Chemoselective Hydrogenation of the Olefinic Bonds Using a Palladium/Magnesium‐Lanthanum Mixed Oxide Catalyst

A palladium/magnesium‐lanthanum mixed oxide catalyst is found to be an efficient heterogeneous catalyst for the chemoselective hydrogenation of olefinic double bonds in the presence of various functional groups. The catalyst was recovered by centrifugation and reused for several cycles with consistent activity and selectivity.     

Monodispersed and Stable Nano Copper(0) from Copper‐ Aluminium Hydrotalcite: Importance in C?C Couplings of Deactivated Aryl Chlorides

A simple one‐step approach for the preparation of highly monodispersed nano copper(0) stabilized on alumina [Cu(0)/Al₂O₃] by thermal reduction of copper‐aluminium hydrotalcite (Cu‐Al HT) under a hydrogen atmosphere is described. The transformation of Cu‐Al HT to Cu(0)/Al₂O₃ occurrs via dehydroxylation of divalent and trivalent metal hydroxides and decarboxylation of carbonate anions present in the interlayers of hydrotalcite, as confirmed by XPS, XANES, XRD and TEM analysis. Cu(0)/Al₂O₃ nano composites were used as an efficient catalyst in the C C coupling of deactivated aryl chlorides. The high efficiency and reusability exhibited by Cu(0)/Al₂O₃ outline its potential as an alternative over traditional noble metal‐based catalysts in C C coupling reactions.     

Tris(acetylacetonato)rhodium(III)‐Catalyzed α‐Alkylation of Ketones, β‐Alkylation of Secondary Alcohols and Alkylation of Amines with Primary Alcohols

The tris(acetylacetonato)rhodium(III) catalyst is shown to be a versatile catalyst in the presence of DABCO (1,4‐diazabicyclo[2.2.2]octane) as ligand for the α‐alkylation of ketones followed by transfer hydrogenation, for the one‐pot β‐alkylation of secondary alcohols with primary alcohols and for the alkylation of aromatic amines in the presence of an inorganic base in toluene.     

Solid–liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99

BACKGROUND: In this work, the solid‐liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99, an equivalent of di‐2‐ethylhexyl phosphoric acid, has been investigated. The parameters studied include equilibration time, acid concentration, amount of resin, metal concentration, kinetics, temperature, loading, elution, regeneration and recycling. RESULTS: FT‐IR results confirm the physical interaction of the extractant with the resin. The extraction of terbium with TOPS 99 impregnated Amberlite XAD 4 resin was acid dependent and transfer of metal follows a cation exchange mechanism. The loading capacity of TOPS 99‐impregnated resin for terbium was calculated to be 23.8 mg g^?1 resin. Controlling mechanism of the adsorption was found to be a chemical reaction following pseudo‐second‐order kinetics. The endothermic nature of extraction was confirmed by temperature studies. Among the various eluants studied, H₂SO₄ was the best. Regeneration and recycling of the resin indicated the resin can be used for continuous cycles. CONCLUSIONS: Terbium was successfully extracted from phosphoric acid using TOPS 99 extractant impregnated into Amberlite XAD4 with a maximum loading of 23.8 mg g^?1 resin and fully recovered with 1 mol L^?1sulfuric acid. The resin was subjected to seven cycles of extraction and elution without any loss of performance. Further studies showed that terbium could be separated from lutetium. Copyright © 2010 Society of Chemical Industry     

Heterogeneous Bifunctional Catalysts for the Synthesis of Chiral Vicinal Diols

Heterogeneous bifunctional catalysts consisting of palladate–osmate and osmate–tungstate developed by the ion exchange on quaternary ammonium salts covalently bound to resin, and their homogeneous bimetallic analogs are evaluated for the synthesis of chiral vicinal diols. The heterogeneous bifunctional catalyst (resin-PdOs) and its homogeneous analog are used in the tandem Heck-asymmetric dihydroxylation (AD) to afford diols with excellent yields and enantiomeric excesses (ee's) in the presence of various co-oxidants. The other bifunctional catalyst (resin-OsW) and its homogeneous analog are used in a simultaneous asymmetric dihydroxylation-N-oxidation of a wide range of olefins to obtain chiral vicinal diols with higher yields and ee's using H₂O₂ as terminal oxidant. The bifunctional resin catalysts are recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity.     

