TY - JOUR

T1 - The Kinetics of 1,3-Dipolar Cycloaddition of Vinyl Monomers to 2,2,5,5-Tetramethyl-3-imidazoline-3-oxides

AU - Cherkasov, Sergey A.

AU - Semikina, Anastasiya D.

AU - Kaletina, Polina M.

AU - Polienko, Yulia F.

AU - Morozov, Denis A.

AU - Maksimov, Alexander M.

AU - Kirilyuk, Igor A.

AU - Bagryanskaya, Elena G.

AU - Parkhomenko, Dmitriy A.

N1 - Funding Information: The kinetics measurements were supported by the Russian Science Foundation (grant No. 20‐73‐00350). The synthesis of nitroxide and alkoxyamine was performed under the financial support of the Ministry of Science and Higher Education of the Russian Federation (grant No. 14.W03.31.0034). The authors are grateful to the Multi‐Access Chemical Service Center SB RAS for analysis and characterization of 4‐perfluorotolyl vinyl sulfide and . 1 2 3 Funding Information: The kinetics measurements were supported by the Russian Science Foundation (grant No. 20-73-00350). The synthesis of nitroxide 1 and alkoxyamine 2 was performed under the financial support of the Ministry of Science and Higher Education of the Russian Federation (grant No. 14.W03.31.0034). The authors are grateful to the Multi-Access Chemical Service Center SB RAS for analysis and characterization of 4-perfluorotolyl vinyl sulfide and 3. Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/8

Y1 - 2021/8

N2 - 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.

AB - 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.

KW - 1,3-dipolar cycloaddition

KW - alkoxyamine

KW - kinetics

KW - nitroxide

KW - nitroxide-mediated polymerization

UR - http://www.scopus.com/inward/record.url?scp=85113809494&partnerID=8YFLogxK

U2 - 10.1002/cplu.202100266

DO - 10.1002/cplu.202100266

M3 - Article

C2 - 34402220

AN - SCOPUS:85113809494

VL - 86

SP - 1080

EP - 1086

JO - ChemPlusChem

JF - ChemPlusChem

SN - 2192-6506

IS - 8

ER -