Oxidation of azo dyes in oil-in-water microemulsions catalyzed by metalloporphyrins in presence of lipophilic acids

Hydrogen peroxide oxidation of two aqueous azo dyes, methyl orange and amaranth, catalyzed by manganese porphyrins, have been performed in an oil-in-water microemulsion based on a nonionic surfactant, C12E8. A lipophilic acid was used as cocatalyst in a variable amount. The oxidation was followed by UV spectroscopy. It was shown that the reactions performed in the microemulsion were rapid for both dyes and the reaction rate increased strongly with increasing amount of lipophilic acid added to the reaction mixture. As reference, the same reactions were performed in a two-phase system without surfactant. The reaction profiles in the two-phase system were similar to those in the microemulsion, but the rate was considerably lower. The effect of addition of small amounts of ionic surfactant was also investigated. Addition of anionic surfactant gave a pronounced decrease in reaction rate, whereas a cationic surfactant gave a small reduction in rate. We propose that the rate-limiting step is formation of a metallo-acylperoxy complex at the boundary between oil and water domains. The metallo-acylperoxy complex oxidizes the azo dye in a subsequent step.http://www.sciencedirect.com/science/article/B6TFR-42XB6YN-S/1/352062a0cb1c2de6c2c5b2c0de5f428

Reactivity of azafulvenium methides derived from pyrrolo[1,2-c]thiazole-2,2-dioxides: synthesis of functionalised pyrroles

Extrusion of sulfur dioxide from pyrrolo[1,2-c]thiazole-2,2-dioxides led to the synthesis of functionalised pyrroles via the generation of 1-azafulvenium methides. Sealed tube reaction conditions allowed the synthesis of N- and C-vinylpyrroles whereas from FVP methyl 1,3-dimethyl-5-oxo-5H-pyrrolizine-2-carboxylate and 4-oxo-1,4-dihydro-1-aza-benzo[f]azulene-3-carboxylates were obtained. These last compounds could also be obtained from the FVP of the N- and C-vinylpyrroles.http://www.sciencedirect.com/science/article/B6THS-4C4DX0X-4/1/eac3571d66ca5b141129aa261f28132

Reactivity of 2-halo-2H-azirines. Part 3: Dehalogenation of 2-halo-2H-azirine-2-carboxylates

The dehalogenation of 2-halo-3-phenyl-2H-azirine-2-carboxylates is described. Using sodium borohydride and tributyltin hydride 3-phenyl-2H-azirine-2-carboxylates were obtained in moderate yields. The synthesis of a new 2-bromo-2H-azirines with a chiral auxiliary, 10-phenylsulfonylisobornyl 2-bromo-3-phenyl-2H-azirine-2-carboxylate, is reported. Its dehalogenation led to 10-phenylsulfonylisobornyl 2H-azirine-2-carboxylate as single stereoisomer together with the formation of 10-phenylsulfonylisobornyl acetate.http://www.sciencedirect.com/science/article/B6THR-482NK06-7/1/b576da25bb07c16918052295f89735c

Contribution to the synthesis of chiral allenic esters

A phosphorus ylide bearing a 10-phenylsulfonylisoborneol unit reacted with ketenes, generated in situ from acid chlorides and triethylamine, to give allenic compounds. The reaction with methylketene led to asymmetric induction with the selective synthesis of an allene with axial chirality corresponding to an S configuration. The structure of the chiral allene 10-phenylsulfonylisobornyl penta-2,3-dienoate was determined by X-ray crystallography. Chirooptical studies of the chiral allene derivatives were done.http://www.sciencedirect.com/science/article/B6THS-495V85W-H/1/c946b9b7c8443e7586a0402c58d86df

One-step synthesis of dipyrromethanes in water

In this communication we describe the first results of an efficient synthesis of [beta]-free-dipyrromethanes in water. This new method affords very pure products in moderate to high yields, using a cheap, non-toxic, environment friendly solvent, in a one-step procedure from pyrrole and carbonyl compounds, needing little or no work up procedures.http://www.sciencedirect.com/science/article/B6THS-48FBYP9-W/1/58e27991754d6f7646fd28ad555927b