Phosphine‐Free Palladium‐Catalyzed Decarboxylative Coupling of Alkynylcarboxylic Acids with Aryl and Heteroaryl Halides

We herein report the design and development of a carboxyamido/carbene ligand and its Pd‐complex for the decarboxylative coupling of alkynylcarboxylic acids with aryl and heteroaryl halides to afford arylalkynes.     

An Improved Process for Selective Liquid-Phase Air Oxidation of Toluene

An improved process for the oxidation of toluene to obtain benzaldehyde and benzyl alcohol with high selectivities using a Co/Mn/Br^– composite catalytic system in liquid phase is described. A protocol for recovery and reuse of the composite catalyst is developed. The use of low concentrations of composite catalytic systems aimed at minimizing corrosion of the reaction, and higher concentrations of toluene affording higher productivity and recyclability of the catalyst giving high turnover number, are the remarkable achievements of the present methodology. Investigation into the recycle, aging and spectroscopic studies of the catalytic system improves the understanding of the process, chemistry and mechanism of the reaction. As the market demand for each product fluctuates, the dynamic system developed here to meet changing demands is very important to obtain one of the products in excess quantities with a change of the ratio of Br^–/Cl^–.     

MFCC-GMM based accent recognition system for Telugu speech signals

Speech processing is very important research area where speaker recognition, speech synthesis, speech codec, speech noise reduction are some of the research areas. Many of the languages have different speaking styles called accents or dialects. Identification of the accent before the speech recognition can improve performance of the speech recognition systems. If the number of accents is more in a language, the accent recognition becomes crucial. Telugu is an Indian language which is widely spoken in Southern part of India. Telugu language has different accents. The main accents are coastal Andhra, Telangana, and Rayalaseema. In this present work the samples of speeches are collected from the native speakers of different accents of Telugu language for both training and testing. In this work, Mel frequency cepstral coefficients (MFCC) features are extracted for each speech of both training and test samples. In the next step Gaussian mixture model (GMM) is used for classification of the speech based on accent. The overall efficiency of the proposed system to recognize the speaker, about the region he belongs, based on accent is 91 %.     

Chemo‐enzymatic synthesis of lipophilic ferulates and their evaluation for antioxidant and antimicrobial activities

An efficient chemo‐enzymatic synthesis of ferulic acid‐based structured lipids mimicking triacylglycerol with a pendant phenolic moiety was carried out for the first time. Initially, ferulic acid was reduced to coniferyl alcohol, followed by its esterification with fatty acids. The key step in the synthesis was dihydroxylation of the olefinic side chain of coniferyl ester, which was eventually esterified with fatty acids to generate phenolic structured lipids. Two such compounds of varying fatty acid chain lengths were synthesized in good yield. Structural confirmation of both compounds is based on IR, ¹H and ¹³C NMR, and MS techniques. The synthesized compounds were tested for in vitro antioxidant and antimicrobial activities. Both compounds exhibited moderate to good antioxidant activity. The phenolic structured lipid with only shorter‐chain fatty acids showed antibacterial activity. Both compounds did not show any antifungal activity.     

MCM-41 Anchored Cinchona Alkaloid for Catalytic Asymmetric Dihydroxylation of Olefins: A Clean Protocol for Chiral Diols Using Molecular Oxygen

MCM-41 anchored 1,4-bis(9-O-quininyl)phthalazine (MCM-(QN)₂PHAL)-OsO₄, is prepared for the first time and used in the heterogeneous asymmetric dihydroxylation of olefins to afford diols with good to excellent enantiomeric excesses in the presence of N-methylmorpholine N-oxide, K₃Fe(CN)₆ or molecular oxygen as cooxidants.