RESUMO
1,3-Dimethylimidazol-2-ylidene difluoroborane (NHC-BF2 H) was prepared in a one-pot, two-step reaction from the parent ligated borane (NHC-BH3 ). The derived difluoroboryl radical (NHC-BF2. ) was generated by laser flash photolysis experiments and characterized by UVâ spectroscopy and rate-constant measurements. It is transient and reacts quickly with O2 . Unusually, it also reacts more rapidly with ethyl vinyl ether than with methyl acrylate. By this measure, it is the first electrophilic ligated boryl radical. Both NHC-BH3 and NHC-BF2 H serve as co-initiators in bulk photopolymerizations, converting both electron-poor and electron-rich monomers at roughly similar rates. However, the difluorinated coinitiator provides polymers with dramatically increased chain lengths from both monomers.
RESUMO
The photopolymerization of styrene in emulsion is achieved in a conventional double-wall reactor equipped with a LED ribbon coiled around the external glass wall. Styrene mixed to acridine orange is added to the water phase containing sodium dodecyl sulfate, a water-soluble N-heterocyclic carbene-borane and disulfide, and irradiated. Highly stable latexes are obtained, with particles up to a diameter of 300â nm. The ability to reach such large particle sizes via a photochemical process in a dispersed medium is due to the use of visible light: the photons in the visible range are less scattered by larger objects and thus penetrate and initiate better the polymerizations. They are also greener and cheaper to produce via LEDs, and much safer than UVs. The method presented does not require any specific glassware; it works at lower temperature and delivers larger particles compared to thermal processes at similar solids contents and surfactant concentrations.
RESUMO
Perkin condensations of arylglyoxylic acids with arylacetic acids, followed by the addition of alkylamine, yield diarylmaleimides in a one-pot procedure. The arylglyoxylic acids are obtained by arene acylation with ClCOCO2Et and reduced with NaI and hypophosphorous acid to the arylacetic acids. With 2,7-di-tert-butyl-pyren-4-yl or chrysen-6-yl as the aryl, photocyclodehydrogenation of the diarylmaleimides yields substituted helicenes which can be reduced to stable anions. The helicenes combine bathochromically shifted absorption with hypsochromically shifted fluorescence with respect to their precursors.