The water‐promoted Diels–Alder reaction in quaternary ammonium salts

Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO₄ act as salting‐in (S/I) and LiCl, NaCl act as salting‐out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO₄ and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R₄NX, R = alkyl group, X = Br group) behave like salting‐in salts. The physicochemical origin of the salting in effect of R₄NX type of salts has been discussed elaborately in the present work. The role of cations in terms of substitution of various alkyl groups on R₄NX has been systematically presented here on the basis of experimental kinetic and thermodynamic studies. The abnormal behaviour of R₄NX salts in aqueous solution has also been explained by the Setschenov equation (k_s) and Δμ_solvation values, which highlights their individual nature out of common properties of R₄NX. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and metal complexation studies of [2n]thiacalix[m]arene[m]pyrazine

Novel [2_n]thiacalixarenepyrazine and [2_n]thiacalixarenetriazine systems were synthesised by one-pot S_NAr reactions. A screening of the metal-complexing ability of [2₆]hexathiacalix[3]arene[3]pyrazine revealed its affinity for Cu^I, Cu^II and Ag^I metal salts.     

Evidence for the involvement of silver nanoclusters during the Wolff rearrangement of alpha-diazoketones

In situ-generated silver nanoclusters(Ag(n)) during the reduction of either silver(I) oxide or other salts presumably catalyze the Wolff rearrangement of alpha-diazoketones. Their optical, physical, and catalytic properties depend on the starting silver(I) compound and the reaction conditions. [reaction: see text]     

Light-mediated transformations of olefins into alcohols: reactions of hydroxyl radicals with cycloalkenes

Reactions of hydroxyl radicals, generated by photodecomposition of hydrogen peroxide in acetonitrile, with a wide variety of cycloalkenes have been examined. The results show that the major reaction is the addition of hydroxyl radicals to the less substituted end of the double bond, furnishing the secondary alcohols. The reactivity pattern and the observed regio- and stereoselectivity clearly reveal that the steric parameters associated with the substrates play a dominant role in directing the addition reactions. More importantly, this study led to the development of a new methodology for the facile conversions of olefins essentially into secondary alcohols, and includes a few examples which demonstrate the potential of the method.     

2-aminothiophenes by the gewald reaction

The review presents the most elegant and promising set of synthetic routes for the synthesis of 2-aminothiophenes by the Gewald reaction. Applications of this facile methodology to pharmaceuticals and dyestuffs have been demonstrated.     

A new methodology for the synthesis of bicyclo [3.2.0]heptenes from cis-methylvinylcyclopropanes

A practical photolytic approach has been developed to furnish synthetically useful bicyclo[3.2.O]heptene derivatives from $\text{cis}$-methylvinylcyclopropanes; such products are not generally accessible by thermal processes owing to the competing retro-ene reaction.     

Highly diastereoselective formation and reactions of a non-mesomerically stabilized, lithiated alpha-thiocarbanion

A new class of non-mesomerically stabilized, unbranched, configurationally stable lithiated alpha-thiocarbanion has been synthesized and its stereospecific reactions with several electrophiles were investigated.     

Production of cerium zinc molybdate nano pigment by innovative ultrasound assisted approach

Ultrasound assisted synthesis of yellow rare earth cerium zinc molybdate anticorrosion nanopigment is presented. This new class of pigment is eco-friendly alternatives to lead, cadmium and chromium pigment as these pigments contains carcinogenic species like Cr⁶⁺ which is responsible for human disease. The synthesis of nanosized cerium zinc molybdate was carried out using cerium nitrate, sodium zinc molybdate as a precursor materials by conventional and ultrasound assisted chemical precipitation method without addition of emulsification agent. XRD, FTIR and elemental analysis confirm the formation of cerium zinc molybdate nanoparticles. The conductivity results indicate that conventional synthesis takes longer time, while in sonochemical technique (US), reaction completes within short period of time. Improved solute transfer rate, rapid nucleation, and formation of large number of nuclei are attributed to presence of cavitation. Saturation of the Ce³⁺ ions reaches earlier in case of sonochemical technique which restricts the growth of particles hence smaller size is obtained. The crystallite size of cerium zinc molybdate was found to be 27 nm from XRD analysis.