Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window


Autoria(s): Mancebo Aracil, Juan; Muñoz Guillena, María José; Such-Basañez, Ion; Sansano, Jose M.
Contribuinte(s)

Universidad de Alicante. Departamento de Química Orgánica

Universidad de Alicante. Servicios Técnicos de Investigación

Procesos Catalíticos en Síntesis Orgánica

Materiales Carbonosos y Medio Ambiente

Data(s)

20/09/2012

20/09/2012

2012

26/06/2012

Resumo

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

This work has been supported by the Spanish Ministerio de Ciencia e Innovación (MICINN) (Consolider INGENIO 2010 CSD2007-00006, CTQ2010-20387, FEDER, Generalitat Valenciana (PROMETEO/2009/039), and by the University of Alicante.

Identificador

MANCEBO-ARACIL, Juan, et al. “Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window”. ChemPlusChem. Vol. 77, Issue 9 (Sept. 2012). ISSN 2192-6506, pp. 770-777

2192-6506

http://hdl.handle.net/10045/24276

10.1002/cplu.201200107

Idioma(s)

eng

Publicador

Wiley-VCH Verlag GmbH & Co. KGaA

Relação

http://dx.doi.org/10.1002/cplu.201200107

Direitos

info:eu-repo/semantics/openAccess

Palavras-Chave #Autocatalysis #Azomethine ylides #Cycloaddition #Differential scanning calorimetry #Kinetics #Química Orgánica
Tipo

info:eu-repo/semantics/article