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Radical Propagation Facilitating Aerobic Oxidation of Substituted Aromatics Promoted by Tert‐Butyl Hydroperoxide
Author(s) -
Bai Jiatong,
Huang Jiangnan,
Jiang Qi,
Li Yuhang,
Wang Hongjuan,
Yu Hao,
Zhang Qiao,
Cao Yonghai,
Peng Feng
Publication year - 2021
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202101805
Subject(s) - radical , chemistry , toluene , catalysis , decomposition , substrate (aquarium) , oxygen , alkyl , selectivity , peroxide , molecule , photochemistry , organic chemistry , oceanography , geology
Abstract The selective oxidation of aromatics to synthesize valued‐added products is of great significance for chemical industry. Molecule oxygen as oxidant is the priority for this process, however, low efficiency was usually obtained. In this work, a new strategy for aromatics oxidation using O 2 and Tert‐butyl hydroperoxide (TBHP) as dual oxidants without catalyst was proposed. Typical radical process was observed when Toluene was used as the substrate. As high as 47.1 % conversion and 87.6 % selectivity of benzol acid were obtained, while a negligible or low activity were observed under O 2 or TBHP oxidative systems. Detailed investigation shows that the distribution of products was almost the same between TBHP+N 2 and TBHP+O 2 processes, in which the very close active energies were obtained (46.0 and 46.3 kJ/mol). These results indicated that TBHP+N 2 or TBHP+O 2 involved reactions underwent the same reaction process. The mechanism study demonstrated that the decomposition of TBHP could produce abundance of t ‐BuO . and . OH radicals, which significantly enhanced the αH abstraction from toluene and formed alkyl radicals. The alkyl radicals then react with O 2 to produce peroxides, which started the radical propagation cycle. The overall rate would be enhanced subsequently. Furthermore, an extension application of other aromatic substrates was investigated and displayed a great promising future to produce aromatic products.