31053-94-8Relevant academic research and scientific papers
Encounter geometry determines product characteristics of electron transfer from 4-hydroxythiophenol to n-butyl chloride radical cations
Dey,Hermann,Naumov,Brede
, p. 137 - 144 (1999)
The electron transfer reaction between the n-butyl chloride parent ion and 4-thiophenol was studied using pulse radiolysis in solutions of 4-thiophenol in n-butyl chloride. It was found to have a diffusion-controlled rate constant of 1.5×1010 dm3 mol-1 s-1 and to involve contributions from all functional groups, i.e. -SH, -OH and the aromatic ring. Consequently, thiyl and phenoxyl radicals and 4-hydroxythiophenol radical cations were observed as direct products of this ion-molecule reaction. This unexpected reaction behavior could be explained by the hypothesis that the encounter geometry of the reaction partners determines the product characteristics.
Photochemical properties of excited triplet state of 6H-purine-6-thione investigated by laser flash photolysis
Alam,Fujitsuka,Watanabe,Ito
, p. 1338 - 1344 (2007/10/03)
Photochemical reactions of 6H-purine-6-thione (PuT) via the excited triplet state [3(PuT)*] have been studied by means of laser flash photolysis in organic solvents. Transient absorption bands at 475 and 690 nm were assigned to 3(PuT)*. Intersystem quantum yield and the lowest triplet energy of 3(PuT)* were evaluated to be 0.99 and 63 kcal/mol, respectively. The self-quenching rate constant is quite large (2.3×109 M-1 s-1 in THF). In photoinduced electron transfer, 3(PuT)* acts as electron acceptor for tetramethylbenzidine, while 3(PuT)* acts as electron donor for p-dinitrobenzene. Rate constants for H-atom abstraction (khT) of 3(PuT)* from benzenethiols, tocopherol, and 1,4-cyclohexadiene are on the order of 108 M-1 s-1. From the Hammett plots of khT for substituted benzenethiols, a negative ρ value indicates that 3(PuT)* has electrophilic character. In the addition reaction of 3(PuT)* toward various alkenes, the electrophilic character of 3(PuT)* was also confirmed. By steady-light photolysis of PuT, purine was produced via 3(PuT)* after H-atom abstraction. On combination of these results, the character of the lowest 3(PuT)* was presumed.
