Compostos altament fluorats. Aplicacions en catálisi i preparació de nous materials

Resumen

The synthetic route of pivotal macrocycle (E,E,E)-1,6,11-tris[(4-fluorophenyl)sulphonyl]-1,6,11-triazaciclopentadeca-3,8,13-triene has been scaled up at multigram scale. The final cyclization step has shown to be sensitive to the intermediate's purity and product has been achieved in a reproducible form in fractions of 1.2 g free of higher order macrocycles and polymers. An equimolar SNAr method of fluorine has been developed for 4-fluorobenzenesulphonamides with thiols and alcohols as nucleophiles. Reaction proceeds in soft conditions and 8 new derivatives of the N,N-(diethyl)-p-fluorobenzenesulphonamide have been achieved in good to excellent yields. The SNAr method has been used to prepare macrocycles containing perfluorinated chains which, at their turn, have shown liquid crystal properties with SmA mesophases. Macrocycles with affinity for BMIM ionic liquids have also been prepared and studied as catalysts for the Sonogashira coupling with aryl iodides and aryl bromides. The macrocycles with perfluorinated chains have shown the ability to coordinate Pd(0) and stabilize Pd(0) nanoparticles. Several Pd sources and preparation conditions have been studied. The achieved nanoparticles are small (1 nm), well defined and dispersed. Nanoparticles adsorbed on Fluorous Reverse Phase Silica Gel have also been prepared. These nanoparticulated materials have been studied as catalysts for the Mizoroki-Heck and Sonogashira couplings with aryl iodides. Carbon-aerogels containing Pd(0) nanoparticles have also been studied as easy recoverable and reusable catalysts. The diazotization of anilines containing perfluorinated chains has been achieved for the first time. From the corresponding diazonium salts, several azo dyes containing perfluorinated chains have been prepared in good yields. The hydrophobic behaviour of these new dyes has been studied. A reactive dye containing a dichlorotriazine unit has been prepared and successfully attached to a cotton fabric in a non aqueous media, rendering the fabric coloured and highly hydrophobic. A dye containing a triethoxysilyl group has been synthesized and attached to an activated glass, also rendering the glass surface coloured and highly hydrophobic.