The Kinetics of 1,3-Dipolar Cycloaddition of Vinyl Monomers to 2,2,5,5-Tetramethyl-3-imidazoline-3-oxides

Sergey A. Cherkasov, Anastasiya D. Semikina, Polina M. Kaletina, Yulia F. Polienko, Denis A. Morozov, Alexander M. Maksimov, Igor A. Kirilyuk, Elena G. Bagryanskaya, Dmitriy A. Parkhomenko

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование

Аннотация

In our previous work [Edeleva et al. Chem. Commun. 2019, 55, 190–193], we proposed a versatile approach to the activation of the homolysis of an aldonitrone group–containing alkoxyamine by 1,3-dipolar cycloaddition to a vinyl monomer. Both nitroxide- and alkoxyamine-containing aldonitrones were found to be capable of reacting with the activated alkenes. In the present study, the kinetics of these reactions with 11 different vinyl monomers were investigated using EPR and NMR spectroscopy, and apparent activation energies as well as pre-exponential factors were determined. The influence of monomer structure on the rate of the 1,3-dipolar cycloaddition is discussed. For the vinyl monomers typically used in nitroxide mediated polymerization (styrene, methyl methacrylate) the rate coefficient of cycloaddition to the nitroxide is around k(353 K) ∼4 ⋅ 10−4 L mol−1 s−1, whereas for n-butyl acrylate and methyl vinyl ketone we observed the fastest cycloaddition reaction with k(353 K)=8 ⋅ 10−3 and 4 ⋅ 10−2 L mol−1 s−1 respectively.

Язык оригиналаанглийский
Страницы (с-по)1080-1086
Число страниц7
ЖурналChemPlusChem
Том86
Номер выпуска8
Ранняя дата в режиме онлайн26 июл 2021
DOI
СостояниеОпубликовано - авг 2021

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