Collect. Czech. Chem. Commun.
1992, 57, 1951-1959
https://doi.org/10.1135/cccc19921951
Kinetic Studies of [4n+2]π-Thermal Cyclodimerization of 1-(3-Pyridazinyl)-3-oxidopyridinium Betaines
Madlene L. Iskandera, Samia A. El-Abbadyb, Alyaa A. Shalabya and Ahmed H. Moustafaa
a Department of Chemistry, Faculty of Science, Ain Shams University, Cairo, Egypt
b Department of Chemistry, University College for Women, Ain Shams University, Cairo, Egyp
Abstract
The reactivity of the base induced cyclodimerization of 1-(6-arylpyridazin-3-yl)-3-oxidopyridinium chlorides in a pericyclic process have been investigated kinetically at λ 380 nm. The reaction was found to be second order with respect to the liberated betaine and zero order with respect to the base. On the other hand dedimerization (monomer formation) was found to be first order. It was shown that dimerization is favoured at low temperature, whereas dedimerization process is favoured at relatively high temperature (ca 70 °C). Solvent effects on the reaction rate have been found to follow the order ethanol > chloroform ≈ 1,2-dichloroethane. Complete dissociation was accomplished only in 1,2-dichloroethane at ca 70 °C. The thermodynamic activation parameters have been calculated by a standard method. Thus, ∆G# has been found to be independent on substituents and solvents. The high negative values of ∆S# supports the cyclic transition state which is in favour with the concerted mechanism. MO calculations using SCF-PPP approximation method indicated low HOMO-LUMO energy gap of the investigated betaines.
