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

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)1080-1086
Number of pages7
JournalChemPlusChem
Volume86
Issue number8
Early online date26 Jul 2021
DOIs
Publication statusPublished - Aug 2021

Keywords

  • 1,3-dipolar cycloaddition
  • alkoxyamine
  • kinetics
  • nitroxide
  • nitroxide-mediated polymerization

OECD FOS+WOS

  • 1.04 CHEMICAL SCIENCES

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