79635-02-2Relevant articles and documents
Organic Peroxides, XIV. The Thermal Decomposition of Polycyclic tert-Butyl Bridgehead Peroxycarboxylates
Ruechardt, Christoph,Golzke, Volker,Range, Guenter
, p. 2769 - 2785 (2007/10/02)
Eleven bridgehead peresters (1, 2, 5 - 8, 10, 12, 14, 18, 21) have been prepared for the first time and the products and the kinetics of their thermal decomposition were investigated.The correlations of all known thermolysis constants of bridgehead peresters with the steric substituent constants φf, with the solvolysis constants of the corresponding bridgehead bromides, as well as with the change in strain enthalpy ΔHsp for hydride abstraction from the bridgehead, as calculated by the procedure of v.R.Schleyer, were analysed.The thermolysis constants of these peresters are mainly determined by the polar effect in the transition state of the perester fragmentation.