Kinetics issues of CuBr lasers with added hydrogen

A computational kinetics model of the CuBr laser with added hydrogen is presented. The space-time behaviour of the lasers and lasants is described in detail. Besides the discharge field, it is confirmed that the dissociation/recombination of the CuBr molecule plays an important role in the plasma electron temperature. The radial field, which peaks at 30% of the discharge field and has two opposite directions along the radius, results in the skin of electron density and the black centre of the large-bore laser beam.     

Chemistry of 1-Alkoxy-1-glycosyl Radicals: The Manno- and Rhamnopyranosyl Series. Inversion of alpha- to beta-Pyranosides and the Fragmentation of Anomeric Radicals

The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.