Thirteen mono-, bis-and trifluorinated bromobenzene derivatives have been coupled with cyclohexyl magnesium bromide or the corresponding lithiumchloride or lithiumbromide adducts. Iron, nickel and palladium complexes of the general formula [MCl2(dppx)] (x = (CH2)n, n = 1, 2, 3) have been used as the precatalysts. Palladium based catalysts give high yields of the coupling product with the Grignard reagent itself whereas lithium halides are needed as additives to achieve comparable efficiencies if nickel and iron catalysts are used. Yields also depend on the chain length of the bridging units and on the fact whether fluorine substituents are present in ortho position with respect to bromine.
Kinetics of oxidation of L-lysine by permanganate ion in a perchloric acid medium was investigated to explore the order of the reaction with respect to oxidant and substrate and to study the catalytic behaviour of sodium lauryl sulphate (SLS) and polyethylene glycol (PEG). The reaction was found to be first-order with respect to the oxidant and the substrate and zero-order with respect to hydrogen ion. Changes in the sodium sulphate concentration produce a non-significant variation in the rate of the reaction. SLS and PEG were found to catalyze the reaction. Surfactant catalysis was modelled by Piszkiewicz's cooperativity model, while polymer catalysis was explained with the help of the Benesi-Hildebrand equation. The temperature dependence of the rate of the reaction was elucidated, and activation parameters were obtained. Interestingly, the reaction was found to possess positive activation entropy indicating the dissociative nature of the transition state and outer-sphere electron transfer mechanism. A mechanism of the reaction that is supported by the experimental findings was suggested. KEYWORDS L-lysine, permanganate ion, micellar catalysis, polymer catalysis, outer sphere electron transfer mechanism.
Micellar catalysis exhibited by mixed surfactant systems and gemini surfactants was reviewed. The
review focused on mixed surfactant systems and tried to correlate the changes in the physico-chemical
properties of these systems to the variations of their catalytic activities. Mixed surfactant systems are
promising as the catalytic efficiency of some single surfactants was significantly enhanced in the
presence of other critically selected surfactants. The selection should consider the charge, size, and
structures of the head group as well as an appropriate length of hydrocarbon tail. The overall conclusion
has arrived the mixed surfactant systems could be a tool by which the reaction rate can be tuned by
changing the composition and/or the components’ structures. The higher catalytic activity of gemini
surfactants compared to conventional ones, their facile synthesis and liability for structure control
made them of superior choice for micellar catalysis.
The nickel and palladium catalyzed Kumada-Tamao-Corriu cross-coupling reaction is a powerful method for the formation of carbon-carbon bonds, employed in many large-scale applications in the pharmaceutical and electronic material industries. Kumada cross-coupling is the reaction of an organohalide substrate with a Grignard reagent to produce the corresponding coupled product using a palladium or nickel catalyst. This review covers key developments in Kumada cross-coupling reactions over the past ten years.
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