Search results for "Ketyl"
showing 4 items of 4 documents
Photoreaction Between Benzoylthiophenes and N-BOC-Tryptophan Methyl Ester‡
2005
Drug-induced photoallergy requires as the first step formation of covalent drug-protein photoadducts. One of the key amino acids involved in this process is tryptophan (Trp). In this context, several diaryl ketones, including 2-benzoylthiophene (BT), [2-(5-benzoyl-5-thienyl)]-2-methylpropanoic methyl ester (TPA methyl ester) and 4-(2-thienylcarbonyl)phenyl]-2-methylpropanoic methyl ester (SUP methyl ester) have been irradiated in the presence of N-BOC-(L)-tryptophan methyl ester. Laser flash photolysis has allowed to detect three neutral radicals (ketyl, indolyl and skatolyl radicals) resulting from formal hydrogen-atom abstraction. This correlates well with the isolation of homodimers, as …
Size Reduction of CdSe/ZnS Core−Shell Quantum Dots Photosensitized by Benzophenone: Where Does the Cd(0) Go?
2011
The size of core-shell CdSe/ZnS quantum dots can be decreased by using the combined action of an n,π* aromatic ketone and UVA light. Energy-dispersive X-ray spectroscopy as well as X-ray photoelectron spectroscopy techniques gave information on the photosensitization mechanism and the eventual destiny of Cd(2+) and Se(2-) core ions. Our data support the electron transfer from the BP ketyl radical to Cd(2+), leading to Cd(0) and H(+), as well as to the recovery of benzophenone. Elemental Cd remains on the core and, eventually, can be oxidized to CdO. In addition, Se(2-) counterions disperse inside the solution mainly attached to protonated amine ligands. The Se(2-) combines with H(+), leadin…
Kinetic solvent effects on the reaction of an aromatic ketone pi,pi* triplet with phenol. rate-retarding and rate-accelerating effects of hydrogen-bo…
2007
Quenching of the 2-benzoylthiophene π,π* triplet, 3BT*, by phenol yields the corresponding ketyl and phenoxyl radicals. Reaction rates were measured in 10 solvents having a range of hydrogen-bond acceptor strengths (β2H values). There appear to be two mechanisms: (i) a bimolecular reaction of 3BT* with “free” (i.e., not H-bonded) phenol in which the 3BT* accepts both a proton and an electron from the phenol, the rate decreasing as β2H increases; (ii) a trimolecular reaction of 3BT* with phenol that is H-bonded to a solvent molecule, PhO−H···S, in which the proton goes to the S and the electron to the 3BT*, the rate increasing as β2H increases.
Electrocarboxylation of aromatic ketones: Influence of operative parameters on the competition between ketyl and ring carboxylation
2007
Abstract The purpose of this work is to investigate the effect of operational parameters on the competition between the formation of the target 2-hydroxy-2-arylpropanoic acid and ring carboxylation in the electrocarboxylation of aromatic ketones. For the investigated ketones, this competition has been found to be dramatically influenced by different parameters such as the water content and the ratio between the carbon dioxide and the ketone concentrations (q = [CO2]/[ketone]). In particular, the target carboxylic acid formation can be favoured with respect to ring carboxylation by operating at high q ratios or by addition of small amounts of H2O to the reaction medium. An increase of the wa…