176507-69-0Relevant academic research and scientific papers
Lewis Acid Activation and Catalysis of Dialkylaminyl Radical Reactions
Ha, Chau,Musa, Osama M.,Martinez, Felix N.,Newcomb, Martin
, p. 2704 - 2710 (2007/10/03)
Lewis acid activation and catalysis of dialkylaminyl radical reactions is demonstrated both qualitatively and quantitatively. Cyclization of the N-butyl-4-pentenaminyl radical (1) in the presence of a wide range of Lewis acids was shown to be efficient with good to excellent yields of cyclic products obtained in reactions conducted even at -78°C. Rate constants for fragmentation of the N-ethyl-2,2-diphenylethylaminyl radical (6), 6-exo cyclization of the N-methyl-6,6-diphenyl-5-hexenaminyl radical (7), and 5-exo cyclization of the N-methyl-5,5-diphenyl-4-pentenaminyl radical (8) in the presence of the Lewis acids LiBF4, MgBr2, and BF3 were measured by laser flash photolysis (LFP) methods. The LFP studies demonstrated saturation kinetic behavior with respect to the Lewis acids. Equilibrium binding constants for the Lewis acids with the dialkylaminyl radicals and rate constants for reactions of the Lewis acid complexed dialkylaminyl radicals were obtained from nonlinear regression analysis of the observed rate constants.
Kinetics of dialkylaminium cation radical reactions: Radical clocks, solvent effects, acidity constants, and rate constants for reactions with hydrogen atom donors
Horner, John H.,Martinez, Felix N.,Musa, Osama M.,Newcomb, Martin,Shahin, Haifa E.
, p. 11124 - 11133 (2007/10/03)
Dialkylaminium cation radical kinetics were studied directly by laser flash photolysis methods. Irradiation of N-hydroxypyridine-2-thione carbamates with 355-nm light gave dialkylaminyl radicals that were protonated to produce dialkylaminium cation radica
