32353-14-3Relevant academic research and scientific papers
Kinetics of the solvolyses of benzhydryl derivatives: Basis for the construction of a comprehensive nucleofugality scale
Denegri, Bernard,Streiter, Andre,Juric, Sandra,Ofial, Armin R.,Kronja, Olga,Mayr, Herbert
, p. 1648 - 1656 (2007/10/03)
A series of 21 benzhydrylium ions (diarylmethylium ions) are proposed as reference electrofuges for the development of a general nucleofugality scale, where nucleofugality refers to a combination of leaving group and solvent. A total of 167 solvolysis rate constants of benzhydrylium tosylates, bromides, chlorides, trifluoroacetates, 3,5-dinitrobenzoates, and 4-nitroben-zoates, two-thirds of which have been determined during this work, were subjected to a least-squares fit according to the correlation equation log k 25°C = Sf(Nf + Ef), where s f and Nf are nucleofuge-specific parameters and E f is an electrofuge-specific parameter. Although nucleofuges and electrofuges characterized in this way cover more than 12 orders of magnitude, a single set of the parameters, namely sf, Nf, and E f, is sufficient to calculate the solvolysis rate constants at 25°C with an accuracy of ± 16%. Because sf ≈ 1 for all nucleofuges, that is, leaving group/ solvent combinations, studied so far, qualitative discussions of nucleofugality can be based on Nf.
Mechanism for Diacyl Peroxide Decomposition
Linhardt, R.J.,Murr, B.L.,Montgomery, E.,Osby, J.,Sherbine, J.
, p. 2242 - 2251 (2007/10/02)
The presence of ion-pair intermediates in diacyl peroxide decomposition has been established.Various substituted (4-X-phenyl)phenylacetyl Y-benzoyl peroxides and three corresponding 4-X-benzhydryl-4-nitrobenzoic carbonic anhydrides (X = CH3, H, Cl) were prepared.All compounds decomposed in 90percent acetone-water (v/v), giving the ionic products ester, alkohol, and acid.The fraction of ester (R) was similar to that found in the solvolysis of substituted benzhydryl-N-nitrosoamides, indicating a similar spectrum of ion-pair intermediates.The yield of ester product could be increased markedly by the addition of common ion.The mixed carbonic carboxylic anhydrides were not products of peroxide decomposition in either nucleophilic or nonnucleophilic solvents and showed a lower decompositin rate than the peroxide.Lastly, both the peroxide and the mixed carbonic carboxylic anhydride decomposed in chloroform with net retention.Neither CIDNP nor any radical abstraction product was detected.
