10490-07-0Relevant articles and documents
Tagaki et al.
, p. 917,919 (1966)
Kinetic resolution of α-bromophenylacetamides using quinine or Cinchona alkaloid salts
Marzorati, Liliana,Fejfar, Jose L.,Tormena, Claudio F.,Vitta, Claudio Di
experimental part, p. 748 - 753 (2012/09/05)
The kinetic resolution of racemic α-bromophenylacetamides 1 was achieved in the presence of benzenethiolate and Cinchona alkaloid salts as phase-transfer catalysts or benzenethiol and quinine, yielding (S)-enantioenriched α-sulfanylated products. The observed stereoselection was rationalized on the basis of the best fitting of 1 and the resolving agent in the ternary complexes.
Sulfur radical cations. Kinetic and product study of the photoinduced fragmentation reactions of (phenylsulfanylalkyl)trimethylsilanes and phenylsulfanylacetic acid radical cations
Baciocchi, Enrico,Giacco, Tiziana Del,Elisei, Fausto,Lapi, Andrea
, p. 853 - 860 (2007/10/03)
Laser and steady-state photolysis, sensitized by NMQ+, of PhSCH(R)X 1-4 (R = H, Ph; X =SiMe3, CO2H) was carried out in CH3CN. The formation of 1+.-4+. was clearly shown. All radical cations undergo a fast first-order fragmentation reaction involving C-Si bond cleavage with 1+. and 2+. and C-C bond cleavage with 3+. and 4+.. The desilylation reaction of 1+. and 2+. was nucleophilically assisted, and the decarboxylation rates of 3+. and 4+. increased in the presence of H2O. A deuterium kinetic isotope effect of 2.0 was observed when H2O was replaced by D2O. Pyridines too were found to accelerate the decarboxylation rate of 3+. and 4 +.. The rate increase, however, was not a linear function of the base concentration, but a plateau was reached. A fast and reversible formation of a H-bonded complex between the radical cation and the base is suggested, which undergoes C-C bond cleavage. It is probable that the H-bond complex undergoes first a rate determining proton-coupled electron transfer forming a carboxyl radical that then loses CO2. The steady-state photolysis study showed that PhSCH3 was the exclusive product formed from 1 and 3 whereas [PhS(Ph)CH-]2 was the only product with 3 and 4.
