Abstract

QUIJANO, JAIRO et al. THERMOLYSIS OF SUBSTITUTED ß-HYDROXYKETONES-ß-ARYL. A COMPUTATIONAL STUDY. Dyna rev.fac.nac.minas [online]. 2006, vol.73, n.150, pp.89-96. ISSN 0012-7353.

Theoretical studies on the thermolysis of (m,p) substituted b -hydroxiketones-b-aryl to produce a mixtures of aromatic aldehydes and acetone at 429,15K were carried out using ab-initio theoretical methods, at the MP2/6-31G(d)//HF/6-31G(d) levels of theory. The reaction profiles for the studied substituents m and p show in all the cases that the second step of the tautomerization reaction of acetone (DG =217.6 kJmol-1) is the slowest. The first step includes a six-membered cyclic transition state and on this one the studies of a possible Linear Free Energy Relationship were centered. The results show there is no a very well agreement with the Hammett correlation indicative of perpendicular effect to the reaction coordinate.

Keywords : Thermolysis; Transition state(TS); Hammett; Yukawa T-suno; Ab-initio.

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