Catalytic Three‐Component Domino Reaction for the Preparation of Trisubstituted Oxazoles

Multicomponent reactions are attractive for assembling functionalized heterocyclic compounds. To this end, an efficient gold‐catalyzed three‐component domino reaction to form oxazoles directly from imines, alkynes, and acid chlorides is presented. The reaction proceeds in a single synthetic step by using a gold(III)–N,N′‐ethylenebis(salicylimine) (salen) catalyst to give trisubstituted oxazoles in up to 96 % yield. The substrate scope, a mechanistic study exploring the role of the gold catalyst, and the synthetic applications of the oxazole products are discussed.     

Synthesis of mutual azo prodrugs of anti-inflammatory agents and peptides facilitated by α-aminoisobutyric acid

Reported is the synthesis of azo mutual prodrugs of the nonsteroidal anti-inflammatory agents (NSAIDs) 4-aminophenylacetic acid (4-APAA) or 5-aminosalicylic acid (5-ASA) with peptides, including an antibiotic peptide temporin analogue modified at the amino terminal by an α-aminoisobutyric acid (Aib) residue. These prodrugs are designed for colonic delivery of two agents to treat infection and inflammation by the bacterial pathogen Clostridium difficile .     

Determination of the 14N quadrupole coupling constant of nitroxide spin probes by W-band ELDOR-detected NMR

Nitroxide spin probe electron paramagnetic resonance (EPR) has proven to be a very successful method to probe local polarity and solvent hydrogen bonding properties at the molecular level. The g(xx) and the (14)N hyperfine A(zz) principal values are the EPR parameters of the nitroxide spin probe that are sensitive to these properties and are therefore monitored experimentally. Recently, the (14)N quadrupole interaction of nitroxides has been shown to be also highly sensitive to polarity and H-bonding (A. Savitsky et al., J. Phys. Chem. B 112 (2008) 9079). High-field electron spin echo envelope modulation (ESEEM) was used successfully to determine the P(xx) and P(yy) principal components of the (14)N quadrupole tensor. The P(zz) value was calculated from the traceless character of the quadrupole tensor. We introduce here high-field (W-band, 95 GHz, 3.5 T) electron-electron double resonance (ELDOR)-detected NMR as a method to obtain the (14)N P(zz) value directly, together with A(zz). This is complemented by W-band hyperfine sublevel correlation (HYSCORE) measurements carried out along the g(xx) direction to determine the principal P(xx) and P(yy) components. Through measurements of TEMPOL dissolved in solvents of different polarities, we show that A(zz) increases, while |P(zz)| decreases with polarity, as predicted by Savitsky et al.     

Crystal engineering via C—H⋯F and C—H⋯π interactions in two substituted indoles

The crystal structures of 1‐(4‐fluoro­phenyl)‐2‐phenyl‐4,5,6,7‐tetra­hydro‐1H‐indole, C₂₀H₁₈FN, and 1‐(4‐fluoro­phenyl)‐6,6‐di­methyl‐2‐phenyl‐4,5,6,7‐tetra­hydro‐1H‐indole, C₂₂H₂₂FN, have been determined in order to study the role of `organic fluorine' in crystal engineering. These mol­ecules pack in the crystal structure via different types of molecular motifs utilizing weak C—H⋯F and C—H⋯π interactions.     

Layer architecture in 4‐nitro­phenyl and 4‐chloro­phenyl 3‐nitro­benzene­sulfonate at 100 K

The structures of the title compounds, C₁₂H₈N₂O₇S and C₁₂H₈ClNO₅S, contain weak C—H⋯O interactions creating layers of mol­ecules which, taking the conformation of the mol­ecules into account, are arranged in an ABAB sequence. Both structures can be designated, therefore, as ordered racemates of rotameric species.     

High-pressure studies on electronic and mechanical properties of FeBO3 (B = Ti,Mn, Cr) ceramics – a first-principles study

Using the density functional theory (DFT) method, the electronic and mechanical properties of perovskites FeBO₃ (B = Ti, Mn, Cr) nanostructures were studied in the pressure range of 0–100 GPa. The band structure studies show the change in the band structure upon substitution of different B cation in FeBO₃ perovskite structure. The density of states spectrum gives the perception of change in the electronic properties of FeBO₃ with the substitution of B cation. The bulk, shear and Young's moduli were calculated and an increase in the moduli is noticed. Moreover, the hardness increases under high pressure. The high-pressure studies of FeBO₃ perovskite nanostructures are explored at atomistic level. The findings show that ductility and hardness of FeBO₃ get increased upon an increase in the applied pressure. The substitution of Ti, Mn and Cr on FeBO₃ shows a significant change in the electronic and mechanical properties.     

Synthesis of poly(ethylene glycol) block copolymers by a redox process and their spectral characterization

Novel block copolymers of poly(ethylene glycol) (PEG) with acrylamide (AAm) and methacrylic acid (MAA) were synthesized using a redox system consisting of ceric ions and PEG in aqueous acidic medium. The molecular weight of PEG in the redox system was varied to obtain a series of block copolymers with differing molecular weights of PEG segment. The polymerization proceeded via macroradical generation, which was substantiated by ESR spectroscopy. This macroradical acted as a redox macroinitiator for the block copolymerization of the vinyl monomers. The formation of the block copolymers was confirmed by fractional precipitation technique.     

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis,Structural and Magnetic Studies

Starting from sterically encumbered 2,6-di-tert-butylphenyl phosphate (dtbppH₂) and co-ligand 3,5-dimethyl pyrazole (dmpz), it is possible to isolate either mono-, di- or tetranuclear copper phosphates by varying the copper source and making attendant changes in the reaction conditions. For example, reaction of copper nitrate with dtbppH₂ and dmpz at 60 °C leads to the isolation of the mononuclear copper phosphate [Cu(dtbppH)₂(dmpz)(MeOH)₂] ( 1 ) as the only product. However, the use of copper acetate in place of copper nitrate and conducting the reaction at the room temperature leads to the formation of both dinuclear [Cu(dtbpp)(dmpz)₂]₂ ( 2 ) and tetranuclear [Cu₂(dtbpp)(dmpz)₂(OAc)(MeO)]₂ ( 3 ) from the same reaction mixture. Compounds 2 and 3 could be isolated in pure form through fractional crystallization. Copper phosphates 1 – 3 have been characterized by both analytical and spectroscopic methods including EPR and magnetic measurements. The molecular structures of all three compounds were established through single crystal diffraction studies. Dc magnetic measurements indicate antiferromagnetic interactions between the metal centres in all the compounds.     

Dependence of positron capture rate on dislocation density in solid solutions of KCl—KBr

Generally well-annealed alkali halide crystals exhibit three lifetime components. τ₁ arises due to annihilation with anion and τ₂ due to Bloch Ps. The origin of τ₃ is not well understood. Positron lifetime and etching techniques have been performed on solid solutions of KCl_100−xBr_x with mole % of x = 0.0, 15, 30, 37, 50, 70, and 100. The positron lifetime spectra have been analysed to resolve into three components. The positron capture rate K₃ for the longest lived component and the dislocation density shows a non-linear variation with composition. The positron capture rate varies linearly with the dislocation density of the samples. The origin of τ₃ is identified as due to positronium formation in the dislocations present in the samples. The trapping probability per dislocation has been estimated to be 2.2 × 10⁻¹²/s.