Solvent and Substituent Effects on the Thermolysis of Antimalarial Fluorophenyl Substituted 1,2.4-Trioxanes 英文参考文献.docVIP

Molecules 2003, 8, 655-662 molecules ISSN 1420-3049 Solvent and Substituent Effects on the Thermolysis of Antimalarial Fluorophenyl Substituted 1,2.4-Trioxanes Lazaro F. R. Cafferata* and Ruben S. Rimada Laboratorio LADECOR (UNLP) and CINDECA (CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Calles 47 Y 115, (1900) La Plata, República Argentina. * Author to whom correspondence should be addressed: caferata@.ar Received: 25 September 2002; in revised form: 18 July 2003/ Accepted: 20 July / Published: 15 August 2003 Abstract: The kinetics and mechanism of the thermal decomposition reaction of cis-6-(4- fluoropheny1)-5,6-[2-(4-fluorophenyl)-propylidene]-3,3-tetramethylene-l,2,4-trioxacyclo- hexane (I) were investigated separately in n-hexane and in methanol solutions over the temperature and concentration ranges of 393.2-443.2 K and 2.7-54 x l0 M, respectively. -5 The values of the activation parameters for both reactions were compared with the corresponding ones for the thermolysis of cis-6-(4-fluorophenyl-5,6-[2-(4-fluorophenyl)- 3-hydroxypropylidene]-3,3-tetramethylene-1,2,4-trioxacyclohexane (II), investigated in the same solvents and temperature range. Substituent and solvent effects on the initial homolytic rupture of the O-O peroxydic bonds of those molecules were evaluated. Keywords: Peroxides – Thermolysis - Fluorophenyl Substituted 1,2,4-trioxanes - Thermal decomposition Reactions - Solvent and Substituents Effects - Antimalarial Compounds  Molecules 2003, 8 656 Introduction Cyclic peroxides of the substituted 1,2,4-trioxane type are structurally related to the six-member ring 1,2,4,5-tetroxanes and 1,2,4,5-trioxazines already investigated by kinetic methods [1,2]. Examples of those compounds, which are available through new synthetic methods, are related to the antimalarial activity of molecules with