Naslov
Thermal E-Z Isomerization of Aromatic Azodioxides in Solid State

Autori
Vančik, Hrvoj ; Varga, Katarina

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
European Symposium on Organic Reactivity-ESOR 2015 Book of Abstracts / - Kiehl, 2015

Skup
European Symposium on Organic Reactivity

Mjesto i datum
Kiel, Njemačka, 30.08.2015. - 04.09.2015

Vrsta sudjelovanja
Poster

Vrsta recenzije
Nije recenziran

Ključne riječi
activation parameters; aromatic azodioxides; kinetics of reaction; thermal solid-state E-Z isomerization

Sažetak
Most of the investigations of solid-state E-Z isomerizations have been focused on photoreactions. Thermal solid-state isomerizations of double bonds in organic molecules are very rare and not studied in details. In our previous works we have developed the approach to the study of the solid-state reaction mechanisms by using the dimerizations and dissociations of the aromatic C-nitroso compounds as models. The E-Z isomerizations of azodioxides in solution exclusively follow the pathway through the formation of the nitroso monomer intermediates. Direct “torsional” E-Z isomerization has not yet been observed. Here we demonstrate that the azodioxide Z-E isomerization in solid state can occur without the formation of the free nitroso molecule. The reaction is studied by measuring the kinetics of isomerizations of 3-chloro- and 3-bromonitrosobenzene dimers. The mechanism is discussed on the basis of the measured activation parameters, DSC, and time-resolved XPRD. It is proposed that the two concurrent reactions, the azodioxide E-Z isomerization, and the dimerization of C-nitroso molecules, respectively, occur through the same type of the transition state.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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