85963-93-5Relevant articles and documents
KINETICS AND MECHANISM OF THE MONOMOLECULAR HETEROLYSIS OF FRAMEWORK COMPOUNDS IX. CORRELATION ANALYSIS OF THE SOLVATION EFFECTS DURING THE HETEROLYSIS OF 1-ADAMANTYL PICRATE
Ponomareva, E. A.,Yavorskaya, I. F.,Dvorko, G. F.,Kulik, N. I.,Brus, A. V.
, p. 504 - 511 (2007/10/02)
The heterolysis rate of 1-adamantyl picrate at 25 deg C was determined in seven proton-donating and 21 aprotic solvents with triphenylverdazyls as internal indicators, v = k.A correlation analysis of the effect of the solvent parameters on the reaction rate in 35 solvents was made.The heterolysis rate depends on the polarity, electrophilicity, and cohesion of the solvent.A comparative analysis was made of the effect of the solvent nature on the heterolysis rate of the 1-adamantyl picrate, tert-butyl chloride, tert-butyl bromide, 7α-bromocholesterol benzoate, 1-adamantyl iodide, 1-adamantyl p-toluenesulfonate, diphenylmethyl bromide.Nucleophilic solvation of the solvent reduces the heterolysis rate of the first five substrates.
KINETICS AND MECHANISM OF MONOMOLECULAR HETEROLYSIS OF FRAMEWORK COMPOUNDS. II. IONIZATION OF 1-ADAMANTYL IODIDE IN ACETONITRILE
Ponomareva, E. A.,Tarasenko, P. V.,Yurchenko, A. G.,Dvorko, G. F.
, p. 2191 - 2203 (2007/10/02)
The heterolysis of 1-adamantyl iodide in acetonitrile was studied preparatively and kinetically (in the presence of triphenylverdazyl as internal indicator).Additions of LiClO4, Et4N+ClO4-, Et4N+OTs-, Et4N+I-, and Et4N+Br- do not affect the reaction rate; the normal salt effect and the salt effect of the law of mass action do not appear.Additions of water increase the reaction rate a little, while additions of LiBr, Bu4N+NO3-, LiCl, and Et4N+Cl- reduce it greatly.It is suggested that an intimate ion pair of the substrate is converted into a solvent- separated ion pair in the controlling stage of the reaction.
