TsNBr2 promoted decarboxylative bromination of α,β-unsaturated carboxylic acids

A rapid process for decarboxylative bromination of α,β-unsaturated carboxylic acids have been developed using N,N-dibromo-p-toluenesulfonamide (TsNBr₂). Treatment of cinnamic acids with TsNBr₂ in presence of potassium carbonate in acetonitrile produces corresponding β-bromostyrenes at room temperature. Exclusive formation of (E)-β-bromostyrenes was observed in a stereoselective manner within a very short period of time (5–15?min). This method was further extended for obtaining 1-bromoalkynes from corresponding propiolic acids. Instantaneous formation of bromoalkynes was observed when the reaction was carried out in presence of DBU as a base in acetonitrile at room temperature. A wide variety of cinnamic acids and propiolic acids could be converted to corresponding β-bromostyrenes and 1-bromoalkynes respectively under mild reaction condition with high to excellent yield.     

New oxo-bridged dinuclear peroxotungsten(VI) complexes: Synthesis, stability and activity in bromoperoxidation

Two new dinuclear oxo-bridged peroxo complexes of tungsten with coordinated dipeptides of the type, Na₂[W₂O₃(O₂)₄(glycyl-glycine)₂] · 3H₂O (1) and Na₂[W₂O₃(O₂)₄(glycyl-leucine)₂] · 3H₂O (2) have been synthesized from the reaction of H₂WO₄, 30% H₂O₂ and the respective dipeptide at pH ca. 2.5. Synthesis of the compounds, in addition to pH, is sensitive to reaction temperature and concentrations of the components. The compounds were characterized by elemental analysis, spectral and physico-chemical methods including thermal analysis. In the dimeric complexes the two W(VI) centres with edge bound peroxo groups are bridged by an oxo group. The dipeptides occurring as zwitterions bind the metal centers through O (carboxylate) atoms leading to hepta co-ordination around each W(VI). Thermal stability of the compounds as well as their stability in solution were determined. The compounds are highly stable toward decomposition in solutions of acidic as well as physiological pH. These compounds, besides another similar dimeric compound Na₂[W₂O₃(O₂)₄(cystine)] · 4H₂O (3) efficiently oxidized bromide to a bromination competent intermediate in phosphate buffer at physiological pH, a reaction in which only two of the peroxide groups of the complex species were found to be active. The complexes could also mediate bromination of organic substrate in aqueous-organic media.     

Sol-hydrothermally derived gadolinium oxide (Gd2O3) nanorods and tamarind-like shape evolution under 80 MeV C6+ ion impact

The present work highlights swift heavy ion irradiation-induced shape evolution of gadolinium oxide (Gd₂O₃) nanorods synthesized via a sol-hydrothermal route. Upon dispersing Gd₂O₃ nanorods in the polyvinyl alcohol matrix, thin solid films were cast on borosilicate glass substrates. The films were then exposed to 80?MeV carbon-ion irradiation, while fluence was varied in the range of 1×10¹¹–3×10¹²?ions/cm². The post analyses were carried out by using X-ray diffraction, high resolution transmission electron microscopy (TEM) and Raman spectroscopy studies. An apparently observable shortening of length (L) and diameter (D) of the nanorods can be revealed through the TEM imaging analyses. Moreover, while exhibiting an aspect ratio (L/D) between 3.3 and 4.7, the nanorods were found to exist in the form of bunching at higher fluences. The irradiation-induced tamarind-like shape evolution at higher fluences was attributed to the overlapping of ion impacts on certain regions of the nanorods. The most intense Raman active peak of the pristine sample located at ～360?cm^?1 was seen to experience blue-shifting (～375?cm^?1) when irradiated at the highest fluence (～3×10¹²?ions/cm²). An altered shape evolution of a thermally and mechanically stable oxide system by the energetic ion impact would bring in new insights as regards construction of surface patterns and their potential use in miniaturized devices.     

Endocrine disruption: molecular interactions of chlorpyrifos and its degradation products with estrogen receptor

Structural Chemistry - Chlorpyrifos is an extensively used organophosphate pesticide showing broad-spectrum effectiveness on various target pests. Long-term sublethal exposure to this pesticide is...     

Metal free synthesis of quinoxalines from alkynes via a cascade process using TsNBr2

A metal free protocol for the synthesis of quinoxalines from alkynes has been developed. The reaction was carried out by treating alkynes with TsNBr₂ in presence of O-phenylenediamines in a mixture of acetonitrile and water (9:1). This one-pot reaction proceeds via an oxidative transformation of alkynes to α,α-dibromoketones in presence of TsNBr₂ and eventually to quinoxalines in presence of 1,2-diamines in a cascade process.     

Surfactant/I2/water: an efficient system for deprotection of oximes and imines to carbonyls under neutral conditions in water

I2/surfactant/water system deprotecting oximes and imines to the corresponding carbonyl compounds under neutral conditions in water at 25-40 degrees C with very high to excellent yields.     

Effect of oxalic acid (complexing agent) on anodic dissolution of Cobalt in hydrogen peroxide solutions: mechanism and kinetic analysis by electrochemical impedance spectroscopy

Journal of Solid State Electrochemistry - The anodic dissolution of Cobalt in H2O2 solution is investigated in the presence and absence of a complexing agent, oxalic acid, using various techniques...