2348-52-9Relevant articles and documents
Sehested et al.
, p. 1363,1364 (1977)
Kinetics and activation energy of the oxidation of para-tolyl radical by cobalt(III) in acetic acid: Competition kinetics
Espenson, James H.,Yiu, Douglas Tak-Yeung
, p. 599 - 604 (2007/10/03)
The title reaction gives rise to a benzylic cation that is rapidly transformed to its bromide in competition with the reaction of the radical with carbon tetrachloride. Experiments were carried out over 17-69°C in acetic acid containing cobalt(II) acetate, para-xylene, hydrobromic acid, carbon tetrachloride, and meta-chloroperoxybenzoic acid. The product ratio, ArCH 2Cl/ArCH2Br, in combination with other pertinent rate constants, was used to determine the rate constant for the step of interest: log script k sign (L mol-1 s-1) = 19.9 - (75 ± 11 kJ mol-1/2.303 RT). The large pre-exponential factor, which gives ΔS? = 128 J K-1 mol-1, signals an unusual transition state, because a negative value of ΔS? would be expected for a simple bimolecular reaction. The production of the ion pair ArCH 2+||OAc- in HOAc, which has the same dielectric constant as benzene, may be responsible, at least in part. Furthermore, inner sphere reorganization of cobalt may also contribute.
Kinetic Study of the Phthalimide N-Oxyl Radical in Acetic Acid. Hydrogen Abstraction from Substituted Toluenes, Benzaldehydes, and Benzyl Alcohols
Koshino, Nobuyoshi,Saha, Basudeb,Espenson, James H.
, p. 9364 - 9370 (2007/10/03)
The phthalimide N-oxyl (PINO) radical was generated by the oxidation of N-hydroxyphthalimide (NHPI) with Pb(OAc)4 in acetic acid. The molar absorptivity of PINO. is 1.36 × 103 L mol -1 cm-1 at λmax 382 nm. The PINO radical decomposes slowly with a second-order rate constant of 0.6 ± 0.1 L mol-1 s-1 at 25°C. The reactions of PINO . with substituted toluenes, benzaldehydes, and benzyl alcohols were investigated under an argon atmosphere. The second-order rate constants were correlated by means of a Hammett analysis. The reactions with toluenes and benzyl alcohols have better correlations with σ+ (ρ = -1.3 and -0.41), and the reaction with benzaldehydes correlates better with σ (ρ = -0.91). The kinetic isotope effect was also studied and significantly large values of kH/kD were obtained: 25.0 (p-xylene), 27. 1 (toluene), 27.5 (benzaldehyde), and 16.9 (benzyl alcohol) at 25°C. From the Arrhenius plot for the reactions with p-xylene and p-xylene-d10, the difference of the activation energies, EaD - E aH, was 12.6 ± 0.8 kJ mol-1 and the ratio of preexponential factors, AH/AD, was 0.17 ± 0.05. These findings indicate that quantum mechanical tunneling plays an important role in these reactions.
