13 research outputs found
Relations entre la composition chimique et minéralogique de sols cohérents et leur texture
Facile and regioselective synthesis of substituted 1H-pyrazolo[3,4-b]quinolines from 2-fluorobenzaldehydes and 1H-pyrazol-5-amines
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
Excited-State Double Proton Transfer in 1H-Pyrazolo[3,4-b]quinoline Dimers
Pyrazoloquinolines are highly fluorescent, both in liquid solutions and in the solid state, which makes them good candidates for various optical devices. The aim of the current work is to understand the photochemical behavior of pyrazolo[3,4-b]quinoline (PQ), which is quite complicated since in n-alkane solvents PQ tends to form strong complexes with protic solvent constituents (often present as minor impurities), as well as dimers. Both types of H-bond complexes were studied systematically by temperature-dependent conventional absorption and fluorescence spectroscopy; the effect of protic solvent constituents was mimicked by varying the ethanol concentration in n-octane in the range from 0.0 to 0.8%. At room temperature the PQ:ethanol association constant was estimated at 80 M-1 and the dimerization constant at 2 x 103 M-1. Dimer formation is enhanced upon lowering the temperature in pure n-alkane down to 220 K, and the fluorescence is strongly reduced since the dimer is nonfluorescent. Surprisingly, when irradiating a frozen sample for several minutes at very low temperatures (<40 K), a narrow-banded Shpol'skii-type fluorescence spectrum gradually appears. To explain this unusual photochemical behavior, PQ and its deuterated analogue were studied using low- temperature absorption and fluorescence spectroscopy over the 300-5 K temperature range. In the case of normal (protonated) PQ, very fast excited-state intermolecular double proton transfer is responsible for the efficient quenching of PQ dimer fluorescence. Deuteration significantly slows down this proton transfer process, and in that case under cryogenic conditions a fluorescent dimer is observed. Photoirradiation under cryogenic conditions leads to molecular rearrangement of the dimers and the appearance of monomer spectra. For both H-PQ and D-PQ, these processes were found to be reversible. A simplified reaction scheme, in which the excited tautomeric dimer plays a crucial role, is presented to explain the observations. © 2009 American Chemical Society