Synthesis of biodiesel in supercritical alcohols and supercritical carbon dioxide

Biodiesel was synthesized in supercritical fluids by two routes: non-catalytically in supercritical alcohols and by enzyme catalysis in supercritical carbon dioxide. Two oils, sesame oil and mustard oil, and two alcohols, methanol and ethanol, were used for the synthesis. Complete conversion was observed for synthesis in supercritical alcohols whereas only a maximum of 70% conversion was observed for the enzymatic synthesis in supercritical carbon dioxide. For the synthesis in supercritical alcohols, the activation energies and pseudo-first order rate constants were determined. For the reactions in supercritical carbon dioxide, a mechanism based on ping pong bi-bi was proposed and the kinetic parameters were determined. (C) 2009 Elsevier Ltd. All rights reserved.

Studies in the polarographic and coulometric behaviour of aromatic nitro compounds—III. nitrosobenzene in ethanol, acetone and dioxan

The green nitrosobenzene monomer is reduced polarographically to phenylhydroxylamine in the pH range 4—9. Though this reduction is known to be a two-electron process, coulometry invariably gives a lower value of n because of the reaction of unreacted nitrosobenzene and the phenylhydroxylamine formed. The green monomer is attacked by mercury in acid medium. In alkaline medium, the green monomer undergoes a change that follows first-order kinetics with respect to nitrosobenzene. The rate of the transformation depends on the solvent. It decreases in the order acetone > ethanol > dioxan.

Mechanism of hydroxylation of aromatic compounds: Evidence for the involvement of superoxide anion in a model system

Hydroxylation of aromatic compounds was observed in NADH-phenazine methosulfate-O2 model system known to generate superoxide anions (Image ). Addition of superoxide dismutase prepared from ovine erythrocytes to this hydroxylating system resulted in complete inhibition, suggesting an involvement of Image in aromatic hydroxylations.

Enzyme catalysed non-oxidative decarboxylation of aromatic acids II. Identification of active site residues of 2,3-dihydroxybenzoic acid decarboxylase from Aspergillus niger

In order to understand the mechanism of decarboxylation by 2,3-dihydroxybenzoic acid decarboxylase, chemical modification studies were carried out. Specific modification of the amino acid residues with diethylpyrocarbonate, N-bromosuccinimide and N-ethylmaleiimide revealed that at least one residue each of histidine, tryptophan and cysteine were essential for the activity. Various substrate analogs which were potential inhibitors significantly protected the enzyme against inactivation. The modification of residues at low concentration of the reagents and the protection experiments suggested that these amino acid residues might be present at the active site. Studies also suggested that the carboxyl and ortho-hydroxyl groups of the substrate are essential for interaction with the enzyme.

NQR study of complexes between p-dichlorobenzene and some aromatic π acceptors

The charge-transfer complexes of p-dichlorobenzene (PDB) with some aromatic π acceptors such as m-nitrobenzaldehyde (MNB), picric acid (PA), p-nitrobenzoic acid (PNB), and m-dinitrobenzene (MDNB) were prepared by slowly adding the acceptor to the molten donor and then cooling the mass to 15°C. The NQR frequencies of these complexes were measured at room temperature. Contrary to the theoretical prediction, the NQR shift is positive, indicating that the NQR shift in donor-acceptor complexes is indirectly related to the charge-transfer interaction. Bond properties are discussed in terms of frequency shift.

Copper(I) promoted C---C bond forming reactions: direct activation of allyl alcohols

Allylic alcohols, acetates, carbonates and chlorides can be activated by copper(I) salts towards nucleophilic substitution by carbon nucleophiles under relatively mild conditions.

Synthesis of ethyl arylacetates by means of Friedel-Crafts reactions of aromatic compounds with ethyl alpha-chloro-alpha-(ethylthio)acetate catalysed by ytterbium triflate

An efficient Friedel-Crafts alkylation of aromatic compounds with ethyl alpha -chloro-alpha-(ethylthio)acetate catalysed by ytterbium triflate, followed by desulfurisation of the product provides a convenient methodology for the synthesis of ethyl arylacetates of aromatic and heteroaromatic compounds. (C) 2000 Elsevier Science Ltd. All rights reserved.

1,2-Shift in the anodic oxidation of aromatic compounds

The 1,2-shift observed during oxidation of organic substrates can arise by involvement of cation radicals.

Regiospecific hydroxylation of acyclic monoterpene alcohols by aspergillus_niger

Aspergillus niger was shown to carry out the regiospecific hydroxylation of acyclic monoterpene alcohols.

Mechanism of interaction of the antileukemic drug cytosine arabinoside with aromatic peptides : role of sugar conformation and peptide backbone

Interaction of the antileukemic drugs, cytosine-arabinoside (Ara-C) and adenosine-arabinoside (Ara-A) and a structural analogue, cytidine, with aromatic dipeptides has been studied by fluorescence and NMR spectroscopy. Ara-C and cytidine bind tryptophanyl and histidyl dipeptides but not tyrosyl dipeptides, while Ara-A does not bind to any of them. Both studies indicate association involving stacking of aromatic moieties. NMR spectra also indicate a protonation of the histidine moiety by Ara-C. In case of cytidine, the chemical shifts observed on binding to His-Phe imply that the backbone protons of the dipeptide participate in the binding. The conformation of the sugar and the base seem to play a very important role in the binding phenomenon as three similar molecules, Ara-C, Ara-A and cytidine bind in totally different ways.