5798-80-1Relevant articles and documents
Kinetic study of the self-reactions of the BrCH2CH2O2 and BrCH(CH3CH(CH3O2 radicals between 275 and 373 K
Villenave, Eric,Moisan, Sandy,Lesclaux, Robert
, p. 2470 - 2477 (2007/10/03)
A conventional flash photolysis technique was used to measure the self-reaction rate constants of the primary BrCH2CH2O2 (2-bromoethylperoxy) and secondary BrCH(CH3)CH(CH3)O2 (2-bromo-l-methylpropylperoxy) β-brominated peroxy radicals, at temperatures in the range of 275-373 K. The absolute UV absorption spectra of BrCH2CH2O2 and BrCH(CH3)CH(CH3)O2 were also measured and compared to those obtained previously for these radicals. The temperature dependence of the self-reaction rate constants provided the following Arrhenius expressions: k(BrCH2CH2O2 + BrCH2CH2O2) = (6.15+5.152.99) × 10-14 exp{(1247 ± 203) K/T} cm3 molecule-1 s-1 and k(BrCH(CH3)CH(CH3)O2 + BrCH(CH3)CH(CH3)O2) = (7.60+22.05-5.65) × 10-15 exp{(1305 ± 428) K/T} cm3 molecule-1 s-1, where the uncertainties represent 95% confidence limits associated with the statistical fitting procedure and include the contribution for the expanded uncertainties in the individual rate constant. These results confirm the enhancement of the peroxy radical self-reaction reactivity upon β-substitution, which is similar for Br, Cl, or OH substituents. Structure-activity relationships are proposed for self-reactions of β-substituted peroxy radicals.
HETEROGENEOUS ASYMMETRIC RING-OPENING REACTIONS OF PROCHIRAL EPOXIDES INCLUDED AS GUEST MOLECULES IN TRI-o-THYMOTIDE CLATHRATES.
Gerdil, Raymond,Barchietto, Giacomo
, p. 4685 - 4688 (2007/10/02)
Enantiomorphous tri-o-thymotide clathrates of prochiral oxiranes were submitted to the action of gaseous hydrogen halides.Ring-opening reactions ensued that differ from those reported in homogeneous phase, showing a considerable modification of the chemical reactivity of the external reagent in the host lattice.Chirality transfer from the host receptors to the guest products was also observed, but with a poor efficiency.