Catalysis by Ir(III), Rh(III) and Pd(II) metal ions in the oxidation of organic compounds with H2O2

Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H₂O₂. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Photocatalysed eosin Y mediated C(sp3)-H alkylation of amine substrates via direct HAT

A visible light promoted, photoredox catalysed, green one-pot approach for the alkylation of amine substrates with sp² carbon has been developed. This eosin Y based organic transformations, can behave as an effective direct hydrogen-atom transfer catalyst for coupling reaction. The proposed strategy includes simple procedure which can make adduct product with sp² carbon. This eosin Y based photocatalytic hydrogen-atom transfer strategy may hold great potential for diverse functionalization of a wide range of native CH bonds in an economical and sustainable manner.     

Glass and polymeric membrane electrodes for the measurement of pH in milk and cheese

While there is a considerable interest in the food industry in determining various analytes using ion-selective electrodes (ISEs), only few reports describe their use for direct measurements in food. In this study, the suitability of glass electrodes and ionophore-based solvent polymeric ISEs for the determination of pH in Process cheese, Cheddar cheese and milk was investigated. The liquid junction potential between a 3 M KCl bridge electrolyte and diluted as well as undiluted Process cheese was found to be negligible. Reference electrodes with ceramic plug and sleeve-type junctions performed well, although precautions needed to be taken to prevent plugging at the junctions. While the protein rennet casein posed no problems in pH measurements, the extraction of neutral lipophilic compounds or hydrophobic peptides into solvent polymeric membranes was evident, resulting in some loss of selectivity for monovalent cations upon exposure to cheese. However, it was found that ISEs based on tridodecylamine (R₃N) as ionophore and o-nitrophenyl octyl ether (oNPOE) as plasticizer can be used to accurately measure the pH of milk and, after desensitization of the electrodes in a cheese emulsion, of diluted Process cheese. Since pH measurements with a glass electrode showed that emulsions of cheese moderately diluted to a cheese content of 70% have the same pH as undiluted cheeses, it is possible to determine the pH in cheese with ionophore-based ISEs. R₃N membranes also performed well in undiluted milk.     

Stereoselective synthesis of (−)-microcarpalide

A highly convergent and efficient synthesis of (−)-microcarpalide, a 10-membered lactone displaying remarkable microfilament disrupting activity is described. Ring-closing metathesis and Sharpless asymmetric dihydroxylations are the key steps. Our strategy highlights the application of novel hydroxy lactone precursors for the stereoselective synthesis of (−)-microcarpalide.     

Novel reactions of phosphorus(III) azides and isocyanates: unusual modes of cycloaddition with dipolarophiles and an unexpected case of ring expansion

New modes of 1,3-dipolar cycloaddition are uncovered by the isolation of [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)N[NP(N3)(OC6H2-6-t-Bu-4-Me)2CH2]N) (3) and [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)C(O)N) (4) on treating [CH2(6-t-Bu-4-Me-C6H2O)2]P-X [X = N3 (1) and NCO (2)] with the dipolarophile MeO2CC identical to CCO2Me; compound 4 undergoes an unprecedented ring expansion upon addition of 2-(methylamino)ethanol to afford the spirocycle [CH2(6-t-Bu-4-Me-C6H2O)2]P(OCH2CH2N(Me)CH(CO2Me)CH(CO2Me)C(O)N) (5).     

Solid phase extractive preconcentration of uranium(VI) using quinoline-8-ol anchored chloromethylated polymeric resin beads

A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with quinoline-8-ol (HQ). The modified polymeric resin was characterized by FT-IR spectroscopy and elemental analysis. The HQ anchored resin showed superior binding affinity for U(VI) over Th(IV) and La(III). The influence of various physicochemical parameters on the recovery of U(VI) were optimized by both static and dynamic methods. The phase exchange kinetic studies performed for U(VI) revealed that <5 min was sufficient for reaching equilibrium metal ion sorption. The maximum sorption capacity of HQ anchored resin for U(VI) was found to be 120.30 mg g⁻¹ of resin which is higher than other solid phase extraction sorbents reported so far excepting N,N-dibutyl, N′-benzoyl thiourea sorbed Amberlite XAD-16. The developed HQ anchored polymeric resin is highly selective as none of the extraneous species were found to have any deleterious effect. Solid phase extraction (SPE) studies performed using HQ anchored polymeric resin offered enrichment factor of 100 and the lowest concentration below which recoveries become non-quantitative is 5 μg l⁻¹. The accuracy of the developed SPE method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA–Soil 7) reference materials. Furthermore, the above procedure has been successfully employed for the analysis of real soil and sediment samples.     

Cycloaddition profile of pentafulvenes with 3-oxidopyrylium betaine: experimental and theoretical investigations

A detailed investigation on the effect of solvent polarity, temperature, and microwave irradiation on periselectivity in cycloaddition reactions of pentafulvenes with 3-oxidopyrylium betaine is described. The base catalyzed generation of 3-oxidopyrylium betaine in CHCl₃ resulted in the exclusive formation of [6+3] adducts. With increase in solvent polarity and temperature, mixtures of [6+3] and [3+2] adducts were formed, where as under microwave irradiation, [3+2] adducts were formed exclusively. The experimental results have been rationalized on the basis of theoretical calculations.     

Photosensitivity,substituent and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester liquid crystals: a comparative theoretical approach

The substituent- and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester nematic liquid crystals, viz., 4-octylphenyl-6-octyloxy-2-naphthoate (NAPHE1) and 6-octyloxy-2-naphthylyl-4-octyloxybenzoate (NAPHE2), have been investigated using the DFT, CNDO/S and INDO/S methods. A correlation has been made between molecular charge distribution and phase stability based on Mulliken, Loewdin, AM1, PM3, MNDO, CNDO/S and INDO/S methods. The observed π→π* and n→π* electronic transitions have been reported. The substituent- and solvent-induced shifts in absorption bands, transition energies and energy gaps have been discussed. The photosensitivity of the molecules has been analysed based on these shifts. It has been observed that the substituent has a dominant role on both absorption maxima and energy band gap, whereas the solvent has a dominant role only on absorption maxima, and no effect has been observed on the energy gap. These shifts may provide beneficial consequences in determining the end use of compounds.     

Water-Mediated Synthesis of Benzazole and Thiourea Motifs by Reacting Naturally Occurring Isothiocyanate with Amines

An efficient, green, and facile method has been developed for the synthesis of benzazole and thiourea analogues from naturally occurring erucin in moderate to good yields. The reaction was carried out in water without using any metal catalyst or base. The present method tolerated the various functional groups on aromatic rings and also applicable for other isothiocyanates.