85963-93-5Relevant academic research and scientific papers
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. V. IONIZATION-FRAGMENTATION PROCESS IN DECOMPOSITION OF 1-ADAMANTYL CHLOROFORMATE
Ponomareva, E. A.,Yavorskaya, I. F.,Dvorko, G. V.
, p. 477 - 489 (2007/10/02)
The decomposition of 1-adamantyl chloroformate in acetonitrile, nitrobenzene, benzene, and isopropyl and tert-butyl alcohols in the presence of triphenylverdazyls as internal indicator was investigated preparatively and kinetically.In nitrobenzene small addition of water increase the reaction rate, and additions of tetraethylammonium halides reduce it.In isopropyl and tert-butyl alcohols and in nitrobenzene in the presence of tetraethylammonium halides the reaction rate depends on the nature of the substituent in the verdazyl.The reaction rate increases linearly with increase in the dielectric constant of the medium.It is assumed that an intimate ion pair is formed at the first stage of the reaction and undergoes fragmentation in the controlling stage to 1-adamantyl chloride or is converted into a solvent-separated ion pair.The latter reacts with the verdazyl or undergoes fragmentation to 1-adamantyl chloride.
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.
KINETICS AND MECHANISM OF MONOMOLECULAR HETEROLYSIS OF FRAMEWORK COMPOUNDS. I. IONIZATION OF 1-ADAMANTYL p-TOLUENESULFONATE IN ACETONITRILE
Ponomareva, E. A.,Tarasenko, P. V.,Yurchenko, A. G.,Dvorko, G. F.
, p. 481 - 493 (2007/10/02)
The heterolysis of 1-adamantyl p-toluenesulfonate in acetonitrile was investigated preparatively and kinetically (in the presence of triphenylverdazyl as internal indicator) ( v = k, k25 = 1.97E-6 sec-1, ΔH = 88.8 kJ/mole, ΔS25 = -57.3 J/mole*deg).Additions of tetraethylammonium bromide, tetraethylammonium perchlorate, tetraethylammonium p-toluenesulfonate, and N-butylquinolinium p-toluenesulfonate ( 0.05 - 0.005 M ) do not affect the reaction rate, and the normal salt effect and the effect of the law of mass action do not appear.The reaction rate is increased a little by the addition of water and phenol, and is increased greatly by the addition of sodium perchlorate, lithium perchlorate, and lithium bromide.The salt effect increases with decrease in the size of the cation ( electrophilic catalysis ).The addition of the cation was confirmed by additions of dibenzo-18-crown-6.It is suggested that the controlling stage of the reaction involves conversion of an intimate ion pair of the substrate into a solvent-separated ion pair.
