info:eu-repo/semantics/article
E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3
Registro en:
Fracaroli, Alejandro Matías; Granados, Alejandro Manuel; Hoyos, Maria Rita Micaela; E-Z isomerization and aggregation Phenomena of Dithiafulvenes in CHCl3; American Chemical Society; Journal of Organic Chemistry; 74; 5; 3-2009; 2114-2119
0022-3263
1520-6904
CONICET Digital
CONICET
Autor
Fracaroli, Alejandro Matías
Granados, Alejandro Manuel
Hoyos, Maria Rita Micaela
Resumen
The physical-chemical properties of several 1,3-dithiafulvene (DTF) derivatives having a donor and acceptor group in the molecule were studied. The synthesis of these compounds produces selectively the E isomer, but when the compound is dissolved in CHCl3 isomerization to the Z isomer takes place with a rate that depends on the substituents. The interconversion rate is slow on the NMR time scale; therefore, two separated signals are observed, and they are used to measure the rate constant of isomerization. The equilibrium constant is, in all cases, very close to 1, and this is coincident with the fact that theoretical calculations of the energy of the two isomers in the gas phase differ by less than 0.1 kcal/mol. The isomerization reaction is completely reversible, and the E isomer can be obtained in pure form by selective crystallization. The derivatives with fhioalkyl groups have a strong tendency to aggregate in CDCl3. The formation of the aggregates is evidenced from the changes in ID 1H NMR and DOSY spectra as a function of concentration. The compounds are highly delocalized, and this is reflected by the low activation energy for the isomerization Fil: Fracaroli, Alejandro Matías. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Granados, Alejandro Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Hoyos, Maria Rita Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina