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Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules.
Kubota, Koji; Jiang, Julong; Kamakura, Yuri; Hisazumi, Reon; Endo, Tsubura; Miura, Daiyo; Kubo, Shotaro; Maeda, Satoshi; Ito, Hajime.
Afiliação
  • Kubota K; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Jiang J; Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Hokkaido, Japan.
  • Kamakura Y; Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
  • Hisazumi R; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Endo T; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Miura D; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Kubo S; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Maeda S; Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, Japan.
  • Ito H; Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Hokkaido, Japan.
J Am Chem Soc ; 146(1): 1062-1070, 2024 Jan 10.
Article em En | MEDLINE | ID: mdl-38134051
ABSTRACT
Radical initiators such as azo compounds and organic peroxides have been widely used to facilitate numerous transformations of free radicals, which enable the efficient synthesis of structurally complex molecules, natural products, polymers, and functional materials. However, these high-energy reagents are potentially explosive and thus often require special precautions or delicate operating conditions. We postulated that a more convenient and safer alternative for radical chain initiation could be developed by mechanical activation of thermodynamically stable covalent bonds. Here, we show that commodity plastics such as polyethylene and poly(vinyl acetate) are capable of acting as efficient initiators for radical chain reactions under solvent-free mechanochemical conditions. In this approach, polymeric mechanoradicals, which are generated by homolytic cleavage of the polymer chains in response to the applied mechanical energy provided by ball milling, react with tris(trimethylsilyl)silane to initiate radical chain dehalogenation of organic halides. Preliminary calculations support our proposed force-induced radical chain mechanism.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Japão

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Japão