest alkaline and hydrazine stability with minor losses in the conductivity, water uptake, and dry weight. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 383–389     

Cu-deposits on Mg metal surfaces promote electron transfer reactions

The enhancement of the electron transfer processes in the Grignard reagent formation-type ring silylation and the defluorination–silylation of perfluoroalkyl benzenes by Cu(0)-deposited Mg metal were confirmed. Microscopic analysis and substituent effects implied a different reduction process in the presence of Cu-deposited Mg metal than in the presence of bare Mg metal.     

Total Synthesis of the 7,10‐Epimer of the Proposed Structure of Amphidinolide N,Part II: Synthesis of C17–C29 Subunit and Completion of the Synthesis

The total synthesis of 7,10‐epimer of the proposed structure of amphidinolide N was accomplished. The requisite chiral C17–C29 subunit was assembled stereoselectively via Keck allylation, Shi epoxidation, diastereoselective 1,3‐reduction, and a later oxidative synthesis of the THF framework. The C1–C13 and C17–C29 subunits were successfully coupled using a Enders RAMP “linchpin” as the C14–C16 three carbon unit, thereby controlling the chirality at C14 and C16. The labile allyl epoxy moiety was successfully constructed by Grieco–Nishizawa olefination at a final stage of the synthesis.     

Comparative investigation of Au nano-particle formation process dependent upon various protective agents

Formation process of gold nanoparticles was investigated by near-field heterodyne transient grating method. In the absence of the protective agents, although the diffusion of H[Au^ICl₂] could be observed after the photo-reduction of H[Au^IIICl₄], the diffusion of nanoparticle-seeds was not observed. On the other hand, in the presence of the protective agents, the diffusion of a complex molecule (Au and protective agent) and nanoparticle-seeds could be observed. From these results, it was found that enough amount of the complex is essential for the nanoparticle formation. We also investigated the formation process with four different chemicals as a protective agent. The hydrodynamic radius of nanoparticle-seeds generated in the poly(vinyl pyrrolidone) and TritonX-100 solutions were larger than those generated in the Tween 20 and Brij 58 solutions. The former two have hydrophilic chain in the molecular structure; on the other hand, the latter two have hydrophobic alkyl chain. Based on those facts, we concluded that the interaction between the chains of the complex molecule plays an important role in the nanoparticle formation process.