Rearrangement of epoxynitriles: a convenient homologation of acyclic and cyclic ketones to carboxylic acids

A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids.     

Interaction potentials of the RG-I anions, neutrals, and cations (RG = He, Ne, Ar)

Interaction potentials of the iodine atom, atomic cation, and anion with light rare-gas atoms from He to Ar are calculated within the unified ab initio approach using the unrestricted coupled-cluster with singles and doubles and perturbative treatment of triples correlation treatment, relativistic small-core pseudopotential, and an extended basis set. Ab initio points are fit to a flexible analytical function. The calculated potentials are compared with available literature data, assessed in the I(-)-and I+-ion mobility calculations and the Ar-I(-)-anion zero electron kinetic-energy spectra simulations, and analyzed using the correlation rules. The results indicate a high precision of the reported potentials.     

Synthesis of TiO2 based on hydrothermal methods using elevated pressures and microwave conditions

Titanium dioxide (TiO₂), especially in its anatase form, is an effective photocatalyst under ultraviolet (UV) light. The particle size of TiO₂ is a critical factor to determine its photoactivity based on its quantum effectiveness under light irradiations. Thus, nanocrystalline TiO₂ has been widely accepted to significantly enhance this effect. The sol–gel method is generally used to synthesize the anatase form of nanocrystalline TiO₂. In this study, we expanded the synthesis method of TiO₂ to high pressures under direct heating (hydrothermal method) and indirect heating (microwave-assisted method). It was found that pH value is one of the major factors to control nano-sizes of TiO₂ particles, and the neutral condition in all methods is preferable for controlling the sizes of the prepared TiO₂ particles. The microwave-assisted method further improves quality of synthesized nano-size TiO₂ below 10 nm. These results have been confirmed by both the direct size measurement using TEM images and indirect determination using XRD peaks. The collected samples are further analyzed using UV–Vis spectroscopy to identify the particle size-dependent photoreactivity and to confirm the effectiveness of microwave-assisting under neutral conditions. DSC is also a powerful tool to identify the crystalline transition of TiO₂.     

Poling and crosslinking processes in NLO polymers

A series of photocrosslinkable polymers bearing hyperpolarizable side chain chromophores was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation (SHG). Photoinitiation allowed for control of the onset of curing. Crosslinking was monitored by infrared spectroscopy and optimal conversion was achieved by applying a slow temperature ramp during exposure. The ultimate stability of the poled polymers was directly related to the number of crosslinking substituents that were attached to the chromophore pendant group. With two reactive groups per chromophore significant SHG was retained at temperatures above the initial polymer glass transition temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2769–2775     

Interface broadening during ion plating

Radiation damaged fluorite single crystals iso-thermally annealed showed an oscillating structure of the intensity of a diffracted neutron beam. This is in accord with previous report on crystalline cobaltic compound examined for reconstitution of parent complex ions from recoil hot atoms and for annealing of radiation damage by neutron diffraction. The oscillation phenomenon already found by radiochemical means in various solids irrespectively of their chemical constitution combined by a pure physical method as the neutron diffraction, greatly supports a hypothesis of a spatial temporal oscillatory diffusion of defects in isothermal annealing of radiation damaged crystalline lattice.     

Selective Reductions of 1-(Carbonyl)Substituted 2-Nitro-Imidazoles with Alkali Metal Borohydrides and with Borane. Tetrahydrofuran

Sodium borohydride, lithium borohydride and borane. THF reduce carbonyl groups (esters, amide) in 1-substituted 2-nitroimidazoIes in high yield without reduction of the nitroheterocycle.     

Two Efficient and Practical Syntheses of Methyl 4-Mercaptobenzoate

Two efficient syntheses of methyl 4-mercaptobenzoate are described, one utilizing the dianion of 4-bromothiophenol, the other a S_NAr reaction starting with 4-fluorobenzonitrile.