Novel Cleavage of Propargylamines by Reaction with Organolithium Compounds

Treatment of secondary aliphatic 2-bromoallylamines with an excess of an organolithium compound led to saturated amines in which the organic group of the organolithium compound is incorporated at the alpha carbon. On the other hand, the successive reaction of the former amines with BuLi and t-BuLi between -80 degrees C and rt gave 1,3-diamines or hexahydropyrimidines depending on the reaction time. The formation of these unexpected products involves initial generation of lithium propargylamides, which subsequently undergo cleavage of the C propargylic-C acetylenic bond induced by the organolithium present in each case in the reaction medium. A mechanism which takes into account all the different reaction products has been proposed and additionally supported by successful trapping of dilithium acetylide.     

Thermal Cyclodimerization of Aliphatic Secondary C,N-Dilithioallylamine Derivatives

beta-Nitrogen-functionalized vinylic organolithium compounds derived from secondary aliphatic allylamines have been found to undergo upon heating (reflux of THF) either a dimerization or a regio- and stereoselective cyclodimerization reaction affording diamino 1,4-dienes or cis-2,3-disubstituted 4-methylenepyrrolidines, respectively, according to reaction time. In contrast, the corresponding dianions derived from aromatic allylamines underwent protonation by the solvent under analogous thermal treatment. A mechanism accounting for all these results has been proposed, which involves a spontaneous beta-elimination of lithium hydride and an intramolecular nucleophilic cyclization by addition of a lithium amide to an alkene group as critical steps. In addition, experimental evidence is provided about the formation of 3-lithio-1-aza 1,3-dienes as intermediates in these unusual thermal transformations.     

Removal of atrazine from water using an iron photo catalyst supported on activated carbon

Atrazine is a systemic triazine herbicide, which has been classified as an endocrine disrupting pesticide of hormones and the reproductive systems of humans. Moreover, atrazine was recently considered as a potential carcinogen by several reports. The aim of this work was to synthesize and to evaluate an iron catalyst supported on activated carbon to remove atrazine from water. Five different treatment schemas were evaluated: (1) adsorption with the photocatalyst’s support alone, (2) adsorption with the supported photocatalyst alone, (3) adsorption coupled to heterogeneous Fenton reaction, (4) adsorption coupled to heterogeneous advanced oxidation with UV light and (5) adsorption coupled to heterogeneous photo assisted Fenton reaction. The photocatalyst synthesized, via the incipient wet impregnation method, showed 1176 ± 24 m²/g of Langmuir area and 1.6 % wt/wt of iron content. After 120 min of reaction time, total removal efficiencies in the treatment schemas using the photocatalyst ranged from 70 % (mainly adsorption with the photocatalyst alone) to 96 % (Adsorption and heterogeneous photo assisted Fenton reaction). The heterogeneous photo assisted Fenton reaction was the fastest and most efficient treatment schema, with results better than that reported for similar materials. The adsorption data was fitted to a kinetic model of pseudo-second order and the results of advanced oxidation process were fitted to a kinetic model of fractional order.     

Synthesis and photochemical behavior of phosphorus dendrimers containing azobenzene units within the branches and/or on the surface

We describe the synthesis of three series of phosphorus-containing dendrimers having azobenzene derivatives specifically placed at some generations in the interior and/or on the surface. The largest compound obtained possesses 48 azobenzene groups on the surface. Irradiation at 350 nm induces isomerization of the azobenzene groups from the E form to the Z form, whatever their location. The thermal back-isomerization to the E form in the dark at room temperature was observed in all cases. The kinetics of this Z-->E back-isomerization was studied in several cases; the rate is not dependent on the number of azobenzene units or of the generation, when the azobenzene groups are linked to the surface of the dendrimer. A different behavior was observed when the azobenzene groups were located within the framework of the dendrimer.     

N-Heterocyclic carbene adducts of orthopalladated triarylphosphite complexes

Carbene adducts of orthopalladated triarylphosphite complexes have been synthesised and characterised. The structures of three of these complexes were determined by single-crystal X-ray analysis. The complexes are active in the Suzuki coupling of a range of aryl bromide substrates.